University of Helsinki

Department of Chemistry

Annual Report 2008

CONTENTS DEPARTMENT OF CHEMISTRY 2008 5 ADMINISTRATION 7 TEACHING 8 CHEMISTRY TEACHER EDUCATION 8 LABORATORY OF ANALYTICAL CHEMISTRY 13 INTRODUCTION 13 PERSONNEL 13 RESEARCH ACTIVITIES 15 PROJECTS AND FUNDING 15

BIOANALYTICAL RESEARCH 16 ENVIRONMENTAL RESEARCH 16 INSTRUMENTAL DEVELOPMENT 18

PUBLICATIONS 25 LABORATORY OF INORGANIC CHEMISTRY 30 PERSONNEL 30 RESEARCH ACTIVITIES 31 GENERAL 31

CATALYSIS AND GREEN CHEMISTRY 34 THIN FILMS 35 NANOSTRUCTURES AND NANOMATERIALS 38 CHEMICAL CRYSTALLOGRAPHY 40 TLBR CRYSTAL GROWTH AND CHARACTERIZATION 41 COMPUTATIONAL CHEMISTRY 42 SOLUTION CHEMISTRY 42

PUBLICATIONS 43 LABORATORY OF PHYSICAL CHEMISTRY 50 PERSONNEL 50 RESEARCH ACTIVITIES 51 MOLECULAR SPECTROSCOPY, AND COMPUTATIONAL AND THEORETICAL CHEMISTRY 51

SOLID STATE SPECTROSCOPY AND PHOTOCHEMISTRY 55 ATMOSPHERIC AND COMBUSTION CHEMISTRY RESEARCH 58 RESEARCH IN MOLECULAR MAGNETISM 59

PUBLICATIONS 61 LABORATORY OF ORGANIC CHEMISTRY 64 PERSONNEL 65 RESEARCH ACTIVITIES 66 CHEMISTRY OF NATURAL POLYPHENOLICS 67 SYNTHESIS AND LABELING OF STEROIDS 68 DRUG DISCOVERY 68 GREEN TECHNOLOGYIQUES IN PRACTICE: NATURAL PRODUCT SYNTHESIS IN IONIC LIQUIDS 69 WOOD CHEMISTRY 69 CHEMISTRY OF NATURAL TETRAPYRROLES AND QUINONES 71 CHEMISTRY OF NUCLEOSIDES AND NUCLEOTIDES 71 FATTY ACID CHEMISTRY 73 MISCELLANEOUS SYNTHETIC STUDIES 74 PUBLICATIONS 75 LABORATORY OF POLYMER CHEMISTRY 80 PERSONNEL 80 RESEARCH ACTIVITIES 83

CONTROLLED RADICAL POLYMERISATION 83 ENVIRONMENTALLY RESPONSIVE POLYMERS 83 SELF-ORGANIZATION OF BLOCK COPOLYMERS IN AQUEOUS SOLUTIONS 83 METAL NANO PARTICLES 84 POLYELECTROLYTE COMPLEXES 84

STRUCTURE ANALYSIS OF POLYMERS AND MULTIMOLECULAR ASSOCIATES WITH COMPLEX ARCHITECTURES IN SOLUTION 85

GLOBULES AND MESOGLOBULES IN AQUEOUS MEDIA 85 COMPUTER SIMULATION OF AMPHIPHILIC STAR COPOLYMERS 85

NEW POLYMERIC EMULSIFIERS 85 WATER DISPERSIBLE CONDUCTING POLYMERS 85 ELECTROACTIVE POLYMERS 86 SOLID STATE NMR STUDIES OF FIBER ULTRASTUCTURE 86 NEW CELLULOSE DERIVATIVES 86 NEW WATER-BORNE COATING FORMULATIONS 86 NMR SPECTROSCOPY OF DRUGS 87 STIMULI-RESPONSIVE HYDROGELS 87

PUBLICATIONS 88 LABORATORY OF RADIOCHEMISTRY 92 PERSONNEL 92 RESEARCH ACTIVITIES 93

INORGANIC ION EXCHANGE MATERIALS FOR NUCLEAR WASTE TREATMENT 94 STUDY OF NATURAL REDOX PERTURBATIONS IN THE BEDROCK 95 SORPTION OF LONG-LIVED RADIONUCLIDES IN SOIL AT THE OLKILUOTO SITE 97 SORPTION AND REACTIVE TRANSPORT OF RADIONUCLIDES 97 THE RELEVANCE OF COLLOIDS IN PROMOTING THE TRANSPORT OF RADIONUCLIDES 98 RADIONUCLIDE TRANSPORT IN GRANITIC ROCK: CHARACTERISATION OF PORE 99 SOLID-WATER INTERFACE CHEMISTRY: SORPTION OF TRIVALENT ACTINIDES ONTO ALUMINIUM(HYDR)OXIDE AND CLAY MINERALS 102 ENVIRONMENTAL RESEARCH 103 RADIOPHARMACEUTICAL CHEMISTRY 104 THE CYCLOTRON IN THE LABORATORY OF RADIOCHEMISTRY 106 RADIATION CHEMISTRY 107

PUBLICATIONS 109 LABORATORY FOR INSTRUCTION IN SWEDISH 112 PERSONNEL 113 RESEARCH ACTIVITIES 113

QUANTUM DOTS 113 DENSITY-FUNCTIONAL STUDIES OF BIOMOLECULES AND CLUSTERS 113 MAGNETICALLY INDUCED CURRENTS 114 COMPUTATIONAL INORGANIC CHEMISTRY 115 NUCLEAR MOMENTS, HYPERFINE PROPERTIES AND NMR PAPAMETERS 116 OTHER TOPICS 117 NUMERICAL METHODS 117 COOPERATION BETWEEN THE LABORATORY AND SECONDARY-SCHOOL TEACHERS AND PUPILS 117 RESEARCH COLLABORATION 117 WINTER SCHOOL 118 HONOURS 118

PUBLICATIONS 118 LABORATORY, ADMINISTRATIVE AND OTHER STAFF 121

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DEPARTMENT OF CHEMISTRY 2008

The economic budget for the Department of Chemistry in 2008 remained virtually unaltered from the previous year. However, the external funding continued to grow very satisfactorily and when averaged over the different laboratories of chemistry external funding amounted more than half of the total budget.

The activities of different laboratories in graduate schools and centers of excellence are quite positive. A center of excellence in computational molecular science is coordinated from the Department of Chemistry, and in connects in Kumpula partners from both chemistry and physics. Also, analytical and polymer chemistry were successful to win a CoE status, starting in 2008.

The chemistry department moved to the Kumpula Campus in 1995. It has been a pleasure to welcome the other departments of the Faculty of Science to the same hill, and see many new interdisciplinary activities growing. Meeting scientists from different fields, for example at lunch, gives new and rich colour to discussions and makes it possible to discover and grow scientific connections within our community. Besides the traditional series of seminars of different laboratories, the KCCP (Kumpula Computational Chemistry and Physics) seminar series connects researchers from chemistry and physics.

The number of scientific papers published in 2008 in peer-reviewed international journals was 218 (213 in 2007, 149 in 2006, 167 in 2005, 195 in 2004, 194 in 2003 and 215 in 2002) and, as in past years, the number of other publications (general articles, conference abstracts, textbooks etc.) exceeded one hundred. The research strategy and the most important areas of research are described in the www pages of the department: http://www.helsinki.fi/kemia/english/.

A total of 126 master’s degrees, 16 licentiate degrees and 16 doctorates were awarded in chemistry in 2008. The variation in the number of degrees awarded for the years 2002–2008 is shown in the diagrams below and this shows that educationally year 2006 was below average. The exceptionally high number of master’s degrees id due to the fact that 2008 was the last year to get a degree before change to new requirements.

The number of credits earned in chemistry has remained fairly constant at

11,000 to 12,000 during the last 10 to 15 years. The figure for 2008 (19,167 ECTS credits) accords well with the long-term statistics (18,300 ECTS credits in 2007, 17,368 ECTS credits in 2006, 11,505 credits in 2005, 10,716 in 2004 11,207 in 2003, 11,022 in 2002, 11,907 in 2001, 12,148 in 2000).

020406080

100

120

140

2 0 0 2 2 0 0 3 2 0 0 4 2 0 0 5 2 0 0 6 2 0 0 7 2 0 0 8

M.Sc.

0

5

10

15

20

25

2002 2003 2004 2005 2006 2007 2008

Ph.D.Lic.Phil.

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The quotas set for admission to the undergraduate programmes in chemistry were 150 students for the regular chemistry programme and 15 students for the chemistry teacher programme. These figures have remained the same for several years. In 2008 the number of the first-choice applicants in the spring selection process was 534 for programme and 29 for the chemistry teacher programme. Although it has not enjoyed particular success, the fall selection process for students seeking to enter the education programme was arranged once again in 2008, and 3 students were accepted (2 in 2007, 2 in 2006, 3 in 2005, 15 in 2004, 5 in 2003, 2 in 2002). Variations in the number of first-choice applicants (610 in 2007, 679 in 2006, 619 in 2005, 564 in 2004, 570 in 2003, 518 in 2002) suggests that the popularity of chemistry as an academic discipline and as a subject in the Finnish upper secondary schools seems to show a marked upward trend although the variation has been small in the last five years.

Considerable emphasis has been placed on cooperation with secondary schools in the recent years to make chemistry a more attractive subject. This cooperation has established permanent usage with the new university post in chemical education. A laboratory facility for schoolchildren, named Gadolin-class, was established in a special collaboration with chemical industries, schools and our university. In 2008 about 1500 students and more than 530 teachers from schools in the capital area and southern Finland visited the department or participated in courses arranged specially for them. In addition, school teachers were informed of matters of current interest by e-mail and post. Visits by teacher-students to local schools were also arranged. These efforts will most probably increase the number of motivated applicants to chemistry.

At the end of year 2008 the departmental staff, composed of teaching and research personnel, docents (assistant professors with part-time teaching responsibilities), externally funded researchers, and administrative and technical staff, numbered about 320 in total. The personnel of individual laboratories, the main fields of research and the major research facilities can be found in the laboratory reports.

From the administrative point of view year 2008 was quite hectic again, and several major evolutionary programs were running concurrently. Most importantly, we prepared ourselves for the big change in Finnish Universities, which takes place in the beginning of 2010.

Development of our infrastructure could be continued in 2008, and about 1 M€ was invested to new equipment. Helsinki, 7. September, 2009 Prof. Markku Räsänen Director of the Department

0

200

400

600

800

2002 2003 2004 2005 2006 2007 2008

applicants

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ADMINISTRATION

The Department of Chemistry is composed of the seven laboratories detailed in this report, each led by its own Head of Laboratory. Director Markku Räsänen and a steering committee conduct executive leadership of the Department. This adminis-trative structure combines the advantages of personal leadership with the representation of various categories of personnel.

The Departmental steering committee guidelines make it possible to invite ex-ternal members to participate in committee work. Ph.D. Lars Gädda, Research Director of the Finnish Forest Cluster, and Ph.D. Eeva-Liisa Poutanen, Director General of the Finnish Institute of Marine Research, were appointed as full mem-bers of the Department of Chemistry steering committee on February 5, 2007.

The members of and substitutions to the Steering Committee are: Ilkka Kilpeläinen Professor (Mikko Oivanen; Professor) Jukka Lehto Professor (Sirkka Liisa Maunu; Professor) Mikko Ritala Professor (Markku Leskelä; Professor) Markku Räsänen Professor (Lauri Halonen; Professor) Risto Harjula University Lecturer (Sami Hietala; University Lecturer) Timo Repo Professor (Maija Aksela; University Lecturer) Jussi Sipilä University Lecturer (Juha Vaara; University Lecturer) Kari Tuomainen Laboratory Technician (Merit Hortling, Secretary) Tatu Iivanainen Undergraduate (Tiina Sarnet; Undergraduate) Kai Kaksonen Undergraduate (Heidi Handolin; Undergraduate) Kristian Meinander Ph.D. student (Nina Huittinen; Ph.D. student) Jaana Saarni Undergraduate (Anne Honkanen; Undergraduate) Lars Gädda Research Director Eeva-Liisa Poutanen Director General Heljä Heikkilä Secretary There were thirteen steering committee meetings in 2008.

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TEACHING

Teaching at the Department of Chemistry comprises lectures, laboratory courses, seminars and computer-aided learning. In addition to the general compulsory courses, the Department offers courses on special areas of chemistry to meet current needs. Many of these special courses are given by experts from industry and other research institutes. A number of lecture courses and seminars are given in English, particularly at the advanced undergraduate and postgraduate levels. The teaching, especially in the advanced courses, is strongly based on the most recent research as most teaching personnel are active in research as well. Research also plays an es-sential role in the education of the students in the final stages of the master’s pro-gram.

Basic chemistry courses are offered to students in inorganic, organic and physi-cal chemistry and, after completion of their basic studies, students specialize in analytical, inorganic, organic, physical, polymer or radiochemistry. Most graduates in chemistry leave the university and enter the labor market with a Master’s degree, which typically requires 5–6 years of study. The intermediate B.Sc. degree is also available. The higher degrees are Licentiate of Philosophy (Lic.Phil.) and Doctor of Philosophy (Ph.D.).

To make chemistry more attractive as a subject in elementary and secondary schools, considerable emphasis has been placed on cooperation with schools. Ap-proximately 1500 students from schools in the capital area and southern Finland visit the Department each year, or take part in courses arranged specially for them. In addition, teachers are informed by e-mail and mail on matters of current interest.

Chemistry teacher education Within the Department of Chemistry, the Unit of Chemistry Teacher Education has the responsibility for preparing teachers of chemistry, conducting research in chemistry education, co-operating with schools and other units of teacher education in the University and the national chemistry education centre called Kemma and science education centre called the LUMA Centre, and student counselling in chemistry teacher education. Information on chemistry teacher education can be found at www-pages (http://www.helsinki.fi/kemia/opettaja/english/ ) or intranet pages, and in a brochure on chemistry teacher education. About 150 teacher students who have a major or a minor in chemistry are studying in the unit. In addition, 20 students are studying for their Ph.D. degrees in chemistry education in the Department.

The aim of chemistry teacher education is to educate enthusiastic and skilful researching chemistry teachers for life-long learning, who are capable of following both the development of chemistry and chemistry teaching, adapting the most up-to-date research information into their work as teachers at the high school level, and engaging in research on chemistry education. Research-based education is being implemented in eight courses on chemistry teaching and a research seminar. During the education, the students acquaint themselves with retrieval of scientific information in their own field, producing and analysing new information, as well as critically assessing information using a variety of methods. The research on

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chemistry teaching is practiced in a small scale in courses and on a wider scale in the Master’s and postgraduate studies in chemistry education.

Instruction in the Department Teacher students study both chemistry and chemistry education courses in the Department. During undergraduate studies pre-service teacher students study most of the same chemistry courses (altogether 92cp.) as other chemistry students. However, there are two special courses for teacher students, Introduction to Chemistry Education (3 cp) and Chemistry in the Community (4 cp) in the program. A goal of the courses in chemistry education is to support students’ life-long learning in chemistry and its teaching. The typical features of the chemistry education courses are new teaching strategies using new ICT technology, research in chemistry and in chemistry education, and collaborative learning in co-operation with in-service chemistry teachers, educational institutions, industry, the science centre called Heureka and museums.

Figure 1. During their studies, teacher students also participate in guiding children and young people in activities arranged by the Centre for Chemistry Education (see more: http://www.helsinki.fi/kemia/opettaja/english/kemma/index.shtml) with the science education centre called the LUMA Centre.

In the Master’s studies, students complete 30 cp in chemistry education and 14 cp in chemistry in the Department. There are six special advanced courses in chemistry education in the Department: Chemistry as Science and Discipline (5 cp.), Models and Visualization in Chemistry Education (5 cp), Practical Work in Chemistry Education I (5 cp), Practical Work in Chemistry Education II (5 cp.), Central Areas

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of Chemistry Education I (6 cp), and Central Areas of Chemistry Education II (4 cp.).

We have offered a post-graduate program in chemistry education (Lic.Phil. and Ph.D.) since 2003. The postgraduate studies in chemistry teaching focus on original research, chemistry teaching research methodology, pursuing research in the postgraduate student’s field of study and representation of research results, as well as participating in scientific discourse. A special research seminar has been arranged once a month since 2005.

Research in chemistry education Research is an important aspect of chemistry education, with many areas of emphasis. Special research has been conducted on chemistry learning and teaching from school to university level. Some main research interests are (a) Meaningful Learning in Chemistry with Technology (e.g. Modelling and Visualization, Microcomputer -Based Laboratory, MBL), (b) Meaningful Learning and Thinking Skills in Chemistry, (c) Research-based Pre-service and In-Service Chemistry Teacher Education, and (d) Meaningful University-Level Chemistry Education. For example, the aims of technology research are (a) to support meaningful chemistry learning through ICT, (b) to develop learning environments for chemistry education where ICT can be applied efficiently and in versatile ways, (c) to help teacher students and teachers adopt and develop models of ICT implementation in their chemistry teaching, and (d) to develop useful digital materials for chemistry instruction. Several Masters Theses and Ph.D. dissertations are active and 15 Master Theses have been completed, based on these projects.

Collaboration with schools and other partners Research is an important aspect of chemistry education, with many areas of emphasis. Special research has been conducted on chemistry learning and teaching from school to university level. Some main research interests are (a) Meaningful Learning in Chemistry with Technology (e.g. Modelling and Visualization, Microcomputer -Based Laboratory, MBL), (b) Meaningful Learning and Thinking Skills in Chemistry, (c) Research-based Pre-service and In-Service Chemistry Teacher Education, and (d) Meaningful University-Level Chemistry Education. For example, the aims of technology research are (a) to support meaningful chemistry learning through ICT, (b) to develop learning environments for chemistry education where ICT can be applied efficiently and in versatile ways, (c) to help teacher students and teachers adopt and develop models of ICT implementation in their chemistry teaching, and (d) to develop useful digital materials for chemistry instruction. Several Masters Theses and Ph.D. dissertations are active and 15 Master Theses have been completed, based on these projects.

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Figure 2. Chemistry clubs are arranged approximately once every school year, in autumn or spring. The children who attend are usually aged between 9 and 12. Summer camps are arranged during summer holidays. They welcome children and youths from different age groups, ranging from elementary school to high school students. Five chemistry camps were arranged in 2008. They are arranged in the Chemistry Class Gadolin.

KEMMA frequently arranges workshops and summer courses for teachers. The workshops are built around a certain theme, for example, science teaching in elementary school, practical science teaching or molecular modelling. The National Days of Chemical Education are arranged every year in a different region of the country. The Days bring together chemistry teachers and student teachers from all over Finland to attend lectures and workshops dealing with current issues in the field of chemical education. A newest innovation has been the www-magazine for children, Jippo (http://www.helsinki.fi/jippo ). The magazine’s goal is to create and support lifelong interest in science (e.g. chemistry) and to open up new perspectives in science, mathematics, and technology. Created for collaboration between schools, university and industry, Chemistry Class Gadolin is a recent innovation. A new learning environment for chemistry teaching, the class aims to advance the positive image of chemistry and offer educational alternatives. Named after Johan Gadolin (1760–1852), the founder of Finnish chemistry research and discoverer of the element Ytrium, the class welcomes study visits by pupils and students aged 7 to 20. Study opportunities include experimental laboratory work, computer modelling, visits to research laboratories and communication with scientists (see: http://www.helsinki.fi/kemianluokka/english/index.html ).

Personnel Maija Aksela, Professor, Leader of the Unit and the Chemistry Education Centre, a coordinator of the LUMA Centre, see: (http://kampela.it.helsinki.fi/apumatti/lcms.php?am=11968-11968-1&page=11969)

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Heidi Handolin, Ph.D. student, Teaching Assistant, a coordinator of Kemma Judit Chikos, Ph. D. student, Teaching Assistant Veli-Matti Ikävalko, Ph.D. student, Assistant of Chemistry Class Gadolin and ask Chemistry -forum Johannes Pernaa, Ph.D. student, Teaching Assistant, second coordinator of Chemistry Class Gadolin Greta Tikkanen, Ph.D. student, Teaching Assistant, Student Counsellor Veli-Matti Vesterinen, Ph.D. student, Teaching Assistant, editor-in chief of the Luova magazine Maria Vänskä, Ph.D. student, a coordinator of Chemistry Class Gadolin Jenni Västinsalo, M.Sc. student, editor-in chide of the Jippo magazine

Publications 23 scientific articles see JULKI in English (Author Aksela Maija): https://julki.linneanet.fi/cgi-bin/Pwebrecon.cgi?LANGUAGE=English&DB=local&PAGE=First

Theses Master of Science 1. Forsström, Päivi: Tutkimuksellinen kokeellisuus lukio-opetuksessa: esimerkkinä

laktaasientsyymi 2. Handolin, Heidi: Opiskelijoiden käsityksiä kokeellisuudesta kemiassa ja lukio-

opetuksessa 3. Hyytiäinen, Kristiina: Orgaaniset hapetus- ja pelkistysreaktiot lukion kemian

ensimmäisen kurssin opetuksessa 4. Järvenpää, Leo: Ilmakehän kemiaa ympäristökasvatuksen näkökulmasta 5. Jääskeläinen, Piia: Kiinnostuksen tukeminen perusopetuksessa: molekyylimallinnus

työtapana 6. Karjalainen, Veikko: Kemian opetus tänään: Kemian opettajien näkemyksiä kemian

opetuksesta ja kemian opetuksen kehittämisestä 7. Laakso, Janina: Metallien kemiaa perusopetuksen 7.-9. luokilla 8. Laitala, Aino: Mittausautomaatio ympäristökemian oppimisen tukena

perusopetuksessa 9. Leppänen, Johannes: Peruskoulun kuudesluokkalaisten käsityksiä kemiasta ja sen

kiinnostavuudesta 10. Marjamäki, Hannu: Kokeellisia vesitutkimuksia mielekkääseen lukion kemian

opiskeluun 11. Ojala, Liisa: Terästeema kemian perusopetuksessa 12. Salmela, Laura: Biotekniikkaa kemian opetuksessa: Kokeellista entsyymikemiaa

oppimissyklin avulla 13. Syrjäläinen, Noora: Lehdet kemian opetuksessa perusopetuksesta korkeakouluihin:

Esimerkkinä Kemia-Kemi-lehti 14. Tähtivaara, Anna: Lasin kemiaa verkossa 15. Pernaa, Johannes: Hyönteisten kemiaa lukion kemian opetuksessa

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LABORATORY OF ANALYTICAL CHEMISTRY

Introduction The research at the Laboratory of Analytical Chemistry is focused on instrumental analytical methods, techniques and tools, and on their implementation in biomate-rials and environmental research. The research projects often integrate the analytical strengths of two or more scientific disciplines. The Laboratory of Analytical Chemistry has for several years played a pioneering role in introducing new analytical techniques to the scientific and industrial community in Finland.

Teaching is given mainly at an advanced level, and courses are frequently structured along the lines of analytical methods. Study of the fundamental concepts assists in understanding, adapting and applying analytical techniques. 45 M.Sc. degrees, one Lic. Phil. degree and five Ph.D. degrees in analytical chemistry were granted in 2008. In addition, several students studied analytical chemistry as a second field of concentration. As the studies of analytical chemistry readily find practical applications, graduating students have been successful in obtaining employment.

Personnel Teaching staff Marja-Liisa Riekkola, Ph.D., Professor of Analytical Chemistry, Head of the Laboratory Kari Hartonen, Ph.D., University Lecturer Tuulia Hyötyläinen, Ph.D., Professor of Environmental Chemistry and Environmental Analytical Chemistry (until September 2008) Pentti Jyske, Lic.Phil., Teaching Assistant Maarit Kivilompolo, Lic.Phil, University Lecturer Tapio Kotiaho, Ph.D., Professor of Mass Spectrometry Juhani Kronholm, Ph.D., University Lecturer Joonas Nurmi, M.Sc., Doctoral Student (Teaching Assistant)

External senior lecturers (docents) Jouni Enqvist, Ph.D., Senior Research Scientist, VTT Chemical Technology, Tampere Sami Franssila, TechD, Group leader, Microfabrication group at Department Micro and nanosciences, Faculty of Electronics, Communications and Systems, Helsinki University of Technology, Finland Kimmo Himberg, Ph.D., Director, Crime Laboratory, National Bureau of Investigation Juho Jumppanen, Ph.D., Development Manager, Danisco Sweeteners Nisse Kalkkinen, Ph.D., Head of the Laboratory, Institute of Biotechnology, University of Helsinki Ernst Kenndler, Ph.D, Professor, University of Vienna, Austria Mirja Kiilunen, Ph.D., Senior Scientist, Finnish Institute of Occupational Health Risto Kostiainen, Ph.D., Professor at Faculty of Pharmacy, University of Helsinki

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Lauri Lajunen, Ph.D., Professor and Rector, University of Oulu Eeva-Liisa Lakomaa, Ph.D., Senior Scientist, Vaisala OyJ Pekka Lehtonen, Ph.D., Laboratory Manager, Alcohol Control Laboratory, Alko Oy Gunilla Lindström, Ph.D., Professor, Örebro University, Sweden Maija-Liisa Mattinen, Ph.D., Senior Research Scientist, VTT Biotechnology; Espoo, Finland Kimmo Peltonen, Ph.D., Professor and Head of the Department of Chemistry and Toxicology, Finnish Food Safety Authority Evira Christina Rosenberg, Ph.D., Head of the Laboratory, Finnish Institute of Occupational Health Heli Sirén, Ph.D., Professor, Lappeenranta University of Technology, Finland Helena Soini, Ph.D., Senior Scientist, Department of Chemistry, Indiana University, Bloomington, USA

Senior Researchers Susanne Wiedmer, Ph.D, Docent, Academy Research Fellow

Postdoctoral Researcher Jie Chen, Ph.D. Geraldine Cilpa, Ph.D. Jana Lokajova, Ph.D. (from October 2008)

Doctoral Students Alexey Adamov, M.Sc Lotta Amundsen, M.Sc. (until June 2008) Lucia D’Ulivo, M.Sc. Anne Helle, B.Sc. (until March 2008) Minna Kallio, M.Sc. (until September 2008) Miika Kuivikko, M.Sc. (until April 2008) Jaakko Laakia, M.Sc. Totti Laitinen, M.Sc. Laura Luosujärvi M.Sc. Jaana Muhonen, M.Sc. Jevgeni Parchintsev, M.Sc. Tiina Sikanen, M.Sc.(Pharm.) Kati Vainikka, M.Sc. Joanna Witos, M.Sc. Gebrenegus Yohannes, Lic. Phil.

Visiting scientists Dr. Alexey Sysoev, Docent (about two weeks) Dr. Norberto Guzman (Biomarker Discovery, Princeton Biochemicals, Inc., P.O. Box 7102, Princeton, New Jersey 08543, U.S.A

Administrative and laboratory staff Liisa Heino, Laboratory Assistant Merit Hortling, M.Sc., Secretary Matti Jussila, Lic.Phil., Laboratory Engineer

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Research activities In addition to instrumental development a special emphasis of the research projects in the Laboratory of Analytical Chemistry has been put on bioanalytical and environmental research. Novel and efficient instrumental tools and techniques constructed in the Laboratory of Analytical Chemistry, such as multidimensional separation systems, an aerosol time-of-flight mass spectrometer, a drift cell ion mobility spectrometer attached to a triple quadrupole mass spectrometer, and a continuous field-flow-fractionation device have all been further developed. Theoretical, methodological and technical challenges and creative approaches have played important role in research activities.

Figure 1. Research profile of Laboratory of Analytical Chemistry.

Projects and funding The Laboratory of Analytical Chemistry is involved in several national and interna-tional projects with external funding: Multidimensional chromatographic techniques in the analysis of complex samples (funded by the Academy of Finland), Urban and rural air pollution - response of ecosystem and society (Helsinki University Environmental Research Centre), Physics, Chemistry, Biology and Meteorology of Atmospheric Composition and Climate Change (the Finnish Centre of Excellence directed by Professor Markku Kulmala, Department of Physical Sciences (http://www.atm.helsinki.fi/FCoE/). Production of smart wood based materials (Academy of Finland), Miniaturised instruments and neoteric techniques for human lipoprotein studies on nanoscale (Academy of Finland), Isomer separation by ion mobility spectrometry (IMS)/ mass spectrometry (MS), (Academy

Applications

Development of InstrumentalTechniquesMass

Spectrometry

Miniaturised & Multidimensional

techniques

EnvironmentalResearch

Aerosol ParticlesAtmospheric ChemistryGreen Chemistry(Pressurised hot water, ionicliquids and supercritical Fluids)

Bioanalytical ResearchCollagenLipoproteinsPharmaceuticalsPhospholipidsProteoglycansComputational studies

LABORATORY OF ANALYTICAL CHEMISTRYRESEARCH PROFILE

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of Finland), Atmospheric pressure laser desorption ionization (API) methods for mass spectrometry (MS) and ion mobility spectrometry (IMS) jointly with the Faculty of Pharmacy (Academy of Finland), Novel capillary/microchip electrochromatographic technique in oxidation, interaction and fusion studies of human lipoproteins (University of Helsinki), Developing chemometrics with the tools of information sciences (the Finnish Funding Agency for Technology and Innovation, Tekes), Biofunctional microchips, a co-operation project between Helsinki University of Technology Microelectronics Center, University of Helsinki Faculty of Pharmacy, Division of Pharmaceutical Chemistry, UH Biomedicum Protein chemistry unit and VTT (Tekes). In addition, financial support for research carried out in the Laboratory of Analytical Chemistry has been obtained from several foundations, including several CIMO fellowships.

The laboratory is involved in the Graduate School of Chemical Sensors and Microanalytical Systems, the Graduate School of Physics, Chemistry, Biology and Meteorology of Atmospheric Composition and Climate Change, the Graduate School of Informational and Structural Biology and in the Finnish National Graduate School in Nanoscience, all funded by the Ministry of Education. In addition the laboratory is involved in the Nordic Graduate School of Biosphere - Carbon - Aerosol - Cloud - Climate Interactions.

Bioanalytical research Microsystems and miniaturized techniques with special nanoscale functions are considered one of the key technologies for future progress in biochemistry, biotechnology and medicine. These new bioanalytical techniques should integrate various analytical steps such as reactions, measurements, analysis and detection under different conditions. By combining expertise on analytical instrumental techniques with that on experimental medicine and biochemistry, novel systems for the clarification of different phenomena can be developed. In the Laboratory of Analytical Chemistry great efforts have been put on instrumental development related to the most abundant membrane lipids, phospholipids as well as on collagen I and III and on human lipoproteins and proteoglycans. Computational studies have been carried out in parallel with experimental studies.

Environmental Research The environment and its pollution are a cause of increasing concern. Modern technology, if properly applied, can be one way to reduce the strain on the environment. The development of new techniques and processes that at the same time are effective, economic, safe, environmentally friendly and practical is of great importance. In the laboratory “Green chemistry” ideology has been actively implemented in analytical instrumentation development, wherever possible.The main focus of environmental research in the Laboratory of Analytical Chemistry is put on atmospheric aerosol particles. Atmospheric aerosol formation consists of a complicated set of processes that include the production on nanometer-size clusters from gaseous vapours, the growth of these clusters to detectable sizes, and their simultaneous removal by coagulation with the pre-existing aerosol particle population. Once formed, aerosol particles need to grow further to sizes >50-100 nm in diameter until they are able to influence climate, even though smaller particle

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may have influences on human health and atmospheric chemistry. Although aerosol formation followed by growth has been observed to take place almost everywhere in the atmosphere as evidenced by prof. Markku Kulmala research group, yet serious gaps in our knowledge regarding this phenomenon exist. Despite considerable efforts have been devoted to the analysis of the chemical compounds responsible for the formation and growth of freshly produced aerosol particles, the actual specific pathways have not been experimentally verified. The Laboratory of Analytical Chemistry is responsible for elucidating the chemical composition of aerosols in the research project belonging to the Finnish Centre of Excellence in Physics, Chemistry, Biology and Meteorology of Atmospheric Composition and Climate Change (2008-2013) on the interaction between the biosphere, aerosols, clouds and climate. The Department of Physical Sciences at the University of Helsinki bears the main responsibility for the centre.

Atmospheric Aerosol Chemistry Atmospheric aerosol particles comprise a complex mixture of inorganic and organic compounds. The number of aerosol particles can rise as high as hundreds million/cm3, and the corresponding mass can be hundreds g/cm3, while the size of the particles range from a few nm to a few hundred m. Depending on the site and the amount of pollution, organic compounds may represent up to 70% of the total dry fine particle mass in the lower troposphere, and the number of organic com-pounds in aerosol particles may be several hundreds. The study of organic composition of freshly-nucleated particles is currently impossible with commercially-available instrumentation. Novel instrumental techniques including sampling and analysis of organic compounds are required, in addition to in situ measurements in order to obtain highly time-resolved analyses that are capable of showing changes in aerosol chemistry.

Short sampling periods are necessary for a reliable knowledge of concentration trends with time during particle formation events. Moreover, size-separating sampling techniques are especially beneficial for a clear picture of the compounds participating in the particle formation. The particle-into-liquid sampler (PILS) combines two conventional techniques in aerosol measurement: particle growth in oversaturated water vapor and further impaction on quartz impactor. Even though several interesting and important studies have been performed with PILS, it has not been applied to the analysis of individual organic compounds. The applicability of PILS to the collection of organic compounds in aerosol samples has been studied. The results were compared to those obtained with conventional filter sampling. The collection time, sample solvent, the number of denuders and their quality, and the analysis for the selected organic compounds were optimized to get the best and reliable results. Most recently, solid phase extraction (SPE) cartridges were employed as collection and fractionation devices in the outlet of PILS sampler.

Due to the low concentrations of organic compounds in rural atmospheres, and the errors occurring during sampling, portable instruments, such as aerosol mass spectrometry, suitable for in situ measurements has been under development. In addition, the great complexity of the carbonaceous fractions complicates the determination of chemical composition. The analysis of an aerosol sample or any other complex sample by a single chromatographic technique often fails or is unsatisfactory because of poor separation efficiency. Efficiency can, however, be improved with the use of multidimensional techniques, employed in the Laboratory of Analytical Chemistry, i.e. by combining two or more techniques in such a way

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that the best features of each can be utilized. In addition, carefully selected organic compounds are used as marker compounds that reflect different states and stages of aerosol formation offering the quantitative and qualitative pattern of those organic compounds that play important roles in the different stages of aerosol formation processes. Furthermore, non-linear data analysis and self organizing maps have been employed in the data analysis for the clarification of correlations between different parameters affecting the aerosol formation. Oxidation products of -caryophyllene (its aldehydes selected as marker compounds) were successfully prepared in the laboratory and they could be found first time in the real biogenic aerosol samples obtained with both filter sampling and PILS. Also vapor pressures for these aldehydes were determined by applying a GC method.

Photolytic decomposition of polybrominated diphenyl ethers Large quantities of brominated flame retardants, such as polybrominated diphenyl ethers (PBDE), are produced and used in everyday consumer products. Unfortunately, PBDEs can accumulate in biota, with endocrinic and neurotoxic effects. According to the laboratory experiments, PBDEs decompose photochemically, but their photolytic half-lives in environment are not well known. The objective of our study is to assess the direct photolytic decomposition rates of PBDEs in coastal and oceanic surface waters. Photochemical decomposition experiments have revealed the decay kinetics of model congeners in isooctane under surface solar radiation in summer and resulted congener-specific half-lives of polybrominated diphenyl ethers ranging from a few minutes to days. Although numerous studies have suggested that photochemistry is the major pathway for the decomposition of brominated fire retardants in the environment, the data collected in our study combined with modelling provided the first estimates about the actual rates of direct photochemical decomposition of brominated fire retardants in situ.

Instrumental development Research in the field of analytical chemistry is focused on the development of instrumental techniques for the solution of analytical problems and for the clarifica-tion of special biological, environmental and medical phenomena. Often totally new analytical instrumentation has to be constructed. The development of environmen-tally-friendly instrumental sample-pretreatment techniques has also played an important role in the studies during the last years together with the integration of different techniques within one instrument. Special attention of instrumental development has been focused on methodological and technical challenges. A more detail description of the results achieved in the research projects of the Laboratory of Analytical Chemistry is given below together with the instrumental techniques employed/developed.

Modern environmentally friendly extraction methods

Sonication-assisted extraction In sonication-assisted extraction, ultrasound waves are utilised to enhance the extraction procedure. Ultrasound waves have frequencies higher than 20 kHz and they are mechanical vibrations in a solid, liquid or gas. Sound waves must pass through matter and they involve compression and expansion cycles during their

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passage through a medium. This cycle creates bubbles. These bubbles are compressed and expanded till they finally collapse. As a result, high local temperatures and pressures are produced. This phenomenon is known as cavitation. This improves the contact between solid and liquid phases. The mechanical effects of ultrasound enhance penetration of the solvent into the sample matrix and accelerate the mass transfer. A dynamic sonication-assisted ethanol extraction system has been coupled on-line to liquid chromatography to analyse antioxidant phenolic acids from herbs of Lamiaceae family (basil, oregano, rosemary, sage, spearmint and thyme).

Supercritical fluid extraction and pressurised hot water extraction Supercritical fluid extraction fully exploits the favourable properties of supercritical fluids (good solvation properties, high diffusivity, low viscosity and zero surface tension) as extraction medium. The addition of modifiers and derivatisation reagents to the most frequently used fluid, CO2, widens its use to the extraction of more polar compounds.

Pressurised hot water can also be used as an extraction medium (PHWE). The solubility of many low polarity compounds in water is high enough for their extrac-tion at temperatures far below the critical temperature and pressure of water (374oC, 221 bar). Both liquid water and steam at temperatures from 100 to 350oC have been used to efficiently extract high, medium or low polarity organic compounds from solid sample matrices.

Supercritical fluid (carbon dioxide) with ionic liquid has been under investigation for use in chemical modification of cellulose. Phase behavior, viscosity and solubility with supercritical carbon dioxide/ionic liquid or pressurized hot water/ionic liquid systems has been studied as well. Fractionation of hemicellulose with PHWE was successfully done.

Gas and liquid chromatographic research Gas chromatography-mass spectrometry Gas chromatography-mass spectrometry (GC-MS) is still the most widely applied technique to the analysis of volatile nonpolar analytes in various samples. Straight-forward on-line coupling of GC with MS makes the identification of compounds relatively easy. In the Laboratory of Analytical Chemistry GC-MS has been frequently applied to the identification and quantification of relatively non-polar compounds in aerosol samples. The target compounds were even numbered n-alkanes (C10–C28), PAHs, oxygen-containing PAHs, sesquiterpenes copaene and longifolene, and an oxidised monoterpenes, pinonaldehyde and verbenone. GC-MS method for the oxidation products of beta-caryophyllene was also developed.

Liquid chromatography-mass spectrometry Liquid chromatography coupled with mass spectrometry (LC-MS) has gained more and more interest in the determination of polar compounds. Electrospray ionisation (ESI) in negative ion mode enables selective and efficient ionisation. The combination of LC-ESI-ion-trap MS (ITMS) for structural information and LC-ESI-time-of-flight MS (TOFMS) for accurate mass measurement provides a powerful tool for the identification of unknown compounds in complex sample matrices.

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Comprehensive two-dimensional chromatography In comprehensive techniques the whole sample is separated in all separation dimensions applied. This is in contrast to conventional multidimensional techniques in which only one or a few fractions are transferred from the first dimension to the second dimension. Comprehensive chromatographic techniques provide more efficient separation of complex samples. The idea of a two-dimensional comprehensive system is to combine two separation systems so that short fractions are taken from the first column and transferred to the second column for very fast separation. While the separation is taking place in the second column, the next fraction is being collected from the first column. The analysis time of the first dimension varies from one to two hours, while the analysis time in the second dimension is usually significantly shorter, from a few seconds to a few minutes. The systems are in principle relatively simple in terms of instrumentation and use, in comparison with conventional multidimensional chromatographic systems. For example, only one detector is typically employed in these systems.

Mass spectrometry The departmental mass spectrometry (MS) centre started fully its operation in 2005. The premises have three mass spectrometers; an atmospheric pressure ionization ion trap mass spectrometer for tandem mass spectrometry, an atmospheric pressure ionization time-of-flight mass spectrometer for exact mass measurements and a matrix assisted laser desorption ionization time-of-flight instrument for large molecules. The mass spectrometers are widely used by different laboratories in the Department of Chemistry. In addition to these MS instruments the Laboratory of Analytical Chemistry has several own mass spectrometers coupled to different chromatographic and capillary electromigration systems. Furthermore, aerosol time-of-flight mass spectrometry and ion mobility spectrometry mass spectrometry have been actively under development. Moreover, together with several research partners the development of different miniaturized ionization techniques has been continued.

Aerosol time-of-flight mass spectrometry Aerosol time-of-flight mass spectrometer (ATOFMS) has been further constructed and developed together with the Department of Physical Sciences and the Finnish Meteorological Institute. The aim is to get reliable real time information on chemical composition of fine atmospheric particles with diameters smaller than 50 nm. In the instrument particles are first charged, size separated and collected onto a surface for short period (5-10 min). Collected particles are then subjected to laser desorption and ionisation with subsequent TOFMS analysis. A special, patented sampling valve for collection and desorption of aerosol particles into the mass spectrometer has been constructed and tested with the potential to perform size-selective collection. Particle charging, size separation and sample collection/desorption (valve) have functioned well. Recent research has been mainly focused on the updating the MS side and maximisation of the MS performance (resolution and sensitivity) with the aid of two foreign cooperative companies. Several standards as well as real atmospheric samples have been successfully analysed with the smallest analyte amounts being in the few pg range or even less. Aerosol-MS analyses of 20 nm ambient air particles in 40 min were demonstrated. In addition, aerosol-MS analyses of wood pyrolysis particles were successfully done from 30, 50 and 70 nm particles with 15 min collection time.

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Ion mobility spectrometry mass spectrometry Ion mobility spectrometry (IMS) studies were done using two different IMS instruments, namely with a high resolution drift cell ion mobility spectrometer attached to a triple quadrupole mass spectrometer and a high resolution drift cell IMS equipped with a faraday cup detector. With both devices different atmospheric pressure ionization modes can be used, e.g. ESI, atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) techniques. Studies of applicability of ion mobility spectrometry for separation of isomeric compounds continued. The possibility to use phenolic compounds as mobility standards and to separate different ionic forms of an analyte was studied. Also development of laser desorption ionization techniques for use with mass spectrometry and/or IMS started. The general goals of the IMS development work are (i) development of ionization methods for IMS, (ii) studies of fundamentals of the different ionization methods and IMS, (iii) development of IMS instrumentation and (iv) application development, especially for environmental screening and bioanalysis.

Miniaturisation of mass spectrometric devices Co-operation with several research partners was continued, e.g. further development of miniaturized APCI and APPI. Liquid chromatography and gas chromatography can be interfaced to an atmospheric pressure ion source mass spectrometer utilizing these miniaturized ion sources. The method development work included for example development a gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry (GC-µAPPI-MS) method for analysis of three selective androgen receptor modulators (SARMs) from spiked urine samples. In addition, desorption ionization techniques, such as DAPPI and DIOS have been studied. Main application areas of interest are environmental analysis and bioanalysis.

Capillary and on-chip capillary electromigration methods Capillary electrophoresis (CE) is a group of electromigration techniques that allow rapid and efficient separation and high resolution of components present in small sample volumes. Capillary electrophoresis is defined as the electromigration of compounds inside a narrow-bore capillary or microchannel filled with background electrolyte solution. The separation is based on differences in electrophoretic mobilities of the analytes caused by their effective charge and size. There are two distinct modes of capillary (zone) electrophoresis – aqueous and nonaqueous – depending on the medium employed. Electrokinetic capillary chromatography and open tubular capillary electrochromatography are the techniques most widely used at the present in the Laboratory of Analytical Chemistry.

Non-aqueous and aqueous background electrolyte solutions In non-aqueous capillary electrophoresis (suitable for the separation of both uncharged and charged analytes) parameters such as resolution, analysis time, and selectivity can be fine-tuned or even drastically altered by adjustment of background electrolyte (BGE) composition. Because the effects of organic solvents on acid-base behavior and the solvation of analytes and additives vary so widely, and because through mixing of different solvents these properties can be modified, novel selectivity, noticeably different from that in aqueous media, can be achieved.

The complicated and heterogeneous structure of diuretics makes their analysis by capillary electrophoresis a nontrivial task. Various hydrophilic and hydrophobic

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functional groups exist in their structure and, depending on the pH of the environment; the diuretics may be neutral, mono-charged or multi-charged. Our main goal was to measure the dissociation constants and actual mobilities of six diuretics and probenecid in methanol and to find the optimal experimental conditions for their separation in methanolic BGE. In addition, the hypothesis that the pKa shift, from water to methanol, is strongly correlated with the acidity of the compounds in aqueous media was proved.

Liposomes Fused silica capillaries have been coated with phospholipids by implementing a fast and simple coating procedure developed in our laboratory. In addition, liposomes have been used as pseudostationary phase in electrokinetic capillary chromatography. The target of the project has been to demonstrate the potential of phospholipid membranes, mimicking cell membranes, in the study of interactions between membranes and drugs, pesticides, antibiotics, biomolecules and other compounds with electromigration techniques. Anionic and zwitterionic phospholipid and PEGylated lipid aggregates have been used as coating materials or pseudostationary phases. In addition to study of parameters that affect the stability of coatings much emphasis has been put on the effect of the lipid acyl chains on the retention factor of compounds. The use of proteins immobilized in lipid membranes on fused silica capillary for chiral separation of amino acids has been demonstrated as well. The phospholipid coatings formed on silica have been studied by various microscopic techniques.

Collagen I and III, human lipoproteins and proteoglycans The intimal extracellular matrix forms an organized, tight network that has the potential to bind lipoproteins, and lipoprotein retention by extracellular matrix proteoglycans is important in atherogenesis. The polyanionic and hydrophilic glycosaminoglycan (GAG) chains dominate the physical properties of proteoglycans. Proteoglycans are assumed to bind apolipoprotein B and E containing lipoproteins, and especially chondroitin-6- sulfate (C6S) that is a GAG component of several PGs appears to participate in numerous crucial biological interactions, which have an entire or partial, direct or indirect role in serious diseases such atherosclerosis. Collagens that represent the most abundant family of protein in the human body, take part also in the formation of the extracellular matrix. Among the 29 known types of collagen, collagen I and III are the major ones found in tissues, tissues and they seem to be involved also in the development and progression of atherosclerosis.

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Figure 2. Different techniques and tools employed and developed for the understanding of the molecular properties of human surface nanodomains.

Capillary electromigration techniques can be exploited, not only as efficient separation, but also as biomimicking instrumental techniques applicable to studies on the understanding of the molecular properties of human surface nanodomains. In our previous studies, the coating procedures have been developed and optimized also for aortic proteoglycans, and for collagen I and III. Interactions of collagen I and collagen III with other extracellular matrix components, such as decorin and chondroitin-6-sulfate, have been clarified. In addition, interactions between positive, neutral and negative peptide fragments of apolipoprotein B-100 (apoB-100), the main protein of low-density lipoprotein particles, and proteoglycans, collagen and collagen-decorin coatings have been elucidated. Low-density lipoprotein coated capillaries have been exploited also for the in situ isolation of apoB-100 from LDL particles through treatment with non-ionic surfactant Nonidet P-40. The in situ delipidation of LDL particles in capillaries represents a novel approach for the isolation of immobilized apoB-100, and for the determination of its pI value. Atomic force microscope images have provided valuable topography on different human biomaterial coatings on the capillary wall. Because molecular interactions involving the C6S chain are of considerable interest, a computational model for atomistic simulation has been built. The results of an extensive molecular dynamics simulation performed with the new force field provide novel insight into the structure and dynamics of the C6S chain. The designed force field allows a proper description of chondroitin-6-sulfate and lay foundation for critical interactions of chondroitin-6-sulfate with its pathological counterparts. Different nanoscale functional studies have been carried out in cooperation with the Wihuri

Lipoproteins

AFM

MD

CE MICROCHIP High voltage

Computer

DetectorEOF

PMT

Fluo

f osc

quartz crystal d=4 mm

Goldelectrodes

QCM

CapillaryElectrochromatography

Quarz Crystal Microbalance

Field-Flow FractionationFFF

collagen

PG

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Research Institute and National Institute for Health and Welfare, Public Health Genomics Research Unit and Finnish Institute for Molecular Medicine.

Bacterial biofilms Microorganisms can attach onto available non-living surfaces in many natural, industrial and medical environments, enveloped within extracellular polymeric substances resulting in the formation of the so called biofilms. Biofilms are reported to exist in the 65 to 80% of bacterial infections refractory to host defenses and antibiotics therapy and have been regarded as a key problem in nowadays medical microbiology. Accordingly the understanding of parameters governing the interaction of antimicrobials with biofilms is of great interest on the attempts of increasing biocides efficacy. A novel electrochromatographic technique involving coating of open tubular fused-silica capillaries with living planktonic cells, Staphylococcus aureus, has been developed for viable bacterial biofilm studies. The technique allows highly efficient and easy characterization of interactions between biofilms and potentially active antimicrobial compounds under different conditions, e.g. continuous flow.

Other applications with capillary electromigration techniques Immobilization of drugs into poly(lactic acid) nanoparticles has been studied by electromigration techniques. Methods based on capillary electrophoresis and microemulsion electrokinetic capillary chromatography were developed. Special emphasis was put on the development of quantitative methods for determining the drug content in poly(lactic acid) nanoparticles. The research was carried out in close cooperation with the Division of Pharmaceutical Technology, Faculty of Pharmacy, University of Helsinki. The results demonstrated that the applied electromigration techniques were suitable for the interaction, drug entrapment and dissolution studies of pharmaceutical nanoparticles.

Field-flow fractionation Field-Flow Fractionation (FFF) is a series of techniques for the analysis of macromolecules and particles. The method is based on the use of a parabolic flow profile to boost the primary separation affected by mass transfer phenomena such as diffusion, thermal diffusion, electrophoresis or sedimentation. In the Laboratory of Analytical Chemistry, in addition to thermal field-flow fractionation (ThFFF) and asymmetrical flow field-flow fractionation (AsFlFFF), an innovative continuous two-dimensional thermal ThFFF instrument has been constructed for semipreparative separations of macromolecules. In recent studies, attention has been paid to the further development of the continuous system and to its theoretical guidelines, and application in the separation of different sample types. The continuous system is expected to gain applications in the production of standards and reference materials.

Interaction of lipid membranes with fusidic acid and elongation factor-G (a protein) has been investigated by AsFlFFF. The AsFlFFF studies on EF-G with increasing amount of lipids were carried out in order to get information on the size of the proteins and about possible absorption of lipids to EF-G. The results showed that there were no lipids bound to EF-G (data not shown), which was expected considering the physical properties and physiological function of the protein.

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Publications Papers in refereed journals 1. Aura, S., Sikanen, T., Kotiaho, T., Franssila, S.; Novel Hybrid Material for

Microfluidic Devices, Sensors Actuators 132 (2008) 397-403. 2. Chen, J., Fallarero, A., Määttänen, A., Sandberg, M., Peltonen, J., Vuorela,

P.M., Riekkola, M.-L.; Living Cells of Staphylococcus aureus Immobilized onto the Capillary Surface in Electrochromatography: A Tool for Screening of Biofilms, Anal. Chem. 80 (2008) 5103-5109.

3. D’Ulivo, L., Chen, J., Meinander, K., Öörni, K., Kovanen, P.T., Riekkola, M.-L.; In Situ Delipidation of Low-Density Lipoproteins in Capillary Electrochromatography Yields Apolipoprotein B-100-coated Surfaces for Interaction studies, Anal. Biochem. 383 (2008) 38–43.

4. Haddad, R., Sparrapan, R., Kotiaho, T., Eberlin, M.N.; Easy Ambient Sonic-Spray Ionization-Membrane Interface Mass Spectrometry for Direct Analysis of Solution Constituents, Anal. Chem. 80 (2008) 898-903.

5. Hartonen, K., Riekkola, M.-L.; Liquid chromatography at elevated temperatures with pure water as the mobile phase. TrAC 27 (2008) 1-14.

6. Helle, A., Hirsjärvi, S., Peltonen, L., Hirvonen, J., Wiedmer, S.K.; Quantitative Determination of Drug Encapsulation in Poly(lactic acid) Nanoparticles by Capillary Electrophoresis, J. Chromatogr. A 1178 (2008) 248-255.

7. Helle, A., Mäkitalo, J., Huhtanen, J., Holopainen, J.M., Wiedmer, S.K.; Antibiotic Fusidic Acid Has Strong Interactions with Negatively Charged Lipid Membranes: An electrokinetic Capillary Chromatographic Study. Biochim. Biophys. Acta 1778 (2008) 2640–2647.

8. Hyötyläinen, T., Riekkola, M.-L.; Sorbent- and Liquid-Phase Microextraction Techniques and Membrane-Assisted Extraction in Combination with Gas Chromatographic Analysis: A Review, Anal. Chim. Acta 614 (2008) 27-37.

9. Hyötyläinen, T.; On-line Coupling of Extraction with Gas Chromatography, J. Chromatogr. A 1186 (2008) 39-50.

10. Kallio, M., Viikari, J., Kallonen, R., Lehtonen, P., Patrikainen, E., Hyötyläinen, T.; Characterisation of Wines by Comprehensive Two-Dimensional Gas Chromatography and Chemometric Methods, Bulletin de L’OIV 81 (2008) 213-219.

11. Kallio, M., Hyötyläinen, T.; Simple Calibration Method for Comprehensive Two-Dimensional Gas Chromatography, J. Chromatogr. A, 1200 (2008) 264-267.

12. Kallio, M., Jussila, M., Raimi, P., Hyötyläinen, T.; Modified Semi-Rotating Cryogenic Modulator for Comprehensive Two-Dimensional Gas Chromatography, Anal. Bioanal.Chem. 391 (2008) 2357-2363.

13. Kauppila, T., Arvola, V., Haapala, M., Pol, J., Aalberg, L., Saarela, V., Franssila, S., Kotiaho, T., Kostiainen, R.; Direct Analysis of Illicit Drugs by Desorption Atmospheric Pressure Photoionization, Rapid Commun. Mass Spectrom. 22 (2008) 979-985.

14. Kauppila, T., Talaty, N., Jackson, A., Kotiaho, T., Kostiainen, R., Cooks, R.G.; Carbohydrate and Steroid Analysis by Desorption Electrospray Ionization Mass Spectrometry, Chem. Commun. (2008) 2674 – 2676.

15. Ketola, R.A., Tarkiainen, V., Kiuru, J. Savolahti, P., Kotiaho, T., Juujärvi, J., Ridderstad, M., Heikkonen, J.; Evaluation of Mathematical Algorithm for Solving of Fourier Transform Infrared Spectroscopic and Mass Spectra, Ind. Eng. Chem. Res. 47 (2008) 8101-8106.

16. Kivilompolo, M., Ob rka, V., Hyötyläinen, T.; Comprehensive Two-Dimensional Liquid Chromatography in Analysis of Antioxidant Phenolic Compounds in Wines and Juices, Anal. Bioanal. Chem. 391 (2008) 373.

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17. Kotiaho, T., Baumann, M., Franssila, S., Demiova, Z., Kostiainen, R., Pöysä, E.; A device for multi-dimensional separation and analysis of molecules and biomols. Brit. UK Pat. Appl. (2008) 29pp.

18. Kulmala, M., Kerminen,V.-M., Laaksonen, A., Riipinen, I., Sipilä, M., Ruuskanen, T.M., Sogacheva, L., Hari, P., Bäck, J., Lehtinen, K.E.J., Viisanen, Y., Bilde, M., Svenningsson, B., Lazaridis, M., Torseth, K., Tunved, P., Nilsson, E.D., Pryor, S., Sørensen, L.-L., Hõrrak, U., Winkler, P.M., Swietlicki, E., Riekkola, M.-L., Krejci, R., Grini, A., Hoyle, C., Hov, Ø., Myhre G., Hansson, H.-C.; Overview of the BACCI (Biosphere-Aerosol-Cloud-Climate Interactions) Studies, Tellus B 60 (2008) 300-317.

19. Laaksonen, A., Kulmala, M., O’Dowd, C.D., Joutsensaari, J., Vaattovaara, P., Mikkonen, S., Lehtinen, K.E.J., Sogacheva, L., Dal Maso, M., Aalto, P., Petäjä, T., Sogachev, A., Yoon, Y.J., Lihavainen, H., Nilsson, D., Facchini, M.C., Cavalli, F., Fuzzi, S., Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., Junkermann, W., Coe, H., Allan, J.D., Alfarra, M.R., Worsnop, D.R., Riekkola, M.-L., Hyötyläinen, T., Viisanen,Y.; The Role of VOC Oxidation Products in New Particle Formation, Atmospheric Chemistry and Physics 8 (2008) 2657-2665.

20. Lindén, M.V., Meinander, K., Helle, A., Yohannes, G., Riekkola, M.-L., Butcher, S.J., Viitala, T., Wiedmer, S.K.; Characterization of Phosphatidylcholine/ Polyethylene Glycol-Lipid Aggregates and Their Use as Coatings and Carriers in Capillary Electrophoresis, Electrophoresis 29 (2008) 852–862.

21. Luosujärvi, L., Arvola, V., Haapala, M., Pol, J., Saarela, V., Franssila, S., Kotiaho, T., Kostiainen, R., Kauppila, T.; Desorption and Ionization Mechanisms in Desorption Atmospheric Pressure Photoionization, Anal. Chem. 80 (2008) 7460 – 7466.

22. Luosujärvi, L., Karikko, M.-M., Haapala, M., Saarela, V., Huhtala, S., Franssila, S., Kostiainen, R., Kotiaho, T., Kauppila, T.; Gas Chromatography/Mass Spectrometry of Polychlorinated Biphenyls Using Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization Microchips, Rapid Commun. Mass Spectrom. 22 (2008) 425-431.

23. Muhonen, J., Vidgren, J., Helle, A., Yohannes, G., Viitala, T., Holopainen, J.M., Wiedmer, S.K.; Interactions of Fusidic Acid and Elongation Factor-G with Lipid Membranes, Anal. Biochem. 374 (2008) 133–142.

24. Parshintsev, J., Nurmi, J., Kilpeläinen, I., Hartonen, K., Kulmala, M., Riekkola, M.-L.; Preparation of -caryophyllene Oxidation Products and Their Determination in Ambient Aerosol Samples, Anal. Bioanal. Chem. 390 (2008) 913–919.

25. Pedersen, C., Lauritsen, F., Sysoev, A., Viitanen, A.-K., Mäkelä, J.M., Adamov, A., Laakia, J., Mauriala, T., Kotiaho, T.; Characterization of Proton-Bound Acetate Dimers in Ion Mobility Spectrometry, J. Am. Soc. Mass Spectrom. 19 (2008) 1361-1366.

26. Pol, J., Hyötyläinen, T.; Comprehensive Two-Dimensional Liquid Chromatography Coupled with Mass Spectrometry, Anal. Bioanal. Chem. 391 (2008) 21-31.

27. Sainiemi, L., Nissilä, T., Jokinen, V., Sikanen, T., Kotiaho, T., Kostiainen, R., Ketola, R.A., Franssila, S.; Fabrication and Fluidic Characterization of Silicon Micropillar Array Electrospray Ionization Chip, Sensors Actuators 132 (2008) 380-387.

28. Sikanen, T., Tuomikoski, S., Ketola, R. A., Kostiainen, R., Franssila, S., Kotiaho, T.; Analytical Characterization of Microfabricated SU-8 Emitters for Electrospray Ionization Mass Spectrometry, J. Mass Spectrom. 43 (2008) 726-735.

29. Sikanen, T., Zwinger, T., Tuomikoski, S., Franssila, S., Lehtiniemi, R., Fager, C.-M. Kotiaho, T., Pursula, A.; Temperature Modeling and Measurement of an Electrokinetic Separation Chip, Microfluid Nanofluid 5 (2008) 479-491.

30. Sirén, H., Shimmo, R., Sipola, P., Abenet, S., Riekkola, M.-L.; Capillary Electrophoresis of Diuretics and Probenecid in Methanol. J. Chromatogr. A 1198-1199 (2008) 215-219.

31. Verma, A. Hartonen, K. Riekkola, M.-L.; Optimisation of Supercritical Fluid Extraction of Indole Alkaloids from Catharanthus roseus using Experimental Design

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Methodology—Comparison with other Extraction Techniques, Phytochem. Anal. 19 (2008) 52–63.

32. Viitanen, A.-K., Mauriala, T., Mattila, T., Adamov, A., Pedersen, C., Mäkelä, J.M., Marjamäki, M., Sysoev, A., Keskinen, J., Kotiaho, T.; Adjusting Mobility Scales of Ion Mobility Spectrometers Using 2,6-DtBP as a Reference Compound, Talanta 76 (2008) 1218-1223.

33. Wiedmer, S.K, Bo, T., Riekkola, M.-L.; Phospholipid-Protein Coatings for Chiral Capillary Electrochromatography, Anal. Biochem 373 (2008) 26-33.

34. Wiedmer, S.K., Kulovesi, P., Riekkola, M.-L.; Liposome Electrokinetic Capillary Chromatography in the Study of Analyte–Phospholipid Membrane Interactions. Application to Pesticides and Related Compounds, J. Sep. Sci. 31 (2008) 2714 – 2721.

Other publications 1. Parshintsev, J., Laitinen, T., Nurmi, J., Hartonen, K., Riekkola, M.-L., Kulmala,

M.; I. Synthesis of -caryophyllene Oxidation Products and Their Analysis in Ambient Aerosol Samples. II. Novel Aerosol Inlet for Introduction of Aerosol Particle Samples to Mass Spectrometric Analysis in Close to Real-Time. Report Series in Aerosol Science no 92 (Finnish Association for Aerosol Research), M.Kulmala, J.Bäck, M.Salonen (eds), 2008, pp. 158-163.

2. Kallio, M., Pól, J., Järvimäki, S., Lietzen, N., Parshintsev, J., Riekkola, M.-L. and Hyötyläinen, T.; Characterisation of Organic Compounds in Aerosol Particles Using Multidimentional and Hyphenated Chromatographic Techniques. Report Series in Aerosol Science no 92 (Finnish Association for Aerosol Research), M.Kulmala, J.Bäck, M.Salonen (eds), 2008, pp. 103-109.

3. Parshintsev, J., Räsänen, R., Hartonen, K., Kulmala, M. and Riekkola, M.-L.; Utilization of Particle-into-Liquid Sampler (PILS) in Ambient Aerosol Sampling for Further Analysis of Organic Matter. Report Series in Aerosol Science no 97 (Finnish Association for Aerosol Research), M.Kulmala, A.Lauri (eds), 2008, pp. 58.

4. Riekkola, M.-L.; Extending the Molecular Application Range of Gas Chromatography by E. Kaal and H.-G. Janssen, J. Chromatogr. A 1184 (2008) 42.

5. Parshintsev, J., Hyötyläinen, T., Hartonen, K., .Kulmala, M. and Riekkola, M.-L.; Organic Acids in Atmospheric Aerosols Collected by Particle-into-Liquid Sampler. Their Extraction with Anion Exchange Material and Determination by Liquid Chromatography-Mass Spectrometry, NOSA Aerosol Symposium proceeding (Nordic Society for Aerosol Research), 2008, pp. 87-89.

6. Laitinen, T., Herrero-Martin, S., Parshintsev, J., Hyötyläinen, T., Hartonen, K. and Riekkola, M.-L.; Collection and Chemical Characterization of Nanomer Size Aerosol Particles from Wood Pyrolysis, NOSA Aerosol Symposium proceeding (Nordic Society for Aerosol Research), 2008, pp. 69-71.

Patents and patent applications 1. K. Hartonen, K. Kuuspalo, H. Lihavainen, P. Aalto, M. Rasilainen, M.-L.

Riekkola, M. Kulmala and Y. Viisanen, US patent no. 7485854 (2009), International patent application, PCT/IB2007/001340, Chinese patent application 200780018681.2, European patent application 07734646.8-1226, Japanese patent application 2009-511601. ”Sampling device for introduction of samples into analysis system”

Theses Doctor of Philosophy 1. Amundsen, Lotta: Use of non-specific and specific interactions in the analysis of

testosterone and related compounds by capillary electromigration techniques 2. Kallio, Minna: Comprehensive Two-Dimensional Gas Chromatography: Instrumental

and Methodological Development 3. Lindén, Maria: Stabilization of Phospholipid Coatings in Capillary Electrophoresis

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4. Pikkarainen, Anna-Liisa: Organic Contaminants - Occurence and Biological Effects in the Baltic Sea

5. Saarikoski, Sanna: Chemical Mass Closure and Source-Specific Composition of Atmospheric Particles

Licentiate of Philosophy 1. Rovio, Stella: Determination of Mono- and Disaccharides and Sugar Alcohols by

Capillary Zone Eletrophoresis with Direct UV Detection Master of Science 1. Aho, Jari: Deriving structural information from non-coding ribonucleic acids by mass

spectrometry 2. Ahonen, Linda: Surface Modification of Microchannels for Electrophoretic

Separation (in Finnish) 3. Halme, Mia: Isolation, Sample Preparation and Analysis Methods of Toxins

Produced by Dinoflagellates (in Finnish) 4. Heikkinen, Susanna: Capillary Electrochromatography using Monolithic Stationary

Phases – Environmental and Food Applications (in Finnish) 5. Hokkanen, Mirja: Extraction of Metals from Environmental Samples Using

Supercritical Fluid and Pressurized Solvent (in Finnish) 6. Hokkanen, Sanna: Analysis of the Peptide Hormones by High-Performance Liquid

Chromatography (in Finnish) 7. Ikonen, Jussi: Sample Introduction Systems in Inductively Coupled Plasma Mass

Spectrometry (in Finnish) 8. Jokinen, Eeva-Maija: Interactions between Local Anesthetics and Lipid Membranes:

Methods and their Applications (in Finnish) 9. Jokinen, Tuija: Speciation Analysis of Arsenic and Tin (in Finnish) 10. Järvenpää, Leo: Atmospheric Chemistry in a Perspective of Environmental Education

(in Finnish) 11. Järvimäki, Sari: The Current State and Applications of Solid-Phase Microextraction

(in Finnish) 12. Kaltio, Laura: Two-Dimensional Chromatographic Techniques in Environmental

Analysis (in Finnish) 13. Karaste (Leppänen), Suvi: Glass Electrodes in Power Plant On-Line Analysers (in

Finnish) 14. Kivinen, Jelena: Liquid Chromatographic Separation of Enantiomers (in Finnish) 15. Koskela, Pirjo: The Isolation and Analysis of Functional Compounds from Wood (in

Finnish) 16. Kottelin, Katriina: Analysis of Glycosaminoglycans Which Are Attached to

Proteoglycans (in Finnish) 17. Kulomaa, Anu: Capillary Electromogration Techniques in the Analysis of Flavonoids

(in Finnish) 18. Kulovesi, Pipsa: Interactions between Drugs and Lipidmembranes (in Finnish) 19. Lahtinen, Katri: Determination of Perfluorinated Compounds from Environmental

and Biological Matrices (in Finnish) 20. Lehtonen, Mervi: Determination of Polycyclic Compounds Containing Nitrogen,

Oxygen and Sulphur from Environmental Samples (in Finnish) 21. Leppänen, Kaisu: Determination of Brominated Flame Retardants from Biological

and Environmental Samples (in Finnish) 22. Lietzén, Niina: Liquid Comprehensive Two-Dimensional Chromatography (in

Finnish) 23. Lindqvist, Pertti: Planar Chromatographic Methods in Pharmaceutical Analyses (in

Finnish)

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24. Marjamäki, Hannu: Experimental Studies of Water for Meaningful High School Chemistry Education (in Finnish)

25. Markkola, Maija: Inverse Gas Chromatogaphy (in Finnish) 26. Metsä (Ylikarjula), Sanna: Current Analytical Techniques for theDetermination of

Biogenic Amines in Food (in Finnish) 27. Mäkitalo, Johanna: Double Chained Surfactants and Lipids in Capillary

Eletrophoresis (in Finnish) 28. Perkola, Noora: Gas Chromatography – Time of Flight Mass Spectrometry as an

Analytical Method (in Finnish) 29. Ranta-aho, Outi: Determination of Polyphenols in Biological Samples (in Finnish) 30. Ristimaa, Johanna: Hair as a Sample Matrix in Forensic and Clinical Toxicology (in

Finnish) 31. Räsänen, Riikka: The Use of Membranes in Analytical Chemistry (in Finnish) 32. Salminen, Reija: Analysis of Plant Alcaloids (in Finnish) 33. Surakka, Päivi: Chromatography and Capillary Electromigration Techniques for

Identification of phospholipids from Biological Matrices (in Finnish) 34. Säle, Pirjo: Chemicals and Water Quality Control in Water- Steam Circulation

Process of Power Plant (in Finnish) 35. Takku, Mari: Determination of Free and Total Sulphur dioxide in Alcoholic

Beverages (in Finnish) 36. Tanner, Johanna: Utilization of Temperature in Capillary Electrochromatography and

Liquid hromatography (in Finnish) 37. Tohmola, Niina: One- and Two Dimensional Liquid Chromatography in Peptide

Analysis (in Finnish) 38. Tuomi, Ilona: Determination of Organic Acids in Wine (in Finnish) 39. Valtari, Sonja: The Current State of Speciation Analysis of Aluminium, Cadmium,

Chromium, Iron and Selenium in the Analysis of Environmental Samples (in Finnish) 40. Vestenius, Mika: Continous Determination of Organic Compounds and Selected

Gases in Air (in Finnish) 41. Vettenranta, Hilkka: Analysis of Antioxidative Compounds in Food by LC-MS and

Antioxidant Activity Measurements (in Finnish) 42. Viinamäki, Jenni: Hydrophilic Interaction Chromatography (in Finnish) 43. Vuorela, Arja: The Analysis and Applications of Single Cell by Capillary

Electromigration Techniques (in Finnish) 44. Väisänen (Törmikoski), Virve: Bioapplications of Field-Flow-Fractionation (in

Finnish) 45. Välinen, Elina: Chromatographic and Electromigration Techniques in Process

Monitoring of Forest, Pharmaceutical and Food Industry (in Finnish)

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LABORATORY OF INORGANIC CHEMISTRY

Personnel Teaching staff Hyvönen, Helena, Ph.D., Teaching Assistant Kivekäs, Raikko, Ph.D., Teaching Assistant (until Jan 31) Leskelä, Markku, D.Techn., Academy Professor, Head of the Laboratory Lindroos, Seppo, Ph.D., University Lecturer Muhonen, Heikki, Ph.D., University Teacher Näsäkkälä, Matti, Ph.D., Lecturer, Docent Polamo, Mika, Ph.D., University Lecturer, Docent Repo, Timo, Ph.D., Professor, Docent Ritala, Mikko, Ph.D., Professor Sundberg, Markku, Ph.D., University Lecturer, Docent Talja, Markku, Ph.D., Doctoral Assistant Turpeinen, Urho, Ph.D., Teaching Assistant (until Aug 31) Valo, Jaana, Ph.D., Doctoral Assistant

External senior lecturers (Docents) Abu-Surrah, Adnan, Ph.D., Professor Mäkelä, Milja, Ph.D. Orama, Olli, Ph.D.

Research staff Aitola, Erkki, Ph.D. Grafov, Andriy, Ph.D., Visiting professor Guo, Hongfan, Ph.D. (from Aug 1) Kemell, Marianna, Ph.D., Docent Kukli, Kaupo, Ph.D. Lahtinen, Petro, Ph.D. Nieger, Martin, Ph.D., Docent, Senior researcher Niinistö, Jaakko, D.Techn. Puukilainen, Esa, Ph.D. Pärssinen, Antti, Ph.D. Sood, Anjali, Ph.D. Uggla, Rolf, D.Techn. Vehkamäki, Marko, Ph.D.

Doctoral Students Ahmad, Jahir Uddin, M.Sc. Al-Hunaiti, Afnan, M.Sc. Färm, Elina, M.Sc. Hakola, Maija, M.Sc. Hatanpää, Timo, M.Sc. Heikkilä, Mikko, M.Sc. Hämäläinen, Jani, M.Sc. Härkönen, Emma, M.Sc. (from Sep 1)

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Ihanus, Jarkko, M.Sc. Knapas, Kjell, M.Sc. Kozlov, Vasilij, Lic.Phil. Lankinen, Elina, M.Sc. (on leave) Lankinen, Mikko, M.Sc. (until Jan 31) Lindqvist, Markus, M.Sc. Pilvi, Tero, M.Sc. Pore, Viljami, M.Sc. Puranen, Arto, Lic.Phil. Rautiainen, Jukka, Lic.Phil. Rautiainen, Sari, BSc Riekkola, Tiina, M.Sc. (from Jun 2) Ryynänen, Hannu, M.Sc. Salonen, Markku, Lic.Phil. Saloniemi, Timo, M.Sc. (techn) Santala, Eero, M.Sc. Sibaouih, Ahlam, M.Sc. Sumerin, Victor, M.Sc. Tupala, Jere, M.Sc. Vuorinen, Sirpa, M.Sc. (techn)

Administrative and technical staff Jussila, Raija, Secretary Kaija, Eeva, Laboratory Technician Kansikas, Jarno, Ph.D., Docent, Amanuensis Mutikainen, Ilpo, Ph.D., Docent, Laboratory Manager

Research activities

General The research activities of the Laboratory comprise topics in materials, coordination and metalorganic chemistry. In materials chemistry the main emphasis is in chemical fabrication of thin films and nanomaterials. Coordination and organometallic chemistry research has four main areas: coordination and organometallic compounds for catalysts, synthesis of volatile complexes for thin film fabrication, chemical crystallography and studies on complexation equilibria in solution. Nanomaterials and nanostructures form an increasing research area of the Laboratory. It combines the know-how gained in thin film deposition and organometallic synthesis studies.

Graduate school The Laboratory participates in the national graduate school (coordinated by the University of Joensuu) on inorganic materials chemistry. Five Ph.D. students are funded via the graduate school. The University also supports graduate studies and two doctoral students are funded from this source.

International cooperation International cooperation plays an important role in the research and components of such were the Laboratory’s participation in the following international projects: EU

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project in FP 6 on deposition of high-k oxide thin films, and another on nanomaterials, in FP 7 on ALD of protective coatings, ESA funded project on grid filters and a Nordic project on photocatalysts. The DAAD-Academy of Finland exchange program between the Macromolecular Chemistry at Technical University of Munich and our Laboratory continued for the fourteenth consecutive year. The receiving partner (prof. B. Rieger) has within the years moved from Tubingen to Ulm and now in Munich. The major part of the international cooperation has, however, been based on personal contacts and the Laboratory cooperates with numerous universities and institutes worldwide. In addition, the collaboration with foreign industry is lively and that forms an important basis for funding of the research.

Research projects During the year 2008 the following TEKES projects were completed:

“Development of ALD process for noble metal films and their applications in X-ray optics”. The project is co-funded by ASM Microchemistry, Oxford Instruments Analytical and Picosun.

“Biofunctional microchips”. The project is coordinated by Department of Pharmacy and is participated by Laboratory of Analytical Chemistry and Helsinki University of Technology.

“Improvement of optical properties of paper by increasing refractive indices of materials”. The project is co-funded by J.M. Huber Finland, M-real, Omya, UPM-Kymmene.

“New pre-treatment techniques for biomass” in collaboration with VTT Biotechnology.

The following new TEKES projects were started:

“Nanocoatings with tailored roughness for controlled surface bonding” in collaboration with VTT Microelectronics, University of Jyväskylä, University of Tokyo, Nagoya University, LAAS-CNRS Toulouse, and co-funded by Okmetic, VTI Technologies and Picosun.

“Hydrolysis technology for production of sugars from biomass for raw materials for chemical industry” in collaboration with VTT Biotechnology, and Department of Applied Chemistry and Microbiology, and co-funded by UPM-Kymmene, Roal, Neste Oil, Danisco Sweeteners, Larox, Metso.

“Lignin valorisation” in collaboration with VTT Biotechnology, and Department of Applied Chemistry and Microbiology, and co-funded by Stora-Enso, UPM-Kymmene, Roal, Metsa-Botnia, Metso.

The Academy of Finland funded the following projects:

“Nanodevices using functionality in ferroelectrics (FERNAND)” and “Functional nanoparticles and devices (FUNANO” both projects belonging to the FinNano program. Both projects belong to consortia the former being coordinated by University of Oulu and the latter by University of Jyväskylä.

“Nanomaterials and Nanostructures via Metalorganic Synthesis and Deposition of Thin Films” is the title of the project connected to the Academy Professor position of Markku Leskelä.

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“Novel metal complexes in polymerization of functionalized monomers”, a project connected to the Academy Researcher position of Timo Repo, was completed during the year.

“Fundamentals of ALD chemistry”.

“Activation of CO2”. The project is carried out in collaboration with VTT Processes. The same topic is also funded by Fortum Foundation.

“Enhanced organocatalyzed redox processes for sustainable chemical synthesis” project is collaboration with Laboratory of Organic Chemistry at Helsinki University of Technology.

“Catalytic decomposition of wood” to be carried out in collaboration with VTT Biotechnology. The project is part of Sustainable energy program of Academy of Finland.

“Development of theoretical and experimental approaches to the formation of catalytically active gold tailored nanoparticles supported on various carriers for selective synthesis of multifunctional organic molecules from biorenewables.”, to be carried out in collaboration with Process chemistry centre at Åbo Akademi University and Boreskov Institute of Catalysis, Novosibirsk, Russia. The project is part of Russian co-operation program of Academy of Finland.

“Nanodevices using functionality in ferroelectrics” which is carried out in collaboration with University of Oulu, VTT Information Technology, and Helsinki University of Technology.

“Functional nanoparticles and –devices” which is carried out with University of Jyväskylä and Tampere University of Technology. These two projects belong to the FinNano program of Academy of Finland.

''Functional nano- and microstructures by atomic layer deposition and electrodeposition'' a post-doctoral researcher's project of Marianna Kemell funded by the Academy of Finland.

European Union Framework Program 6 funded the following

STREP project:”Rare earth oxide atomic layer deposition for innovations in electronics (REALISE)”. The project is coordinated by Tyndall Institute at University College Cork, Ireland and participated by leading European microelectronics companies involving tool and precursors manufacturers and a few universities.

IP project: “Advanced nanotechnological detection and detoxification of harmful airborne substances for improved public security (NANOSECURE)”. The project has 28 partners from which 19 are small companies, 6 research institutes and 3 universities. The project is coordinated by C-Tech Innovation Ltd, UK.

FP7 project “Corrosion protection with perfect atomic layers (CORRAL)”. The project is coordinated by University of Applied Sciences of Western Switzerland, Geneva and participated by four other universities, three research institutes and seven companies.

European Space Agency ESA has funded the project:

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”Optical IR rejection filter technology”. The research has been carried out with University of Joensuu and Oxford Instruments Analytical.

Laboratory of Inorganic Chemistry is a subcontractor in a Nordic-MINT project:

“Enhanced functionality of self-cleaning and antibacterial surface coatings”, a project which has five contractors, two industrial partners and four subcontractors. The project ended during the year.

The following projects were sponsored by industry.

As a part of the contract made in connection to a placement of the research laboratory of ASM Microchemistry in the premises of Department of Chemistry ASMM supports a few graduate students in Laboratory of Inorganic Chemistry. The research made under this contract deals with new ALD processes for oxide and metal films including the precursor chemistry and area selective ALD.

“ALD for DRAM” project was funded by Qimonda, Dresden, Germany.

New thin film materials for photovoltaics funded by OmniPV, Palo Alto, CA, USA

During the year several smaller projects were carried out with different companies. The research in those projects has dealt with a variety of topics from characterization of materials, to thin film depositions and catalytic activity tests.

Catalysis and green chemistry The common theme in the catalyst research group is the activation of small molecules and development of sustainable catalytic processes. The research is divided into four topics: polymerization catalysts (i), catalytic oxidation (ii), activation of carbon dioxide (iii), and activation of hydrogen (iv). In all topics the focus is on the preparation of structurally verified metal compounds, where the function of the catalytically active metal centre is tuned by a ligand framework. In addition, the projects find their cohesion on research planning, instrumentation including combinatorial chemistry and required analytics.

(i) A wide range of different complexes of early (Ti, Zr, Hf) and late transition metals (Mn, Fe, Co, Ni, Pd) have been developed for olefin polymerization. The topics include ethene homo- and copolymerization with different zirconocenes (2) and aminopyridinato complexes of group 4 metals (70, 71). The research on new catalysts as selective initiators for the ring opening polymerization of lactides and lactones has been also continued. During the year new tin and titanium trimethylsilyl amido complexes have been in ROP catalysts. The resulting polymers have interesting fibrous textures (28). (Aitola, Leskelä, Nieger, Polamo, Puranen, Pärssinen, Repo, Ryynänen, Sood, Talja, Vuorinen)

(ii) The aim in the catalytic oxidation studies is to develop in situ generated metal catalysts suitable for activation of molecular oxygen in aqueous solution and capable of oxidizing of alcohols. During the year new catalyst systems have been developed for this process. The concept used in oxidation reactions: alkali solution, O2 pressure and Cu(II) catalyst have been studied in treatment of wood. In this treatment hemicellulose and lignin dissolve and cellulose fibers remain as solid. The studies show that the cellulose formed can be efficiently hydrolyzed by enzymes and fermented to ethanol. (Ahmad, Figiel, Lahtinen, E. Lankinen, Leskelä, Repo).

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(iii) Activation of CO2 by homogeneous catalysis and its conversion either to polymeric materials or higher value organic molecules has been carried out. Interesting results were obtained for example from coupling of CO2 and epoxides to cyclic carbonates and making cyclic urethanes from CO2 and amino alcohols using different cobalt complexes as catalysts. (Al-Hunaiti, Leskelä, Repo, Sibaouih).

(iv) Hydrogen activation has been studied in systems not containing metal but amines and B(C6F5)3. A facile heterolytic cleavage of H2 under mild reaction conditions was possible by the co-operative action of Lewis acid B(C6F5)3 and Lewis base amines (68). The further development of the system was an ansa-aminoborane which is able to reversibly activate H2 through an intermolecular mechanism (Figure 1). The molecule acts like a tweezer for hydrogen molecule. The activated compound is an efficient reducing agent in reduction of imines and enamines to amines (67). (Leskelä, Repo, Sumerin)

Figure 1. Crystal structure of hydrogen activated ansa-N-TMPN-CH2C6H4B(C6F5)2 molecule where TMPN = 2,2,6,6-tetramethylpiperidine. (67).

Thin films Atomic Layer Deposition studies have focused on materials needed in silicon based microelectronics. The topics include: (i) high-k oxide films for MOSFET gate dielectrics and DRAM capacitors, and (ii) metal films and conductive oxides for interconnects and electrodes for MOSFETs and DRAM capacitors. In these studies the development of precursor chemistry is essential. In addition, (iii) films for photocatalytic self-cleaning surfaces, (iv) in situ characterization of ALD growth by quadrupole mass spectrometer (QMS) and quartz crystal microbalance (QCM), (v) area selective ALD, (vi) deposition of metal fluoride and (vii) chalcogenide films, (viii) ALD of hybrid inorganic-organic materials and (ix) corrosion protection films have been studied. (x) The excellent conformality of ALD has been exploited in deposition on porous substrates as templates in preparation of nanomaterials and nanostructures.

(i) In ALD studies on high-k oxides the emphasis has been in HfO2 and ZrO2 films but some studies have been made on rare earth oxides. The focus has been in process development and studies of new precursors. The precursor chemistry development has been carried out partly in collaboration with chemical manufacturers (Air Liquide, ATMI, SAFC Hitech). Most of the precursors have been based on cyclopentadienyl (Cp) compounds (18, 49) or mixed ligand

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compounds containing Cp (48). In addition, some diamide and amide-amine complexes of zirconium have been tested (80). In ALD of ZrO2 and HfO2 depositions in deep trenches is an important topic since the materials are aimed for DRAMs (48, 49). The main focus in studies on oxide films for DRAM capacitors has been in high-k forms of ZrO2 and HfO2. The desired cubic or tetragonal phases show k value >30. The selection of the metal precursor can enhance the formation of these high-k structures but in addition doping with rare earth or alkaline earth ions is known to stabilize these forms. The importance of precursor chemistry in ALD and especially in group IV metal oxide films was also emphasized in review article (Tero Pilvi, doctoral thesis 2008). TiO2 based mixed films and nanolaminates have been studied in collaboration with University of Tartu giving emphasis in electric properties (36). Structural characterization has been made in collaboration with the University of Uppsala and electrical characterization of high-k oxides with University of Valladolid has been very active (19, 20, 25). The studies with ternary oxides have been continued and dielectric properties of (Sr,Ba)TiO3 films have been characterized in collaboration with University of Oulu (75).

(ii) Studies on ALD of noble metal and noble metal oxide films have been continued. The existing metal precursors have been used together with ozone in oxide processes (Figure 2) (33, 34). ALD of noble metal oxide films can be carried out at low temperatures (< 200 oC) and at higher temperatures metal films are formed. Studies on new metal processes have been continued with special attention on ruthenium films.

Figure 2. SEM images of IrO2 films grown into narrow trench from Ir(acac)3 and ozone at 165 oC (33).

(iii) Studies on photocatalytic, self-cleaning surfaces based on ALD TiO2 thin films were continued. The films were deposited from TiF4 and were unintentionally doped with fluorine. The films showed unexpectedly strong photocatalytic activity under visible light (58). In addition, photocatalytic activity of TiO2 films made by other methods (sol gel, flame pyrolysis) has been examined in collaboration with Tampere University of Technology and Åbo Akademi University.

(iv) In situ surface reaction studies were continued with the QMS-QCM-ALD system. During the year ZrO2 processes using Cp compounds together with ozone or water were investigated. The results from ozone process are interesting and indicate formation of active oxygen on the surface (41).

(v) Area selective ALD has been studied by different approaches: using self-assembled monolayers (SAM) of silanes made by microcontact printing to inhibit the ALD growth on printed areas (23), or using spin-coated polymer films patterned by UV illumination through mechanical masks (22). Both methods result in selective ALD as tested by different oxide and metal film depositions (Figure. 3).

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Removal and patterning of SAMs have also been made by electric discharge in a study aimed for fabrication of microfluidic devices (69).

Figure 3. (A) SEM image of a microcontact printing patterned TiO2 film. Dark lines are TiO2 and lighter lines OTS-SAM (octadecyltrichlorosilane – self-assembled monolayer). (B) EDX measurements on dark and light lines (23).

(vi) Alkaline earth and rare earth fluorides are interesting materials because they are optically transparent over a wide wavelength range down to vacuum ultraviolet regime (Tero Pilvi, Ph.D. thesis 2008). These fluorides were successfully deposited using volatile metal fluorides (TiF4, TaF5) as fluoride precursors and the optic and electric properties of the materials were characterized (54–56).

(vii) Sulphides are well-known chalcogenide materials studied and applied in ALD since its discovery in early 70s whereas ALD of selenide and telluride films have suffered from the lack of good precursors. The recent interest towards selenide and telluride films stems from phase change materials (PCM) aimed for memory applications. Ge2Sb2Te5 (GST) is considered as one of the most potential PCRAM material. New alkyl silyl tellurium precursors were developed for ALD of GST materials (83). Sulphide materials have been studied for photovoltaic applications.

(viii) Studies on ALD of inorganic-organic hybrid materials have been focused on polyimide-tantalum oxide nanolaminate structures. The polyimide was also synthesized by ALD using pyromellitic dianhydride and 1,6-diaminohexane as precursors.

(ix) Different oxide films and their nanolaminates are studied as potential corrosion protection layers for steels in connection to the EU-project CORRAL.

(x) Micro- and nanostructured substrates are important in many potential applications ranging from DRAM capacitors to different membranes and high surface area catalysts. ALD is suited well for depositing films on 3D structures of

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complex shapes and many research projects of the Laboratory require depositions on micro and nanostructured substrates (see below). During the year oxide depositions were made on highly porous metallic fibre material and thermoplastics (Figure 4) (39, 40).

Figure 4. Cross-section BSE images of metal fibers coated by ALD Al2O3 films (40).

Studies on area selective ALD were continued using both self-assembled monolayers (SAM) of silane derivatives (23) and UV-patterned spin-coated polymer films (22). Patterned SAM layers prepared by microcontact printing were able to passivate the growth surfaces against ALD of iridium and TiO2, resulting in patterned Ir and TiO2 films with extremely fine features of 1.5 m (23). Spin-coated poly(methyl methacrylate) (PMMA) films were patterned by UV lithography and tested for area-selective ALD of various oxides and noble metals (23). Depending on the ALD processes, the PMMA film either passivated the surface against ALD growth, or enabled the formation of a patterned surface via a lift-off process (22).

ALD was studied also for surface modification of various thermoplastics (39). Already very thin Al2O3 and TiO2 thin films were found to affect the surface wetting properties of thermoplastics (39). Crystalline TiO2 thin films showed decreasing water contact angles upon UV illumination, allowing thus wettability engineering even for the hydrophobic fluoropolymer surfaces (39). (Färm, Hatanpää, Heikkilä, Hämäläinen, Härkönen, Knapas, Kukli, Leskelä, Niinistö, Pilvi, Pore, Puukilainen, Ritala, Salmi, Saloniemi, Vehkamäki)

Nanostructures and nanomaterials Nanostructures and nanomaterials form an important research area for the Laboratory of Inorganic Chemistry. Several approaches have been taken to prepare nanomaterials using both thin films and organometallic synthesis know-how.

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Because of the self-limiting growth principle Atomic Layer Deposition (ALD) suits very well for making and modifying of nanomaterials. Different inorganic and polymeric materials, both porous and fibrous ones can be used as templates in ALD. Porous alumina is among the most interesting and feasible template materials. This due to the straightforward preparation of dense, regular arrays of straight, deep, cylindrical nanopores with uniform pore sizes ranging from 10 to 400 nm. Two types of porous alumina membranes were used as templates: through-porous self-supporting alumina membranes and Si-supported thin-film membranes. Various materials, including Al2O3, TiO2, Ta2O5 and Pt, have been deposited on the pore walls of porous alumina templates by ALD (Figure 5) These nanostructures have potential applications in several areas including catalysis, sensing, optics and electronics. In another process system the pores of the alumina templates were filled with metal by electrodeposition. Metal nanorods are obtained after removal of the template. Next the nanorods were coated with an oxide by ALD. If TiO2 is used as the oxide, the material is a high surface area photo(electro)catalyst (Figure 6).

Figure 5. Ta2O5 nanotubes in porous alumina template.

Figure 6. TiO2 coated Ni nanorods.

Electrospinning has been one method used for fabrication of nanofibers. Both polymer and inorganic fibres have been made. Polymer fibres have been utilized further as templates for nanotubes by depositing inorganic coating on them by ALD and annealing them to get rid of the polymer kernel.

Self-assembly of salen-type complexes of Co on gold surfaces has been studied and the ability of the complex to act as sensor has been characterized (Figure 7). It

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revealed that the complexes bind reversibly molecular oxygen and are thus potential nano- and molecular level sensors (64).

Through-porous silicon and alumina membranes were prepared by electrochemical etching (Emma Härkönen, M.Sc. thesis 2008). Main emphasis of the work was on porous Al2O3 membranes, both self-supporting and thin-film membranes, but also the preparation of porous Si membranes was studied. The membranes were further modified by electrodeposition and atomic layer deposition (ALD). Electrodeposition resulted in filling the membrane pores with metallic nanorods, whereas ALD coating of the pore walls resulted in the formation of nanotubes in the pores.

Highly porous metal fiber matrices were coated with Al2O3 and Ir thin films by ALD in order to provide additional functionalities while leaving the structural features of the fiber matrices virtually unchanged. Thin, conformal Al2O3 coatings were able to protect the fiber matrices against electrochemical corrosion and thermal oxidation, whereas a thin Ir coating may enable their use as catalytic filters, for example (40). (Färm, Härkönen, Kemell, Leskelä, Pore, Puukilainen, Repo, Ritala, Räisänen, Santala)

Figure 7 Two different gold surfaces (A and B) have been treated first with 4-pyridinethiol and then with Co-salen complexes 4 and 5. (64).

Chemical crystallography Single-crystal X-ray structure determination has for years been an important field of research in this Laboratory. Crystallography has been a widely used method in analyzing crystalline reaction products supplied by several synthetic groups in the Laboratory. (28, 65, 67, 68, 70, 71) (Hatanpää, Leskelä, Mutikainen, Nieger, Polamo, Räisänen, Talja)

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Numerous compounds have, however, originated from a foreign cooperative group at the University of Leiden. (3–9, 16, 27, 29–30, 45, 72, 76) (Mutikainen, Turpeinen)

One part of the foreign cooperative crystallographic studies deals with metal complexes of o-carborane derivatives. The goal in this study is to obtain complexes which act as catalysts for polymerization, hydrogenation and asymmetric synthesis. This work is carried out in collaboration with the Material Science Institute of Barcelona and the Department of Chemistry at the University of Jyväskylä. (11, 13, 26, 37, 50, 73) (Kivekäs)

There is an additional strong cooperation with the Universities of Stuttgart and Karlsruhe. Prof. D. Gudat’s group investigates aromatic phosphorus heterocycles, carbine analogues and functional phosphines, and is also focused on NMR spectroscopy (Department of Inorganic Chemistry, University of Stuttgart, Germany; http://www.iac.uni-stuttgart.de/arbeitskreise/AKGudat/; (12, 14, 15, 17). This cooperation induces a new DAAD-Academy of Finland exchange program between the Department of Inorganic Chemistry, University of Stuttgart, and our Laboratory. The research of Prof. S. Bräse’s group in Karlsruhe is focused on asymmetric catalysis, solid phase synthesis, molecular transporters, nanostructures (MOF’s) and natural product synthesis (Department of Organic Chemistry, University of Karlsruhe (KIT), Germany; http://www.ioc.uni-karlsruhe.de/Professoren/Braese/; (10, 35, 62). There are several additional cooperations with foreign groups in Inorganic Chemistry, Organic/Organometallic Chemistry (24, 47, 59, 60, 66) and Pharmacology (51, 52). (Nieger).

TlBr crystal growth and characterization Among wide bandgap semiconductor materials single crystals of TlBr (2.68 eV) are the most promising for gamma-ray detectors. Its high stopping power and density (7.56 g/cm3) makes it unique for space astrophysics, medicine and military applications. Unfortunately the material is toxic and soft, impeding considerably the development of TlBr material as a single crystal.

For improving the purity of material, the combination of the following techniques was used: Bridgman-Stockbarger, re-crystallization from water solution and travelling molten zone (TMZ) methods (42). This combination permitted to obtain a 4mm thick detector with the mobility-lifetime product for electrons estimated as 3.3x10-4 cm2/V. In order to decrease strain inside the crystal, its adhesion to crucible, effect of temperature of molten TlBr phase and annealing procedures were studied using X-ray and optical methods, imaging with a field emission scanning electron microscope (FESEM) and surface analysis with energy dispersive X-ray spectrometry (EDS). Electrical and detector characteristics of the samples were reported, as well. (Vasilij Kozlov, Lic.Phil. thesis 2008)

The detector manufacturing process was optimized by characterisation of material and crystals using methods such as HR-ICPM, XRD, polarisation microscopy, FTIR, UV-Vis spectroscopy, FESEM and EDS, I-V and CV, and photoconductivity, as well direct detector examination.

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Computational chemistry The evaluation, both qualitatively and quantitatively, of a chemical bond is essential in understanding chemistry. There are at least three well-based approaches to evaluate the nature of bonding. The first method is based upon electron density between atoms. Topological analysis of charge density gives new insight. This concept can be applied to analysis of both experimental and theoretically computed electron density. The basis of the topological analysis of charge density is the AIM (Atoms-in-Molecules) theory developed mainly by prof. Richard Bader. A parallel concept is the so-called ELF (Electron-Localization-Function) theory. In the second approach the energy in a bond is analyzed by quantum chemical methods. The third method is based upon domain-averaged Fermi hole analysis. All of these methods give accurate descriptions of chemical bonds.

The main target of the ‘Computational Chemistry’ project is to study such chemical bonds, where the bonding seems to be ambiguous. (74, 82) (Sundberg, Uggla, Valo)

Solution chemistry Studies on complexation of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with oxime ligands such as pyridine oximes and aminoalkanamidoximes using potentiometric method have continued. (Saarinen, Salonen) (65)

In area of applied coordination chemistry the complexation of the chiral compounds of biodegradable aminopolycarboxylic acids with Mg(II), Ca(II), Mn(II), Cu(II), Zn(II), Fe(III), La(III), Cd(II), Hg(II) and Pb(II) ions have been studied in co-operation with Kemira Oyj/ERC, Helsinki University of Technology and VTT Chemical Technology. (Hyvönen, Saarinen) (31, 32, Helena Hyvönen, Ph.D. thesis 2008)

The temperature dependence of the Ni(II) complex formation with ammonia in aqueous ammoniumsulphate solutions has been investigated as an application for hydrometallurgy with collaboration of Helsinki University of Technology. (Hyvönen)

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Publications Papers in refereed journals (impact factor for the year 2007 in parentheses) 1. Abu-Surrah, A.S., Kettunen, M., Leskelä, M. and Al-Abed, Y.; Platinum and

Palladium Complexes Bearing New (1R,2R)-(-)1,2-Diaminocyclohexane(DACH)-based Nitrogen Ligands: Evaluation of the Complexes Against L1210 Leukemia, Z. Anorg. Allg. Chem. 643 (2008) 2655–2658. (1.260)

2. Aitola, E., Hakala, K., Byman-Fagerholm, H., Repo, T. and Leskelä, M.; High Molar Mass Ethene/1-olefin Copolymers Synthesized with Acenaphtyl Substituted Cyclopentadienyl Metallocene Catalysts, J. Pol. Sci. A Pol. Chem. 46 (2008) 373–382. (3.529)

3. van Albada, G.A., Dominicus, I., Viciano-Chumillas, M., Mutikainen, I, Turpeinen, U. and Reedijk, J.; A Unique Chain of Trinuclear Cu(II) Units Containing both Neutral and Anionic N-(pyrimidin-2-yl) Acetamide (Haapm, resp aapm) as a Ligand and Dicyanamide (dca): Synthesis, Characterization, X-ray Structure and Magnetism of [Cu3 -aapm)2-( -dca)2-(Haapm)2] (CF3SO3)2, Polyhedron 27 (2008) 617–22. (1.756)

4. van Albada, G.A., van der Horst, M.G., Mutikainen, I., Turpeinen, U. and Reedijk, J.; Synthesis, Crystal Structure and Spectroscopy of Catena-polybis(azido-N1,N1)(2-aminopyrimidine)Copper(II), J. Chem.Crystallogr. 38 (2008) 413–417. (0.597)

5. van Albada, G.A., van der Horst, M.G., Mutikainen, I., Turpeinen, U. and Reedijk, J.; Two Mononuclear Compounds with bis(pyrimidin-2-yl)amine as a Ligand and as a Hydrogen-bonded Lattice Molecule. Synthesis, Structure and Spectroscopy of {[M(dipm) (H2O)(A)] (dipm)(A)(H2O)} (M = Cd with A = ClO4; and Zn with A = BF4), J. Chem. Crystallogr. 38 (2008) 519–523. (0.597)

6. van Albada, G.A., van der Horst, M.G., Mutikainen, I., Turpeinen, U. and Reedijk, J.; New 3,5-dimethylpyrazole Copper(II) Compounds with a Variety of Hydrogen Bonds, Synthesized by Using a Dehydrating Agent: Synthesis, Characterization, Structures and Intermolecular Interactions, Inorg. Chim. Acta 361 (2008) 3380–3387. (1.713)

7. van Albada, G.A., Nur, S., van der Horst, M.G., Mutikainen, I., Turpeinen, U. and Reedijk, J.; Characterisation and Structure of Two Cu(II) Mononuclear Compounds with 7-azaindole as a Ligand that Display Interesting H-bond Properties, J. Mol. Struct. 874 (2008) 41–45. (1.486)

8. van Albada, G.A., Nur, S.,. Mutikainen, I, Turpeinen, U. and Reedijk, J.; Characterisation and Structure Determination of Two Mononuclear CuII(ClO4)2 Compounds with 2,2'-bipyridine-1,1'-dioxide, J. Mol. Struct. 875 (2008) 91–95. (1.486)

9. van Albada, G.A., Tanase, S. Mutikainen, I. Turpeinen, U. and Reedijk, J.: A bis(chlorido)-bridged Linear Chain Cu(II) Compound with 7-azaindole as an Axial Ligand; Synthesis, Structure, Hydrogen Bonding and Magnetism. Inorg. Chim. Acta 361 (2008) 1463–1468. (1.713)

10. Ay, S., Nieger, M. and Bräse, S.; Co-metal-free Enantioselective Conjugate Addition Reactions of Zinc Reagents, Chem. Eur. J. 14 (2008) 11539–11556. (5.330)

11. Barberà, G., Vaca, A., Teixidor, F., Sillanpää, R., Kivekäs, R. and Viñas, C.; Designed Synthesis of New ortho-carborane Derivatives: from Mono- to Polysubstituted Frameworks, Inorg. Chem. 47 (2008) 7309–7316. (4.123)

12. Benko, Z., Burck, S., Gudat, D., Nieger, M., Nyulaszi, L. and Shore, N.; Pyrido-annellated Diazaphospholenes and Phospholenium Ions, Dalton Trans. (2008) 4937–4945. (3.212)

13. Bould, J., Laromaine, A., Bullen, N.J.; Viñas, C., Thornton-Pett, M., Sillanpää, R., Kivekäs, R., Kennedy, J. and Teixidor, F.; Borane Reaction Chemistry. Alkyne

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Insertion Reactions into Boron-containing Clusters. Products from the Thermolysis of [6,9-(2-HC C-C5H4N)2-arachno-B10H12], Dalton Trans. (2008) 1552–1563. (3.212)

14. Burck, S., Gudat, D., Nieger, M., Schalley, C.A. and Weilandt, T.: Phosphazene vs. Diazaphospholene PN-bond Cleavage in Spirocyclic Cyclodiphosphazenes. Dalton Trans. (2008) 3478–3485. (3.212)

15. Burck, S., Gudat, D., Nieger, M. and Vindus, D.; Increasing the Lability of Polarised Phosphorus-phosphorus Bonds, Eur. J. Inorg. Chem. (2008) 704–707. (2.597)

16. Castro, A.G., Costa, J.S., Pievo, R., Massera, C., Mutikainen, I., Turpeinen, U., Gamez, P. and Reedijk, J.; A New Sulfur-containing Schiff-base Ligand and Binding to Copper(II) and Cobalt(II), Z. Anorg. Allg. Chem. 634 (2008) 2477–2482. (1.260)

17. Chikkali, S., Magens, S., Gudat, D., Nieger, M., Hartenbach, I. and Schleid T.; A Phosphanyl-substituted Benzo-1,3,2-dioxaborol as Ambiphilic Bifunctional Lewis Donor-acceptor Unit, Eur. J. Inorg. Chem. (2008) 2207–2213. (2.597)

18. Dezelah, C.L. Niinistö, J. Kukli, K. Munnik, F. Lu, J. Ritala, M. Leskelä M. and Niinistö, L.; The Atomic Layer Deposition of ZrO2 and HfO2 Using Advanced Metallocene Precursors and H2O as Oxidant, Chem. Vap. Deposition 14 (2008) 358–365. (1.936)

19. Dueñas, S., Castán, H., García, H., Bailón, L. Kukli, K., Lu, J., Ritala, M. and Leskelä, M.; Selection of Post-growth Treatment Parameters for Atomic Layer Deposition of Structurally Disordered TiO2 Thin Films, J. Non-Cryst. Solids 354 (2008) 404–408. (1.319)

20. Dueñas, S., Castán, H., García, H., Gomez, A., Bailón, L., Kukli, K., Aarik, J., Ritala, M. and Leskelä, M.; Comparative Study of Flat-band Voltage Transients on High-k Dielectric Based Metal-Insulator-Semiconductor Capacitors, J. Electrochem. Soc. 155 (2008) G241–G246. (2.483)

21. Farras, P., Teixidor, F., Kivekäs, R., Sillanpää, R., Viñas, C., Gruner, B. and Cisarova, I.; Metallacarboranes as Building Blocks for Polyanionic Polyarmed Aryl-ether Materials, Inorg. Chem. 47 (2008) 9497–9508. (4.123)

22. Färm, E., Kemell, M., Ritala, M. and Leskelä, M.: Selective-area Atomic Layer Deposition Using Poly(methyl Methacrylate) Films as Mask Layers. J. Phys. Chem. C. 112 (2008) 15791–15795. (n/a)

23. Färm, E., Kemell, M., Ritala, M. and Leskelä, M.; Selective-area Atomic Layer Deposition with Microcontact Printed Self-assembled Octadecyltrichlorosilane Monolayers as Mask Layers, Thin Solid Films 517 (2008) 972–975. (1.693)

24. Gansäuer, A., Winkler, I., Worgull, D., Franke, D., Lauterbach, T., Okkel, A. and Nieger M.; Modular Synthesis of Functional Titanocenes, Organometallics 27 (2008) 5699–5707. (3.833)

25. Garcia, H., Dueñas, S., Castán, H., Bailón, L., Kukli, K., Aarik, J. Ritala, M. and Leskelä, M.; Identification of Spatial Localization and Energetic Position of Electrically Active Defects in Amorphous High-k Dielectrics for Advanced Devices, J. Non-Cryst. Solids 354 (2008) 393–398. (1.319)

26. Gonzáles-Campo, A., Juarez-Perez, E.J., Viñas, C., Boury, B., Sillanpää, R., Kivekäs, R., Nuñez, R.: Carboranyl Substituted Siloxanes and Octasilsesquioxanes: Synthesis, Characterization and Reactivity, Macromolecules 41 (2008) 8458–8466. (4.411)

27. van Gorkum, R., Berding, J., Mills, A.M., Kooijman, H. D., Tooke, M., Spek, A.L., Mutikainen, I., Turpeinen, U., Reedijk, J. and Bouwman, E.; The Synthesis, Structures and Characterisation of New Mixed-ligand Manganese and Iron Complexes with Tripodal, Tetradentate Ligands. Eur. J. Inorg. Chem. (2008) 1487–1496. (2.597)

28. Grafov, A., Vuorinen, S., Repo, T., Kemell, M., Nieger, M. and Leskelä, M.; New Sn(IV) and Ti(IV) bis(trimethylsilyl)amides in D,L-lactide Polymerization, SEM Characterization of Polymers, Eur. Polym. J. 44 (2008) 3797–3805. (2.248)

29. Götz, R.J., Robertazzi, A., Mutikainen, I., Turpeinen, U., Gamez, P. and Reedijk, J.; Concurrent Anion Interactions between a Perchlorate Ion and Two -

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acidic Aromatic Rings, Namely Pentafluorophenol and 1,3,5-triazine, Chem. Commun. (2008) 3384–3386. (5.141)

30. van der Horst, M.G., van Albada, G.A., Ion, R.-M., Mutikainen, I., Turpeinen, U., Tanase, S. and Reedijk, J.; Extended Networks Generated from the Interaction of Rare Earth(III) Ions and Pyridine-2-carboxamide-based Ligands, Eur. J. Inorg. Chem. (2008) 2170–2176. (2.597)

31. Hyvönen, H. and Aksela, R.; Complexation of [S,S,S]- and [R,S,R]-isomers of N-bis[2-(1,2-dicarboxyethoxy)ethyl] Aspartic Acid with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) Ions in Aqueous Solution, J. Coord. Chem. 61 (2008) 2515–2527. (0.867)

32. Hyvönen, H., Lehtinen, P. and Aksela, R.; Complexation of N-bis[2-(1,2-dicarb-oxyethoxy)ethyl] Aspartic Acid with Cd(II), Hg(II) and Pb(II) Ions in Aqueous Solution, J. Coord. Chem. 61 (2008) 984–996. (0.867)

33. Hämäläinen, J., Kemell, M., Munnik, F., Kreissig, U., Ritala, M. and Leskelä, M.; Atomic Layer Deposition of Iridium Oxide Thin Films from Ir(acac)3 and Ozone, Chem. Mater. 20 (2008) 2903–2907. (4.883)

34. Hämäläinen, J., Munnik, F., Ritala, M. and Leskelä, M.; Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac)2 and Ozone, Chem. Mater. 20 (2008) 6840–6846. (4.883)

35. Jainta, M., Nieger, M. and Bräse, S.; Microwave-Assisted Stereoselective One-pot Synthesis of Symmetrical and Unsymmetrical 2,5-Diketopiperazines from Unprotected Amino Acids, Eur. J. Org. Chem. (2008) 5418–5424. (2.914)

36. Jõgi, I., Pars, M., Aarik, J., Aidla, A., Laan, M., Sundqvist, J., Oberbeck, L., Heitmann, J. and Kukli, K.; Conformity and Structure of Titanium Oxide Films Grown by Atomic Layer Deposition on Silicon Substrates, Thin Solid Films 516 (2008) 4855–4862. (1.693)

37. Juárez-Perez, E.J., Viñas, C., Gonzáles-Campo, A., Teixidor, F., Sillanpää, R., Kivekäs, R. and Nuñez, R.; Controlled Direct Synthesis of C-mono- and C-disubstituted Derivatives of [3,3'-Co(1,2-C2B9H11)2]- with Organosilane Groups: Theoretical Calculations Compared with Experimental Results, Chem.–Eur. J. 14 (2008) 4924–4938. (5.330)

38. Kaila, R.K., Gutiérrez, A., Slioor, R., Kemell, M., Leskelä, M. and Krause, A.O.I.; Zirconia-supported Bimetallic RhPt Catalysts: Characterization and Testing in Autothermal Reforming of Simulated Gasoline, Appl. Catal. B. 84 (2008) 223–232. (4.651)

39. Kemell, M., Färm, E., Ritala, M. and Leskelä, M.; Surface Modification of Thermoplastics by Atomic Layer Deposition of Al2O3 and TiO2 Thin Films, Eur. Polym. J. 44 (2008) 3564–3570. (2.248)

40. Kemell, M., Ritala, M., Leskelä, M., Groenen, R., Lindfors, S.; Coating of Highly Porous Fibre Matrices by Atomic Layer Deposition, Chem. Vap. Deposition 14 (2008) 347–352. (1.936)

41. Knapas, K. and Ritala, M.; In Situ Reaction Mechanism Studies on Atomic Layer Deposition of ZrO2 from (CpMe)2Zr(OMe)Me and Water or Ozone, Chem. Mater. 20 (2008) 5698–5705. (4.883)

42. Kozlov, V., Andersson, H., Gostilo, V., Leskelä, M., Owens, A., Shorov, M. and Sipilä, H.; Improved Process for the TlBr Single Crystal Detector, Nucl. Instr. Meth. Phys. Res. A 591 (2008) 209–212. (1.114)

43. Polini, F., Gallo, V., Mastrorilli, P., Calmuschi-Cula, B., Englert, U., Re, N., Repo, T. and Räisänen, M.; Site Selectivity in the Protonation of a Phosphinito Bridged PtI-PtI Complex: a Combined NMR and Density-functional Theory Mechanistic Study, Inorg. Chem. 47 (2008) 9779–9796. (4.123)

44. Marchetti, F., Pampaloni, G. and Repo, T.; The Polymerization of Tetrahydrofuran Initiated by Niobium(V) and Tantalum(V) Halides, Eur. J. Inorg. Chem. 12 (2008) 2107–2112. (2.597)

45. Lu, Z.L. Costa, J.S. Roubeau, O. Mutikainen, I. Turpeinen, U. Teat, S.J. Gamez, P. and Reedijk, J.; A Copper Complex Bearing a TEMPO Moiety as Catalyst for the Aerobic Oxidation of Primary Alcohols, Dalton Trans. (2008) 3567–3573. (3.212)

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46. Miikkulainen, V., Rasilainen, T., Puukilainen, E., Suvanto, M., Pakkanen, T.A.; Atomic Layer Deposition as Pore Diameter Adjustment Tool for Nanoporous Aluminum Oxide Injection Molding Masks, Langmuir 24 (2008) 4473–4477. (4.009)

47. Muniz, K., Hövelmann, C.H., Campos-Gomez, E., Barluenga, J., Gonzales, J. M., Streuff, J. and Nieger, M.; Intramolecular Diamination of Alkenes with Palladium(II)/Copper(II) Bromide and IPy2BF4: The Role of Halogenated Intermediates, Chem. Asian J. 3 (2008) 776–788. (2.340)

48. Niinistö, J., Kukli, K., Kariniemi, M., Ritala, M., Leskelä, M., Blasco, N., Pinchart, A., Lachaud, C., Laaroussi, N., Wang, Z., and Dussarrat, C.; Novel Mixed Alkylamido-cyclopentadienyl Precursors for ALD of ZrO2 Thin Films, J. Mater. Chem. 18 (2008) 5243–5247. (4.339)

49. Niinistö, J., Kukli, K., Tamm, A., Putkonen, M., Dezelah, C.L., Niinistö, L., Lu, J., Song, F., Williams, P., Heys, P.N., Ritala, M. and Leskelä, M.; Advanced Cyclopentadienyl Precursors for Atomic Layer Deposition of ZrO2 Thin Films, J. Mater. Chem. 18 (2008) 3385–3390. (4.339)

50. Nuñez, R., Teixidor, F., Kivekäs, R., Sillanpää, R., Viñas, C.; Influence of the Solvent and R Groups on the Structure of (Carboranyl)R2PI2 Compounds in Solution. Crystal Structure of the First Iodophosphonium Salt Incorporating the Anion [7,8-nido-C2B9H10]-, Dalton Trans. (2008) 1471–1480. (3.212)

51. Ottersbach, P.A., Bolek, D., Lepicova, E., Nieger, M. and Gütschow, M.; Darzens Reaction of 2-Bromo-4,6-dimethoxy-3(2H)-benzofuranone with Aromatic Aldehydes to Form Flavenoids, J. Heterocyclic Chem. 45 (2008) 1149–1153. (0.813)

52. Pietsch, M., Häcker, H.-G., Schnakenburg, G., Hoffbauer, W., Nieger, M. and Gütschow‚ M.; Structural Characterization of Two Salts Derived from Tetrafluorophthalic Acid and Isopropylamine, J. Mol. Struct. 878 (2008) 131–138. (1.486)

53. De Pilli, T., Jouppila, K., Ikonen, J., Kansikas, J., Derossi, A. and Severini, C.; Study on Formation of Starch-lipid Complexes During Extrusion-cooking of Almond Flour, J. Food Eng. 87 (2008) 495–504. (1.848)

54. Pilvi, T., Puukilainen, E., Arstila, K., Leskelä, M., Ritala M.; Atomic Layer Deposition of LaF3 Thin Films Using La(thd)3 and TiF4 as Precursors, Chem. Vap. Deposition 14 (2008) 85–91. (1.936)

55. Pilvi, T., Puukilainen, E., Kreissing, U., Leskelä, M. and Ritala M.; Atomic Layer Deposition of MgF2 Thin Films Using TaF5 as a Novel Fluorine Source, Chem. Mater. 20 (2008) 5023–5028. (4.883)

56. Pilvi, T., Ritala, M., Leskelä, M., Bischoff, M., Kaiser, U., and Kaiser, N.; Atomic Layer Deposition Process with TiF4 as a Precursor for Depositing Metal Fluoride Thin Films, Appl. Opt. 47 (2008) C271–C274. (1.701)

57. Ponec, R., Lendvay, G. and Sundberg, M.R.; Structure and Bonding in Binuclear Metal Carbonyls from the Analysis of Domain Averaged Fermi Holes. II [Fe2(CO)8]2

- and [Fe2(CO)8], J. Phys. Chem. A 112 (2008) 9936–9945. (2.918)

58. Pore, V., Kivelä, T., Ritala, M. and Leskelä, M.; Atomic Layer Deposition of Photo Catalytic TiO2 Thin Films from TiF4 and H2O, Dalton Trans. (2008) 6467–6474. (3.212)

59. Rang, A., Engeser, M., Maier, N.M., Nieger, M., Lindner, W. and Schalley, C. A.; Synthesis of Axially Chiral 4,4’-Bipyridines and Their Remarkably Selective Self-Assembly into Chiral Metallo-supramolecular Squares, Chem. Eur. J. 14 (2008) 3855–3859. (5.330)

60. Rang, A., Nieger, M., Engeser, M., Lützen, A. and Schalley, C. A.; Self-assembling Squares with Amino Acid-decorated Bipyridines: Heterochiral Self-sorting of Dynamically Interconverting Diastereomers, J. Chem. Soc. Chem. Commun. (2008) 4789–4791. (5.141)

61. Raula, J., Thielmann, F., Kansikas, J., Hietala, S., Annala, M., Seppälä, J., Lähde, A. and Kauppinen, E.I.; Investigations on the Humidity-induced Transformations of Salbutamol Sulphate Particles Coated with L-leucine, Pharm. Res. 25 (2008) 2250–2261. (2.678)

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62. Reingruber, R., Vanderheiden, S., Wagner, A., Nieger, M., Muller, T., Es-Sayed, M., Bräse, S.; 1-Aryl-3,3-diisopropyltriazenes: An Easily Accessible and Particular Stable Class of Triazenes Towards Strong Basic and Lewis Acid Conditions, Eur. J. Org. Chem. (2008) 3314–3327. (2.914)

63. Rooth, M., Johansson, A., Kukli, K., Aarik, J., Boman, M., Haarsta, A.; Atomic Layer Deposition of Iron Oxide Thin Films and Nanotubes Using Ferrocene and Oxygen as Precursors, Chem. Vap. Deposition 14 (2008) 67–70. (1.936)

64 Räisänen, M.T., de Almeida, P., Meinander, K., Kemell, M., Mutikainen, I., Leskelä, M. and Repo, T.; Cobalt Salen Functionalised Polycrystalline Gold Surfaces, Thin Solid Films 516 (2008) 2948–2956. (1.693)

65. Salonen, M., Saarinen, H. and Mutikainen I.; Equilibrium and Structural Studies of Copper(II) and Nickel(II) Complexes with Pyridine-2,6-diamidoxime in Aqueous Solution, J. Coord. Chem. 61 (2008) 1462-1474. (0.867)

66. Schmidt, A. Lindner, A. S. Shilabin, A. G. Nieger, M.; New Derivatives and Ring Systems of Annulated Pyrrolobenzo[1,4]diazepines, Tetrahedron 64 (2008) 2048–2056. (2.869)

67. Sumerin, V., Schulz, F., Atsumi, M., Wang, C., Nieger, M., Leskelä, M., Repo, T., Pyykkö, P. and Rieger, B.; Molecular Tweezers for Hydrogen: Synthesis, Characterization and Reactivity, J. Am. Chem. Soc. 130 (2008) 14117–14119. (7.885)

68. Sumerin, V., Schulz, F., Nieger, M., Leskelä, M., Repo, T. and Rieger, B.; Facile Heterolytic H2 Activation by Amines and B(C6F5)3, Angew. Chem. Int. Ed. 47 (2008) 6001–6003. (and cover picture). (10.031)

69. Suni, N.M., Haapala, M., Mäkinen, A., Sainiemi, L., Franssila, S., Färm, E., Puukilainen, E., Ritala, M., Kostiainen R.; Selective Surface Patterning with Electric Discharge in the Fabrication of Microfluidic Structures, Angew. Chem. Int. Ed. 47 (2008) 7442–7445. (10.031)

70. Talja, M., Luhtanen, T., Polamo, M., Leskelä, M. and Pakkanen, T.A.; Synthesis, Characterization and Ethylene Polymerization Activity of Titanium Aminopyridinato Complexes, Inorg. Chim. Acta 361 (2008) 2195–2202. (1.713)

71. Talja, M., Polamo, M. and Leskelä, M.; Bis(alkylphenylaminopyridinato)titanium Dichlorides as Ethylene Polymerization Catalysts, J. Mol. Cat. A 280 (2008) 102–105. (2.707)

72. Tang, J., Costa, J.S., Pevec, A., Kozlevcar, B., Massera, C., Roubeau, O., Mutikainen, I., Turpeinen, U., Gamez, P., and Reedijk, J.; Influence of Coordinating and Noncoordinating Anions and of a Methoxy Substituent on the Formation of Copper-based Coordination Assemblies, Cryst. Growth Des. 8 (2008) 1005–1012. (4.046)

73. Teixidor, F., Laromaine, A., Kivekäs, R., Sillanpää, R., Viñas, C., Vespalec, R. and Horakova, H.; Synthesis, Reactivity and Complexation Studies of N,S Exo-heterodisubstituted o-carborane Ligands. Carborane as a Platform to Produce the Uncommon Bidentate Chelating (Pyridine)N-C-C-C-S(H) Motif, Dalton Trans. (2008) 345–354. (3.212)

74. Torres, J., Veiga, N., Gancheff, J., Dominguez, S., Mederos, A., Sundberg, M., Sanchez, A., Castiglioni, J., Diaz, A. and Kremer, C.; Interaction of Myo-inositol Hexakisphosphate with Alkali and Alkaline Earth Metal Ions: Spectroscopic, Potentiometric and Theoretical Studies, J. Mol. Struct. 874 (2008) 77–88. (1.486)

75. Tyunina, M., Plekh, M., Levoska, J., Vehkamäki, M., Ritala, M., Leskelä, M.; Dielectric Properties of Atomic Layer Deposited (Ba,Sr)TiO3 Thin Films, Intergr. Ferroelectr. 102 (2008) 29–36. (0.334)

76. Viciano-Chumillas, M., Tanase, S., Mutikainen, I., Turpeinen, U., de Jongh, L.J., and Reedijk, J.; Mononuclear Manganese(III) Complexes as Building Blocks for the Design of Trinuclear Manganese Clusters: Study of the Ligand Influence on the Magnetic Properties of the [Mn3 3-O)]7+ Core, Inorg. Chem. 47 (2008) 5919–5929. (4.123)

77. Zhang, X., Honkanen, M., Järn, M., Peltonen, J., Pore, V., Levänen, E. and Mäntylä, T.; Thermal Stability of the Structural Features in the Superhydrophobic

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Boehmite Films on Austenitic Stainless Steels, Appl. Surf. Sci. 254 (2008) 5129–5133. (1.406)

78. Zhang, X., Järn, M., Peltonen, J., Pore, V., Vuorinen, T., Levänen, E. and Mäntylä, T.; Analysis of Roughness Parameters to Specify Superhydrophobic Antireflective Boehmite Films Made by the Sol-gel Process, J. Eur. Ceram. Soc. 28 (2008) 2177–2181 (1.562)

Reviews 79. Ritala, M. and Niinistö, J.; Atomic Layer Deposition Chemical Vapour Deposition:

Precursors, Processes and Applications, Eds. Jones, A. C. and Hitchman, M. J., Royal Society of Chemistry (2008), pp. 158–206. DOI: 10.1039/9781847558794 ISBN (online): 978-1-84755-879-4 ISBN (print): 978-0-85404-465-8

Conference proceedings 80. Chen, T., Cameron, T. M., Nguyen, S. D., Stauf, G. T., Peters, D. W., Maylott,

L., Li, W., Xu, C., Roeder, J.F., Hilgarth, M., Niinistö, J., Kukli, K., Ritala, M. and Leskelä, M.; Novel Zirconium Precursors for Atomic Layer Deposition of ZrO2 Films, Electrochemical Society Transactions 16 (2008) 87–101.

81. Lahtinen, P., von Weymarn, N., Lankinen, E., Repo, T., Leskelä, M., Kallioinen, A., Uusitalo, J., Siika-aho, M. and Tamminen, T.; Catalytic Pre-treatment of Lignocellulosic Raw Materials, Proceedings of the EWLP2008 Conference.

82. Sundberg, M.R.; Lennard Jones and the 18 Electrons Rule, invited lecture, XVI International Winter School on Coordination Chemistry, Karpacz 2008, Proceedings, 32–33, ISBN 978-83-60043-01-9.

Patents 83. Pore, V. Hatanpää, T. Ritala, M. and Leskelä, M.; Synthesis and Use of Precursors

for ALD of Tellurium and Selenium Thin Films, U.S. Pat. Appl. 2008 84. Pore, V. Ritala, M. and Leskelä, M.; Methods for Forming of Conductive Titanium

Oxides Thin Films, U.S. Pat. Appl. 2008 85. Sundqvist, J., Oberbeck, L., Hintze, B., Schröder U., Kukli, K., Ritala, M. and

Leskelä, M.; Improved Ru Electrodes for Capacitor Applications, Ger. Offen. 10 2008 015 270.6.

Books and chapters in books 86. Antila, A.-M., Karppinen, M., Leskelä, M., Mölsä, H. and Pohjakallio, M.;

Tekniikan kemiaa (Chemistry of Technology) (in Finnish) 10th renewed ed., Edita, Helsinki 2008, 366 pp.

87. Hannola-Teitto, M., Jokela, R., Leskelä, M., Näsäkkälä, E., Pohjakallio, M., and Rassi, M.; Neon. Kemian kertauskirja, (Chemistry for high schools) (In Finnish), Edita, Helsinki 2008, 191 pp.

88. Grafov, A. and Mano, E.B., Eds.; Nine Language Dictionary of Polymers and Composites (a comprehensive dictionary in English, Chinese, French, Italian, Japanese, Portuguese, Russian, Spanish, and Ukrainian). J.Wiley & Sons, Hoboken (NJ) 2008, xxiii+1086 pp.ISBN 978-0-470-28248-9.

89. Grafov, A. and Mano, E.B.; English terminology, In Nine Language Dictionary of Polymers and Composites, Grafov A. and Mano, E.B., Eds. J.Wiley & Sons, Hoboken (NJ) 2008, ISBN 978-0-470-28248-9.

90. Grafov, A.; Russian terminology and Russian key, in Nine Language Dictionary of Polymers and Composites, A. Grafov and E.B.Mano, Eds. J.Wiley & Sons, Hoboken (NJ) 2008, ISBN 978-0-470-28248-9.

Theses Doctor of Philosophy 1. Elers, Kai: Copper Diffusion Barrier Deposition on Integrated Circuit Devices by

Atomic Layer Deposition Technique

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2. Hyvönen, Helena: Studies on Metal Complex Formation of Environmental Friendly Aminopolycarboxylate Chelating Agents

3. Pilvi, Tero: Atomic Layer Deposition for Optical Applications: Metal Fluoride Thin Films and Novel Applications

Licentiate of Philosophy 1. Feodorow, Santeri: Magnetically separable chiral metal-salen catalysts 2. Kozlov, Vasilij: TlBr raw material purification, crystal growth, annealing, detector

fabrication and characterization for gamma-ray detection applications Master of Science 1. Alakoski, Heikki: Titanium dioxide photocatalysts modified by metal particles and

metal ions (in Finnish). 2. Hakola, Maija: Catalytic liberation of hydrogen from amines and alcohols –

applications in hydrogen storage and racemisation (in Finnish). 3. Härkönen, Emma: Preparation of through porous structures of silicon and aluminum

oxides (in Finnish). 4. Kivelä, Tiina: Potential controlled surface phenomena in microchip analysis (in

Finnish). 5. Markkanen, Heini: Polymerization methods for lactides and lactones (in Finnish). 6. Ranki, Hannu: Effect of annealing on high permittivity thin films: Studies with high

temperature X-ray diffractometry and atomic force microscopy (in Finnish). 7. Tupala, Jere: Fabrication of pigments by hydrolysis (in Finnish). Master of Science for teachers 1. Handolin, Heidi: Opinons of the students on experiments in chemistry and in high-

school teaching (in Finnish). 2. Karjalainen, Veikko: Teaching of chemistry today: Teachers’ opinions on teaching of

chemistry and development of the chemistry teaching (in Finnish). 3. Laakso, Janina: Teaching chemistry of metals in 7–9 grades (in Finnish). 4. Leppänen, Johannes: Opinions and interest in chemistry among the pupils in 6th grade

in elementary school (in Finnish). 5. Ojala, Liisa: Steel as teaching topic in middle school (in Finnish). 6. Tähtivaara, Anna: Chemistry of glass in www (in Finnish). 7. Wirtanen, Mikko: QTAIM and chemical bond (in Finnish).

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LABORATORY OF PHYSICAL CHEMISTRY

Personnel Teaching staff Arkke Eskola, M.Sc. (Eng.), Teaching Assistant (on leave) Lauri Halonen, D.Sc., Professor, Head of the Laboratory Vesa Hänninen, Ph.D., Teaching Assistant Arimatti Jutila, Ph.D., Teaching Assistant Hanna Lignell, Teaching Assistant (on leave) Pekka Manninen, Ph.D., Doc. Janne Pesonen, Ph.D., Doc Markku Räsänen, Ph.D., Professor, Director of the Department Jorma Seetula, Ph.D., Doc. Elina Sälli, M.Sc., Teaching Assistant Raimo Timonen, Ph.D., Doc., Lecturer Juha Vaara, Ph.D., Doc., Lecturer Olavi Vaittinen, Ph.D., Doc.

Research staff Carina Asara, Ph.D. Damien Amedro Suula Arppe Alice Corani Joseph Guss, Ph.D. Matti Hanni, M.Sc. Marja Hyvärinen Marvin Ihlenborg Suvi Ikäläinen, M.Sc. Karoliina Isokoski Sanna Kangasvieri Jouni Karjalainen Leonid Khryashchev, Ph.D., Doc. Oona Kupiainen Tommi Lantta, M.Sc. Antti Lignell, Ph.D.. Helmi Liimatainen Kseniya Marushkevitch Mia Melavuori, M.Sc. Timur Nikitin Jari Peltola Teemu O. Pennanen, M.Sc. Teemu S. Pennanen, M.Sc. Teemu Rajala Matti Rissanen, M.Sc. Teemu Salmi, M.Sc. Mikael Siltanen, Ph.D.

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Stanislav Standara, M.Sc. Stefan Taubert, M.Sc. Markku Vainio, Ph.D. Nergiz Özcan, M.Sc.

Administrative and technical staff Seija Koivisto, Secretary Hannele Rantanen, Secretary Markus Metsälä, Ph.D., Laboratory Engineer (on leave) Peeter Mälk, M.Sc., Laboratory Technician Kari Tuomainen, Laboratory Technician (on leave)

Research activities

The research topics of the laboratory include laser and infrared spectroscopy, solid state photochemistry and dynamics, theoretical molecular physics, computational quantum chemistry, theory of magnetic resonance, reaction kinetics and combustion chemistry. Experimental, computational and theoretical methods are used to investigate modern molecular problems in both spectroscopy and dynamics. Particular emphasis is placed on the development of new laser spectroscopic techniques, on the application of modern mathematical theories to molecular problems, on the theory and computation of spectral parameters both in optical and magnetic resonance spectroscopies, and on the detection of new rare-gas containing molecular species. A large number of papers are published annually in the most prominent international journals of physical chemistry and chemical physics. Extensive collaboration with many leading laboratories in other European countries has led to funding from European science programs. The laboratory has belonged to the Center of Excellence in Computational Molecular Science since 2006.

The Physical Chemistry Laboratory is well equipped for modern spectroscopic, gas kinetics and computational research. The major research instruments available include the following: Coherent Titanium:Sapphire/dye ring lasers MBR 111 and 899-21, Neodymium:Vanadate laser Verdi 10 W @ 532 nm, Fiber laser IPG YLR-20-1064-LP-SF, diode laser New Focus Velocity 6328, Bruker high resolution infrared interferometer IFS 120 HR, two Nicolet SX-60 FTIR spectrometers, three cryostats for matrix isolation spectroscopy, CCD-based Raman spectrometer, MGX-250 F2 excimer lasers, Nd:YAG-laser pumped optical parametric oscillator (Sunlite, Continuum 225nm - 4 m, bandwidth 0.1 cm-1) with gated CCD detection, and a fast flow reactor coupled to a photoionization quadrupole mass spectrometer (Extrel) and excimer laser (ELI-76E ArF/KrF exciplex). The Laboratory is a partner in the nation-wide Materials Grid Consortium where large-scale PC-cluster facilities have been established for computational materials science use.

Molecular spectroscopy, and computational and theoretical chemistry Our research consists of experimental, theoretical and computational work. We have built several high-resolution laser spectrometers to be used with gaseous samples. These include: a photo-acoustic intracavity laser spectrometer, a laser-

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locked high repetition rate cavity ringdown spectrometer, a Fourier transform intracavity laser absorption spectrometer and a continuous wave parametric oscillator in the infrared region. A commercial high-resolution Fourier transform infrared (FTIR) instrument can be used in the 500–20 000 cm-1 wavenumber region. We also work on new quantum mechanical models and numerical methods that are used both for spectroscopic and surface science research. We have used a mathematical method called geometric algebra. State-of-the-art electronic structure calculations have also been performed. The theoretical and numerical work is related to our experimental studies.

Experimental work in laser spectroscopy

We are developing new laser spectroscopic methods and applying them to the study of the rovibrational states of polyatomic molecules. The laser spectroscopy of small molecules is applied to medical investigations of human breath samples.

Cavity ring-down laser spectroscopy (CRDS). We have built a cavity ring-down laser spectrometer where a continuous wave ring laser is frequency stabilised to a high-finesse optical cavity. This allows us to run the experiment at higher repetition rates than those possible in standard CRDS setups. The sensitivity of the spectrometer belongs to the state-of-the-art in the field and the high repetition rate can also be beneficial in other fields such as the reaction kinetics of short lived intermediates.

Dispersed vibration-rotation fluorescence spectroscopy. A new method we have developed is the detection of the dispersed laser-induced vibration-rotation fluorescence in the ground electronic state of polyatomic molecules. For this purpose, an intracavity cell equipped with light-collecting optics has been built. Vibration-rotation fluorescence in the infrared region is dispersed with our high-resolution infrared interferometer. Beautiful, rotationally-resolved fluorescence spectra induced by molecular collisions have been observed for molecules such as acetylene and water. Vibrational states not directly accessible by infrared spectroscopy have been accessed for the first time. We have been able to investigate possible ortho-para nuclear spin conversion in HCCH.

Development of a tunable continuous-wave (cw) optical parametric oscillator (OPO). We have developed a stable singly-resonant cw OPO working in the mid-infrared region. We plan to use this versatile mid-infrared source for cavity ring down spectroscopy and also for multi-photon spectroscopy, in combination with our titanium:sapphire ring laser. The OPO contains no intracavity etalon and can be tuned in wavelength simply by adjusting the temperature of the non-linear crystal and the wavelength of the pump laser. We have also quantitatively studied a number of thermally induced phenomena that take place in such a singly resonant cw OPO. We have successfully demonstrated a new method that allows simple and rapid tuning of the OPO wavelength through a rotatable diffraction grating inside the OPO cavity. A patent application has been filed concerning the new tuning method and we have performed preliminary research on other promising tuning methods, whose applicability will be tested. In addition, we have begun working on mid-infrared sources that are based on another non-linear optical effect called difference-frequency generation (DFG). Such sources would benefit from the immensely flexible tuning range of our titanium:sapphire ring laser, which is

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otherwise unavailable in the mid-infrared region. We have built a working test version of a cw DFG apparatus.

Medical applications of laser spectroscopy. We are using the CRDS method to diagnose various diseases from human breath samples. A collaborative study with the Tampere University Hospital to diagnose Helicobacter pylori infection has been started by measuring ammonia from human breath. A diode laser based spectrometer, operational at about 6500 cm-1, is used for this purpose. Minute quantities of ammonia and hydrogen cyanide have been measured in breath samples at the parts-per-billion level. In collaboration with the Karolinska Institutet in Stockholm, results of an investigation into the possibility of diagnosing hydrogen cyanide poisoning from breath have been submitted for publication. This background level study included the measurement of hydrogen cyanide concentrations in the exhaled breath of 40 healthy subjects.

Theoretical, numerical and computational methods in molecular spec-troscopy and surface science

The group is interested in the quantum behaviour of polyatomic molecules and chemical reactivity on catalytic surfaces.

Geometric algebra. We have used a branch of mathematics called geometric algebra in our spectroscopic problems. In recent years, geometric algebra has been applied to some areas of physics but it is less familiar to chemists. We have obtained some original results with this method. For example, the previous formulation of molecular vibrations has been shown to be incomplete. We are now able to form both vibrational and rovibrational quantum mechanical Hamiltonian operators in an algebraic way. Our approach is much faster and simpler than those used before. We have also been able to produce the first practical method to form volume elements for integration, and to form molecular Hamiltonians in non-orthogonal molecule-fixed axis systems. We have developed the original mathematical tools needed to formulate geometry in a coordinate-independent manner. These tools will be needed, for example, in the effective modelling of sub-unit motions in large biomolecules.

Hamiltonians in curvilinear and linearized internal coordinates. At present, it is customary to describe molecular vibrations using as exact kinetic energy operators and potentials as possible. It has become a standard approach to express Hamiltonians in curvilinear internal displacement coordinates, because such coordinates offer a simple and physical picture of vibrational motions, including large amplitude changes in the shape. On the other hand, in the older normal mode model of molecular vibrations, the nuclei are considered as vibrating infinitesimally about the reference configuration, and the shape of the molecule is described using linearized approximations of the true geometrically-defined internal displacement coordinates.

We have formed a simple, yet general way to express curvilinear internal displacement coordinates as closed functions of their linearized counterparts, and vice versa. We also present a simple yet general way to construct exact kinetic energy operators in linearized internal displacement coordinates. The "vibrational", "rotational" and Coriolis metric tensor elements and Jacobians are produced as the result. Because potential energy operators can be transformed from one

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representation to another by simply making the necessary coordinate transformation, the present method makes it possible to easily compare Hamiltonians parametrized in the true curvilinear displacement coordinates to their counterparts parametrized in linearized displacement coordinates. In this way the two different views of molecular vibrations can be explicitly related.

Theoretical modelling of vibrational overtone spectra and large amplitude motions. An accurate theoretical treatment of large amplitude motions in small molecular systems is a challenge. Our main interests are the description of the coordinate system, the formation of the kinetic energy operator, and the interactions between large and small amplitude vibrations. In connection with the theory work, we develop and use various numerical approaches such as variational calculations with suitable basis sets and discrete variable methods in obtaining eigenvalues of our Hamiltonian operators. The calculated energies range from fundamentals up to high overtones. Approximate approaches such as perturbation theory, contact transformations and adiabatic approximations are also employed. In order to compare calculations with experimental results, we use both quantum mechanical ab initio calculations and the non-linear least squares method to obtain potential energy surfaces and spectroscopic parameters.

We have applied these theoretical and numerical approaches to real molecular problems such as the torsional motion in methanol, the inversion in ammonia, aniline and the hydronium ion, and the acceptor tunneling motion in the water dimer.

Computational studies on water complexes. We have calculated high-frequency stretching and bending vibrational energy levels up to the high-overtone excitations in some water complexes (water dimer and the trimer, and water nitric oxide). The monomer units are coupled only indirectly via monomer potential surfaces which take into account the presence of the other monomer unit. These surfaces have been computed at the CCSD(T) ab initio level. We have employed an exact kinetic energy operator for the water monomer units and calculated the eigenvalues variationally. We are currently studying the effect of intermolecular vibrations on the high-frequency spectrum.

We have simulated the acceptor tunneling motion in the water dimer with good accuracy compared to experiment. Moreover, the coupling between the acceptor tunneling motion and the high-frequency stretching and bending vibrations has been modelled. The geometric algebra approach was used to derive the kinetic energy operator for the large amplitude tunneling motion. The potential energy surfaces were calculated with the high-level CCSD(T) ab initio method including a large basis set.

Molecules on surfaces.. Recently, ammonia and water adsorption on different sites of metal surfaces have been studied computationally with density functional theory employing periodic boundary conditions. All three internal vibrational motions of adsorbed water have been modelled variationally using the computed anharmonic potential energy surfaces. The same kind of approach has been used for ammonia including all six vibrational motions of the isolated molecule.

The nature of long-distance interactions between molecules on metal surfaces has been investigated with classical mirror image charge model and density functional theory with periodic boundary conditions.

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Metal nanoclusters on surfaces. In pursuit of understanding the adsorption processes of nanosized species on surfaces, density functional theory is applied to systems consisting of metal clusters on semiconductor surfaces. Systems of this kind offer exciting possibilities in many areas, such as nanoelectronics, information storage and catalysis. The properties of small metal clusters, from dozens to a few hundred atoms, are quite dissimilar to bulk properties and change as a function of cluster size. A good example of the peculiar behaviour of metal clusters is gold. Gold itself as a bulk material is not catalytically active, but small gold clusters on a MgO surface are. This has sparked a renewed interest in the chemistry of gold and has made it a very active field of research recently. So far, our investigations have concentrated on small gold and silver clusters on graphite surfaces.We have also been modelling dispersion forces which are significant in this context. The common DFT functionals lack the effects of electron correlation at long distances. Thus, we have employed CCSD(T) and MP2 ab initio methods and the cc-pVTZ-PP basis set to study long range dispersion forces between complexes H2–Ag2, Ag2–Ag2, and Ag2–C6H6. We have developed a novel method to extract the C6 coefficients for silver-silver, silver-hydrogen, and silver-carbon atom systems from ab initio data. This method can be extended to determine the C6 coefficients of other atom pairs.

Solid state spectroscopy and photochemistry Experimental studies

One efficient way to study the properties of molecules, their reactions and reaction intermediates is to isolate these species in an inert solid environment, for example in solid noble gases or nitrogen. Such low-temperature (4–50 K) samples are probed by different spectroscopic methods such as FTIR or Raman spectroscopy and time-resolved laser induced fluorescence (LIF). The photochemical processes are initiated at wavelengths varying from vacuum UV to mid-infrared by using different lasers, discharge lamps, and a tunable (225 nm–4 µm) narrowband optical parametric oscillator (OPO, Sunlite, Continuum). Research on the ground and excited state properties of molecules, decomposition pathways, interactions with the surroundings, and the properties of the photoproducts are of interest to us. The goal is to combine the experimental and computational techniques, exploiting the advantages of both approaches, to expand our understanding of the frontiers of chemical bonding. The activities of the research group can be found on the internet at http://www.helsinki.fi/kemia/matrix/index_eng.htm

New noble-gas-containing molecules. Noble gases were assumed to be inert to-wards chemical bond formation for a long time. The first noble-gas-containing molecule was prepared by Bartlett in 1962. Today, a large number of chemically bound noble gas compounds are known, mainly containing xenon and to a lesser extent krypton. In our laboratory, we have prepared and characterized a group of novel noble-gas-containing molecules with the general formula HNgY, where Ng is a noble gas atom and Y is an electronegative fragment. Until now, most of these molecules have been observed in low-temperature solids and in a few cases also in gas-phase Xe clusters. The HNgY molecules possess a number of previously unknown bonds between noble-gas atoms and other elements. They are formed from neutral fragments in most cases by the thermal mobilization of H atoms, the H atoms being produced by UV photolysis of the HY precursor. Large fractions (20–

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40%) of the H atoms produced during photolysis are consumed in the formation of the HNgY molecules. Formation of noble-gas hydrides and decay of solvated protons were revisited in 2008 with emphasis on diffusion-controlled reactions and hydrogen atom losses in solid noble gases (22.). Moreover, a direct formation of some HNgY molecules takes place during photolysis, indicating that the photolysis of small hydrides in solid noble gases is a local process and that the formation of HNgY type molecules plays a crucial role in the photodissociation dynamics.

Table 1. The experimentally observed HNgY compounds.

Argon Krypton Xenon

HArF HKrCl HXeCl HXeH HXeSH

HKrCN HXeBr HXeI HXeOH

HKrF HXeCN HXeNC HXeNCO

HKrCCH HXeO HXeCCH HXeCC

HKrC4H HXeCCXeH HXeC4H HXeC3N

HKrC3N HXeOXeH

The first neutral chemically-bound argon-containing molecule, hydridoargon fluo-ride (HArF), was produced by photolysis of hydrogen fluoride in solid argon, and it was identified by the vibrational shifts on isotopic substitution of H/D and 40Ar/36Ar. Extensive ab initio calculations indicate that HArF is intrinsically stable, owing to significant ionic and covalent contributions in its bonding. We have recently investigated in cooperation with Moscow State University hindered rotation of HArF in solid argon (2.). The first Xe-containing open-shell species (HXeO and HXeCC) have been characterized as well as organo-noble-gas species (HXeCCH, HXeCCXeH, HXeCC, HKrCCH, HKrC3N, HXeC4H, HKrC4H and HXeC3N). The family of HNgY molecules increased in 2008 by reporting HXeOXeH, which contains two Xe atoms (9.). We also continued investigations of the HNgY complexes identifying the HXeY···HX structures (X, Y = Cl and Br) giving an example of exceptionally large complexation effect (13.). In the feature article (12.), the intermolecular interactions involving noble-gas hydrides, where the blue shift of the H-Ng vibrational frequency is a normal effect, are described.

Conformational change and solid-state photochemistry. We are searching for new conformers of small organic molecules and studying the possible differences between the chemistry of various conformers. With tuneable narrowband IR irradiation from the OPO, different vibrational levels are selectively excited pro-moting conformational change. The conformational change can be achieved through excitation of fundamental, overtone or combination bands of the initial conformer, or even by excitation of the host. In the review (8.), rotational isomers of small molecules in noble-gas solids are described showing differences between monomers and hydrogen-bonded complexes. Matrix and complexation effects on hydrogen tunnelling are important parts of these studies. The results show that hydrogen

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bonding can terminate hydrogen tunnelling reactions and completely stabilize intrinsically-unstable conformational structures.

Gas analysis. Collaboration with industry involves testing and searching for new applications of a gas phase analyzer. The GASMET analyzer is based on a small interferometer for the mid-infrared region. Its multi-component analysis software is capable of handling 20 compounds simultaneously and the sensitivity is, depending on the optical path length, at best in the ppb region. A fast diagnostic tool for methanol intoxication, based on low-resolution FTIR-measurements, has been de-veloped.

Optical spectroscopy of thin solid films and nanoparticles. Raman and photoluminescence studies of Si-based optical materials have been performed within the FinNano Program (Project OPNA). Transmission electron microscopy is an important tool in nanotechnology. In cooperation with TKK, free-standing SiO2 films containing Si nanocrystals directly suitable for transmission electron microscopy are designed and studied (15.). In this work, the researches from TKK were able to grow very thin free-standing films containing luminescent Si nanocrystals. Optical properties and laser-induced thermal effects on silicon nanocrystals in silica were described in the book chapter (28.). Spectral filtering allows us to determine optical properties of theses materials, showing, for instance, birefringence of Si nanocrystals. The thermal effects produced by continuous-wave laser radiation on free-standing Si/SiO2 films are also carefully described. The intense laser irradiation of the as-prepared samples enhances the Raman scattering of Si-nc by two orders of magnitude. This laser-induced crystallization originates from melting of Si nanostructures in a silica matrix, which makes Si-nc better ordered and better isolated from the oxide surroundings. Continuous-wave laser control of Si-nc stress was achieved in these samples. In the proposed model, the intense laser radiation melts Si-nc, and Si crystallization upon quick cooling from the liquid phase in a silica matrix leads to a compressive stress. The stress can be tuned in the 3 GPa range using laser annealing below the melting temperature. The high laser-induced temperatures were verified with Raman spectroscopy. The laser-induced heat leads to a strongly nonlinear rise in light emission. The laser-induced temperature is essentially controlled by the absorbed power. Valuable information on optical and structural properties of Si nanocrystals is obtained from m-line measurements and X-ray photoelectron spectroscopy (cooperation with TKK and the Southampton University) (10.). These additional results agree well with the Raman data and are consistent with the known theoretical models. In the book (29.), various aspects of Silicon Nanophotonics are described, from basic principles to present status and perspectives.

Power of Raman spectroscopy was demonstrated in studies of solution properties of an aqueous poly(methacryl oxyethyl trimethylammonium chloride) and its poly(oxyethylene) grafted analogue (1.), performed in cooperation with the Laboratory of Polymer Chemistry. We applied Raman spectroscopy to study ion irradiation of carbon nanotubes encapsulating cobalt crystals (cooperation with the Accelerator Laboratory) (11.). A number of research methods were used to investigate structural investigation of re-deposited layers in JET, which was coordinated by VTT (14.). In this research, we were responsible for Raman spectroscopic characterization. In cooperation with the Physics Department (UH),

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we have started to study silver nanoparticles embedded in low-temperature matrices.

Computational studies

Extensive computational efforts are devoted to aid in the understanding of the bonding and structures of the experimentally studied novel molecules and the environmental effects on these properties. It was shown previously that complexation of the HNgY molecules with impurities, for example N2 or H2O, strengthens the H-X bond. Our computational studies have been extended from quantum chemical electronic structure calculations of novel compounds and their complexes to include interactions of these species with their environment. The aims have been to interpret the fine structure of the observed spectral lines of the HXY molecules, to attain a good understanding of the specific interactions of HXY molecules with one adjacent noble gas atom, and also to comprehend the motions of the molecules in the host cage. Computational work has been performed in collaboration with various theoretical chemistry groups.

Atmospheric and combustion chemistry research The basic studies of reaction mechanisms and rates in atmospheric and combustion chemistry have been carried out in this laboratory using a flow reactor system coupled to a changeable ionization quadrupole mass spectrometer. There are plans to improve this method in near future. Another apparatus, a time-resolved cavity ring down laser spectrometer system, is under construction. We have studied reactions of about 20 different radicals with 7 different small molecules, which exist for example in atmosphere. These studies will continue and apparatuses mentioned above will be used for basic and applied kinetic studies in the gas phase and on surfaces in the future.

Kinetic absorption spectroscopy. A cavity ring-down laser spectroscopy detection system for time resolved absorption spectroscopic studies of radical reactions in the gas phase is under construction. A long-cavity dye laser pumped by a CW Ar-ion laser or a CW OPO (a future plan) will be used for detection, while an excimer laser will be used for radical production. This apparatus will also be used for the surface kinetics studies in the future. This work is a part of our atmospheric chemistry research.

Flow reactor coupled to a quadrupole mass spectrometer. The photoionization option is currently used in our fast flow reactor coupled to a changeable ionization quadrupole mass spectrometer (QMS; http://www.helsinki.fi/kemia/fysikaalinen/research/kinetics/index.html). There are also options in the apparatus for chemical ionization, thermal electron, and electron impact ionization in the QMS. Laser induced fluorescence and resonance fluorescence can also be used for detection in the same apparatus. The flow reactors can be placed inside or outside of the vacuum chambers and the reactants (radicals) can be introduced into the reactor by the photodecomposition of precursor molecules in an excimer laser pulse as well as through moveable inlet systems.

In 2008 the kinetics of the reactions of a few radicals (CH3CHBr, CHBr2, CDBr2, CH3, and CCl2) with molecules like nitrogen dioxide, chlorine, bromine, and hydrogen bromide in the gas phase were measured to understand reactivity and thermochemistry of different radicals under the conditions of atmospheric

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chemistry. (Matti P. Rissanen, Suula L. Arppe, Arkke J. Eskola, Damien Amedro, Matti M. Tammi, Marvin Ihlenborg, and R S Timonen)

In addition, we also studied the kinetics of the R + NO2 reactions (R= i-C3H7, n-C3H7, s-C4H9 and t-C4H9) at temperatures 201 - 489 K, but did not publish the study yet in 2008.

Research in molecular magnetism The group carries out both fundamental and applied theoretical and computational research of the properties of atomic, molecular and nanosystem in the presence of external and internal electromagnetic fields. In particular, we are interested in the spectral parameters of magnetic resonance spectroscopies, nuclear magnetic resonance (NMR) and electron spin resonance (ESR).

NMR and ESR are the principal analytical tools in various disciplines in chemistry, physics, materials science, biology and medicine. Nuclear and electronic spins, i.e. magnetic moments, act as microscopic “spies” in the sample under study, revealing through their energy levels the prevailing local magnetic fields. These magnetic fields can be related to electronic and molecular structure, as well as to the other properties of the studied molecule or material.

Our detailed research interests include relativistic effects on NMR and ESR pa-rameters, rovibrational and thermal effects on NMR and ESR parameters, solvation and matrix effects on NMR and ESR parameters, magnetic-field dependence of NMR parameters, NMR parameters of paramagnetic molecules (pNMR), as well as noble gas NMR parameters in molecular and materials research.

In practice, our work consists of various different factors that do not necessarily occur in every project: formulation of theory, implementation of methods to com-puter programs, and applications of the theory to current scientific problems in the field of magnetic resonance. In the applications we use quantum chemical electronic structure calculations as the properties of interest to us typically originate in the electron cloud. In addition, molecular dynamics and Monte Carlo simulations are carried out with the purpose of sampling the conformations of the nuclear frame-work. We use many of the world’s leading academic quantum chemical codes as well as developing our own modelling and analysis software.

We are equipped with local PC/Linux workstation facilities and use extensively the supercomputer resources of CSC Scientific Computing Ltd. (Espoo, Finland) and the 132-CPU ametisti-cluster that is a part of the Materials Grid project.

In our research in 2008 we reached a milestone in the long project where the pNMR theory, as well as the methods of computation of its spectral parameters, are developed. A few years of work culminated in the publication of theory of the most important NMR parameter, the nuclear shielding tensor, in open-shell systems. The theory is valid for an arbitrary spin state and spatial symmetry of the molecule. The contemporary experimental procedure, as well as the calculations hitherto performed, are based on an approximate limit of the theory that neglects zero-field splitting (ZFS) and is, hence, valid only for doublet systems. Our new rigorous theory includes the ZFS effects and generalises the earlier-considered contributions to both the isotropic and anisotropic shielding, and among other things introduces novel isotropic chemical shift terms. The most important of the latter appears to be a term arising from the nonrelativistic spin-dipolar interaction between the electron and nuclear spins, which obtains a large isotropic contribution in triplet and higher

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multiplicity systems after being averaged in the zero-field-split ground-state manifold of electronic Zeeman states. This contribution exceeds in some cases in magnitude the sc. pseudocontact shift that is experimentally often employed in the structure determination of metallo-organic systems. Computational procedures for the new theory were implemented in a stand-alone analysis code that communicates with the diverse electronic structure packages in use in the group. Further development of theory and computational methods, as well as applications to systems of interest in metallo-organic chemistry as well as pNMR relaxation, are underway.

As a prototypic system for xenon enclosed in material cavities, we published a paper on the 129Xe NMR chemical shift in the endohedral Xe@C60. While earlier computational work has reproduced the experimental shift to good accuracy using nonrelativistic quantum chemical calculations at a fixed molecular geometry, we examined all the contributing physical effects carefully. These effects include the level of theory employed for the structure of the cage, the choice of the density-functional theory method employed in the shift calculation, treatment of relativistic effects, and the dynamics of both the guest atom and the host cage. All these factors were found to significantly affect the final observable, and the successful study published prior to ours was found to be purely coincidental. The experience gained in our work is used in investigations of related endohedral and other types of nanocavity systems. As an example of these, a paper appeared on the structure and dynamics of the endohedral Sc3C2@C80, which is an interesting example of complex intramolecular dynamics. While the confined Sc3C2 entity performs a ratcheting motion along the equatorial six-ring belt of the C80 cage, the C2 unit flips through the plane defined by the three scandium atoms, and the cage responds by breathing. The many time scales involved in the dynamics of the system make it challenging to come up with predictions of molecular properties, e.g., ESR/pNMR and NMR properties for the different charge states of the molecule. We continue to pursue these issues in ongoing work.

A methodological investigation was performed on the parity-violation (PV) effects on NMR shielding constant as a function of the system size, for a complex silicon-based polymer system in which experimental claim of this effect was earlier made. While we could based on the calculations verify the a priori expectation that PV effects are much too small to have caused the experimental findings, we also reached important conclusions about the scaling of, on the one hand, energetic and, on the other hand, NMR effects arising from parity-non-conservation. While the quantum mechanical operators corresponding to the former exemplify extensive molecular properties due to involving a sum over the nuclei of the system, the latter only refer to the considered NMR nucleus, and consequently are not amplified in large molecules. Hence, the search for PV effects in the molecular realm from the NMR parameters, may be fruitless.

Studies on the energetics of new molecules including carbon and gold nanosystems were continued, in collaboration with workers at the Laboratory for Instruction in Swedish. This work involves heavy computational chemistry where electron correlation as well as relativistic effects are paid special attention to. The classic chemical concept of aromaticity plays a significant role in the stability of many of the investigated systems.

We employed the completeness-optimization (co) paradigm for the basis sets of molecular electronic structure calculations (developed in this group a couple of

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years ago), in its first large-scale application. In any kind of matter, circularly polarised light (CPL) induces an interaction corresponding to a magnetic field along the light beam, and such fields are in principle possible to detect by NMR spectroscopy. Left and right CPL cause small, oppositely signed shifts of the NMR resonances, and we used third-order time-dependent perturbation theory to evaluate these effects for a group of increasingly large and polarisable hydrocarbon molecules. The very economic nature of the co-basis sets made it possible to calculate such a demanding magneto-optical molecular property for systems of the investigated size (up to 72 atoms) practically at the basis-set convergence limit. This was crucial because we wanted to investigate the laser-induced NMR effects amplified by the proximity of optical resonance frequencies, and finding suitable experimental laser sources is more likely for large systems in which the excitation energies are low. We are continuing to apply the co-basis sets with extremely promising results in other large-scale projects involving the NMR parameters of carbon nanosystems, as well as fundamental investigations of the opposite effect, nuclear spin-induced optical rotation, in small molecules.

Further computational work was published in the fields of biological nanoscience and x-ray scattering, in collaboration with the Bioscience and Physics departments of the University of Helsinki.

Publications 1. Andersson, T., Sumela, M., Khriachtchev, L., Räsänen, M., Aseyev, V. and

Tenhu, H.; Solution Properties of an Aqueous Poly(methacryl Oxyethyl Trimethylammonium Chloride) and Its Poly(oxyethylene) Grafted Analogue, J. Polymer Science B: Polymer Physics 46 (2008) 547-557.

2. Bochenkova, A.V. Khriachtchev, L., Lignell, A., Räsänen, M, Lignell, H., Granovsky, A.A. and Nemukhin, A.V.; Hindered Rotation of HArF in Solid Argon: Infrared Spectroscopy and a Theoretical Model, Phys. Rev. B 77 (2008) 094301.

3. Eskola, A.J., Golonka, I., Rissanen, M.P. and Timonen, R.S.; Kinetics of the CCl2+Br2 and CCl2+NO2 Reactions in the Temperature Range 266-365 K and Reactivity of the CCl2 Biradical, Chem. Phys. Lett. 460 (2008) 401–405.

4. Eskola, A., Timonen, R.S., Marshall, P, Chesnokov, E.N., Evgeni, N. and Krasnoperov, L.N.; Rate Constants and Hydrogen Isotope Substitution Effects in the CH3+HCl and CH3+Cl2 Reactions, J. Phys. Chem. A 112 (2008). 7391–7401.

5. Garden, A.L., Halonen, L. and Kjaergaard, H.G.; Calculated Band Profiles of the OH-stretching Transitions in Water Dimer, J. Phys. Chem. A 112 (2008) 7439–7447

6. Ikäläinen, S., Lantto, P., Manninen, P. and Vaara, J.; Laser-Induced Nuclear Magnetic Resonance Splitting in Hydrocarbons, J. Chem. Phys. 129 (2008) 124102:1-8.

7. Johansson, M.P., Vaara, J. and Sundholm, D.; Exploring the Stability of Golden Fullerenes, J. Phys. Chem. C 112 (2008) 19311-19315.

8. Khriachtchev, L.; Rotational Isomers of Small Molecules in Noble-Gas Solids: From Monomers to Hydrogen-bonded Complexes, J. Mol. Structure 880 (2008) 14-22.

9. Khriachtchev, L., Isokoski, K., Cohen, A., Räsänen, M. and Gerber, R.B.; A Small Neutral Molecule with Two Noble-Gas Atoms: HXeOXeH, J. Am. Chem. Soc. 130 (2008) 6114-6118.

10. Khriachtchev, L., Nikitin, T., Oton, C.J., Velagapudi, R., Sainio, J., Lahtinen, J. and Novikov, S.; Optical Properties of Silicon Nanocrystals in Silica: Results from Spectral Filtering Effect, m-Line Technique, and X-ray Photoelectron Spectroscopy, J. Appl. Phys. 104 (2008) 104316.

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11. Lehtinen, O., Sun, L., Nikitin, T., Krasheninnikov, A.V., Khriachtchev, L., Rodríguez-Manzo, J.A., Terrones, M., Banhart, F. and Keinonen, J.; Ion Irradiation of Carbon Nanotubes Encapsulating Cobalt Crystals, Physica E 40 (2008) 2618-2621.

12. Lignell, A. and Khriachtchev, L.; Intermolecular Interactions Involving Noble-Gas Hydrides: Where the Blue Shift of Vibrational Frequency Is a Normal Effect, J. Mol. Structure 889 (2008) 1-11.

13. Lignell, A., Lundell, J., Khriachtchev, L. and Räsänen, M.; Experimental and Computational Study of HXeY···HX Complexes (X, Y = Cl and Br): An Example of Exceptionally Large Complexation Effect, J. Phys. Chem. A 112 (2008) 5486-5494.

14. Likonen, J., Vainonen-Ahlgren, E., Khriachtchev, L., Coad, J.P., Rubel, M., Renvall, T., Arstila, K. and Hole, D.E.; Structural Investigation of Re-Deposited Layers in JET, J. Nuc. Mater. 377 (2008) 486-491.

15. Novikov, S., Sinkkonen, J., Nikitin, T., Khriachtchev, L., Räsänen, M. and Haimi,E.; Free-Standing SiO2 Films Containing Si Nanocrystals Directly Suitable for Transmission Electron Microscopy, Microelectronics J. 39 (2008) 518-522.

16. Pennanen T. O. and Vaara, J,; Nuclear Magnetic Resonance Chemical Shift in an Arbitrary Electronic Spin State, Phys. Rev. Lett. 100 (2008) 133002:1-4.

17. Pesonen, J.; Kinetic Energy Operators in Linearized Internal Coordinates, J. Chem. Phys. 128 (2008)044319/1-044319/8.

18. Riedel, S., Straka, M. and Pyykkö, P.; Theoretical Mapping of New L-(N+)-L Family of Species with a Donor-Acceptor Bonding between N+ and Ligand L, J. Mol. Struct.: THEOCHEM 860 (2008) 128-136.

19. Salmi, T., Hänninen, V., Garden, A.L., Kjaergaard, H.G., Tennyson, J. and Halonen, L. Calculation of the OH Stretching Vibrational Overtone Spectrum of the Water Dimer, J. Phys. Chem. A 112 (2008) 6305-6312.

20. Seetula J. and Eskola A.; Kinetics of the R + HBr RH + Br (CH3CHBr, CHBr2 or CDBr2) Equilibrium. Thermochemistry of the CH3CHBr and CHBr2 Radicals, Chem. Phys. 351 (2008) 141-146.

21. Straka M., Lantto, P. and Vaara, J.; Toward Calculations of the 129Xe Chemical Shift in Xe@C60 at Experimental Conditions: Relativity, Correlation, and Dynamics, J. Phys. Chem. A 112 (2008) 2658-2668.

22. Tanskanen, H., Khriachtchev, L., Lignell, A., Räsänen, M., Johansson, S., Khyzhniy, I. and Savchenko, E.; Formation of Noble-Gas Hydrides and Decay of Solvated Protons Revisited: Diffusion-Controlled Reactions and Hydrogen Atom Losses in Solid Noble Gases, Phys. Chem. Chem. Phys. 10 (2008), 692-701.

23. Taubert, S.; Straka, M.; Pennanen, T. O., Sundholm, D., Vaara, J.; Dynamics and Magnetic Resonance Properties of Sc3C2@C80 and Its Monoanion, Phys. Chem. Chem. Phys. 10 (2008) 7158-7168.

24. Taubert, S., Sundholm, D., Juselius, J., Klopper, W. and Fliegl, H.; Calculation of Magnetically Induced Currents in Hydrocarbon Nanorings, J. Phys. Chem. A 112 (2008) 13584-13592.

25. Telenius, J., Wallin, A. E., Straka, M., Zhang, H., Mancini, E. J. and Tuma, R.; RNA Packaging Motor: From Structure to Quantum Mechanical Modelling and Sequential-Stochastic Mechanism, Comp. Math. Meth. Med. 9 (2008) 351-369.

26. Vainio, M., Peltola, J., Persijn, S., Harren, F.J.M. and Halonen, L.; Singly Resonant cw OPO with Simple Wavelength Tuning, Opt. Express 16 (2008) 11141-11146.

27. Weijo, V., Manninen, P. and Vaara, J.; Effect of Molecular Size on the Parity-Non-Conserving Contributions to the Nuclear Magnetic Resonance Shielding Constant, Theor. Chem. Acc. 121 (2008) 53-57.

Other publications 28. Khriachtchev, L.; Silicon Nanocrystals in Silica: Optical Properties and Laser-

Induced Thermal Effects, in Silicon Nanophotonics: Basic Principles, Present Status, and Perspectives, L. Khriachtchev (Ed.), World Scientific Publishing, 2008, 297-326.

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29. Khriachtchev, L. (Ed.); Silicon Nanophotonics: Basic Principles, Present Status, and Perspectives, World Scientific Publishing, 2008.

Patent Applications 30. Vainio, M. and Halonen, L.; Optinen resonaattori, Patent Application #0086044,

Finland, 03.11.2008 (in Finnish).

Theses Doctor of Philosophy 1. Weijo Ville: Parity violation in molecular magnetic resonance properties Master of Science 1. Ikäläinen Suvi: A computational study of laser-induced NMR splittings in

hydrocarbons 2. Isokoski Karoliina: A new rare-gas compound: HXeOXeH 3. Mattila Juha-Pekka: Fosfolipidikalvojen pääfaasitransition molekyylitason

mekanismin tutkimus fluoresenssispektroskooppisin menetelmin 4. Jääskeläinen Piia: Kiinnostuksen tukeminen perusopetuksessa: molekyylimallinnus

työtapana 5. Laitala Aino: Mittausautomaatio ympäristökemian oppimisen tukena

perusopetuksessa 6. Lignell Hanna: Tunneloitumisreaktiot ja ionien kompleksoituminen

jalokaasumatriiseissa 7. Peurala Marjo: EU:n lainsäädännönmukainen haihtuvien orgaanisten yhdisteiden

FTIR-analyysi 8. Sälli Hannu: Spectral quantification of styrene-butadiene latex from coated paper

surface 9. Syrjäläinen Noora: Lehdet kemian opetuksessa perusopetuksesta korkeakouluihin:

Esimerkkinä Kemia-Kemi-lehti

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LABORATORY OF ORGANIC CHEMISTRY

The chair of organic chemistry carries the distinction of being the first chemistry professorship in the oldest university in Finland; the present holder is the eleventh person to have been nominated for the post. P.A. Gadd and his nine successors have played a central role in the intervening years in Finnish science, industry and busi-ness.

Present research efforts center on organic synthesis on a wide front, including the use and development of computer aids, with interests both in target-oriented work and in new synthetic methods. The Laboratory has broken new ground in Finland in the comprehensive application of the various components of drug dis-covery. At present, an intensive drug discovery program is underway involving en-zyme/inhibitor modelling work, target or diversity oriented synthesis planning, ex-perimental synthetic work, and lead identification. A major goal is to develop strategies for the multistep syntheses of pharmaceuticals and other fine chemicals, with special attention to green chemistry aspects. The chemistry of lignin, a by-product of the pulping industry, continues to attract attention, much of the work be-ing in fact specialized synthetic organic chemistry. Another major research group is working on the phytoestrogen anticancer compounds. Work has also continued on the controlled multiple isotopic labeling, deuteration in particular, of organic compounds.

Many of the above topics have featured prominently in programmes of a number of large international scientific conferences that members of the laboratory have planned, organized and chaired. These include the 22nd International Conference on Polyphenols (500 participants) and the 14th European Symposium on Organic Chemistry (600 participants), both held in Helsinki.

As regards university teaching in chemistry, representatives from the Laboratory have taken part in follow-up international developments of the Bologna process. These include work on Tuning of Educational Structures in Europe, the establishment of the first Joint Degree Programmes between European chemistry departments, and the inauguration of the Eurobachelor in Chemistry programme where the University of Helsinki became the first European university to be granted the Eurobachelor label. On the domestic level, the Laboratory created the first Finnish net-based teaching facility in organic chemistry called The Net Laboratory (“Nettilabra”), where undergraduates receive help and directions for the laboratory practical courses in organic chemistry. This effort brought the University of Helsinki Teaching Technology award to the working group composed of members of the laboratory who were responsible for devising and creating the Net Laboratory facility.

In advanced undergraduate teaching, the emphasis is on organic synthesis. Working in seminar type courses, the students receive practical training in the use of various reaction database, synthesis design and reaction simulation software. The undergraduates are also offered the full range of organic analytical techniques (UV, IR, NMR, MS, GC, HPLC, flash chromatography, etc.) in connection with the vari-ous laboratory courses and research projects. About one half of the advanced courses are given in English.

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Personnel Teaching staff Reetta Hakanen, M.Sc., Teaching Assistant Petri Heinonen, Ph.D., University Lecturer Outi Heikkinen, M.Sc., Teaching Assistant Jari Kavakka, M.Sc., Teaching Assistant Ilkka Kilpeläinen, Ph.D., Professor, Head of the Laboratory Jorma Koskimies, Ph.D., Doc., Senior Teaching Assistant Mikko Oivanen, Ph.D., Professor Monika Pohjoispää, M.Sc., Teaching Assistant Jussi Sipilä, Ph.D., University Lecturer Emilia Väisänen, M.Sc., Teaching Assistant Kristiina Wähälä, Ph.D., Professor

External senior lecturers (docents) Richard Ede, Ph.D. (CSIRO, Melbourne, Australia) Juho Helaja, Ph.D. (University of Helsinki, Finland) Hilkka Kenttämaa, Ph.D., Professor (Purdue University, USA) Salme Koskimies, Ph.D. (VTT Technical Research Centre) Ari Koskinen, Ph.D., Professor (Helsinki University of Technology) Tarja Laitalainen, Ph.D. Margus Lopp, Ph.D. (The Estonian Academy of Sciences) Markku Mesilaakso, Ph.D. (The Scientific Advisory Board for Defence) Vesa Nevalainen, Ph.D., Assistant Professor (University of Massachusetts, Darthmouth, USA) Kristiina Poppius-Levlin, Ph.D. (KCL) Andrei Tauber, Ph.D. (Kemira Oyj) Pirjo Vainiotalo, Ph.D., Professor (University of Joensuu) Stefan Willför, Ph.D. (Åbo Academi, Finland)

Research staff Sari Alho-Richmond, Ph.D. Somdatta Deb, Lic.Phil. Erika Fager-Jokela, M.Sc. (techn.) Mari Granström, M.Sc. Raisa Haavikko, M.Sc. Paula Järvi, M.Sc. Pirkko Karhunen, Ph.D. Sampo Karkola, M.Sc. Alistair King, Ph.D. Sanna Laaksonen, M.Sc. Tom Lagerwall, M.Sc. Maarit Lahtinen, M.Sc. Eija Leppälä, M.Sc. Timo Leskinen Johanna Majoinen, M.Sc. Jorma Matikainen, Ph.D. Valtteri Mäkelä, M.Sc

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Taru Nikkonen, M.Sc. Paula Nousiainen, M.Sc. Anna Olszewska, M.Sc. Barbara Raffaelli, M.Sc. Raili Seppälä-Lehto, Ph.D. Annastiina Veistinen, M.Sc. Pauli Wrigstedt, M.Sc. Gösta Brunow, Ph.D., Professor Emeritus Tapio Hase, Ph.D., Professor Emeritus Paavo Hynninen, Ph.D., Professor Emeritus

Visitors Mark Bradley, Prof., University of Edinburgh, UK Béatrice Delpouve, Ph.D., University of Lille, France Pedro Gómez Calzada Prof., University of Complutense Madrid, Spain Blanka Kralova, Prof., Institute of Chemical Technology in Prague, the Czech Republic Audrey Lacombe, ERASMUS student, Université Paul Sabatier, Toulouse, France Matthias Lang, ERASMUS student, University of Leipzig, Germany Verity Litchfield, ERASMUS student Nottingham Trent University, UK Pascal Mimero, Ph.D., CPE Lyon, Department of Chemistry, France Jorge Ruiz Olles, ERASMUS student, University of Zaragoza, Spain Martin Pausch, ERASMUS student, Graz University of Technology, Austria Ken Seddon, Prof., QUILL, The Queen's University of Belfast, UK Laura Senges, ERASMUS student, Université Paul Sabatier, Toulouse, France Barry Thomas, Dr., University of York, UK Arne van der Gen, Prof., University of Leiden, the Netherlands Raymond Wallace, Ph.D., University of Nottingham Trent, UK

Administrative and technical staff Sami Heikkinen, Ph.D., Laboratory Engineer Anna-Maaret Järvikivi, Secretary Leena Kaisalo, Ph.D., Amanuensis (acting) Tia Kakko, Laboratory Assistant Matti Keinänen, Eng., Laboratory Technician Ulla-Maija Lakkisto, Lic.Phil., Amanuensis (on leave) Gudrun Silvennoinen, Laboratory Worker

Research activities The state-of-the-art research instrumentation in the laboratory includes FT-IR, 300 and 500 MHz NMR, GC-MS-MS and LC-MS facilities. SciFinder, Crossfire, ORAC, LHASA, CAMEO, CHIRON, SPROUT, CAESA, MDL databases, Cerius2, Insight II, Gaussian, Quanta, Macromodel, Gromacs, SYBYL, UNITY, Cambridge Structural Database and other databases and software are widely used in synthetic research.

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Chemistry of natural polyphenolics Flavonoid and lignan chemistry This research is part of an interdisciplinary international research project entitled

Lignans, Phytoœstrogens and Human Health. Natural poly-oxyflavonoids and -isoflavonoids, plant lignans and enterolignans of medical and biological interest, their pre-cursors and metabolites and deuterium labeled analogues are synthesized for studies of their presence, biological properties and intestinal metabolism in mammals and man particularly. Many of these nonsteroidal naturally occur-ring compounds, also known as phytoœstrogens, possess weak œstrogenic activity and are constituents of foods con-sumed by animals and man. The immediate motivation for

this research stems from the evidence of their beneficial role in hormone based cancers and their potential importance as antitumor agents (1, 7’-hydroxyma-tairesinol).

Green chemistry synthetic methods for the regio- and isotopically selective polydeuteration are developed for polyphenolic compounds such as flavonoids, isoflavonoids, plant lignans, enterolignans and endocrine steroids. Up to ten deute-rium atoms can be introduced by microwave and ultrasound techniques into these compounds. The isotopic and regiochemical purity of the polydeuterated product is verified by 2D NMR and MS techniques.

Due to the potential of phytoestrogens as health dietary factors, the demand for analytical methods that are more cost-effective and sensitive, and less time-con-suming than those presently used led us to develop analytical methods based on immunochemistry. Synthesis methods for the production of phytoestrogen haptens for mono- and polyclonal antibodies are carried out. (1, 2, 4, 7, 14, 18, 21, 40, 41)

(Wähälä, Hoikkala, Jokela, Leppälä, Pohjoispää, Raffaelli, Hase, in col-laboration with the Institute of Clinical Medicine; Helsinki University Central Hospital; Div. of Clin. Chem., Folkhälsan; Fred Hutchinson Cancer Research Center, Seattle; Univ. of Minnesota; Lab. of Biol. Chemistry, University of Ioannina, Greece; University of Vienna, AKH, Austria; Federal Research Centre, Karlsruhe, Germany; Institute of Endocrinology, Prague, Czech Rebublic; INRAN, Rome, Italy; National Cancer Center Research Institute, Tokyo; National and Kapodistrian University of Athens, Greece; Faculty of Veterinary Medicine, Helsinki; Perkin-Elmer Life Sciences; Wallac Oy; Biohit-Locus-Genex; research supported by Finnish Academy; EU-projects: VENUS, PHYTOS, PHYTOPREVENT, PHYTOHEALTH)

Antioxidants of natural origin This research is an extension of the research on dietary compounds and the search for new plant derived food supplements that can act as antioxidants and particularly substances that can prevent cardiovascular diseases and possibly cancer. Current research is focused on the development of isolation procedures, identification and synthesis of polyphenolics and steroid conjugates, e.g. alkylresorcinols in rye, and phytosterol esters present in domestic rape seed oil. (16) (Wähälä, Karkola; in collaboration with the School of Biomedicinal Sciences, University of Ulster, UK, National Public Health Institute, Department of Applied Chemistry and Microbiology, Food Chemistry, University of Helsinki)

O

HHO

OMe

OH

MeO

HOO

1

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Synthesis and labeling of steroids Endocrinic estrogens and androgens, their metabolites and biologically active de-rivatives are synthesized and labelled with 3-6 D atoms (for example, 2 and 3) for use in studying their formation and estimating their levels in the human body. Similarly, methods for the preparation of deuterated standards of certain steroid structures are developed for quantitation in doping analysis. Other steroid structures such as cholesterolic compounds and bile acids are synthesized for studies of their biosynthesis in man and metabolism in the small and large intestine.

D

D

D

D

HO

D

D

HO

OD

D

D

O

6

6

2 3 Environmentally benign synthetic methods are developed for estrogen deriva-

tives to study the oxidation of low-density lipoprotein (LDL) and their role in car-diovascular diseases. (22, 24, 25, 42) (Wähälä, Deb, Hakala in collaboration with Helsinki University Central Hospital; the Dept. of Clin. Chem., Dept. of Obstetrics and Gynaecology, Inst. of Clin. Med. and Div. of Clin. Chem., Folkhälsan, at the U. of Helsinki; Institute of Occupational Health, Helsinki, Perkin-Elmer Life Sciences, Wallac Oy)

Drug discovery Synthesis, small molecule design and protein modeling studies are carried out to develop novel potential inhibitors for steroid hormone biosynthesis in order to pre-vent and treat certain hormonal based cancers. At present the research is focused on the discovery and synthesis of innovative pharmaceutical compounds to control the function of steroid receptors and enzymes responsible for endocrinic estrogen and androgen production. State-of-the-art molecular visualisation and computational tools (the SPROUT software package, CAESA, SYBYL, Insight II, Cerius2, GOLD) are used for modeling protein structure and protein-ligand interactions, and de novo ligand design. This allows the quick generation of rational drug ideas for diversity-oriented syntheses and retro synthetic analyses. Combinatorial and parallel synthetic techniques are used to create libraries of molecules for the target proteins. The products are analysed by LC-MS, GC-MS/MS or LC-NMR (500 MHz). (10, 28, 29, 30, 31, 35)

(Wähälä, Karkola, Väisänen in collaboration with Hormos Medical Ltd; WHO Centre, University of Oulu; University of Turku; University of Leeds; Heinrich Heine Universität Düsseldorf; Solvay Pharmaceuticals, Hannover); research supported by University Research Funds, Finnish Academy

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Green technology in practice: Natural product synthesis in ionic liquids The aim of this research is to develop new greener synthetic routes for certain natu-ral products, highly promising bioactive materials that are not readily obtained in quantity from natural sources and whose synthesis has traditionally relied on un-wieldy Friedel-Crafts and similar reactions. The present research is focused on us-ing ionic liquids as reaction media and the application of microwave reaction en-hancement techniques.

Ionic liquids have been recognized as one of the new classes of solvents or ma-terials that offer new, cleaner, green technologies in which waste streams are mini-mized (the 12 principles of green chemistry).

Ionic liquids are usually the salts of an organic cation and an organic or inorganic anion (for examples, see Fig. 1). They have low melting points (< 100ºC), which are influenced by asymmetry of the cation and the nature of the anion. Ionic liquids possess many useful properties, making them good media for homogeneous catalysis: they are able to dissolve a wide range of organic, inorganic and organometallic compounds, they are nonvolatile, inflammable, fairly non-toxic and can be easily recycled. Also, polarity and hydrophilicity/lipophilicity can be adjusted by the appropriate choice of cations/anions—ionic liquids have been referred to as “designer solvents”.

Figure 1. Some ionic liquid compounds.

(4, 27) (Wähälä, Hakala in collaboration with Prof. Ken Seddon and Dr. Martyn Earle at QUILL, the Queen’s University Ionic Liquids Laboratory, Belfast, Northern Ireland)

Wood chemistry Wood as a primary source of renewable biomaterials forms the basis of chemical energy flow on earth. The present chemical interest in wood science consists, for example, of elucidation of the biochemistry of wood formation, studies exploiting wood as a pool of chiral auxiliarity and suppressing the environmental concerns connected to technical wood biomass applications by means of “green chemistry”

NN

N

R2

R3

R4R5

R1R4

R5

R6

R1

R2

R3

N

R1

R2

R4

R3

P

R1

R3

R2

R4

Cations:

Anions:

Cl /[AlCl3], Cl , Br , I , [NO3] , [CF3COO] , [CF3SO2] , [BF4] , [PF6] , [(CF3SO2)2N]

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approaches. At the Laboratory of Organic Chemistry at the Department of Chemis-try, University of Helsinki, the main topics in wood science are:

Lignin biosynthesis Mechanistic studies on the biosynthesis of wood lignins. The role of oxidative en-zymes during plant cell wall biosynthesis is presently studied. Oxidative cross-cou-

pling experiments on lignin model compounds yield new facts about the formation of lignins in plant cell walls. Particular attention is paid to the chemistry of 5,5-biphenyl structures that constitute the most impor-tant branching structures in lignins. Transition metal complexes as mimics for oxidative en-zymes in lignin biochemistry. As a reference for oxida-tive enzymes in vivo, the chemistry of lignin oxidation is studied using transition metal complexes, such as Salen-type Schiff bases, porphyrins, phthalocyanine and bimetallic catalysts. Typical metals in the catalysts are Mn, Fe, Cu and Co.

Application of 2D and 3D NMR spectroscopies to lignin structure determination. The use of multidimensional NMR has provided unambiguous assignments of side chain structures in lignins. The work is carried out by comparing the NMR information of natural preparates to those given by synthetic oligomeric lignin samples. These studies are carried out using 2D and 3D on 500 and 800 MHz NMR techniques. Synthesis of oligomeric lignin model compounds. Procedures for new, convenient large-scale preparation of arylglycerol -ether and biphenyl type oligomeric (trimers, tetramers, hexamers) lignin model compounds are under continuous study in the laboratory.

Pulping and bleaching chemistry Modern NMR techniques and model studies in the analysis of changes in lignin chemical structure during pulping. The so called “Kraft”-process using NaOH and NaHS as active cooking chemicals forms the basis of modern chemical wood pulping procedures. At present, several modifications to the process have been introduced. To elucidate the effects of the different process variables on the chemistry of the cook, laboratory cooks with oligomeric lignin models of defined structures are performed and the results compared with the information obtained from “technical” lignins isolated from industrial processes. The work includes modern 1D and 2D NMR analysis methods as well as LC-MS studies. Transition metal complexes as pulp bleaching catalysts. The modern pulping pro-cedure involves either a one or two-stage oxygen treatment of the pulp. In this procedure approximately half of the lignin remaining in the pulp can be removed without significant loss in pulp properties. The effect of different transition metal complexes on pulp residual lignin oxidative degradation is studied on model compounds and technical lignins.

Selective oxidative coupling of phenols Oxidative reactions using peroxidases and metal-centered catalysts on chiral cou-pling of phenols are studied. Recent themes in this project include the mechanism of formation of dimeric products and oxygenated products from phenolic cinnamyl

OO

OH

HO OMe

OMeMeO

R R

4

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alcohols and esters, and the attachment of chiral auxiliaries to phenolic cinnamyl alcohols and esters to study the induction of enantioselectivity. (3, 13, 23, 36) (Sipilä, Brunow, Filpponen, Haikarainen, Karhunen, Lahtinen, Nousiainen)

Chemistry of natural tetrapyrroles and quinones Recently, research activity has been focused on the following topic.

Horseradish peroxidase catalyzed oxidation of chlorophyll a with hydrogen peroxide. Characterization of the products and mechanism of the reaction Horseradish peroxidase was verified to catalyze the H2O2 oxidation of chlorophyll a (Chl a), solubilized with Triton X-100. The 132(S) and 132(R) diastereomers of 132-hydroxyChl a were characterized as the major oxidation products ( 60%) by TLC on sucrose, UV-vis spectra, 1H and 13C NMR spectra, and FAB MS. The minor side products (~10%) formed were characterized to include the 151(R)- and 151(S)-HO-lactone derivatives of Chl a, the 173-phytyl ester of Mg-purpurin-18, as well as two red components, representing the enolate anions of Chl a and pheophytin a or, alternatively, two different complexes of the Chl a enolate ion with Triton X-100. Our assignment of the red components is inconsistent with the proposal by several researchers that ‘bilirubin-like compounds’ are formed in HRP-catalyzed oxidation of Chl a. A thorough consideration of the mechanism and kinetics of the three reaction steps in the HRP catalytic cycle provided a reasonable explanation for the accumulation of the enolate ions. According to our results, the products of the HRP-catalyzed oxidation of Chl a are compatible with the theory for the free-radical allomerization of Chl a. We conclude that HRP can accelerate the slow initial step of the allomerization by producing highly reactive free-radicals. (Hynninen, Kaartinen, Kolehmainen).

CO2CH3O

N

NN

NMg

CO2Phytyl

132

1

HCO2CH3

O

N

NN

NMg

CO2Phytyl

132

1

HO

HRP, H2O2

Pi buffer, pH 5.9, 0.25% Triton X-100

Side products, ~10% [Chl a/Pheo a enolate anions, 151(S/R)-HO-lactone derivatives]

132(S/R)-HO-Chl a,~ 60%Chl a

+

Chemistry of nucleosides and nucleotides Dynamic combinatorial chemistry Dynamic combinatorial chemistry (DCC) was introduced in the late 1990s as a su-pramolecular and combinatorial method for the target-oriented search for biologically active compounds. A dynamic combinatorial library (DCL) is formed

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of an equilibrium mixture of several functionalities on a defined chemical basis. For one example, aldehydes react with a selection of amines to produce a versatile equilibrium mixture based on imine exchange. Addition of the target molecule – e. g. a receptor, protein or an enzyme – into the DCL solution shifts the equilibrium, and the compounds that have the greatest affinity for the target can be selected. The present project is directed towards building dynamic combinatory libraries on the basis of nucleoside derivatives. One target is to enhance methods for screening of the biological activities of potential drug compounds. The main research effort is, however, focussed on the biological reactivities, reaction mechanisms and factors steering the bonding of nucleoside analogues in the complexes. The interrelation of the components of the DCLs is studied in a quantitative manner (reaction mechanisms and kinetics). Analytical methods are developed on NMR, mass spectrometry and HPLC chromatography. For the screening of biological activities, for example enzyme inhibition, special applications based on spectrophotometry and chromatography will be required. (Oivanen, Hakanen, Lagerwall, Heinonen; in collaboration with the research group at the Engelhardt Institute of Molecular Biology, Moscow)

Molecular recognition of nucleosides for site-selective reactions The molecular recognition of small molecule ligands by artificial receptors has gained increasing interest during the past few decades. The recognition of nucleic acid bases (A-T and C-G pairs) in DNA is the most important molecular recognition process in nature. The binding force is based mainly on hydrogen bonding but, in addition, the -stacking interactions of the aromatic nucleobases play a role in the formation of the 3D-structure of DNA. The aim in our project is to use these “natural” weak interactions in the design of the artificial receptors for nucleosides. The purpose is to apply the approach with the reactive receptors bound on a solid support, which would allow development of recyclable reagents for introducing various groups to the selected site of the nucleoside. The mode of action of these artificial receptors resembles that of natural enzymes. The chemistry involves the synthesis of branched and cyclic structures using synthetic methods such as transition metal catalysis, solid phase synthesis and protection group chemistry. (Heinonen, Oivanen)

Physico-chemical properties of nucleic acid constituents Nucleoside analogues and derivatives used in various biological applications are often susceptible to hydrolytic degradation. For instance, the stability of the N-glycosidic linkage or the modified heteroaromatic base may be the critical factor. In biological systems the cleavage and formation of the bond is affected by phosphorylase and glycosylase enzymes. The mechanisms of the solvolysis reactions of nucleoside and nucleotide derivatives are studied by kinetic methods. The work is, on one hand, aimed at understanding the intrinsic chemical reactivity of the biologically important compounds, but on the other hand, also aims to provide a solid chemical basis for the applications of nucleotide analogues in biological and medical studies. (Oivanen, Lagerwall)

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Fatty acid chemistry Synthesis and modification This research, which originates from the study of tall oil fatty acids, has expanded into a more general research project involving the stereo-controlled synthesis of polyenic fatty acids, their 1,5-sigmatropic hydrogen shift reactions, and intramolecular Diels-Alder reaction. Partly because of the structural similarities of pinolenic and linolenic acids and partly because of the biological and nutritional importance of the latter we have recently focused our isomerization and IMDA studies on linolenic acid. Our results show that structures analogous to cyclopinolenic acids are formed in minor amounts only and that other types of hexahydroindenoid structures are formed as the main products. Our latest activity in this field is a novel simple and potentially large scale synthesis of pinolenic (5Z,9Z,12Z-octadecatrienoic acid) and 12Z,15Z,-octadecadienoic acid methyl esters using the potassium carbonate-mediated Wittig reaction (Kaltia, Matikainen, Hase, Ala-Peijari). A thorough NMR-analysis of these products will be published in the near future. (9)

New chemistry of linolenic acid When linolenic acid methyl ester is heated with alkali and the product is subjected to further heating the following reactions seem to occur.

The heat treatment of edible oils containing linolenic acid has been claimed to produce only trace amounts of bicyclic fatty acids, the main cyclic components being cyclohexadiene derivatives. In our hands, however, heat treatment of linolenic acid methyl ester, as shown above, leads to a complex mixture of cyclic acids where hexahydroindenoic structures predominate. This prompts the question: has hexahydroindenoic chemistry been underestimated so far as regards the chemistry of frying oils? We are now examining this possibility using rapeseed oil as the starting material. Our results show that the main conjugated isomers of linolenic acid, 9Z,14Z,16E- and 8E,10Z,15Z-octadecatrienoic acids are probably responsible for the formation of the most abundant cyclolinolenic acids. (Kaltia, Matikainen, Hase).

Autoxidative reaction mechanisms For the study of the autoxidation reaction of conjugated linoleic acid (CLA) methyl ester, presumed hydroperoxide reaction products are synthesized in a regioselective manner to allow the identification of the actual autoxidation products and to study their further transformations. High field NMR, UV and GC-MS studies are con-ducted to distinguish between the very subtle differences between the hydroxy derivatives of the CLA methyl ester hydroperoxides. In order to provide additional

74

insight into the autoxidation mechanism, the free radicals formed from CLA methyl ester are studied using ESR spectroscopy. (Pajunen, Hase; in collaboration with the Department of Applied Chemistry and Microbiology, Food Chemistry, University of Helsinki and Rowett Research Institute, Scotland, UK)

Miscellaneous synthetic studies Design of biomimetic catalysts During recent years chiral salen-type transition metal complexes have emerged as highly efficient catalysts for various important reactions ranging from oxidations to carbon-carbon bond formations. These complexes with the general structure shown below [salen = N,N'-bis(salicylaldehydo)ethylenediamine] may also bear potentially stereogenic carbon centers in the vicinity of the metal binding site.

The main topics of this project are: 1) the syntheses of salen-type transition

metal complexes that can be used as catalysts in biomimetic oxidations (oxidation of the benzylic position in aromatic compounds, epoxidation of alkenes, oxidation of sulfides to sulphoxides), 2) the design of practical oxidation systems (oxidant, cocatalysts) for the salen-catalyzed oxidation of lignocellulosic materials and epoxidation of alkenes, and 3) asymmetric oxidation of alkenes and asymmetric oxidative coupling of cinnamyl alcohols.

The synthesis and structural determination (X-ray crystallography) of various types of salen complexes have been performed in collaboration with the Laboratory of Inorganic Chemistry, University of Helsinki. The project is also in collaboration with the University of Milan (Prof. M. Orlandi). (Haikarainen, Sipilä, Brunow)

Sulfur compounds This research consists of preparation, reactivity and structural studies of various sul-fur compounds. 1,3-Oxathiane has sometimes been used as a formyl anion reagent. Unlike its analogue 2-lithio-1,3-dithiane, 2-lithio-1,3-oxathiane is quite unstable and undergoes a rapid decomposition at higher temperatures. We have studied this unwanted decomposition reaction mainly by product analysis. The parent com-pound produces a large number of small fragments while the substituted oxathianes give isolable amounts of decomposition products.

Structural studies by molecular mechanics cover a range of molecules, includ-ing non-sulfur compounds. (Koskimies)

Aldehyde activation The target of this project is to generate new industrially applicable and economi-cally feasible technologies to be used in upgrading aldehyde starting materials to reactive intermediates. These intermediates will mainly be used in coating and ad-hesive applications.

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The novel one-pot reaction of simple aliphatic aldehydes, when treated with TiCl4 and Ti(OiPr)4 in CH2Cl2 produce the dimeric diol monoethers. The mechanism is an unprecedented triple tandem aldolization/etherification/Meerwein-Ponndorf-Verley reduction sequence. (Aremo, Hase)

Publications Articles in refereed journals 1. Brink, E., Coxam, V., Robins, S., Wähälä, K., Cassidy, A. and Branca, F.; Long-

term consumption of isoflavone-enriched foods does not affect bone mineral density, bone metabolism, or hormonal status in early postmenopausal women: a randomized, double-blind, placebo controlled study, Am. J.Clin. Nutr. 87 (2008) 761-770.

2. Brouns, F., Doat, S., Joqueviel, N., Wähälä, K. and Branca, F.; Isoflavone-enriched Foods: Aspects of Production, Analysis, Sensory Properties and Self Life-The PHYTOS Project, Foods Food Ingredients J. Jpn. 213 (2008) 131-138.

3. Cameron, S., Cañas, A.I., Nousiainen, P., Record, E., Lomascolo, A., Martinez, M.J. and Martinez, Á.T.; p-Hydroxycinnamic Acids as Natural Mediators for Laccase Oxidation of Recalcitrant Compounds, Environ. Sci. Technol. 42 (2008) 6703-6709.

4. Chanteranne, B., Branca, F., Kaardinal, A., Wähälä, K, Braesco, V., Ladroite, P., Brouns, F. and Coxam, V.; Food Matrix and Isoflavones Bioavailability in Early Post Menopausal Women: An European Clinical Study, Clin. Interv. Aging, 3 (2008) 1-8.

5. Fager-Jokela, E., Kaasalainen, E., Leppänen, K., Tois, J. and Helaja, J.; Development of Intermolecular Additive Free Pauson-Khand Reactions for Estrone E-Ring Extension Using Microwaves, Tetrahedron, 64, (2008) 10381-10387.

6. Granstöm, M., Kavakka, J., King, A., Majoinen, J., Mäkelä, V., Helaja, J., Hietala, S., Virtanen, T., Maunu, S.L., Argyropoulos, D.S. and Kilpeläinen I.; Tosylation and Acylation of Cellulose in 1-Allyl-3-methylimidazolium Chloride, Cellulose, 15 (2008) 481-488.

7. Hashim, Y.Z.H-Y, Rowland, I.R., McGlynn, H., Servili, M., Selvaggini, R., Taticchi, A., Esposito, S., Montedoro, G.F., Kaisalo, L., Wähälä, K. and Gill, C.I.R.; Inhibitory Effects of Olive Oil Phenolics on Invasion in Human Colon Adenocarcinoma Cells In Vitro, Int. J. Cancer 122 (2008) 495-500.

8. Heikkilä, O., Lundholm, N., Timonen, M., Groop, P-H., Heikkinen, S. and Mäkimattila S.; Risk for Metabolic Syndrome Predisposes to Alterations in the Thalamic Metabolism, Metab. Brain Dis. 23 (2008) 315-324.

9. Kaltia, S., Matikainen, J., Ala-Peijari, M. and Hase, T.; Synthesis of Ethyl 5Z,9Z,12Z-Octadecatrienoate (ethyl pinoleate) and Methyl 12Z,15Z-octadecadienoate, J. Am. Oil Chem. Soc. 85 (2008), 561-565.

10. Karkola, S., Lilienkampf, A. and Wähälä, K.; A 3D QSAR Model of 17 -HSD1 Inhibitors Based on a Thieno[2,3-d]pyrimidin-4(3H)-one Core Applying Molecular Dynamics Simulations and Ligand-Protein Docking, ChemMedChem (2008), 461-472.

11. Kavakka J.S., Heikkinen, S. and Helaja, J.; Zn Pyropheophordide a: A -Face Selective Nicotine Receptor, Eur. J. Org. Chem. (2008), 4932-4937.

12. Kudanga, T., Prasetyo, E.N., Sipilä, J., Nousiainen, P., Widsten, P., Kandelbauer, A., Nyanhongo, G.S. and Guebitz, G.; Laccase-Mediated Wood Surface Functionalization, Eng. Life Sci. 8 (2008) 297-302.

13. Kylli, P., Nousiainen, P., Biely, P., Sipilä, J., Tenkanen, M. and Heinonen, M.; Antioxidant Potential of Hydroxycinnamic Acid Glycoside Esters, J. Agr. Food. Chem. 56 (2008) 4797-4805.

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14. Leppälä, E., Pohjoispää, M., Koskimies, J. and Wähälä, K.; Synthesis of New Deuterium-Labelled Lignanolactones, J. Labelled Compd. Rad. 51 (2008) 407-412.

15. Matikainen, J. and Elo, H.; Does Yawning Increase Arousal through Mechanical Stimulation of the Carotid Body? Med. Hypotheses 70 (2008) 488-492.

16. Parikka, K. and Wähälä, K.; Synthesis of Deuterated 5-n-Alkylresorcinols, J. Labelled Compd. Rad. 51 (2008) 12-18.

17. Parshintsev, J., Nurmi, J., Kilpeläinen, I., Hartonen, K., Kulmala, M. and Riekkola, M.-L.; Preparation of -Caryophyllene Oxidation Products and Their Determination in Ambient Aerosol Samples, Anal. Bioanal. Chem. 390 (2008) 913-919.

18. Raffaelli, B., Pohjoispää, M., Hase, T., Cardin, C.J., Gan, Y. and Wähälä, K.; Stereochemistry and Rearrangement Reactions of Hydroxylignanolactones, Org. Biomol. Chem. 6 (2008) 2619-2627.

19. Routasalo, T., Helaja, J., Kavakka, J. and Koskinen, A.M.P.; Development of Bis(2-picolyl)amine-Zinc Chelates for Imidazole Receptors, Eur. J. Org. Chem. (2008) 3190-3199.

20. Sturgeon, S.R., Heersink, J.L., Volpe, S.L., Bertone-johnson, E.R., Puleo, E., Stanczyk, F.Z., Sabelawski, S., Wähälä, K., Kurzer, M.S. and Bigelow, C.; Effect of Dietary Flaxseed on Serum Levels of Estrogens and Androgens in Postmenopausal Women, Nutr. Cancer 60 (2008), 612-618.

21. Tseng M., Olufade T., Kurzer M.S., Wähälä K., Fang C.Y., van der Schouw Y.T. and Daly, M.B.; Food Frequency Questionnaires and Overnight Urines Are Valid Indicators of Daidzein and Genistein Intake in U.S. Women Relative to Multiple 24-h Urine Samples, Nutr. Cancer, 60 (2008) 619-626.

22. Wang, F., Wang, W., Wähälä, K., Adlercreutz, H., Ikonen, E. and Tikkanen, M.J.; Role of Lysosomal Acid Lipase in the Intracellular Metabolism of LDL-transported Dehydroepiandrosterone-fatty Acyl Esters, Am. J. Physiol. Endocrinol. Metab. 295 (2008), E1455-E1461.

23. Zoia, L., Canevali, C., Orlandi, M., Tolppa, E-L., Sipilä, J. and Morazzoni, F.; Radical Formation on TMP Fibers Related Lignin Chemical Changes, BioResources 3 (2008) 21-33.

Articles in congress proceedings and monographs 24. Deb, S. and Wähälä, K.; Synthesis of a 7 -Hydroxy-8 H-estradiol Derivative, 11th

Belgian Organic Synthesis Symposium, July 13-18, 2008, Ghent, Belgium, Book of Abstracts, p. P88, poster presentation.

25. Deb, S. and Wähälä, K.; Synthesis of Fatty Acid Esters of Steroids in Microwave Oven, 2nd EuChemMS Chemistry Congress, Chemistry: The Global Science, September 16-20, 2008, Torino, Italy, Abstract , Poster I.3/P-007.

26. Fager-Jokela, E. and Helaja, J.; Enhanced Intermolecular Pauson-Khand Reactivity under Microwaves: Boost Effect by Gradual Cobalt Complex Addition and Activated Charcoal, 10. Frühjahrssymposium, March 27-29 2008, Rostock, Germany, Book of Abstracts p.102, poster presentation.

27. Järvi, P, Olszewska, A.M., King, A.W.T, Granstöm, M., Hietala, S., Kilpeläinen, I. and Argyropoulos, D.S.; Study of Rheological Behaviour of Micro Crystalline Cellulose Dissolved in Two Different Ionic Liquids, 10th European Workshop on Lignocellulosics and Pulp, August 25-28, 2008, Stockholm, Sweden, Proceedings, p177-180, poster presentation.

28. Karkola, S., Lilienkampf, A. and Wähälä, K.; A 3D QSAR Model of 17beta-HSD1 Inhibitors based on a Thieno[2,3-d]pyrimidin-4(3H)-one Core, Workshop on Pre-receptor steroid metabolism as target for pharmacological treatment, May 26-28, 2008, Eibsee Hotel, Germany, Book of Abstracts, p.P32, poster presentation.

29. Karkola, S.; Lilienkampf, A. and Wähälä K.; Phytoestrogens in Drug Discovery for Controlling Steroid Biosynthesis, in volyme 1 Recent Advances in Polyphenol Research, eds. Daayf, F. and Lattanzio, V. pp 293-316, Wiley-Blackwell, Singapore, 2008, ISBN-13: 978-1-4051-5837-4.

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30. Karkola, S., Lilienkampf, A. and Wähälä, K.; A 3D QSAR Model of 17 -HSD1 Inhibitors Applying Molecular Dynamics Simulations and Protein-Ligand Docking, 18th International Symposium of the Journal of Steroid Biochemistry and Molecular Biology, September 18-21, 2008, Seefeld Tyrol, Austria, Abstract of Lectures and Poster Presentations, 117-P, poster presentation.

31. S. Karkola, S. and Wähälä, K.; The binding of phytoestrogens to CYP 450 Aromatase. A Molecular modelling study, 2nd EuCheMS Chemistry Congress, Chemistry: The Global Science, September 16-20, 2008, Torino, Italy, Abstract , Poster III.1/P-083.

32. Kavakka, J. and Helaja, J.; Integration of Chlorophyll Derivatives on Carbon Nanotubes, 10. Frühjahrssymposium, March 27-29 2008, Rostock, Germany, Book of Abstracts p.113, poster presentation.

33. King, A.W.T., Kilpeläinen, I., Järvi, P., Olszewska, A.M., Heikkinen, S. and Argyropoulos, D.S.; In-Situ Quantitative 31P NMR Analysis of Lignin Functionalities in Wood, Based on Ionic Liquid Pre-Treatment, 10th European Workshop on Lignocellulosics and Pulp, August 25-28, 2008, Stockholm, Sweden, Proceedings, p32-35, oral presentation.

34. King, A.W.T., Sun, H., Xie, H., Kilpeläinen, I. and Argyropoulos, D.S.; Novel ionic solvents for lignocellulose analysis and derivatization., 235th ACS National Meeting, April 6-10, 2008 New Orleans, LA, United States, Abstracts of Papers CELL-212.

35. Lilienkampf, A., Väisänen, E., Koskimies, P. and Wähälä, K.; Synthesis and Biological Activityof Thieno[2,3-d]pyrimidin-4(3H)-one Based on 17 -HSD1 Inhibitors, Workshop on Pre-receptor steroid metabolism as target for pharmacological treatment, May 26-28, 2008, Eibsee Hotel, Germany, Book of Abstracts, p.P30, poster presentation.

36. Nousiainen, P., Maijala, P., Hatakka, A., Martinez, A.T. and Sipilä, J.; Syringyl-Type Simple Planr Phenolics as Mediating Oxidants in Laccase Catalyzed Degradation of Lignocellulosic Materials: Model Compound Studies, 10th European Workshop on Lignocellulosics and Pulp, August 25-28, 2008, Stockholm, Sweden, Proceedings, p461-464, poster presentation.

37. Oivanen, M.; Kemian laitoksen uudet opetusohjelmat -toiko Tutkinnonuudistus uutta sisältöä?, in Uusia lähestymistapoja kemian opetukseen perusopetuksesta korkeakouluihin, eds. Aksela, M. and Montonen, M., pp. 3-8, Opetushallitus, Helsinki, 2008, ISBN 978-952-13-3557-8.

38. Olszewska A.M., Järvi, P., King, A.W.T., Kilpeläinen, I. and Argyropoulos, D.S.; Determination of the Molecular Weight Distribution of Intact Spruce Wood Acetylated in Ionic Liquid Media, 10th European Workshop on Lignocellulosics and Pulp, August 25-28, 2008, Stockholm, Sweden, Proceedings, p222-225, poster presentation.

39. Raffaelli, B., Pohjoispää, M. and Wähälä, K.; Stereochemistry and Rearrangement Mechanisms of Hydroxylignanolactones, XXIVth International Conference on Polyphenols, 8-11.7. 2008, Salamanca, Spain, Polyphenols Communications (2008), 271-272, poster presentation

40. Raffaelli, B., Silvennoinen, G. and Wähälä, K.; Synthesis of Medioresinol and its Analogue, XXIVth International Conference on Polyphenols, 8-11.7. 2008, Salamanca, Spain, Polyphenols Communications (2008), 268-270, poster presentation.

41. Väisänen, E. and Wähälä, K.; Microwave Assisted Synthesis of Phenylacetic Acids via Willgerodt-Kindler –reaction, 17th International Conference on Organic Synthesis, June 22-27, 2008, Daejeon, South-Korea, Book of Abstracts, p. PR-119, poster presentation.

42. Wanf, F., Wang, W., Wähälä, K., Adlercreutz, H and Tikkanen, M.J.; Hydrolysis and Metabolism of LDL-associated DHEA-Fatty Acyl Esters in HeLa Cells and the role of LAL, 18th International Symposium of the Journal of Steroid Biochemistry and Molecular Biology, September 18-21, 2008, Seefeld Tyrol, Austria, Abstract of Lectures and Poster Presentations, 136-P, poster presentation.

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43. Wähälä, K. Echemtests in Applying Research-Based Teaching in Chemistry, International Technology, Education and Development Conference, March 3-5, 2008, Valencia, Spain, Conference Book, p. 419, poster presentation.

44. Wähälä, K., Aremo, N. and Lindblom-Ylänne, S.; EChemTest in Applying Research-Based Teaching in Chemistry, International Technology, Education and Development Conference, INTED2008, March 3-5, 2008, Valencia, Spain, INTED2008-CD-Rom Proceedings.

45. Xie, H., Argyropoulos, D.S., King, A.W.T., Kilpeläinen, I., and Granström, M. Thorough chemical modification of wood-based lignocellulosic materials in ionic liquids, 235th ACS National Meeting, April 6-10, 2008, New Orleans, LA, United States, (2008), Abstracts of Papers CELL-166.

Theses Doctor of Philosophy 1. Karppanen Jari: Preparation of Industrially Important Hydroxy Acids and

Diacidsfrom 2,2-Disubstituted Propane-1,3-Diols and Linear Primary Diols by GreenChemistry Methods

2. Setälä Harri: Regio- and Stereoselectivity of Oxidative Coupling Reactions of Phenols

Master of Science 1. Al-Hunaiti, Afnan H.: Synthesis of 6- and 5,6-Substituted Pyrimidine Nucleosides 2. Avikainen-Eskola, Hanna: Studies on protein dynamics using liquid phase NMR

relaxation measurements (in Finnish) 3. Forsström Päivi: Research based experiments in chemistry teaching in high schools:

Laccase enzyme as an example (in Finnish) 4. Haavikko Raisa: The use of alkylazides in preparation of nitrogen heterocycles (in

Finnish) 5. Hagberg Tero: Paper yellowing and its inhibition (in Finnish) 6. Hokkanen Janne: Anti-inflammatory analgesics and antidepressants in aqueous

environment (in Finnish) 7. Hyytiäinen Kristiina: Organic oxidation and reduction reactions in teaching of the

high school first chemistry course (in Finnish) 8. Ikonen Jari: Studies on the microwave assisted synthesis of the model compounds of

phenolic natural compounds (in Finnish) 9. Johansson Ville: Environmentally benign Suzuki reaction between arylboronic acid

and aryl halide (in Finnish) 10. Kontio, Lea: Flavonoid glycosides and their preparation (in Finnish) 11. Kontro Anna: Blue light emitting diodes (in Finnish) 12. Korhonen Elisa: The transformation reactions of flavonoids during the ageing of red

wines (in Finnish) 13. Lagerwall Tom: Preparation of uracil and 5-and 6-substituted uracils (in Finnish) 14. Lampinen Terhi: Health functional flavonoids (in Finnish) 15. Loponen Meri: Reduction of unsaturated aryl ketones (in Finnish) 16. Mukkonen Andrei: Cyclic O,O-Acetals as Protecting Groups in Organic Synthesis 17. Nissilä Riikka: Bioactive phenolic compounds in arctic bramble (Rubus arcticus L):

cultivation in suspension culture and analysis (in Finnish) 18. Pernaa Johannes: Chemistry of insects. High school chemistry teaching approach (in

Finnish) 19. Rinta-Filppula Niina: Developments in lignan synthesis 2000-2007 (in Finnish)

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20. Sallinen Miika: Ozonization of vegetable oils and vegetable fats for therapeutic and cosmetic purposes (in Finnish)

21. Salmela Laura: Biotechnology in chemistry teaching: experimental enzymatic chemistry with the aid of learning cycle (in Finnish)

22. Samuli Katja: Aromatic sulphinic acids (in Finnish) 23. Sippel, Klaus: Chemical fungus eradication from building materials: Development

research of network material (in Finnish) 24. Sutinen, Harri: Follow-up of solid phase synthesis (in Finnish) 25. Syvänne, Satu: Reactions of fatty acids (in Finnish) 26. Talja Heljä: Preparation of sugar diacids and their derivatives for the starting

materials of polymeric substances (in Finnish) 27. Tuovila, Janne: Alkenylresorcinols (in Finnish) 28. Viinikka Leena: Biscoumarins (in Finnish) 29. Viljanen Ruut: Synthesis of Si-complexes of phtalocyanin and phtalocyanin-fulleren

compounds (in Finnish)

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LABORATORY OF POLYMER CHEMISTRY

The research activities at the Laboratory of Polymer Chemistry focus on the con-trolled synthesis, characterisation and modelling of macromolecular systems. Spe-cial emphasis is placed on synthetic polymers with complex topologies, responsive or functional polymer systems and modified natural polymers. Integrated with the advanced characterisation and modelling methods, the laboratory has gained con-siderable expertise in the studies of well-defined macromolecules for novel tech-nologies, especially in the area of water-soluble and amphiphilic polymers.

The teaching curriculum of the laboratory consists of more than 20 courses covering polymer synthesis, properties, and applications from fundamentals to spe-cialized topics. Teaching at the laboratory is mainly given at advanced undergradu-ate and graduate level. Many students take polymer chemistry as their minor sub-ject. In addition to teaching at the higher level, an introductory course in polymer science – as an optional part of the basic chemistry studies – is also arranged annually.

The laboratory takes part in two graduate schools, the National graduate school in nano science (NANO) and Electrochemical science of polymers and polymer membranes (ESPOM). Also, the laboratory is a member of the “Functional materials” consortium which was in 2007 appointed a centre of excellence of the Academy of Finland. http://www.helsinki.fi/polymeerikemia/english/

Personnel Teaching staff Vladimir Aseyev, Ph.D., Doc., University Lecturer Sami Hietala, Ph.D., Doc., University Lecturer Johan Lindberg, Ph.D., Professor Emeritus, 28.6.2008 Sirkka Liisa Maunu, Ph.D., Professor Franciska Sundholm, Ph.D., Professor Emerita Heikki Tenhu, Ph.D., Professor, Head of the Laboratory

External senior lecturers (docents) Raimo Alén, D.Techn., Professor at the University of Jyväskylä Søren Hvidt, Ph.D., Professor at the University of Roskilde, Denmark Olli Ikkala, D.Techn., Professor at the Helsinki University of Technology Anna-Kaisa Kontturi, D.Techn., Helsinki University of Technology Barbro Löfgren, Ph.D. Jutta Nuortila-Jokinen, D.Techn. Eeva-Liisa Poutanen, Ph.D. Antti Savolainen, Ph.D., Professor at the Tampere University of Technology Carl-Eric Wilén, D.Techn., Professor at Åbo Akademi University Françoise Winnik, Ph.D., Professor at the Université de Montréal, Canada

Research staff Adina Dogaru Anghelescu, Ph.D. Matti Elomaa, Ph.D., Doc.

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Jaana Ennari, Ph.D. Niko Granqvist, B.Sc. Laura Heiskanen, M.Sc. Miia Hiltunen, M.Sc. Sami-Pekka Hirvonen, M.Sc. Harri Jokinen, M.Sc. Katriina Kalliomäki, M.Sc. Heimo Kanerva Mikko Karesoja, M.Sc. Erno Karjalainen, M.Sc. Anu Koponen, M.Sc. Sergey Larin, M.Sc. Elena Lobyntseva, M.Sc. Jason McKee Mikko Mänttäri, M.Sc. Jukka-Pekka Niskanen, M.Sc. Frans Ojala Helena Parviainen, M.Sc. Felix Plamper, Ph.D. Petri Pulkkinen, M.Sc. Simon Riihelä, M.Sc. Juuso Sammaljärvi Jun Shan, Ph.D. Zhenhua Song, B.Sc. Satu Strandman, Ph.D. Aleksey Trusov, M.Sc. Pirita Uschanov, M.Sc., Dipl.Eng. Lauri Valtola, M.Sc. Tommi Virtanen, M.Sc. Szymon Wiktorowicz, M.Sc. Anna Zarembo, Ph.D. Yiming Zhao

Foreign scientists and visitors Vadim V. Annenkov, Dr., Irkutsk Limnological Institute, Russia Stefania Baldursdottir, Dr., University of Copenhagen Denmark Olivier Bertrand, ERASMUS Anne Bohle, Dipl.Chem., Max Planck Institute for Polymer Research, Group of Polymer Spectroscopy, Mainz, Germany Oleg Borisov, Prof., Université de Pau, CNRS, Tamara Bush, Forestry and Forest Products Research Center, CSIR, Natural Resources and the Environment, South Africa Elena Danilovtseva, Dr., Irkutsk Limnological Institute, Russia Anatoly A. Darinskii, Prof., Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia Olivier Deschaume, Dr., School of Biomedical and Natural Sciences, Interdisciplinary Biomedical Research Centre, Nottingham Trent University, UK Søren Hvidt, Prof., University of Roskilde, Denmark Mihkel Koel, Ph.D., Senior research scientist, Tallinn University of Technology, Faculty of Science, Department of Chemistry, Chair of Analytical Chemistry

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Alexander Kozlov, Dr., Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia Lay-Theng Lee, Professor, Laboratoire Léon Brillouin, SEA-Saclay, France Eva Malmström, Prof., Royal Institute of Technology, Stockholm, Sweden Sergey Malyshkin, Dr., Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia Axel Müller, Prof., University of Bayreuth, Germany Carole C. Perry, Prof., School of Biomedical and Natural Sciences, Interdisciplinary Biomedical Research Centre, Nottingham Trent University, UK Alexander Petrov, Prof., Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia Tamara Petrova, Dr., Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia Jukka Rantanen, Prof. University of Copenhagen, Denmark Elodine Ruiz, M.Sc., University of Montpellier, France Aleksey Trusov, M.Sc., Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia Mikhail Zheludkevich, University of Aveiro, Portugal

Laboratory and administrative staff Heljä Heikkilä, B.A., Secretary Seija Lemettinen, Laboratory Technician Juha Solasaari, Lic.Phil., Laboratory Engineer

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Research activities The relationship between the chemical and topological structure and the physical properties of macromolecular substances is the basic theme of the research in the Laboratory of Polymer Chemistry. Amphiphilic and thermally responsive block, graft, and star copolymers, grafted polymer nanoparticles, water-soluble speciality polymers and polyelectrolytes are examples of polymers that are being studied at present. Spectroscopic studies on synthetic and biological polymers are of growing importance. Molecular modelling is an integral part of polymer research.

The instrumental equipment available for research is of a good standard. The laboratory houses 200 MHz and 300 MHz NMR spectrometers, the latter also suitable for solid state work over a wide temperature range, an FTIR spectrometer, laser light scattering, a DSC calorimeter as well as a microcalorimeter for liquid samples, a rheometer and a dynamic mechanical analyser, an optical polarising microscope, two SEC systems for both organic and aqueous samples. AFM, FESEM, and MALDI TOF instruments are in shared use with other laboratories, as well as a Zeta Sizer.

Controlled radical polymerization The synthesis of materials with controlled compositions, architectures and function-alities has been of great scientific interest in recent years owing to the development of controlled radical polymerization methods. These methods allow for the syntheses of tailored polymers and molecular composites with well-defined structures and functionalities, giving control over macroscopic properties. (Anghelescu-Dogaru, Hietala, Koponen, Mänttäri, Nuopponen, Plamper, Strandman, Valtola, Tenhu) Modern synthesis methods have also allowed for the combination of synthetic polymers with biopolymers, e.g. lignin. (Parviainen, Tenhu) more…

Environmentally responsive polymers Environmentally responsive polymers are a fascinating group of water-soluble polymers. These polymers are sensitive to an external stimulus in the environment and have a specific response. The response might be, for example, a volume change of a hydrogel or some other conformational changes in the polymer structure that may induce the pursued response. Such systems are based on well-designed poly-mers that have a particular functionality that is sensitive to the available impulse. Responsive polymers are also applied in the syntheses of new fluorescent polymer particles. (Aseyev, Hietala, Tenhu) more...

Self-organization of block copolymers in aqueous solutions The self-assembly of block copolymers into organized structures in selective solvents which typically favor one of the blocks is of great interest at present. Amphiphilic block copolymers in aqueous media may form micelles with a hydrophobic core and a hydrophilic corona. Often the micelles have a small core

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and a relatively thick corona and are referred to as star-like micelles. Another type of micelle, characterized by a large core and relatively thin corona has also been reported. (Nuopponen, Tenhu) more...

Metal nano particles Monolayer-protected clusters (MPC) of metal nanoparticles constitute a rapidly emerging field due to their very specific electronic, optoelectronic, and catalytic properties. An MPC is a core-shell nanocomposite composed of a metal core and a shell ranging from small organic compounds to macromolecules. The metals studied so far include gold, silver and copper. (Shan, Niskanen, Nuopponen, Pulkkinen, Zhao, Tenhu) more...

Figure 1. Models and TEM micrographs of Au nanoparticles covalently coated with polymer chains.

Polyelectrolyte complexes Polyelectrolyte complexes (PEC) play an important role in nature. By mimicking the complex formation known to take place in living organisms new methods, for example drug delivery and gene therapy in medicine, can be developed. However, it is of great importance to know the complexation mechanisms and the effects of varying conditions on the formation, the solubility, and the stability of the complexes. (Andersson, T., Aseyev, Tenhu) more...

Figure 2. Schematic representation of PEC formation.

[+]/[-] > 1 [+]/[-] = 1 [+]/[-] < 1

Keys: PEO

PMAA P MOTAC

N eutral core

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Structure analysis of polymers and multimolecular associates with complex architectures in solution A considerable expertise in polymer characterization has been gained at the Labo-ratory of Polymer Chemistry. Research focuses on various new polymers with com-plex architectures studied by means of static/classical and dynamic light scattering. Most attention is paid to water-soluble, water-swollen and amphiphilic polymers as self-assembling and bio-mimicking systems. (Aseyev, Anghelescu-Dogaru, Hietala, Tenhu) more...

Globules and mesoglobules in aqueous media Various thermally-responsive polymers and their derivatives form colloidally-stable suspensions of single chain globules or multimolecular aggregates/mesoglobules upon heating of their aqueous solutions instead of the expected macrophase separa-tion. The exact mechanism of colloidal stabilisation is yet to be fully understood. more...

Computer simulation of amphiphilic star copolymers Computer simulation and theoretical methods are applied to the study of complex structures on the basis of environmentally-responsive star block copolymers in aqueous solutions. These polymers find promising applications in medicine, gene therapy and wood preservation and have been synthesised and intensively studied experimentally in the laboratory. To reveal the mechanism of the formation of complexes of stimuli-responsive star polymers and the correlation between their behaviour under changing external conditions (temperature, ionic strength, pH and the solvent composition) and the chemical structure of the constituents, a combination of coarse-graining and atomistic simulation methods, analytical theory as well as new simulation techniques is used. (Larin)

New polymeric emulsifiers Emulsifiers active in nonaqueous media find applications in phase-separated synthesis and separation techniques among other technological uses. Fluorinated materials exhibit both hydrophobicity and lyophobicity and are thus feasible emulsifiers for such applications. In order to develop polymeric emulsifiers, new fluorinated monomers are synthesized and polymerised using controlled radical polymerization methods. (Hietala, Tenhu, Valtola)

Water dispersible conducting polymers Electrically neutral water dispersible derivatives of polyaniline are synthesised either by grafting the preformed polymer, or the aniline monomer, to short water-soluble polymer chains. Water soluble polymeric complexes of polyaniline have been successfully prepared. This research is expected to show great potential for industrial applications. Amphiphilic derivatives of poly(benzimidazobenzo-phenantroline) are synthesised for possible applications in solar cells. (Hirvonen, Tenhu)

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Electroactive polymers Nanocomposites consisting of polyacrylates and polymer-grafted nano-sized filler particles are synthesized for e.g. applications in actuators. The grafting of particles was conducted using ATRP reactions. The mechanical properties of the materials are of special interest. (Karesoja, Tenhu) New proton conducting polymer membranes for high temperature fuel cells have been prepared. The project is conducted in collaboration with several European universities and automotive in-dustries. (Elomaa, Tenhu)

Solid state NMR studies of fiber ultrastructure In wood cell cellulose chains are grouped to form cellulose fibrils, which in turn form larger structures known as fibril aggregates. Aggregation influences the reactivity of cellulose substrates in the chemical modification of cellulose; also, the susceptibility of cellulose substrates to enzymatic hydrolysis is affected. However, the ways in which fibril aggregation affects the macroscale properties of pulp, for example the strength of the fiber, is not very well understood. 13C CPMAS NMR is used to study the ultrastructure of cellulose in various kraft pulps in order to obtain information about the correlation of fibril aggregate size with the macroscale properties of the wood pulp fibers. (Heiskanen, Virtanen, Maunu) more...

New cellulose derivatives Processing cellulose is complicated due to its very strong fibrillar structure. By in-creasing the accessibility of cellulose materials to swelling and reactive agents, more controlled derivatisation is possible. RAFT-polymerization allows the tailoring of macromolecules with sophisticated architectures, including graft copolymers, and is therefore used in this project to build side chains onto CMC, EHEC and cellulose backbones and to prepare new derivatives with well controlled chemical structures. The target products are of high-value e.g. sophisticated pharmaceutical and fine chemical applications, as well as fibres, coatings, casings, sponges and beads. (Hiltunen, Maunu)

Heterogeneous cellulose modification does not require the dissolving of fiber, rather the modification reactions take place on the surfaces of the microfibers. Hence microcrystalline cellulose and nanofibers of cellulose are encapsulated within a polymer matrix in order to improve the mechanical properties of polymer composites or films. (Uschanov, Maunu) more...

New water-borne coating formulations Different types of polymers and combinations of polymers have been developed during the last few years for use as binders in paints and coatings. Recently, research has focused on one hand on the utilization of renewable raw materials and on the other hand on organic solvent-free coatings. The trend towards zero VOC products has led to the development of water-borne emulsions which contain two or more different types of polymer building blocks. Alkyd acrylic binders were pro-duced by the modification of tall oil based alkyds via miniemulsion polymerisation using acrylic monomers. The ratio of alkyd resin to acrylate monomers was varied and the effects on copolymerization and the copolymer binder properties, such as

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particle size, molecular weight, grafting of acrylate to alkyd resin and reaction of double bonds, were studied. (Uschanov, Maunu) more...

NMR spectroscopy of drugs Drug compounds are known to exist in more than one polymorphic form which may differ significantly in their physical properties, e.g. solubility, bioavailability, processability and stability (both chemical and physical). Therefore it is important to obtain solid state information of these substances, both from the bulk state and from the dosage form, since processing into the dosage form can alter the drug, introduce interactions with excipients, and affect stability. Solid state NMR techniques are used in this project to study the polymorphism of API samples. (Virtanen, Maunu)

Stimuli-responsive hydrogels Associative polymers are of industrial importance owing to their adjustable rheological properties, for example in paints, cosmetics formulations and pharmaceutical as well as medical applications such as drug delivery and tissue engineering. Particularly interesting are the stimuli-responsive systems of associating polymers in which free standing gels transform into free-flowing liquids or vice versa. To obtain such systems water-soluble polymers modified with a small number of hydrophobic groups are often used. Enhanced viscosity and reversible gelling behaviour originate from transient intermolecular associations between the hydrophobic groups..

Figure 4 Transition from gel to solution upon heating of (PAA54-b-PS6)4 in water, polymer concentration 26 g/L.

Figure 5. Photograph of stereoblock PNIPAM (i-a-i, 45 g/L) in water at room temperature.

Starlike polyelectrolytes, four-armed poly(acrylic acid)-block-polystyrene (PAA-b-PS)4 (Hietala, Järvi, Strandman, Tenhu) with central hydrophilic PAA core and

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short hydrophobic PS blocks were prepared by means of atom transfer radical polymerization (ATRP). These water-soluble polymers associate via the interaction of the PS blocks and result in the formation of hydrogel at relatively low polymer concentration. The effects of external conditions, such as temperature, ionic strength and polymer concentration were investigated by rheological and scattering methods (Figure 4).

The behaviour in solution of stereoblock polymers of poly(N-isopropyl acrylamide) PNIPAM (Hietala, Kalliomäki, Nuopponen, Tenhu) made via reversible addition–fragmentation chain transfer polymerization (RAFT) was studied. Atactic PNIPAM is a thermosensitive water soluble polymer that dissolves in water at low temperatures but loses its solubility upon heating at about 31°C. Other stereoregular forms of PNIPAM have different solubilities, syndiotactic PNIPAM exhibits low water solublility while the isotactic form is insoluble in water. The so-called stereoregular block polymers comprising isotactic (i) and atactic (a) PNIPAM sequences were studied, the polymers having either an i-a-i or an a-i-a block sequence. Increasing the lengths of the isotactic blocks makes the polymers less water soluble, so that some of the polymers dissolve only upon cooling to 5°C. At room temperature the isotactic blocks associate to form different type of aggregates, and, for i-a-i type polymers at higher concentrations, form hydrogels (Figure 5.) while still retaining their temperature sensitive properties. The properties of the hydrogels were studied with rheology as well as by NMR and DSC.

Publications Papers in refereed journals 1. Andersson, T., Sumela, M., Khriachtchev, L., Räsänen, M., Aseyev, V. and

Tenhu, H.; Solution Properties of an Aqueous poly(methacryl oxyethyl trimethylammonium chloride) and Its Poly(oxyethylene) Grafted Analog. J. Polym. Sci.: Part B: Polym. Phys. 46 (2008) 547-557.

2. Ennari, J.; Modelling of transport properties and state of water of polyelectrolytes containing various amounts of water. Polymer 49 (2008) 2373-2380.

3. Granström, M., Kavakka J., King, A., Majoinen, J., Mäkelä, V., Helaja, J., Hietala, S., Virtanen, T., Maunu, S.-L., Argyropoulos, D. S. and Kilpeläinen, I.; Tosylation and acylation of cellulose in 1-allyl-3-methylimidazolium chloride. Cellulose 15 (2008) 481-488.

4. Hietala, S., Nuopponen, M., Kalliomäki, K. and Tenhu, H.; Thermoassociating Poly(N-isopropylacrylamide) A-B-A Stereoblock Copolymers. Macromolecules 41 (2008) 2627-2631.

5. Huhtinen, P., Kivelä, M., Soukka, T., Tenhu, H., Lövgren, T. and Härmä, H.; Preparation, characterisation and application of europium(III) chelate-dyed polystyrene-acrylic acid nanoparticle labels. Anal. Chim. Acta 630 (2008) 211-216.

6. Johansson, L., Karesoja, M., Ekholm, P., Virkki, L. and H. Tenhu; Comparison of the solution properties of (1 3),(1 4)- -D-glucans extracted from oats and barley. LWT 41 (2008) 180-184.

7. Kjøniksen, A.-L., Laukkanen, A., Tenhu, H. and Nyström, B.; Anomalous turbidity, dynamical, and rheological properties in aqueous mixtures of a thermoresponsive PVCL-g-C11EO42 copolymer and an anionic surfactant. Colloids Surf. A: Physicochem. Eng Aspects 316 (2008) 159-170.

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8. Krasnou, I, Tarabukina, E., Melenevskaya, E., Filippov, A., Aseyev, V., Hietala S. and Tenhu, H.; Rheological Behavior of Poly(vinylpyrrolidone) / Fullerene C60 Complexes in Aqueous Medium. J. Macromol. Sci., Part B: Phys. 47 (2008) 500-510.

9. Kudaibergenov, S. E., Tatykhanova, G. S., Arinov, B. Zh., Kozhakhmetov, S. K. and Aseyev, V. O.; Hybrid inorganic-organic nano- and microcomposites based on silica sols and synthetic polyelectrolytes. eXPRESS Polym. Lett. 2 (2008) 101-110.

10. Kudaibergenov, S.E., Tatykhanova, G.S., Khutoryanskiy, V.V., Aseyev, V. and Tenhu, H.; Investigation of the Physical and Chemical Properties of Nanocomposites on the Basis of Nanoparts of Earth Silicon and Cation Polyelectrolytes. Dokl. Acad. Nauk /Natl. Acad. Nauk Republic of Kazakhstan 1 (2008) 54-64.

11. Kul, D., van Renterghem, L. M., Meier, M. A. R., Strandman, S., Tenhu, H., Yilmaz, S. S., Schubert, U. S. and Du Prez, P. E.; Encapsulation and Release by Star-Shaped Block Copolymers as Unimolecular Nanocontainers. J. Polym. Sci.: Part A: Polym. Chem. 46 (2008) 650-660.

12. Lintinen, K., Efimov, A., Hietala, S., Nagao, S., Jalkanen, P., Tkachenko, N. and Lemmetyinen, H.; Cationic Photopolymerization of Liquid Fullerene Derivative under Visible Light. J. Polym. Sci.: Part A: Polym. Chem. 46 (2008) 5194-5201.

13. Nuopponen, M., Kalliomäki, K., Aseyev, V. and Tenhu, H.; Spontaneous and Thermally Induced Self-Organization of A-B-A Stereoblock Polymers of N-Isopropylacrylamide in Aqueous Solutions. Macromolecules 41 (2008) 4881-4886.

14. Nuopponen, M., Kalliomäki, K., Laukkanen, A., Hietala, S. and Tenhu, H.; A-B-A Stereoblock Copolymers of N-Isopropylacrylamide, J. Polym. Sci.: Part A: Polym. Chem. 46 (2008) 38-46.

15. Nykänen, A., Nuopponen, M., Hiekkataipale, P., Hirvonen, S.-P., Soininen, A., Tenhu, H., Ikkala, O., Mezzenga, R. and Ruokolainen, J.; Direct Imaging of Nanoscopic Plastic Deformation below Bulk Tg and Chain Stretching in Temperature-Responsive Block Copolymer Hydrogels by Cryo-TEM. Macromolecules 41 (2008) 3243-3249.

16. Pitkänen, L., Tuomainen, P., Virkki, L., Aseyev, V. and Tenkanen, M.; Structural Comparison of Arabinoxylans from Two Barley Side-Stream Fractions. J. Agric. Food Chem. 56 (2008) 5059-5077.

17. Raula, J., Thielmann, F., Kansikas, J., Hietala, S., Annala, M., Seppälä, J., Lähde, A. and Kauppinen, E.; Investigations on the Humidity-Induced Transformations of Salbutamol Sulphate Particles Coated with L-Leucine. Pharm. Res. 25 (2008) 2250-2261.

18. Sacca, A., Carbone, A., Pedicini, R., Marrony, M., Barrera, R., Elomaa, M. and Passalacqua, E.; Phosphotungstic Acid Supported on a nanopowdered ZrO2 as a Filler in Nafion-Based membranes for Polymer Electrolyte Fuel Cells. Fuel Cells 08 (2008) 225-235.

19. Shan, J., Pulkkinen, P., Vainio, U., Maijala, J., Merta, J., Jiang, H., Serimaa, R., Kauppinen, E. and Tenhu, H.; Synthesis and characterization of copper sulfide nanocrystallites with low sintering temperatures. J. Mater. Chem. 18 (2008) 3200-3208.

20. Strandman, S., Zarembo, A., Darinskii, A. A., Laurinmäki, P., Butcher, S. J., Vuorimaa, E., Lemmetyinen, H. and Tenhu, H.; Effect of the Number of Arms on the Association of Amphiphilic Star Block Copolymers. Macromolecules 41 (2008) 8855-8864.

21. Tarabukina, E. B., Krasnou, I. L., Tarrassova, E. V., Ratnikova, O. V., Melenevskaja, E. U., Filippov, A. P., Laukkanen, A., Aseyev, V. O. and Tenhu, H.; The Influence of the Poly(vinyl caprolactam) with Fullerene C60. Vysokomolekularnye Soedinenia, Ser. A 50 (2008) 1-9.

22. Tarabukina, E. B., Krasnov, I. L., Tarasova, E. V., Ratnikova, O. V., Melenevskaya, E. Yu., Filippov, A. P., Laukkanen, A., Aseev, V. O. and Tenhu, H.; Effect of the Ultracentrifuge Centrifugal Force on the Molecular Characteristics of Poly(vinylvaprolactam) Complexes with Fullerene C60. Vysokomol. Soed. Ser. A 50 (2008) 315-323.

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23. Tarabukina, E. B., Krasnov, I. L., Tarasova, E. V., Ratnikova, O. V., Melenevskaya, E. Yu., Filippov, A. P., Laukkanen, A., Aseev, V. O. and Tenhu, H.; Effect of the Ultracentrifuge Centrifugal Force on the Molecular Characteristics of Poly(vinylcaprolactam) Complexes with Fullerene C60. Polym. Sci. 50 (2008) 198-205. Original Russian Text: Vysokomol. Soed. Ser. A 50 (2008) 315-323.

24. Uschanov, P., Heiskanen, N., Mononen, P., Maunu, S. L. and Koskimies, S.; Synthesis and characterization of tall oil fatty acids-based alkyd resins and alkyd-acrylate copolymers. Progr. Org. Coat. 63 (2008)) 92-99.

25. Vihola, H., Laukkanen, A., Tenhu, H. and Hirvonen, J.; Drug Release Characteristics of Physically Cross-Linked Thermosensitive Poly(N-vinylcaprolactam) Hydrogel Particles. J. Pharmaceut. Sci. 97 (2008) 4783-4793.

26. Virtanen, T., Maunu, S. L., Tamminen, T., Hortling, B. and Liitiä, T.; Changes in fiber ultrastructure during various kraft pulping conditions evaluated by 13C CPMAS NMR spectroscopy. Carbohyrdate Polymers 73 (2008) 156-163.

27. Wikström, J., Elomaa, M., Syväjärvi, H., Kuokkanen, J., Yliperttula, M., Honkakoski, P. and Urtti, A.; Alginate-based microencapsulation of retinal pigment epithelial cell line for cell therapy. Biomaterials 29 (2008) 869-876.

Book chapter 28. Maunu, S. L.; 13C CPMAS NMR Studies of Wood, Cellulose Fibers, and

Derivatives. In “Characterization of Lignocellulosic Materials” Edited by Thoms Q. Hu, Blackwell Publishing, 2008, pp. 227-248.

Articles in congress proceedings 29. Annenkov, V. V., Danilovtseva, A. N., Aseyev, V. O., Patwardhan, S. V. and

Perry, C. C.; Polymeric Amines: Role in Biosilification and Potential in Nanotechnologies. Oral presentation. IASTED International Association of Science and Technology for Development) International Conference on Nanotechnology and Applications (NANA 2008), Crete, Greece, 29.9.-1.10.2008. Proceedings, 47-52.

30. Aseyev, V. O., Tatykhanova, G., Tenhu, H., Arinov, B. J. and Kudaibergenov, S.; Dynamic and Static Light Scattering Study of Nanoparticles Coated by LbL Multilayers on the Basis of Poly(ethyleneimine) and Poly(acrylic acid). Poster. III International Workshop on Speciality Polymers for Environment Protection, Bio-, Nanotechnology and Medicine. Almaty, Kazakhstan, 28.5.2008. Proceedings, 53, ISBN 9965-877-09-2.

31. Hiltunen, M., Maunu, S. L., Uschanov, P. and Virtanen, T.; Characterization and Modification of Lignocellulosic Materials at the Laboratory of Polymer Chemistry (UH). Invited lecture. 8th International Symposium “Alternative Cellulose”, Rudolstadt, Germany, 3.-4.9.2008. Proceedings, CD & file, 10 pages.

Other publications 32. Sundholm, F.; Kemian tutkimus ja Suomen Akatemia 1990-luvulla ja 2000-luvun

alussa. In ”Suomen Akatemian historia 1-3, osa 3: Kilpailu ja yhteistyö; Hannu Heikkilä (toim.). 366-367.

33. Sundholm, F. and Tenhu, H.; J. Johan Lindberg. Polymeerikemian uuttera uranuurtaja. In memoriam. Kemia-Kemi, 5/2008, 81.

34. Sundholm, F.; Jarl Johan Lindberg. Minnestal hållet vid Finska Vetenskaps-Societetens sammanträde den 15 september 2008. Sphinx Årsbok – Vuosikirja – Yearbook 2008-2009, 141-143.

35. Tenhu, H.; In Memoriam [J. Johan Lindberg]. Muovi-plast (2008) 31. 36. Törmälä, P. and Tenhu, H.; J. Johan Lindberg - *18.9.1921 28.6.2008. J. Johan

Lindberg in Memoriam. Suomalainen Tiedeakatemia, Vuosikirja 2008, 107-110.

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Theses Doctor of Philosophy 1. Nuopponen, Markus: Organized Nanostructures of Thermoresponsive Poly(N-

isopropylacrylamide) Block Copolymers Obtained Through Controlled RAFT Polymerization

2. Strandman, Satu: Syntheses and Self-Assembling Characteristics of Amphiphilic Star Diblock Copolymers

Master of Science 1. Aaltonen, Rami: Alifaattisten sulfobetaiinien polymerointi ja liuoskäyttäytyminen 2. Heiskanen, Laura: Phosphoric and phosphonic acids in high temperature fuel cells (in

Finnish) 3. Karjalainen, Erno: Polydimethylsiloxane based block copolymers (in Finnish) 4. Koponen, Anu: Fluorine containing block copolymers (in Finnish) 5. Laakso, Timo: Thermally induced aggregates of neutral poly(N-isopropyl-

acrylamide), poly(N-vinyl caprolactam) and poly(vinyl methyl ether) and their stability in water at elevated temperatures

6. Laari, Pasi: Polymer bound enantioselective catalysts (in Finnish) 7. Niskanen, Jukka-Pekka: Polymer protected silver nanoparticles 8. Riihelä, Simon: Homo and copolymers of diallyldimethylammonium chloride as

flocculants (in Finnish) 9. Zhao, Yiming: Thermoresponsive Oligomer Brushes Grafted to Gold Nanoparticles

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LABORATORY OF RADIOCHEMISTRY

The Laboratory of Radiochemistry is the only radiochemical institute in the Finnish universities. The main tasks of the laboratory are to teach and study the chemical behaviour and use of radionuclides, as well as to educate new radiochemists for special assignments, e.g. the control of environmental radioactivity, the safe disposal of nuclear waste and the medical use of radionuclides. The master’s programme of the laboratory covers most aspects of radiochemistry. The courses include principles of radioactivity, radiation safety, analytical chemistry of radionuclides, detection and measurement of radionuclides, radiation chemistry, environmental radioactivity, tracer techniques, chemistry of the nuclear fuel cycle, atmospheric radioactivity, chemistry of the uranium series in the environment and radiopharmaceutical chemistry. Every year two doctor’s degrees, in average, and four to five master’s degrees in radiochemistry are granted.

Personnel Teaching staff Jukka Lehto, Ph.D., Professor, Head of the Laboratory Risto Harjula, Ph.D., Doc., Senior Lecturer Kerttuli Helariutta, Ph.D., Senior Laboratory Manager Teija Koivula, M.Sc., Teaching Assistant Marja Siitari-Kauppi, Ph.D., Senior Lecturer

External senior lecturers (docents) Jukka Hiltunen, Ph.D. Sirkka-Liisa Karonen, Ph.D. Jussi Paatero, Ph.D. Mikael Paronen, Ph.D. Rolf Rosenberg, Ph.D. Olof Solin, Ph.D.

Research staff Anu Airaksinen, Ph.D. Heini Ervanne, Ph.D. Nina Huittinen, M.Sc. Pirkko Hölttä, Ph.D. Jussi Ikonen, MSc. Lalli Jokelainen, M.Sc. Maarit Kelokaski, M.Sc. Risto Koivula, Ph.D. Merja Lusa, M.Sc. Leena Malinen, M.Sc. Airi Paajanen, Lic.Phil. Miia Pehkonen, M.Sc. Esa Puukko, M.Sc. Susanna Salminen, M.Sc. Mirkka Sarparanta, M.Sc.

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Juhani Suksi, Ph.D., Doc. Kaisa Vaaramaa, Ph.D.

Assisting persons Sanna Kantola Mari Lahtinen Suvi Lamminmäki Risto Paintner Ville Salo Jussi Segler Miira Sivenius Venla Turtiainen Kirsi Ämmälä

Administrative and technical staff Martti Hakanen, M.Sc., Laboratory Manager Raimo Hyttinen, Laboratory Technician Jarno Jalomäki, M.Sc., Laboratory Manager (acting) Stewart, Makkonen-Craig, M.Sc., Laboratory Manager (acting) Tuija Suoranta, Secretary Katrin Lehiste, Cleaner

Visiting research scientists Edgar Berrezueta, Research Scientist PhD, Departamento de Geología, Universidad de Oviedo, Spain Emad Borai, professor, Egypt Atomic Energy Authority, Cairo, Egypt Daniel Breitner, Ph.D. student, Eötvös University, Budapest, Hungary Evgenia Gromova, V.G. Khlopin Radium Institute, Russia Vladimir Jakovlev, V.G. Khlopin Radium Institute, Russia

Research activities Research projects in the Laboratory of Radiochemistry are mainly application-ori-ented and their main purpose is to meet with the interests of the Finnish society in the fields of behaviour and use of radionuclides. The largest projects are related to the management and final disposal of radioactive waste and spent nuclear fuel from nuclear power plants. Migration and retention of radionuclides in the geosphere are being investigated for the analysis of the long-term safety of the final disposal of spent fuel in bedrock repositories. The laboratory has also developed a wide range of inorganic ion exchangers for the selective removal of radionuclides from nuclear waste effluents. Three of these exchangers are being manufactured and utilized at industrial scales. The cyclotron of the Laboratory of Radiochemistry produces mainly 18F and almost ten hospitals in Finland have used a PET imaging radiopharmaceutical [18F]FDG which has been produced in the premises of the laboratory by a radiopharmaceutical company. Also, new PET radiopharmaceuticals, labelled both with 18F and 11C, are being investigated and developed for their prospective use in PET imaging in clinical diagnosis and in drug development. The oldest field of research in the laboratory is the study of environmental radioactivity that begun already at the beginning of the 1960s. Since

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then, the behaviour of natural radionuclides and radionuclides from nuclear weapons tests and the Chernobyl fallout have been studied in the environment and in food chains. Development of analytical methods for the determination of radionuclides in the environment and in nuclear waste is also an important task of the laboratory.

Inorganic ion exchange materials for nuclear waste treatment Many inorganic ion exchange materials exhibit very high selectivities, exceeding those of organic resins, for metal cations. This makes them suitable for separating trace impurities or pollutants from solution. Today, inorganic ion exchangers are mainly used in “niche” applications, e.g. in detergents for the removal of water hardness and for the separation of some radionuclides from nuclear waste effluents. There is, however, a large potential for other applications, as new families of mi-croporous materials have been and are being made available by synthesis chemists.

Long-term research has been carried out by Ion Exchange Group to develop new highly selective ion exchange materials (e.g. Fig. 1) and processes for the treatment of radioactive waste liquids. Several new inorganic ion exchangers have been developed during the past decade. These include CsTreat , SrTreat and CoTreat , which have been commercialised by Fortum Nuclear Services Oy (FNS, Finland) and which are now being used in various nuclear sites world-wide, e.g. in Finland, Russia, UK and USA, for the purification of nuclear waste effluents. The Ion Exchange Group continuously supports new applications by carrying out testing for specific end-user needs.

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Figure 1. Evaporator concentrate purification system utilising CsTreat material at Loviisa NPP, Finland (left). Removal of Sb-124 from Loviisa Unit-1 primary coolant water by lab column packed with new developmental metal oxide material (right).

Presently the R&D work is focused on the “difficult” separations of radionuclides, e.g. from acidic decontamination solutions and from organic liquids, using novel inorganic materials. A new TEKES-funded programme is underway in cooperation with FNS and Kemira Oy to develop novel multifunctional (adsorption, ion exchange, oxidation) materials for the removal of organic pollutants (including

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radioactive organometallic complexes such as 60Co-EDTA) from solution. Also new materials are under development that can remove oxo-anionic pollutants, e.g., antimonate, chromate and pertechnetate ions from solution with a high efficiency. Recent test carried out using novel metal oxide material demonstrated very efficient removal of Sb-124 (decontamination factor 1000-30000) from the primary coolant water from Loviisa nuclear power plant.

In KETJU research programme funded by Academy of Finland, a project is underway in co-operation with Lappeenranta University of Technology to prepare manganese oxide sorbents from waste effluents of mining industry. Actinide-lanthanide separations with inorganic materials for future nuclear fuel cycles are studied in a project steered by State Research Centre (VTT) under the National Research Programme on Nuclear Waste Management (KYT). (Harjula, Koivula, Paajanen, Malinen).

Study of natural redox perturbations in the bedrock A prerequisite for safe disposal of spent uranium fuel in underground repository is chemically stable and reducing conditions in the repository. Whether this is the case for sufficiently long time is difficult to demonstrate because future repository conditions can only be estimated by modelling. It is known that unstable conditions may occur during the next Ice Age when oxidising melt water recharges into the anoxic bedrock but what would be real range of action is unclear. In addition to modelling there is another way to approach the problem, namely to study the influence of earlier Ice Ages. This is our approach. The approach consists of investigations on uranium behaviour in groundwater system and simulated groundwater conditions in laboratory. Uranium is an excellent tracer since it is sensitive to redox-conditions. Uranium has two stable oxidation states in natural conditions: mobile U(VI) and immobile U(IV). In oxidising conditions U(IV) oxidises to U(VI). If U has mobilised in the past this can be shown by the U decay series measurements provided that the mobilisation event is not older than few hundreds of thousands of years. The features in the 238U decay series that can be linked to redox changes are 230Th/234U and 234U/238U activity ratios that deviate from unity. Both ratios can be measured accurately. Study of future repository conditions is an important part of the Finnish and Swedish nuclear waste research programmes. The topic is also under investigation in the 7th EU framework programme’s ReCoSy project. The Laboratory of Radiochemistry is in on all above mentioned research programmes.

Finnish Research Programme on Nuclear Waste Management (KYT 2010) The title of our project in the programme is “Uranium behaviour as an indicator for groundwater conditions”. In 2008 we focussed on testing our water-rock-interaction (WRI) simulator. WRI simulator was constructed specifically to study the linkage of redox-conditions and 234U/238U fractionation occurred during uranium dissolution. The fact that 234U and 238U can dissolve from rocks in the ratio that is different as their original ratio is based on the different origin of the isotopes. 238U is primordial and its valence state is determined solely by the redox-conditions. 234U is a decay product of 238U that is why its valence state is additionally affected by preceding radioactive chain decay which facilitates 234U to be born in hexavalent

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state. Thus, 234U can occur in both hexavalent and tetravalent states the portion of hexavalent 234U depending on 238U decay time. The WRI simulator can be used to study 234U/238U release ratio in redox-conditions that covers natural solid/aqueous boundaries for U which helps us to better interpret 234U/238U activity ratios observed in the groundwater. WRI simulator consists of two main parts, a water-rock interaction simulator (Fig. x) which is used to prepare groundwater simulants and reactors which will be placed in the N2 glove-box. The simulator consists of massive rock source (~20 kg of crushed rock) placed inside 15 l stainless steel cylinder and flow through cell with positions for four electrodes. The flow-through cell has been designed specifically to allow electrode removal and insertion without disturbing the system. We have been able to prepare groundwater simulants with EH low enough (EH< -100 mV) to study 234U/238U fractionation in natural EH range. (Suksi, Kaksonen).

Figure 2. Water-rock interaction (WRI) simulator. Simulator consists of (1) stainless steel cylinder filled with crushed granite rock, (2) flow-through cell for on-line monitoring of pH, EH, O2 and electrical conductivity, and (3) data logging system. Reservoir simulator (4) is in on the table.

Redox processes in radionuclide transport (EU ReCoSy, WP 5) Our laboratory participates in the EU-project ReCoSy (www.recosy.eu) its work package 5. ReCoSy (Redox-phenomena Controlling Systems) deals with different aspects of redox-controlled long-term behaviour of radionuclides in nuclear waste repository systems. WP5 aims at increasing understanding of the role of redox phenomena on far-field migration of radionuclides. Our main task in the project is to develop wet chemical method to separate hexavalent and tetravalent U from solid uranium. Relevant rock, mineral and sediment material are studied by total and selective dissolution of U followed by solution analysis. Isotope redox-tracers (232,233,236U) with different valence states are added to the sample before U dissolution to monitor redox equilibrium. In 2008 we focussed on improving our anoxic extraction system in order to minimise unwanted redox-reactions which might change original redox-equilibrium of U. We have found reduction of our

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hexavalent redox-tracer during the extraction. This is presumably caused by the ferrous minerals that release reductive Fe2+-ion during the extraction. Whether this is the case with natural uranium dissolving simultaneously with Fe2+-ions is under investigation. (Suksi, Salminen).

Study of changes in redox-conditions at Olkiluoto site (Posiva Co.) A new project dealing with redox-changes in the groundwater system at Olkiluoto study site was started. The aim of the project is to study redox-changes caused by recharging groundwater and glacial melt water. Traces of oxidative water-rock interaction are searched for by studying U series 230Th/234U and 234U/238U activity ratios on fracture lining rock materials. The project is linked to EU ReCoSy. (Suksi, Salminen, Kaksonen).

Sorption of long-lived radionuclides in soil at the Olkiluoto site In 2007 started a new project on migration of long-lived radionuclides from spent nuclear fuel in soil at the Olkiluoto site, Finland, where the final disposal of spent nuclear fuel from the Finnish nuclear power reactors is planned to take place in the future. Special attention in the project is put on anionic radionuclides (99Tc, 94Nb, 93Mo, 129I and 36Cl) and on uranium series nuclides. Soil samples have been taken from various soil layers from three-metre deep excavation holes. The soils have been characterized with respect to their geotechnical character, mineral composition and chemical properties. Sequential extractions have been performed for various grain sizes of soil layers to study association of elements in soil. In 2008 sorption studies on these soils were started with Tc, I and Cs. (Lehto, Lusa, Vaaramaa, Hakanen, Ämmälä)

Sorption and reactive transport of radionuclides Sorption of a solute to rock minerals is the chemical basis for retardation in groundwater transport of radionuclides. Understanding the mechanisms governing this interaction is necessary for measurement of the relevant sorption distribution ratios of radionuclides between groundwater and mineral phases. The interaction is influenced both by the chemical form of the solute and the properties of mineral surface both of which are dependent of the geochemical environment. A sorption model has been used to predict sorption at any relevant condition by using prede-termined equilibrium constants as thermodynamically meaningful input parameters.

The state-of-the-art report on the application of sorption models in prediction of radionuclide sorption on geologic materials surveyed in the NEA Sorption Project Phase II did not include sorption to crystalline rocks that are important to the Finnish disposal concept. The sorption models are an essential part of a more general reactive transport model. In 2008 started the NEA sorption Project Phase III aiming to produce a book on guidance for application of surface complexation approach in sorption. (Hakanen, Posiva)

The Laboratory of Radiochemistry participated 2005-2008 in the WP 1,2 of the EU-project FUNMIG (www.funmig.com) directed to the application of mechanistic sorption modelling of radionuclide interaction with minerals. The studies were directed to development of a sorption model for Ni and Eu on typical geological

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environments at the Finnish coastal region. Rocks were selected from the drilling core archive after scoping sorption experiments and mineralogical characterisation. Biotite was selected for further studies and separated from drill cores. The biotites that were separated from mica gneiss and granodiorite and a pure pegmatitic biotite from Luumäki were titrated for the determination of hydrolysis of the biotite surfaces. The cation exchange capacities of the biotites were determined by the ammonium acetate method. The sorption of nickel and europium on the biotites and on crushed rock was studied in 0.05 M and 0.5 M NaClO4 solutions for the pH range 4-9. Cation exchange reactions and the 1-pKa surface complexation model were applied to modelling the sorption of Ni and Eu. In parallel to experimental studies, a molecular modelling approach was made to increase theoretical understanding of the sorption. This work was done in close co-operation with VTT, GSF and Posiva. (Puukko, Hakanen)

In the studies at Laboratory of Radiochemistry two formalisms in modelling of sorption was applied, cation exchange on permanently negative mineral surfaces and surface complexation on variable charge sorption sites. A cation exchange approach was applied to understand mechanistically the sorption interaction of the non-hydrolysable cations on permanently negatively charged minerals. Scoping of earlier data of sorption of important radionuclides in Olkiluoto geospheric conditions was made and new research programme was constructed to complement the earlier data. It was started by determination of sorption of thorium and selenium onto rocks from Olkiluoto and on quartz. (Ervanne, Jokelainen, Hakanen)

The relevance of colloids in promoting the transport of radionuclides Inorganic colloids are present in natural groundwater but colloids can also be produced from degraded Engineered Barrier System (EBS) materials. The bentonite buffer used in the EBS system is assumed to be a potential source of colloids. Colloids can also be produced from other degraded EBS materials such as copper container, and grouting materials as well as from uranium fuel itself. Release of natural colloids from the minerals can be enhanced due to drilling and excavation. The potential relevance of colloids for radionuclide transport is highly dependent on the release and stability of colloids in different chemical environments and their interaction with radionuclides. Existing information about colloids from EBS materials, colloid characterization methods, colloid mediated radionuclide migration, studies related to geological disposal of spent nuclear fuel and the relevance of colloids for radionuclide transport were reviewed in a state-of-the-art report. (Hölttä)

Silica colloids and their effect on radionuclide sorption Colloidal silica called silica sol (Eka Chemicals, Bohus, Sweden) has been tested in the underground rock characterization facility ONKALO in Olkiluoto for the sealing of the fractures of the hydraulic apertures less than 0.05 mm. To use silica sol as a grout, the injected colloids have to aggregate and form a gel within a predictable time by using an accelerator. The use of colloidal material has to be considered in the long-term safety assessment of a spent nuclear fuel repository. The release and stability of silica colloids from the silica sol gel stored in contact with low salinity Allard and saline OLSO reference groundwater (pH 7–11), in

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deionized milliQ water, NaCl and CaCl2 solutions (10-2 – 10-7M) were followed by analyzing the particle size distribution, zeta potential, pH, colloidal particle and reactive silica concentration. The sorption of Europium–152 on silica sol colloids was determined in OLSO and Allard reference groundwater. Batch sorption experiments were carried out by adding Eu–152 tracer solution to silica sol solution diluted with reference groundwater with adjusted pH values 7–11. The solid phase was separated by filtration using 25 nm MCE membranes or by 40 minute ultra-centrifugation using 80000 rpm corresponding average G-force of 500000.

The release and stability of silica colloids were significantly dependent on groundwater salinity. In low salinity Allard, particle size distribution was rather constant and the mean particle diameter remained less than 100 nm. High negative zeta potential values indicated the existence of stable silica colloids. In saline OLSO, particle size distribution was wide from a nanometer scale to thousands of nanometers. The disappearance of large particles, decrease in colloidal particle concentration and zeta potential near zero suggest flocculation or coagulation. Europium sorption on silica sol colloids was significantly dependent on solution pH. The Kd–values were 2–10 m3 kg-1 for pH 7–8 and 100–140 m3 kg-1 for pH 10–11 reference groundwater. In the samples of the highest pH, almost the entire tracer was rabidly sorbed on colloids resulting in inaccurate Kd determination. (Hölttä, Hakanen)

Radionuclide transport in granitic rock Since the end of 1970s, when the first nuclear power reactors were installed in Finland, one of the major research fields in the Laboratory of Radiochemistry has been the studies related to the safety of the final disposal on spent nuclear fuel. The Laboratory has studied extensively the migration and retention of radionuclides in the geosphere.

Characterisation of pore space geometry using 14C- and 3H- PMMA impregnation and autoradiography Investigations related to the material properties of geological formations that serve as host rocks for nuclear waste repositories require different methodological approaches. The evaluation of the transport and retardation properties of rock matrices proceeds from thorough rock pore space characterisation. The relevant rock properties to be quantified are (i) the accessible internal pore volume that determines the diffusive transport/retardation of non-sorbing and slightly sorbing radionuclides and (ii) the accessible internal surface area that controls sorption/fixation of radionuclides and chemical interactions. These properties are linked to the spatial porosity distribution of the rocks.

Over last two decades, the PMMA method has been used for characterisation of pore space geometry of low permeable granitic rocks as well as for porosity determination of consolidated clays. Impregnation with 14C or 3H labelled methylmethacrylate (MMA) and autoradiography allows the determination of the spatial distribution of porosity. Quantitative measurement of total or mineral-specific, local porosities are also provided using image analysis tools. Furthermore, a new imaging technique is introduced. Radioactivities as well as fluorescent dyes from 2D matrices can be analysed by the digital photostimulated luminescence autoradiography (FLA-5100 scanner, Fuji). The sensitivity and the linearity are increased compared to the conventional film autoradiography technique. Scanning

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electron microscopy with energy dispersive X ray spectroscopy and Hg-porosimetry are used alongside with the PMMA technique.

The porosities of rock matrices adjacent to water conducting fractures and the excavation damages were studied on samples taken from Onkalo Facility at Olkiluoto. The research was financed by Posiva Oy and Svensk Kärnbränslehantering AB. The work was conducted in co-operation with Saanio&Riekkola Consulting Engineers and Geological Survey of Finland. (Jussi Ikonen, Suvi Lamminmäki, Marja Siitari-Kauppi)

Long term diffusion project (LTD) and quantifying diffusion rates through crystalline rock matrices (Geochem) Investigations in the Underground Rock Laboratory at the Grimsel Test Site (GTS) in Switzerland continued under the international research project cluster GTS Phase VI; the Long Term Diffusion Experiment project (LTD).

The LTD project aims at obtaining quantitative information on matrix diffusion in crystalline rocks. Both in situ and laboratory-based experiments are included. An in situ monopole diffusion experiment aims to quantify the extent of matrix diffusion in an undisturbed rock matrix. In addition, in situ porosity and pore connectivity are studied separately by impregnation experiments. The project focuses on comparison of field and laboratory data. Full characterisation of the spatial distribution of porosity in the matrix, and its link with the mineralogy is performed in order to better identify microstructure-derived residence time distributions in the matrix.

The evidence of the uranium migration /fixation in naturally rich uranium deposit was searched in the project Geochem. The aim was to provide an indication of how uranium could retain to the surrounding bedrock if released from the nuclear waste canisters to the bedrock. Uranium phases that occupy inter- and intra-granular porosity within crystalline rock matrices are studied using beta/gamma autoradiography and alpha radiography to select locations for subsequent microscopic investigations. The selected uranium enrichments are studied by electron microscopy and initial chemical analyses are performed by energy dispersive X ray spectroscopy. Isotopic ratios of uranium were studied with LA-ICP-MS technique to define the nature of the conditions in which uranium was precipitated. The geochemical modelling exercises of the processes started at the end of the year 2008.

Japan Atomic Energy Agency (JAEA), the Nuclear Research Institute ež (NRI) from Czech republic and the University of Poitiers; Hydrogeologie, Argiles, Sols et Alterations. (http://www.grimsel.com).

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Figure 3. Picture A. Back scattered electron images show uranium enriched in goethite especially in a rim around the nodules. Drill core sample from Askola, Finland.

The research was financed by the Ministry of Employment and Economy and is part of the project cluster “Finnish research programme on nuclear waste management”. The international collaboration team consists of the National Cooperative for the Disposal of Radioactive Waste (NAGRA) from Switzerland, the Japan Atomic Energy Agency (JAEA), the Nuclear Research Institute ež (NRI) from Czech Republic, the University of Poitiers; Hydrogeologie, Argiles, Sols et Alterations from France and the University of Reading, School of Human & Environmental Sciences from Great Britain. The finnish colleagues come from the Helsinki University of Technology/Geoenvironmental laboratory, the University of Jyväskylä, Department of Physics and Geological Survey of Finland. (Lalli Jokelainen, Jussi ikonen, Maarit Kelokaski, Marja Siitari-Kauppi) (http://www.grimsel.com)

Geochemical study of different soil and sediment samples from Askola, Palmottu and Olkiluoto: basis for the assessment of radon emission Daniel Breitner, Lithosphere Fluid Research Laboratory, Eötvös University, Hungary studied radon sources in different types of sediments and soils. The research program is based on a series of case studies at undisturbed natural sites including area with average uranium content, as well as uranium mineralization. Presence and distribution of easily removable such as, adsorbed, ionic bound etc. and in crystal lattice persistently bound uranium and radium were analyzed in collected soil horizons and sediments. To separate these soil constituents, selective leaching technique were used. Following the extraction, multiple elemental ICP-MS and liquid scintillation counter (LSC) analyses were carried out on the leachates. The activity concentration ratios of radium and uranium in different type of soils and sediments indicate the behaviour of these elements during weathering and soil formation processes. To better understanding of weathering effects on uranium bearing minerals as a major source of persistently bound uranium, we analyzed the chemical composition and textural relations of weathered and unaltered part of minerals using SEM-EDAX and EPMA techniques.

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Figure 4. Picture B. Sampling site in Palmottu, Finland.

The results will build up a scientific basis (i) to better understand the relation of radon emission and geochemical processes in different geological samples, (ii) to estimate the consequences and risks of uranium mining, and (iii) to provide confidence in the geosphere parts of the safety assessment of a geological nuclear waste repository as a basis for a safety evaluation.

The work was partly financed by Centre for International Mobility (CIMO) and it was done in collaboration with Radiation and Nuclear Safety Authority (STUK) and Geological Survey of Finland (GTK). (Daniel Breitner, Jussi Ikonen, Marja Siitari-Kauppi)

Solid-water interface chemistry: Sorption of trivalent actinides onto aluminum(hydr)oxide and clay minerals Deep geological formations are considered for the long-term disposal of radioactive waste. If ground water penetrates the repository, the release of actinides and other radionuclides into the biosphere by migration with groundwater is possible. Solid-water interface reactions belong together with redox- and complexation reactions in solution, to the important geochemical processes determining radionuclide mobility in a natural system. The long-term radiotoxicity of nuclear waste is dominated mainly by transuranium elements plutonium, neptunium, americium and curium. In deep geological formations where oxygen is absent, the actinides are usually found in their reduced oxidation states III and/or IV. Work has been done to understand the retention mechanisms of trivalent actinides on aluminum hydroxide and clay mineral phases. Batch studies have been performed with inactive lanthanide homologues to gain information on the macroscopic sorption behaviour of trivalent metal ions. For speciation purposes time-resolved laser fluorescence spectroscopy

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has been utilized. Due to the specific, environment dependent f-f transitions in actinides, TRLFS is an extremely useful tool to account for the complex speciation of these elements. Cm(III) exhibits excellent fluorescent properties and can be detected in concentrations as low as 10-12 M. It was therefore chosen to represent trivalent actinides in all fluorescence studies. TRLFS work has been done in collaboration with the institute for nuclear waste management (INE, FZK) in Karlsruhe, Germany. Cm(III) complexes on mineral surfaces have been identified from TRLFS data. Emission spectra provide information about the nature and number of complexes, while hydration state data can be extracted from recorded lifetime measurements. NMR studies will be performed in collaboration with the National Institute of Chemical Physics and Biophysics in Tallinn to gain insight in the specific metal ion sorption places on the mineral surfaces. The project is funded by the Finnish national programme (KYT2010). (Huittinen)

Environmental research Behaviour of 210Po and 210Pb in forest environment The general goal was to obtain overview on naturally occurring 210Po and 210Pb behaviour and mobility in forest environment. Binding and mobility of 210Po and 210Pb in soil was studied, as well as transfer of polonium and lead from soil to plants. The activity concentrations of the Chernobyl fallout 137Cs were analysed as a point of comparison.

The soil samples were collected from seven different locations in Finland. The main study areas were located in Scots pine forests in southern and northern Finland. The soil profiles were divided into horizontal layers: litter, organic and mineral soil layers. The vertical distribution of 210Po and 210Pb in soils was determined. In addition to radionuclides, the total element concentrations of soil samples were analysed. Blueberry, lingonberry and mushroom samples were also collected from the study areas. The activity concentrations of 210Po, 210Pb and 137Cs were analysed from roots and rhizomes of the berry samples as well as from berries (i.e. fruits), leaves and stems separately. Mushrooms were divided into caps and stipes and the activity concentrations of 210Po, 210Pb and 137Cs were analysed.

The research results gained in this project will enable an assessment of the mobility of 210Po and 210Pb in the environment and in the food chains and estimation of ensuing radiation doses to humans. (Vaaramaa, Lehto)

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Heavy metal pollution in lakes in the northwestern Russia In 2008 a project on the behaviour of toxic heavy metals (Cu, Ni, Co, Zn, Pb, Hg, Cd) and radionuclides (137Cs) in aquatic ecosystems in the surroundings of the Kostomuksha iron ore and ore dressing mill, was completed. The plant is located only 40 kilometres east of the Finnish border. Surface water samples and sediment cores were collected in 2007. Metal concentrations were determined with ICP-MS from the water samples and from 1-cm vertical slices of the sediment cores. The purpose of the study was to explore the metal pollution effects of the ore and the mill on the surrounding lakes both via air and water transport. In the air transport route to the southwestern direction two lakes were sampled on the Russian side and another two on the Finnish side in Kuhmo. There are rather large metal-bearing effluent discharges into the Kentti river to the Northeast where four lakes were sampled in Russia. The maximum sampling distance in both directions was 60-70 km. No increase of these elements was observed in lakes in southwestern direction towards Finland where air transport was the only pathway. In the northwestern direction increasing concentrations of Ca, Mn, S, Fe and As towards the plant were seen both in water and sediments phases. This was also the trend for Na, K and Mg in water and for Zn, Pb, Cd and Hg in the sediment. No systematic change was seen in case of Al, P and Ni. It is likely that elevated water concentrations of at least K, S and As are due to water releases from the waste pond but for other elements the source is not quite evident. Collaborating institutes within project have been University of Helsinki, Department of Geography and Department of Geology, Finnish Meteorological Institute, Kainuu Regional Environment Centre, Finnish Environment Institute, Joensuu from Finland and Kostomuksha Nature Reserve, Russian Academy of Science, Karelian Research Centre, from Russia (Lehto, Lusa).

Speciation of radionuclides in the environment Jukka Lehto has participated in a Nordic Nuclear Safety (NKS) project Speciation Analysis of Radionuclides in the Environment. Other partners in the project have been Risö National Laboratory, Denmark, Norwegian University of Life Sciences, University of Uppsala, Sweden and Institute of Physics, Lithuania. Laboratory of Radiochemistry has reported within the project on its metal and radionuclides speciation studies with sediments from Kola Peninsula. (Lehto)

Radiopharmaceutical chemistry Radiopharmaceutical chemistry includes selection, radiosynthesis and preclinical evaluation of radiolabelled compounds. As a multidisciplinary research field it combines knowledge from medicinal and organic chemistry, radiochemistry and biomedical sciences. Research in radiopharmaceutical chemistry research group includes development of new synthetic methods for radiolabelling with positron emitting radionuclides and development and preclinical evaluation of new radiopharmaceuticals for drug development and nuclear imaging.

Applications Radiopharmaceuticals i.e. tracers labelled with short living positron emitting ( +) radionuclides are applied in positron emission tomography (PET). The main advantage of this tomographic imaging technique is that it permits us to follow biodistribution and binding of administrated radiolabelled tracers in vivo, non-invasively and with negligible signal attenuation dependent on the depth of the

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signal source. Due to this feature, radiopharmaceuticals are widely used in nuclear medicine as diagnostic agents, in drug development in preclinical and clinical stage, and in biomedical research for studying disease mechanisms as well as normal physiology.

Figure 5. Radiopharmaceutical research facilities at Laboratory of Radiochemistry.

Radiopharmaceutical research Main interest of our research is in radiopharmaceuticals labelled with positron ( +) emitting radionuclides carbon-11 (t1/2 = 20.4 min) and fluorine-18 (t1/2 = 109.7 min). Due to the short half-lives of these radionuclides, synthesis and biological evaluation of PET radiopharmaceuticals has to be performed in close proximity to a cyclotron, in which radionuclides are produced. The IBA 10/5 cyclotron located in the basement of our laboratory has provided 18F for the radiopharmaceutical research since 1998 (Figure 5). In 2007, a target for the production of 11CO2 was installed, which enables research with a wider selection of biologically active compounds.

Development of new radiosynthetic approaches is a pivotal part of radiopharmaceutical research. In 2008, palladium catalyzed cross-coupling reactions with 11CO2 were studied for synthesizing 11C labelled aromatic ketones. New solvent systems were explored aiming to more effective [18F]fluorinations: protic solvents for nucleophilic fluorination reactions with anionic 18F- were studied and compared to commonly used aprotic solvents. In collaboration of other research groups at University of Helsinki and in other Finnish Universities, new radiolabelling methods were also developed for evaluation of particle based drug delivery with radionuclidic methods. A longer living -emitting 131I was exploited in determination of targeting efficiency of oncolytic adenovirus therapy of prostate cancer in mice.

The project for developing new radiopharmaceuticals for studying receptors in the CNS (central neuronal system) was continued and its sub-project in tracer development for imaging of monoamine receptor system in the brain was finalized and the results reported. The project was carried out as a scientific collaboration

Radionuclide production

Cyclotron: IBA cyclone 10/5 installed: 1998 18F and 11C

Radiosynthesis and purification

Characterization and quality control

Shielded hot cell: Radiosynthesis modules

Methods: TLC, HPLC MS, NMR

Preclinical evaluation

Methods: Biodistribution Autoradiography

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with Turku PET Center. PET tracers can be used for following progression of CNS diseases and effects of drug treatment, as well as in drug development. Radiolabelled cocaine analogues, such as -CFT and its derivatives, can be used in diagnosis of a variety of CNS diseases such as in Parkinson’s disease. Within the project, we developed methods for labelling a cocaine analogue, N-(3-fluoropropyl)-2 -carbomethoxy-3 -(4-fluorophenyl)-nortropane ( -CFT-FP) with 18F. The tracer [18F] -CFT-FP was evaluated in pre-clinical studies in rats (Figure 8.).

Figure 6. Radiosynthesis of [18F] -CFT-FP and evaluation of its binding to dopamine transporters in rat brain. A. Ex vivo autoradiography in rat brain sections at 15 min. B. Specific binding after blockade with GBR12909.

Industrial collaboration One of the most widely used radiopharmaceuticals in nuclear medicine is FDG (2-[18F]fluoro-2-deoxy-D-glucose). FDG is an 18F-labelled glucose analogue, which is used in clinical PET imaging for assessment of glucose metabolism. FDG accumulates into tissue with high metabolic activity, which is exploited especially in oncology in localizing tumour tissue and its possible metastases. [18F]FDG has been synthesised in our laboratory since 2000 by MAP Medical Technologies Oy, starting from 18F radionuclide produced with our cyclotron. In 2008, production of [18F]FDG for clinical PET studies continued in our laboratory and it was used for diagnostic studies in several hospitals in Finland. (Airaksinen, Helariutta, Jalomäki, Koivula, Lipponen, Makkonen-Craig, Sarparanta)

The cyclotron in the Laboratory of Radiochemistry The Laboratory of Radiochemistry has an IBA 10/5 cyclotron that is specially designed for the production of light positron emitting radioisotopes. The cyclotron is able to accelerate both protons and deuterons, up to fixed energies 10 MeV and 5 MeV, respectively. The maximum beam intensity for protons is 80 A and for deuterons 40 A.

In year 2008 the total running time of the cyclotron was around 826 hours. Most of the beam time was used for the production of radioisotope 18F for

A. B.

NH O

O

F

NO

O

F

F18

F(CH2)3SO318

DMF, 135 oC, 25 min

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radiopharmaceutical purposes. 18F was utilized in the radiopharmaceutical research in the Laboratory of Radiochemistry as well as for commercial [18F]FDG production by MAP Medical Technologies Oy. Produced activity in 2008 was appr. 32 TBq (19 TBq in 2007), increasing the production with about 70% in compared to the year before. Along with 18F, 11C was produced routinely for radiopharmaceutical tracer studies. The total activity of 11C produced in 2008 was appr. 76 GBq.

In addition to the radiopharmaceutical applications the cyclotron has been used for the studies of production of heavy, short-lived radionuclide tracers. The collaboration with the Laboratory of Polymer Chemistry and with Arcada Polytechnic continued in the area of radiolytic functionalisation of polymer films. (Helariutta, Hyttinen, Jalomäki, Makkonen-Craig, Hatakka, Jokelainen, Salo, Segler, Paintner, Pehkonen, Turtiainen)

Production of short-lived actinide tracers Short-lived radioisotopes of neptunium and plutonium are needed in environmental research and studies of safe disposal of radioactive waste, but their commercial availability is limited. This has motivated the series of experiments done in collaboration with scientists from the Laboratory of Radiochemistry and V. G. Khlopin Radium Institute, St. Petersburg, Russia in which the most efficient way of producing short-lived actinide tracers has been investigated.

In year 2008 the study was combined with an experimental course on radionuclide production. The course was attended by six undergraduate students, taking actively part into the research work. A stack of thin foils of 237Np and 238U were irradiated in IBA 10/5 cyclotron with protons having energies from 6.4 to 9.8 MeV, resulting in extending the excitation functions of 238U(p,xn) and 237Np(p,xn) with n = 1,2 to previously unexplored low energies. The irradiations were followed by chemical separations of different actinide elements and fission products in the irradiated targets. (Gromova, Jakovlev, Aaltonen, Helariutta, Kantola, Keinänen, Lamminmäki, Salo, Turtiainen, Ämmälä)

Radiation chemistry Track etch membranes are an example of industrial applications of ion beam techniques and radiation chemistry. Track etch membranes have clear advantages over conventional membranes due to their narrow pore size distribution. The only known methods used in the production of track etch membranes are based on the use of C or heavier ions for ion beams.

Collaboration project between the Laboratory of Radiochemistry and Arcada (Department of Business Administration, Media and Technology) has been focused on the development of new methods allowing production of track etch membranes with lighter ions (protons and deuterium ions). Successful production of track etch materials by proton beam could decrease the production costs significantly.

Proton irradiation of polymer films with proton beam supplied with the cyclotron followed by subsequent etching has successfully produced track etch materials. The new materials have been characterized both with scanning electron microscope and gas permeation tests. According to the results obtained proton irradiation can be used to produce membranes for separation processes with as small pores as 100 nm. (Multia, Paronen, Helariutta, Jalomäki, Segler, Makkonen-Craig)

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Figure 7. Scanning electron microscope (SEM) image of typical track etched pore produced by proton beam irradiation. The pore diameter is approximately 500 nm.

Co-60 irradiation activities The laboratory has two Co-60 sources for irradiation activities, one (HOT-SPOT, 2.4 TBq) for small size samples in the basement of the present laboratory and one in the former laboratory building (Unioninkatu 25, TBq). The irradiation facility at Unioninkatu 35 is suitable for irradiation of a large number of samples at the same time and is also used for teaching of radiation chemistry. Irradiations for scientific purposes were made for projects within the Laboratory of Radiochemistry and for two external research organisations. The facility was under operation for 237 days during the year. The HOT-SPOT irradiation source was used for 48 irradiations during the year. (Hakanen)

Identification of irradiated foods According to the European Union Directive, of all foods only herbs and spices are allowed to be irradiated. The official control in Finland is the responsibility of the Finnish Food Agency, which closely co-operates with the Finnish Customs Labora-tory. After prescreening of foods by photostimulated luminescence (PSL), those samples showing signs of irradiation are analysed at our Laboratory by the ther-moluminescence (TL) method. The TL method is stated in the EN1788 standard. The analyzed foodstuffs included domestic market control samples: herbs, spices, frozen seafood and meat marinade products. A high portion of samples came from the European market. The control of irradiated foods has been monitored in Finland for about a decade, and it continues. (Paajanen)

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Publications

Refereed research papers 1. Koivula, T., Marjamäki, P., Haaparanta, M., Fagerholm, V., Grönroos, T.,

Lipponen, T., Perhola, O., Vepsäläinen, J., and Solin, O.; Ex Vivo Evaluatuion of N-(3-[18F]fluoropropyl)-2 -carbomethoxy-3 -(4-fluorophenyl)nortropane in Rats, Nucl. Med. Biol. 35 (2008) 177-183.

2. Sonck-Koota, P., Lindroos, A., Lill, J.-O., Rajander, J., Viitanen, E.-M., Marra, F., Pehkonen, M.H., Suksi, J. and Heselius, S.-J.; External-Beam PIXE Characterization of Volcanic Material Used in Ancient Roman Mortars, Nucl. Instrum. Methods Phys. Res. 266 (2008) 2367-2370.

3. Lehto, J., Paatero, J., Pehrman, R., Kulmala, S., Suksi, J., Koivula, T. and Jaakkola, T.; Deposition of Gamma Emitters from Chernobyl Accident and Their Transfer in Lichen-Soil Columns, J. Environ. Radioactivity 99 (2008) 1656-1664.

4. Noseck, U., Brasser, T., Suksi, J., Havlová, V., Hercik, M., Denecke, M.A. and Förster, H-J.; Identification of Uranium Enrichment Scenarios by Multi-Method Characterisation of Immobile Uranium Phases, Phys. Chem. Earth 33 (2008) 969-977.

5. Betti, M., Eriksson, M., Jenrström, J. and Tamborini, G.; Environmental Radioactive Particles: A New Challange for Modern Analytical Instrumental Techniques in Support to Radioecology, Radioactivity in the Environment 11 (2008) 355-370.

6. Hölttä, P., Siitari-Kauppi, M., Kelokaski, M. and Tukiainen, V.; Radionuclide Retardation in Granitic Rocks by Matrix Diffusion and Sorption, Mater. Res. Soc. Symp. Proc. 1107 (2008) 621-628.

7. Hölttä, P., Poteri, A., Siitari-Kauppi, M. and Huittinen, N.; Retardation of Mobile Radionuclides in Granitic Rock Fractures by Matrix Diffusion, Phys. Chem. Earth 33 (2008) 983-990.

8. Gräsbeck, R. and Sarparanta, M.; Preparation and Biodistribution of 32P-Labelled Hydroxocobalamin and Comparison with 57Co-Labelled Cobinamide and Cyanocobalamin, J. Label Compd. Radiopharm. 51 (2008) 59-63.

9. Airaksinen, A., Nag, S., Finnema, S. J., Mukherjee, J., Chattopadhyay, S., Gulyás, B., Farde, L. and Halldin, C.; [11C]Cyclopropyl-FLB 457: A PET Radioligand for Low Densities of Dopamine D2 Receptors, Bioorg. Med. Chem. 16 (2008) 6467-6473.

10. Kairemo, K., Erba, P., Bergström, K. and Pauwels E.K.J.; Nanoparticles in Cancer, Curr. Radiopharm. 1 (2008) 30-36.

11. Kairemo, K. and Bergström, K.; The Role of Radiopharmaceuticals in Drug Discovery, Curr. Radiopharm. 1 (2008) 1.

12. Avramenko, V.A., Bratskaya, S.Yu., Egorin, A.M., Markovtseva, T.G., Ryabushkin, A.N. and Harjula, R.; Nanosize Latexes Containing Polyacrylic Acid and Their Role in Transport and Immobilization of Radionuclides at Nuclear Energy Objects, Problems of Radiation Safety 4 (2008) 23-29 (in Russian).

13. Markovaara-Koivisto, M., Marcos, N., Read, D., Lindberg, A., Siitari-Kauppi, M. and Loukola-Ruskeeniemi, K.; Release of U, REE and Th from Palmottu Granite, Mater. Res. Soc. Symp. Proc. (2008) 1107.

14. Read, D., Black, S., Buckby, T., Hellmuth, K-H., Marcos, N., and Siitari-Kauppi, M.; Secondary Uranium Mineralization in Southern Finland and Its Relationship to Recent Glacial Events, Global and Planetary Change 60 (2008) 235-249.

15. Grahn, T., Dewald, A., Möller, O., Julin, R., Beausang, C.W., Christen, S., Darby, I.G., Eeckhaudt, S., Greenlees, P.T., Görgen, A., Helariutta, K., Jolie, J., Jones, P., Juutinen, S., Kettunen, H., Kröll, T., Krücken, R., Le Coz, Y., Leino, M., Leppänen, A.-P., Maierbeck, P., Meyer, D.A., Melon, B., Nieminen, P., Nyman, M., Page, R.D., Pakarinen, J., Petkov, P., Rahkila, P., Saha, B.,

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Sandzelius, M., Sarén, J., Scholey, C., Uusitalo, J., Bender, M. and Heenen, P.-H.; Lifetimes of Intruder States in 186Pb, 188Pb and 194Po, Nucl. Phys. A 801 (2008) 83.

Conference papers 16. Salminen, S., Paatero, J. and Makkonen, U.,U.; Concentrations of 238Pu, 239+240Pu,

241Am, 90Sr and 137Cs in Surface Air at Sodankylä (Finnish Lapland) in 1963, International Conference on Radioecology & Environmental Radioactivity, 15-20 June 2008 - Bergen, Norway, Posters Proceedings part 2, 277-280.

17. Vaaramaa, K., Aro, L., Solatie, D., and Lehto, J.; 210Po and 210Pb in Soil and in Vegetation in Finland, Proceedings of Int. Conf. on Radioecology & Environmental Radioactivity, 15-20 June 2008, Bergen, Norway, Oral & oral poster presentations, Proceedings – Part 1.

18. Vaaramaa, K., Solatie, D., Aro, L. and Lehto, J.; 210Po and 210Pb Forest Soil and in Wild Berries in Finland, The Natural Radiation Environment, Proceedings of 8th International Symposium (NRE VIII), Buzios, Rio de Janeiro, Brazil 7-12 October 2007, 260-263.

19. Sarparanta, M. and Gräsbeck, R.; Biosynthesis of 32P- and 57Co-Labelled Cobalamin and 57Co-Cobinamide and Their Biodistribution in Rats, Abstract.

20. Sarparanta, M., Jalomäki, J., Makkonen-Craig, S. and Airaksinen, A.; Development of Suzuki-Miyaura Coupling Reactions for 11C-Labelled Aromatic Ketone Synthesis with [11C] CO2, Abstract of the XI Turku PET Symposium, 2008 P15, (Kalliokoski, K., Oikonen, V. and Knuuti, J. eds.).

21. Salminen, S., Paatero, J., Roos, P. and Helariutta, K.; Deposition of 237Np in Finland, Strålevern Rapport 13 (2008), Proceedings of the NSFS XV Conference in Ålesund Norway, 26-30 of May 2008.

22. Alonso, U., Missana, T., García-Gutiérrez, M., Patelli, A., Siitari-Kauppi, M., Leskinen, A. and Rigato, V.; Micro-Scale Diffusion Experiments performed by RBS in Opalinus Clay, 3rd Annual Workshop Proceedings, 6th EC FP – FUNMIG IP, Edinburgh 26th -29th November 2007, 365-372.

23. Koivula, T., Muhonen, J., Lipponen, T., Perhola, O., Kämäräinen, E.-L. and Solin, O.; Assesment of Labelled Impurities during Radiosynthesis of p-[18f]mppf, Abstracts of the XI Turku PET Symposium, 24-27 May 2008, Turku, Finland.

24. Marjamäki, P., Haaparanta, M., Forsback, S., Koivula, T. and Solin, O.; Structure-Activity Relationship of Phenyltropanes; Comparison of [18f] -cft and [18f] -cft-fp As Pet Tracers in Rat, Abstracts of the XI Turku PET Symposium, 24-27 May 2008, Turku, Finland.

25. Lusa, M., Lehto, J., Leskinen, A., Hölttä, P. and Jaakkola, T.; 137Cs, 239,240Pu and 214Am in Bottom Sediments and Surface Water of Lake Päijänne, Finland, The International Conference on Radioecology & Environmental Radioactivity, 15-20 June, 2008 in Bergen, Norway, Proceedings Posters – Part 2.

26. Eberhard Falck, W., Read, D., Black, S., Thornley, D., Markovaara-Koivisto, M. and Siitari-Kauppi, M.; Understanding Uranium Migration in Hard Rocks, Uranium, Mining and Hydrogeology 2008.

Reports 27. Lehto, J., Lusa, M., Virkanen, J., Paatero J., Várkonyi, G., Heikkilä, R.,

Kashevarov, B. and Ieshko, E.; Metal Pollution in Lakes Surrounding the Kostomuksha Ore Dressing Mill in Northwestern Russia, Reports of Kainuu Regional Environment Centre 2/2008, pp. 20-33.

28. Paatero J., Makkonen, U., Hakola, H., Lehto, J., Várkonyi, G. and Heikkilä, R.; Metals and Aerosol Particles in the Atmosphere in Kainuu Province, Finland, Reports of Kainuu Regional Environment Centre 2/2008, pp. 7-13.

29. Paajanen, A. and Harjula, R.; Aktinidien ryhmäerotusmenetelmät ja niiden sekundäärijätteiden käsittely, Tutkimusraportti VTT-R-01919-08, 5.3.2008.

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30. Sandström, B., Tullborg, E-L., Smellie, J., MacKenzie, A.B. and Suksi, J.; Fracture mineralogy of the Forsmark Site, SDM-Site Forsmark, SKB R-08-102.

31. Hölttä, P. and Hakanen, M.; Silica Colloids and Their Effect on Radionuclide Sorption – A literature review, Posiva Working Report 2008-29, May 2008.

32. Paatero, J., Dauvalter, V., Derome, J., Lehto, J., Pasanen, J., Vesala, T., Miettinen, J., Makkonen, U., Kyrö, E-M., Jernström, J., Isaeva, L. andf Derome, K.; Effects of Kola air pollution on the environment in the western part of the Kola peninsula and Finnish Lapland – final report, Ilmatieteen laitos, Raportteja 6 2008.

Patents 33. Harjula, R. and Lehto, J.; Method for removal from radioactive waste liquids and

method for producing hexacyanoferrates, Japanese patent 4, 168, 172, 2008.

Theses Master of Science 1. Hatakka Antti: Radionuklidit ja raskasmetallit arktisissa järvissä 2. Lehto Jyri: Amerikiumin esiintyminen ja määritysmenetelmät ympäristönäytteissä 3. Jalomäki Jarno: Radioleimaus nukleofiilisellä [18f] fluoridilla: substituutioreaktiot

proottisissa liuottimissa 4. Jokelainen Lalli: Po-210:n selektiivinen uutto porakaivovesistä 5. Välimaa Ilkka: Hollandiittirakenteisten mangaanioksidien synteesi ja käyttö

radiostrontiumin erotuksessa 6. Söderlund Mervi: Zirkoniumoksidin sorptio-ominaisuudet ja oksoanionien

pidätysmekanismit

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LABORATORY FOR INSTRUCTION IN SWEDISH The Swedish chair of Chemistry was established in 1908 as the second oldest chair of chemistry in Finland. We notice that 2008 was in this sense a centennial year. The holder of the chair may represent any branch of chemistry but will lecture in Swedish, the second domestic language of Finland. Most students in this subdepartment belong to the Swedish-speaking minority of the country; others share the current scientific interests.

The somewhat unusual mission of the subdepartment has permitted it to pioneer both wood and lignin chemistry and, to an extent, theoretical and computational chemistry in Finland, while safe-guarding the constitutional, linguistic rights of the minority. The subdepartment offers both introductory courses and higher, M.Sc. and postgraduate courses.

Together with partners from the Laboratory of Physical Chemistry and the Department of Physics, a special honour that we obtained for 2006-2011 is the Finnish Centre of Excellence in Computational Molecular Science financed by The Academy of Finland and the University of Helsinki. The Finnish Centre of Excellence in Computational Molecular Science (''CMS'') had its third operating year in 2008.

Figure 1. We celebrate the 100th Anniversary of the Swedish Chair of Chemistry (1908-2008) by showing the recent numbers of the produced M.Sc (FM) and Ph.D. (FD) degrees. The M.Sc. statistics begin 1973. The number of original papers per years is also shown.

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Personnel Teaching staff Gustav Boije af Gennäs, M.Sc., Part-time Teacher Kristian Meinander, M.Sc., Part-time Teacher Michael Patzschke, PhD, Lecturer Pekka Pyykkö, Ph.D., Professor, Head of the Laboratory Nina Siegfrids, M.Sc., Part-time Teacher Anneka Tuomola, M.Sc., Part-time Teacher, Amanuensis Bertel Westermark, Ph.D., Lecturer Research staff and visitors Michiko Atsumi, Ph.D., postdoctoral scientist Krister Henriksson, Ph.D., Research Scientist Olli Lehtonen, Ph.D. (Techn.), postdoctoral scientist Ying-Chan Lin, M.Sc., Graduate Student Sergio Losilla, M.Sc., Graduate Student Janne Pesonen, Ph.D., Doc., Research Scientist Sebastian Riedel, Ph.D., postdoctoral scientist Johan Sjöblom, Ph.D., Prof., Doc. (Norway) Dage Sundholm, Ph.D., Doc., Senior Research Scientist Tommy Vänskä, M.Sc. (Eng.), Graduate Student Cong Wang, M.Sc., Graduate Student Patryk Zaleski Ejgierd, M.Sc., Graduate student Administrative and technical staff Raija Eskelinen, BBA, Secretary Bjarne Lindström, Eng., Laboratory Technician Susanne Lundberg, Dipl. Corr., Secretary (on leave)

Research activities

Quantum dots The computational methods implemented in our quantum-dot program package have been review in a perspective article published in Physical Chemistry Chemical Physics (Lehtonen O. et al.) (11.). The excitation energy spectra of biexcitonic systems confined in quantum-dot and quantum-ring systems were compared. Full correlation interaction calculations on the electron-hole systems show that the correlation effects are much larger for quantum rings than for quantum dots.

Density-functional studies of biomolecules and clusters Our silicon nanocluster calculations were reviewed in the PCCP perspective article (Lehtonen O. et al.) (11.) and in a book chapter (Lehtonen O. et al.)(17.). A comparison of excitation energies calculated at coupled-cluster (CC) and density functional theory (DFT) levels with experimental data shows that calculations with pure DFT functionals underestimate the optical gaps for silicon nanoclusters by

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about 0.8 eV. Time-dependent DFT (TDDFT) calculations using the most popular hybrid functionals yield excitation thresholds that are around 0.3 eV too small as compared to experiment. Approximate second-order coupled-cluster (CC2) calculations yield at the basis-set limit excitation energies in excellent agreement with experiment. The size dependence of the oscillator strength for the lowest excited state was obtained by fitting calculated data. The obtained curve was in reasonable agreement with the experimental one. However, neither the experimental nor the measured oscillator strengths indicate any strong luminescence for unsubstituted silicon nanoclusters. The calculations suggest that the strong photoluminescence observed for some silicon nanoclusters is not merely due to quantum confinement but functional groups at the cluster surface must be responsible for the light emission of bright silicon nanoclusters.

Figure 2. The exciton density is shown for a system consisting of silicon nanoclusters interconnected by a silane chain. The cluster size determines the excitation wavelength whereas the band strength depends on the length of the silane group. TDDFT and CC2 have been employed in studies of the photo-absorption process of the 11-cis-retinal protonated Schiff base chromophore. Ground-state DFT optimization of the retinal molecule with a molecular structure in the vicinity of the conical intersection as starting structure yielded a new curl-shaped retinal isomer. The curl-shaped isomer has a twisted structure at the C11=C12 bond where the isomerization occurs. The curl-shaped retinal structure might play a role for the photo-isomerization reaction. The positions of the two methyl groups on the retinyl chain seems to be optimal for the isomerization to occur at the C11=C12 double bond and not at the other double bonds of the retinyl chain (Send et al.)(12.).

Magnetically induced currents Magnetically induced current densities were calculated for hydrocarbon nanorings at the DFT level. The current densities were obtained using our Gauge-Including Magnetically Induced Current (GIMIC) method. The GIMIC calculations yielded rules to estimate the global and local ring-current strengths and current pathways. A hydrocarbon nanoring sustaining strong ring currents should be large and formally aromatic with many and large aromatic moieties along the edges For overall antiaromatic molecules, aromatic groups such as benzene, naphthalene, anthracene, and pyrene moieties localize the ring current making the global ring currents vanish. The 1H NMR shielding of the inner hydrogen correlates well with the strength of the current circling around the nanoring (Taubert et al.)(23.).

Magnetically induced current densities were calculated for a series of hydrocarbons consisting of hexadehydro[12]annulene rings alternatingly fused with benzenes. The GIMIC calculations show that all molecular rings of the studied

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molecules sustain paramagnetic ring currents. The new class of molecules is therefore coined polycyclic antiaromatic hydrocarbons. (Jusélius et al.)(18.).

Figure 3. Polycyclic antiaromatic hydrocarbons (PAAH) sustain paramagnetic currents in all molecular rings. The strengths of the currents (in nA/T) circling the rings are given. For comparison, the ring-current strength of a free benzene molecule is +11.8 nA/T.

Computational inorganic chemistry The predictions of possible new chemical species include the predicted Au72 by Karttunen et al (2). The symmetry of this theoretical object is interesting being both icosahedral and chiral (symmetry group I, not Ih). A further study on the stabilities of such “golden fullerenes Aun, n = 32, 50, 72 was published by Johansson et al. (22.). By using a different, TPSS density functional, they find both the n = 50 and 72 neutral fullerenes to be less stable than the corresponding compact clusters. Johansson’s previous n = 32 fullerene also survived at the relativistic level. Spin-orbit effects and zero-point energies slightly destabilize it. The Au32 fullerene is the most stable Au32 structure lying 28 kJ/mol below the compact Au32 cluster. Johansson et al. (6.) also studied both computationally and experimentally the 2D-3D structural transitions for the Aun

- anions, and established the cross-over point at n = 12. Thus, negatively charged gold clusters consisting of 12 or less atoms are planar. The experimental work at Karlsruhe used trapped-ion electron diffraction. The theoretical work included spin-orbit effects and used large basis sets.

Density functional theory (DFT) studies on the endohedral scandium carbide fullerene Sc3C2@C80 and its monoanion [Sc3C2@C80] showed that the system consists of a Sc3C2 moiety inside the Ih C80. First principles molecular dynamics simulations at the DFT level on the ps time scale indicated that the triangle formed by the scandium atoms jumps between orientations along the belt of the equatorial six-membered rings, while the confined carbide unit is engaged in a flipping motion through the Sc3 plane. The equilibrium geometry optimisations using large basis sets predict a trigonal bipyramidal structure, whereas a planar Sc3C2-moiety is obtained in the finite-temperature simulation. Sc3C2@C80 is best described as an equilibrium between the two static minimum structures. Calculation of the 13C NMR spectrum yielded strongly deshielded carbon atoms of the carbide implying an incorrect earlier interpretation of the experimental NMR spectrum. The neutral

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system with one unpaired electron was characterized by calculating the hyperfine coupling constants, the g tensor, as well as the paramagnetic NMR (pNMR) 13C shifts for the static isomers (Taubert et al.). (21.).

A possible new series of compounds of type L-(N+)-L was mapped by Riedel et al. (8). Here L was a group with a terminal lone-pair. Likewise with our former Lynen scholar Riedel (5), the energies and structures of trivalent Group-12 fluorides, such as MF3, [MF4]- or [MF5]- were determined, the anions being more stable. The dimers, such as M2F6, M=Zn, Cd, Hg, were more stable than the monomers, but still possessed exothermic decomposition pathways.

Our previous work on the first 32-electron systems of the type Pu@Pb12 was continued. It was realised that the experimentally known series U@C28 also has a perfect 32-electron bonding system. One example could have been a curiosity. Two are a principle. The work was accepted for JACS in 2008 (Dognon, Clavaguera and Pyykkö). Such molecules formally use all the 5f orbitals of the central actinide atom in their bonding.

A further paper on possible gold-glued nanosystems was published by Pyykkö and Zaleski-Ejgierd (1). It was proposed that polyauronaphtyridines could be bent to rings. The elastic properties of these ring molecules were compared with those of polyacenes. This was the first time that a series of molecules was treated as elastic bodies, an approach that worked surprisingly well for the in-plane deformation vibrations and the bending energies.

In our studies on aurophilicity, the basis-set limit was obtained for the first time (at MP2 level) by Pyykkö and Zaleski-Ejgierd (4) for the model systems [ClAuPH3]2 and [P(AuPH3)4]+. A very precise study on the geometries of the gas-phase coinage-metal cyanides MCN, M=Cu, Ag, Au, Rg could reproduce the recent experimental microwave-spectroscopic M-C distances to better than 1 pm accuracy (9). The vibrational frequencies are probably better than any available experimental estimates. This was an excellent test on how far the present quantum-chemical calculations can be carried. The third part of Pyykkö’s reviews “Theoretical Chemistry of Gold” was published (15).

An entirely new domain for our laboratory was our theoretical contribution to the understanding of the new boron-nitrogen based compounds that reversibly split and bind hydrogen (19). In addition to studying the reaction route, we coined the insight that the Coulomb attraction between the two counterions could in principle provide enough energy to split the H2 molecule. The syntheses were carried out in the Inorganic Chemistry laboratory.

With de Macedo, the geometries for a large number of M=CH2 systems were calculated (14). These data were used in later work by Pyykkö and Atsumi to determine double-bond covalent radii.

Nuclear moments, hyperfine properties and NMR parameters A review on “Year-2008 nuclear quadrupole moments” was published by Pyykkö (20). As a preliminary study on 5d96s2 2D states of the gold atom, the calculated magnetic hyperfine coupling constants were published by Bieron et al. (7). This work was later extended to a determination of the 197Au quadrupole moment and represents the limit of current, massive multiconfiguration Dirac-Fock (MCDF) calculations on atoms.

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Other topics Pyykkö and Elmi (10.) returned to deuteron quadrupole coupling in C6D6. The solid-state, single-crystal measurement of Pyykkö and Lähteenmäki in 1966 at 263 K had never been repeated nor extended. Now a “temperature-dependent Einstein model” was devised for the librational corrections to that intramolecular coupling tensor. The results were compared with a recent study in the groups of Jokisaari and Vaara. In view of the importance of aromatic hydrocarbons in chemistry, the obtained standard values of these parameters could be of wide interest. The group-theoretical aspects of nuclear quadrupole coupling tensors for different nuclear site symmetries were discussed the condition for the asymmetry parameter being 1 was new.

Numerical methods A novel finite-element approach for quantum chemical studies is being developed. The electrostatic potential is obtained from the corresponding charge density by a direct integration of the Coulomb interaction using tensorial finite-element Lagrange interpolation polynomials to span the charge density and the potential. Periodic boundary conditions have been implemented, making solid-state applications and defect-studies feasible.

Cooperation with secondary-school teachers and pupils

The cooperation between the Norsen upper secondary school and the laboratory, which started in 1994, continued through 2008 to the satisfaction of all partners involved. In 2007, the school cooperation was extended to "Munksnäs Högstadieskola" and "Gymnasiet Grankulla samskola". The pupils participated in specially planned experimental chemistry courses (laboratory exercises) comprising of theory and practice under the supervision of Nina Siegfrids. Additionally, a number of demonstrations (computational chemistry, presentation of a research laboratory, etc.) and laboratory exercises were arranged. Excellent marks were returned in the course evaluations. Our laboratory has also arranged a number of classic chemistry and computational chemistry demonstrations for schools in the Helsinki region. Our interest in the general training of teachers on every level continues and our laboratory participates in the continuous education of school teachers on all levels.The laboratory has a close collaboration with the National LUMACentre, “Svenska Matematiklärarföreningen” and “Resurscenter för matematik, naturvetenskap och teknik i skolan”.

Research collaboration Pyykkö was the chairman and Sundholm the coordinator for the Finnish Centre of Excellence (CoE) in Computational Molecular Science (CMS). The CoE in ''CMS'' is also one of the four members of the Nordic Centre of Excellence in Computational Chemistry (NcoECC) network. The other members are ''The Centre

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for Theoretical and Computational Chemistry'' (CTCC), Universities of Tromsø and Oslo, ''The Lundbeck Foundation Centre for Theoretical Chemistry'' (LCTC), Aarhus University and ''Centre of Computational and Systems Biology'' (CCMSB), Albanova University Campus Stockholm.

Peeter Burk from Tartu made his yearly visit.

Dr. Jean-Pierre Dognon (CEA) worked one week in the laboratory in August 2008.

Winter School The 24th Winter School in Theoretical Chemistry dealt with "Reactions on Surfaces - Towards Realistic Computational Modelling of Surface Reactions”. The lecturers of the winter school were Thomas Bligaard (Danish Technical University, Copenhagen), Karoliina Honkala, (University of Jyväskylä), and Ari Seitsonen (University of Pierre and Marie Curie, Paris). There were in all about 80 participants.

Honours Pyykkö was invited to University of California, Berkeley, as Seaborg Lecturer. He also spent January 2008 as Visiting Professor at École Polytechnique in Palaiseau, near Paris. The visit was instrumental for writing (10, 20) and the future 32-electron paper.

Publications Papers in refereed journals 1. Pyykkö, P. and Zaleski-Ejgierd, P.; From Nanostrips to Nanorings: the Elastic

Properties of Gold-Glued Polyauronaphthyridines and Polyacenes, Phys. Chem. Chem. Phys. 10 (2008), 114-120.

2. Karttunen, A.J., Linnolahti, M., Pakkanen, T.A. and Pyykkö, P.; Icosahedral Au72 :a Predicted Chiral and Spherically Aromatic Golden Fullerene, Chem. Commun, (2008), 465-467.

3. Johansson, M.P., Kaila, V.R.I and Laakkonen, L.; Charge Parameterization of Metal Centers in Cytochrome c Oxidase, J. Comput. Chem., 29, (2008), 753-767.

4. Pyykkö, P. and Zaleski-Ejgierd, P.; Basis-Set Limit of the Aurophilic Attraction Using the MP2 Method: The Examples of [CIAuPH3]2 Dimer and [P(AuPH3)4 ]+ Ion, J. Chem. Phys., 128, (2008), 124309-1.

5. Riedel, S., Kaupp, M. and Pyykkö, P.; Quantum Chemical Study of Trivalent Group 12 Fluorides, Inorg. Chem. 47, (2008), 3379-3383.

6. Johansson, M.P., Lechtken, A., Schooss, D., Kappes, M.M. and Furche, F.; 2D-3D Transition of Gold Cluster Anions Resolved, Phys. Rev. A, 77, (2008), 053202.

7. Bieron, J., Froese Fischer, C, Jönsson, P. and Pyykkö, P.; Comment on the magnetic dipole hyperfine interaction in the gold atom ground state, J.Phys. B: At. Mol. Opt. Phys. 41 (2008), 115002.

8. Riedel, S., Straka, M. and Pyykkö, P.; Theoretical Mapping of New L-(N+)-L Family of Species with Donor-Acceptor Bonding between N+ and Ligand L, THEOCHEM, 860, (2008), 128-136.

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9. Zaleski-Ejgierd, P., Patzschke, M. and Pyykkö, P.; Structure and Bonding of the MCN Molecules, M=Cu, Ag, Au, Rg, J. Chem. Phys., 128, (2008), 224303.

10. Pyykkö, P. and Elmi, F.; Deuteron Quadrupole Coupling in Benzene: Librational Corrections Using a Temperature-Dependent Einstein Model, and Summary. The Symmetries of Electric Field Gradients and Conditions for = 1, Phys. Chem. Chem. Phys., 10, (2008), 3867-3871.

11. Lehtonen, O., Sundholm, D. and Vänskä, T.; Computational Studies of Semiconductor Quantum Dots, Phys. Chem. Chem. Phys., 10, (2008), 4535-4550.

12. Send, R. and Sundholm, D.; The Molecular Structure of a Curl-Shaped Retinal Isomer, J Mol Model, 14 (2008), 717-726.

13. Pajunen, T.I., Johansson, M.P. Hase, T. and Hopia, A.; Autoxidation of Conjugated Linoleic Acid Methyl Ester in the Presence of -Tocopherol: The Hydroperoxide Parhway, Lipids, 43, (2008), 599-610.

14. de Macedo, L.G.M and Pekka Pyykkö, Bonding Trends in M=CH2 Systems: Simple Orbital Interpretation and Evidence for Double Bonds, Chem. Phys. Lett., 462, (2008), 138-143.

15. Pyykkö, P.; Theoretical Chemistry of Gold. III, Chem. Soc. Rev., 37, (2008), 1967-1997.

16. Johansson, M.P. and Olsen, J.; Torsional Barriers and Equilibrium Angle of Biphenyl: Reconciling Theory with Experiment, J. Chem. Theory Comput., 4, (2008), 1460-1471.

17. Lehtonen, O. and Sundholm, D.; Computational Studies of Free-Standing Silicon Nanoclusters, Chapter 3 in “Silicon Nanophotonics”, Ed. L. Khriachtchev, World Scientific (2009) ISBN-13 978-981-4241-11-3, pp. 61-88.

18. Jusélius, J. and Sundholm, D.; Polycyclic Antiaromatic Hydrocarbons, Phys. Chem. Chem. Phys., 10, (2008), 6630-6634.

19. Sumerin, V., Schulz, F., Atsumi, M., Wang, C., Nieger, M., Leskelä, M., Repo, T., Pyykkö, P. and Rieger, B.; Molecula Tweezers for Hydrogen: synthesis, Characterization, and Reactivity, J. Am. Chem. Soc. 130, (2008), 14117-14119.

20. Pyykkö, P.; Year-2008 Nuclear Quadrupole Moments, Mol. Phys., 106, (2008), 1965-1974.

21. Taubert, S., Straka, M., Pennanen, T.O., Sundholm, D. and Vaara, J.; Dynamics and Magnetic Resonance Properties of Sc3C2@C80 and Its Monoanion, Phys. Chem. Chem. Phys., 10, (2008), 7158-7168.

22. Johansson, M.P., Vaara, J. and Sundholm, D.; Exploring the Stability of Golden Fullerenes, J. Phys. Chem. C 112 (49), (2008), 19311-19315.

23. Taubert, S., Sundholm, D., Jusélius, J., Klopper, W. and Fliegl, H.; Calculation of Magnetically Induced Currents in Hydrocarbon Nanorings, J. Phys. Chem. A, 112 (51), (2008), 13584-13592.

Other publications 24. Pyykkö, P.; interview: Hundra år av kemi, Yliopistolainen, 2, (2008) 16.

Data bases: 25. Pyykkö, P.; A New Version of the RTAM Data Base Was Delivered, see

“rtam.csc.fi”.

Theses Doctor of Philosophy 1. Ying-Chan Lin: Computational Studies on Bimetallic Clusters Master of Science 1. Nina Siegfrids: Fysiologiskt aktiva föreningsklasser i potatis och tomat 2. Joachim von Schantz: Lätta stabila isotopfraktioner som verktyg i biologisk forskning

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3. Markus Lindqvist: Framställning av högre estrar genom katalytisk esterifiering och transesterifiering

4. Anneka Tuomola: Radikalcyklisering vid syntes av polycykliska indoler och pyrroler 5. Niko Salminen: Katalytisk oxidering av alkoholer 6. Toni Alasuvanto: Aza-Wittigringslutningar vid syntes av sammansmälta

kväveheterocykler 7. Kristian Meinander: Nya möjligheter för terpenen betulin

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LABORATORY, ADMINISTRATIVE AND OTHER STAFF

Sari Alho-Richmond Mohammed Al-Huniti, M.Sc. Dimitris Argyropoulos (FiDiPro Professor) Arja Enqvist, Secretary Hassan Haddad, Laboratory Assistant Laura Haikala, Service Adviser Eeva Halonen, Cleaner Anne Hannunen, Specially Trained Cleaner Liisa Helminen, Cleaner Markku Hyytiä, Service Man Kirsi Immonen, Specially Trained Cleaner Kari Janeskari, Porter Kauko Kauhanen, Laboratory Assistant Katrin Lehiste, Cleaner Seija Lemettinen, Laboratory Technician Hilkka Lintula, Secretary Olli Moisio, Technical House Manager Kaija Määttänen, Cleaner Martti Natunen, HPAC Mounter Timo Nieminen, Porter Tuula Niemisalo, Cleaner Arto Nurmi, Service Chief Juhani Pitkänen, M.Sc., IT Support Lauri Sutinen, Porter Sirpa Tikkunen, Service Chief Irja Torkkeli, Cleaner Sirkka-Liisa Torkko, Cleaner Kari Tuomainen, Laboratory Technician Toini Uutela, Specially Trained Cleaner Paula Vesalainen, Porter