The way of greening analytical chemistry

Mihkel Koel,Mihkel Koel, Mihkel KaljurandInstitute of Chemistry, Tallinn University

of TechnologyAkadeemia tee 15

Tallinn 12618, Estoniavmihkel@argus.chemnet.ee

Midsummer eve

Position of analyst

An analytical measurement is the presentation of knowledge about the chemical system that can be transferred, interpreted and processed

Support synthetic chemist and chemical engineer in confirmation of the greenness of their products and processes

Develop the methods and perform the analyses according to green chemistry&engineering principles

Role in society

Participation in knowledge accumulation and theory formulationDevelopment of standards and specifications in cooperation with producers in industry and agriculture

Motivation of new technologies and logistic solutions

Justify the need for new laws and administrative prescriptions

Justify the environmentally friendliness of new methods, processes and products

2009 Greener Reaction Conditions Award

CEM Corporation

“Innovative Analyzer Tags Proteins for Fast, Accurate Results without Hazardous Chemicals or High Temperatures”

This is green analytical chemistry what they are doing !

Analytical systems

LaboratoryOff-line On-line

Analyzer

Analyzer

Analyzer

Monitoring of pollutantsVery low concentration in environment (fish, aquatic and

terrestrial mammals and birds, milk and blood of humans as well as soils and sediments):

Persistent organic pollutants (POPs)polychlorinated biphenyls (PCBs)organochlorine pesticides (OCPs)

Highly toxic effects are proved. Regular monitoring programs existing

• Organohalogens in atmosphere• Destroing ozone layer. Use is banned

complex instrumental analysis providing extremely low limits of detection at currently acceptable international standards - high cost.

BioanalyticsResidues of pharmaceuticals

antibioticswide range of other bioactive compounds

Ungent need to estimate any impact and toxic effects on living organisms. Regular monitoring programs are needed.

• Biomarkers and GMO• Early diagnostic of illness• Accidental spreading of GMO-s

• Active research started

Process analytical chemistry

Effluent treatment and monitoring

ManufacturingHealth and safety monitoring

Raw materials quality control

Process control and monitoring

Product quality control

Analytical signals

The molecule is a source (carrier) of information, and the useof particular method (using proper instrumentation) is theprocedure to extract and present this information – ananalytical signal – in the precise, most selective andeconomical way.

Analytical methods are based on chemical reactions andelectrochemical processes as well as on interactions with allforms of energy, particularly radiation, giving unambiguoussignals directly from the place where something important fora chemist is taking place – be it in the bulk or surface, solid,liquid or gas

Analytical instrumentation

Sensitive to detect single moleculesSelective to identify single moleculeDifferentiate structures of molecules

(Flourescence) SpectroscopyElectrochemistry

Laboratory analytical chemistryField analytical chemistryProcess analytical chemistry (technology)

Analytical laboratory

Analytical chemistry is considered to be independent applied chemical discipline with a multidisciplinary nature.

The control and monitoring laboratories have huge number of sample to analyze →

analytical laboratory ≈ industry of fine chemicalsrelated E-factor (ratio of by-products to the desired products) for

them is 25 - 100

Productively Improvements

Green Chemistry Green Engineering

P - Prevent wastes I - Inherently non-hazardous and safe R - Renewable materials M - Minimize material diversity O - Omit derivatization steps P - Prevention instead of treatment D - Degradable chemical products R - Renewable material and energy inputs U - Use safe synthetic methods O - Output-led design C - Catalytic reagents V - Very simple T - Temperature, Pressure ambient E - Efficient use of mass, energy, space and time I - In-Process monitoring M - Meet the need V - Very few auxillary substances E - Easy to separate by design E - E-factor, maximize feed in product N - Networks for exchange of local mass and

energy L - Low toxicity of chemical products T - Test the life cycle of the design Y - Yes, it is safe S - Sustainability throughout product life cycle

S. Tang, R. Bourne, R.Smith, M.Poliakoff, The 24 Principles of Green Engineering and Green Chemistry: “IMPROVEMENTS PRODUCTIVELY”Green Chem., 2008, 10, 268–269

Green analytical chemistryAnalytical method needs solvents, reagents, energy, and it creates the waste.

The principles of green chemistry in design of new methods:prevention of waste (1);safer solvents and auxiliaries (5);design for energy efficiency (6);avoid chemical derivatives (8)safer chemistry to minimize the potential of chemical accidents (12).

The principles of green engineering in design of new instruments:• all inputs and outputs are inherently nonhazardous (1)• maximize mass, energy, space and time efficiency (4)• limit the underused and unnecessary materials and energy (8)• minimize material diversity (9)• design for commercial “afterlife“ (11)

Choice of analytical methods

Origin of the sample and aim of data obtained on this sample affects the choice of the analytical methodWide choice of preparation methods for sample pre-treatment and separation before the analysisWide choice of determination methods for detection and identification

important is the assessment:of methods about the safety and riskof instrumentation about the economy and efficiency

Availability of mathematical methods for planning of analytical procedures and data processing

Present challengesMicrosystems Remote (wireless) control and data acquisition and analysis

Miniaturization: lab-on-a-chip and total analysis systemsMicrofluidicsNew automated sampling strategies

New materials Polymers, composites, alloys, biomaterialsNanostructured materials, molecular imprinting

Sensors Calibration-free: all sensors equal / total sample conversionReal time: “instantaneous” response, no kinetic effectsBiosensors

Information Multiple, localized simultaneous measurements to give- Spectrum of information- Multidimensional presentation of information

Chemometrics and new data analysis techniques (multivariate calibration, QSPR)

Prevention of waste

Replace wet-chemistry in sample preparation and treatmentUse direct analysis techniques

SpectroscopySurface analysisLaser-spectroscopic techniques

Solventless techniquesDecrease sample volume needed

Use of laboratory-on-chip in analysisUtilization of immunoassays

Alternative solventsSupercritical fluids

Not widely spread, lack of standard proceduresTechnically complicated, needs careful control of extraction parametersPossible losses of analytes during the sample collection after the extraction Not fully studied of handling of liquid samples

Ionic liquidsFew data on toxicity (bioaccumulation, biodegradability)Few data on physical properties and not clear understanding of solvent/material properties with regards to the structural features of IL No official analytical methods where ionic liquids are involvedExpensive and not commercially available

Safer chemistryIntegration sample preparation and separationUse of environmentally friendly solventsand reagents

Avoid derivatization•Direct analysis of sample•Reduce need for derivatization with different dection methods and signal processing

Design for energy efficiency

Efficient sample treatmentUltrasonic irradiationMicrowavesPhotochemical activationMechanical activation

Automation and miniaturizationUse of hyphenated techniques

Simple and economical instrumentation

Development of instrumental methods to replace wet-chemistry methodsAutomation of analysis processesMiniaturization and hyphenation of techniquesLimit the underused and unnecessary materials and functions

Liquid Chromatography

Capillary Electrophoresis

Injected volume 1-100 µL 1-100 nL

Flow rate of liquid phase

1-10 mL/min 1-100 nL/min

Flow profile parabolic plug

Number of separated peaks

20-30 20-100

Analysis time 10-60 min 1-20 min

Separation high pressure electrical field, no back pressure

Solvents different solvents for the different columns

different solvents in the same column

Level of developments

mature technique young, developing fast

Chemometrics

chemometric principles and computer applications are included at all steps of the analytical process:

sampling theory and experimental design,optimization of analytical measurements and separation procedures, signal processing for improvement of signal-to-noise ratio and signal resolution, multivariate statistics and data analysis for extraction of useful information from large (multidimensional) data sets,intelligent laboratory systems and robotics.

Conclusions

Confirm that chemical products and processes are safe Ensure the safety of chemical processesUse economical and efficient instrumentation

Perform analysis in a green way - The waste prevention, economy and life cycle of analyzer must become a part of decision in choosing proper analytical method

Acknowledgements

Estonian Science Fundation – G7303

Chair of analytical chemistry, Tallinn University of Technology

"Nature does not care what we call it, she just

keeps on doing it. "

Richard P. Feynman, "The Feynman Lecture on Physics"