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ALSO IN THIS ISSUE: • Citizen science: the public as research recruits • Hatching a strategy for your research career • Economics of a biodiesel by-product

in Australiachemistry

August 2015

chemistryBeer: a balanced brew of technology and tradition

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news & research6 News11 On the market12 Research42 Cryptic chemistry42 Events

views & reviews4 Editorial5 Your say28 Books32 Plants & soils34 Technology & innovation36 Economics38 Environment39 Grapevine40 Postdoc diary41 Letter from Melbourne

20 Citizen science: the New EnlightenmentRiding on the ICT revolution, recruiting public help for research is on the rise,bringing benefits for both scientists and non-scientists.

24 Your science career: making a strategic planOur working lives can seem simpler when we have a career plan – a timelinewith goals and outcomes. In reality, the path can be far from clear.

Chemistry of beerWhether you’re mashing in a tun, boiling the kettle to make wort, pitchingyeast or hopping a brew, the brewing of beer is both art and science.

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A friend mentioned to me recently that his specialist has apreferred pathology group because their detection limits for aparticular biomarker are ‘lower’. I have read since that someassay manufacturers use limits of detection as a marketing tool.

The ability to detect smaller amounts of substance is amixed blessing in medicine. There’s the prospect of interventionto fix a problem that may or may not exist, sometimes withsignificant associated morbidity along the way, plus the socialand economic implications for population screening to detectdisease. Detection limits in environmental methods have similardilemmas.

What about analytical methods and instrumentation inchemistry? I’m curious to know if the latest equipment hangsits hat on lower detection limits, and what the pitfalls of thismight be.

How important are detection limits in the wider context oferrors? The dangers of automation of analytical methods,particularly for the inexperienced, comes to mind. Someproblems can be embedded in software code. You can see along, fascinating and sometimes humorous error-relatedglossary at www.mistakeproofing.com/glossary.html.

Consider the measurement of analytes in human blood. Bloodis such a complex matrix that it is a significant source ofbackground ‘noise’. Then there’s calibration of equipment,accuracy of measurement of small sample volumes – the list islong. I remember that, in my previous life as a coal chemist,good sample prep ruled supreme. There are, of course, standard

methods, but they too have their limits.Lack of time, care or common sense can render well-

intentioned methods ridiculous. At my daughter’s local athleticstrack, events are regularly delayed because there are notenough volunteers to time all placegetters – which apparentlymust be done in triplicate. The thing is, they hadn’t realised(until my partner pointed it out), that some race distances werebeing marked incorrectly and the kids were running severalmetres short.

I don’t pretend to know the fine detail of the various limits,but just wading through the definitions, such as instrumentdetection limit, method detection limit, practical quantificationlimit and limit of quantification, is a feat in itself. MichaelThompson, Emeritus Professor of Analytical Chemistry atBirkbeck College, University of London, who has written aboutthis subject over many years, describes detection limits as a‘preoccupation’, saying ‘there is a danger that this accumulationof theory and terminology will overwhelm understanding’. Heargues that detection limits are not the best way to describethe ‘bottom end of the useful range of analytical methods’(Analyst doi: 10.1039/A705702D).

What if we didn’t rely so much on detection limits as weknow them? In a more recent paper, Thompson and colleaguessuggest that ‘for many purposes detection limit and relatedlimits are made redundant simply by reporting the measurementresult and its uncertainty’ (Analytical Methods doi:10.1039/C3AY41209A). An oft-repeated quote of Einsteindescribes the folly of trying to solve a problem using the samelevel of thinking that created it. How do we think differentlyabout limits of detection to come up with a better way?

I guess I’m not telling you anything new here. I’ve posedmore questions than answers because I’m hoping you mighthave something to tell me. I would love to hear about yourexperiences and opinions, including about how the concept ofdetection limits is explained to students.

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© 2015 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproduced whollyor in part without written permission. Further details on thewebsite (chemaust.raci.org.au). ISSN 0314-4240 e-ISSN 1839-2539


Chemistry in Australia4 | August 2015

editorial

Limits and limitations of detection

Sally Woollett ([email protected])

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Pledge to Chemists

This is not a “subtle” attempt to obtain more

R.J. Rowe (FRACI)

your say

Chemistry in Australia 5|August 2015

Chemists and vintnersThe letter by John Harvey, ‘Chemists, laborateurs andpharmacists’ in the June 2015 issue (p. 5), reminded me of asimilar situation I learned about when I visited Penfolds Winesat Nuriootpa, South Australia, in the early 1960s.

At that time I was working at the CSIRO Division of ChemicalPhysics, exploring the application of Alan Walsh’s atomicabsorption spectrometer to the measurement of theconcentrations of metals in various materials, and helping otherlaboratories apply the new technique to their own analyticalproblems. Penfolds Wines had recently ordered an instrumentfrom Techtron Pty Ltd, which manufactured them in Melbourne.

The Chief Chemist at Penfolds, Ray Beckwith, told me thatwhen he joined the company in 1935, whoever was responsiblefor his appointment wanted to employ a chemist, but thedirectors of Penfolds would not consider having anyone withthat title – winemaking was a traditional craft, and chemistrywas not talked about in connection with it. So Ray wasappointed initially as an ‘assistant cellar hand’.

My visit to Nuriootpa had to be postponed for some time fora most unlikely reason. The spectrometer had been dispatchedby road from Melbourne, but the truck had broken down and thedriver had gone on foot to seek assistance (no mobile phones inthose days). During his absence thieves broke into the truckand stole most of the contents, including the atomic absorptionspectrometer. I have often wondered how a thief would goabout disposing of this strange piece of equipment, of which hecould only say ‘I don’t know what it is, but it fell off the backof a truck’!

Sadly, I lost contact with Ray Beckwith many years ago,but have now learned, via Google, that his distinguished careeras a chemist in the wine industry was recognised very late inlife by the award of an honorary doctorate from the Universityof Adelaide, and by a Medal of the Order of Australia. He died in2012, still alert and active, at the age of 100.

John B. Willis FRACI CChem

Manners maketh the scientistI would like to thank you and my colleagues at the RACI forallowing me to write for Chemistry in Australia. Although I amexpert in almost nothing I write, I thoroughly enjoy the processof researching and new learning for each article I submit. And Iwelcome Sally’s editorial oversight – every change sherecommends makes me appear smarter than I truly am.

With the strength of our magazine and our society in mind, Iwould like to proffer a suggestion for the consideration of mycolleagues. In some recent issues, I found an exchange ofletters troubling. I have felt that the dialogue extended beyondthe ideas to more personal disagreement, and I interpreted thetone as becoming aggressive, even bickering.

I truly believe in science as more than a profession. For me,it is a vocation. And I believe that we as scientists have afundamental responsibility to be wrong … at least some of thetime.

Clearly, I don’t believe that we should intend to err, butrather that we must commit each day to the scrutiny of ourwork, and to the certain knowledge that our mistakes willimprove our understanding.

We are each of us part of a grand, global endeavourspanning centuries of effort. In the interests of truth, our ideasmust be tested and challenged. And it is our responsibility toparticipate in the resulting intellectual discourse openly,thoroughly, and above all with respect.

I therefore urge all of my colleagues at the RACI, whencomposing your letters to the editor, to please remember thatwe are all part of the same great endeavour. While you maydisagree on certain points and concepts within the pages ofthis journal, I urge you to please keep the joy of science inyour heart, and let every reader of your letter hear that joy.

Dave Sammut FRACI CChem

‘Your say’ guidelinesWe will consider letters of up to 400 words in response tomaterial published in Chemistry in Australia or about novelor topical issues relevant to chemistry. Letters acceptedfor publication will be edited for clarity, space or legalreasons and published in print and online. Full name andRACI membership status will be published. Please supplya daytime contact telephone number (not for publication).

Publication does not constitute an endorsement of anyopinions expressed by contributors. All letters becomecopyright of the Royal Australian Chemical Institute andmust not be reproduced without written permission.Letters should be sent to [email protected].

Got something to say?As your RACI member magazine, Chemistry in Australia is the perfect place to voice your ideas and opinions, and to discuss chemistry issues and recentlypublished articles.

Send your contributions (approx. 400 words)to the Editor at [email protected].

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news

August 2015

An Australian invention, responsible forunboiling an egg, has been used toproduce a fourfold increase in efficacy ofcarboplatin, a commonly used drug forovarian, lung and other cancers.

The latest research, published inScientific Reports (doi:10.1038/srep10414), is just one in agrowing number of importantapplications for the vortex fluidic device(VFD) invented by the South AustralianPremier’s Professorial Research Fellow inClean Technology, Flinders UniversityProfessor Colin Raston FRACI CChem.

The groundbreaking device is beingmanufactured at Flinders University andwill soon be available to researchorganisations around the world.

Raston said the high-tech, yet simpledevice can be used in medical andpharmaceutical research along with arange of industries – all with a focus oncleaner, greener and cheaper production.

‘This device creates a unique way todevelop more sustainable and cost-effective products, services andtechnologies, which can accelerateinnovation in a range of industries, fromdrug manufacturing to food and biodieselproduction,’ he said.

The device’s unique ability to controlchemical processes already has enabledscientists to ‘unfold’ proteins to theirnatural state, in a process likened to‘unboiling an egg’, which could be usedin protein-based drug research.

The machine has the potential torevolutionise the delivery andmanufacture of a wide range ofpharmaceutical processes and products by‘streamlining the loading of drugs intonano-packages’ for better results and lesswaste, Raston said.

‘With ovarian cancer, we found thatthis technology can increase the loadingof second generation anticancercarboplatin drugs into delivery vehiclesfrom 17% to 75%,’ he said.

‘This not only would have a directbenefit of reducing the negative side-effects which affect patient health, butof being able to use less of the drug.’

Using more effective drugs would alsoreduce manufacturing waste, with up tohalf a tonne of waste generated from theproduction of just one kilogram ofanticancer and other drugs.

‘Much of the drugs end up in seweragesystems and possibly create superbugs inour environment,’ Raston added.

Cancer kills about eight million peoplea year worldwide.

The start of VFD sales will escalate theapplication of this new scientific researchwork, Raston said.

‘Our VFD will enable thepharmaceutical and many other industriesto innovate – including furtherimprovements in the chemical delivery ofa range of existing approved drugs, aswell as development of new improveddrugs.’

Contributing authors on the latestproof-of-concept report, entitled ‘Shearinduced carboplatin binding within thecavity of a phospholipid mimic forincreased anticancer efficacy’, are DrJingxin Mo, Professor Lee Yong Lim andMuhammad Rizwan Hussain Ahamed(University of Western Australia), DrThomas Becker (Curtin University) and DrPaul Eggers MRACI CChem, Dr XianjueChen and Professor Raston (FlindersUniversity).FLINDERS UNIVERSITY

Vortex device makes for better cancertreatments

Colin RastonFlinders University

Two Australian scientists working in health and nanoelectronicshave been recognised for excellence in metrology, the scienceof measurement.

The annual Barry Inglis Medal and the NMI Prize, awarded byAustralia’s National Measurement Institute (NMI), acknowledgeand celebrate outstanding achievement in measurementresearch and excellence in practical measurements in Australia.

Sydney’s St Vincent’s Hospital chemical pathologist, Dr Graham Jones, was awarded the Barry Inglis Medal. Jones

was recognised for his work to improve the accuracy andreliability of chemical pathology testing, via bettermeasurement standards, techniques and clinical referenceranges.

The NMI Prize, awarded to an individual under 35 years ofage, went to University of New South Wales research fellow Dr Alessandro Rossi. Rossi’s work in nanoelectronics is helpingto realise an improved definition of the ampere.DEPARTMENT OF INDUSTRY AND SCIENCE

Researchers have demonstrated a newmetal matrix composite that is so light itcan float on water. A boat made of suchlightweight composites will not sinkdespite damage to its structure. The newmaterial also promises to improveautomotive fuel economy because itcombines light weight with heatresistance.

Although syntactic foams have beenaround for many years, this is the firstdevelopment of a lightweight metalmatrix syntactic foam. It is the work of ateam of researchers from Deep SpringsTechnology (DST) and the New YorkUniversity Polytechnic School ofEngineering.

Their magnesium alloy matrixcomposite is reinforced with siliconcarbide hollow particles and has adensity of only 0.92 g/cm3 compared to1.0 g/cm3 of water. Not only is its densitylower than that of water, the metalmatrix is strong enough to withstand therigorous conditions faced in the marineenvironment.

Significant efforts in recent years havefocused on developing lightweightpolymer matrix composites to replaceheavier metal-based components inautomobiles and marine vessels. The

technology for the new composite is veryclose to maturation and could be putinto prototypes for testing within threeyears. Amphibious vehicles such as theultra heavy-lift amphibious connectorbeing developed by the US Marine Corpscan especially benefit from the lightweight and high buoyancy offered by thenew syntactic foams, the researchersexplained.

‘This new development of very lightmetal matrix composites can swing thependulum back in favour of metallicmaterials,’ forecasted co-author ProfessorNikhil Gupta, of the NYU School ofEngineering. ‘The ability of metals towithstand higher temperatures can be ahuge advantage for these composites inengine and exhaust components, quiteapart from structural parts.’

The syntactic foam captures thelightness of foams, but adds substantialstrength. The secret of this syntacticfoam starts with a matrix made of amagnesium alloy, which is then turnedinto foam by adding strong, lightweightsilicon carbide hollow spheres. A singlesphere’s shell can withstand pressure ofover 25 000 (psi) (170 MPa) before itruptures – 100 times the maximumpressure in a fire hose.

The hollow particles also offer impactprotection to the syntactic foam becauseeach shell acts like an energy absorberduring its fracture. The composite can becustomised for density and otherproperties by adding more or fewer shellsinto the metal matrix to fit therequirements of the application. Thisconcept can also be used with othermagnesium alloys that are non-flammable.

The new composite has potentialapplications in boat flooring, automobileparts, and buoyancy modules as well asvehicle armour.

The findings are published in theInternational Journal of ImpactEngineering (doi: 10.1016/j.ijimpeng.2015.04.008).NYU POLYTECHNIC SCHOOL OF ENGINEERING


Metal composite will (literally) float your boat

Chemical pathologist wins science measurement award

news


Australian scientists are in the hunt for the last missing pieceof Einstein’s general theory of relativity, gravitational waves, asthe Advanced LIGO Project in the US comes on line.

LIGO (the Laser Interferometer Gravitational-waveObservatories) aims to find gravitational waves, ripples in thefabric of space and time caused by the most violent events inthe universe such as supernovae or collisions between blackholes.

‘We’ll find things we can’t imagine – gravitational waves area completely different messenger from light,’ said ProfessorDavid McClelland from the Australian National University (ANU),who leads the Australian LIGO team.

Australia is a partner in Advanced LIGO with research groupsfrom ANU and the University of Adelaide directly contributingto its construction and commissioning.

LIGO will ultimately be joined by detectors in Europe, Japanand India seeking evidence for gravitational waves, in the formof movements a fraction of the radius of a proton.

‘Advanced LIGO is easily the most sensitive detector evercreated, at the limits of the Heisenberg uncertainty principle,’said Professor Jesper Munch, leader of the University ofAdelaide research group.

In his 1915 general theory of relativity, Einstein proposedthat large masses such as stars cause curvature in space andtime, which leads to gravity and also bends light.

A number of observations in the past 100 years haveconfirmed other consequences of Einstein’s theory, but only inregions of weak gravity, said LIGO team member ProfessorDaniel Shaddock, from the ANU Research School of Physics andEngineering (RSPE).

‘Gravitational waves are produced when massive objectsaccelerate or collide,’ he said.

‘Finding gravitational waves would test our theories in acompletely different scenario, where huge gravitational forcesare at play. It is the ultimate test for general relativity.’

Gravitational waves have been proven to exist indirectly

through the decay of the orbit of two neutron stars rotatingaround each other. However, McClelland says direct detection ofthem is within our grasp.

‘By the end of the year there’s a chance that the 100-yearsearch will be over,’ he said.

‘Or, if we don’t see something in the next 12–24 months,then we may have found either a problem with Einstein’sgeneral relativity or some new insight about the universe,’ hesaid.

LIGO is an identical pair of laboratories in opposite cornersof the US. Each laboratory consists of two four-kilometre-longvacuum pipes at right angles to each other, with mirrorssuspended at either end. A laser beam is sent back and forthbetween the mirrors to form an interferometer.

They were built by Caltech and MIT in the 1990s. However,they only now have the sensitivity levels required to detectgravitational waves with a tenfold improvement following acomplete redesign and replacement of the detectors.

A gravitational wave passing through the interferometershould momentarily move the mirrors at a frequency of about akilohertz somewhere in the region of 10–19 of a metre (one ten-thousandth of the radius of a proton), which will be picked upby the laser system.

The team at ANU have developed a system that locks thelaser beam to the 40-kilogram mirrors to ensure thatinfinitesimal movements caused by a passing gravitational waveare identified, while other small movements are nullified.

The University of Adelaide group has developed a system tocorrect for any deformation of the mirrors due to heat, a crucialfactor with the stored laser power of the system approachinghalf a megawatt.

‘The technology required pushes the limit of all thecomponents, including low noise detectors, high power lasers,quantum effects and technology such as optical polishing,coatings and vacuum systems,’ said Munch.

‘It is a crowning achievement in optical sensing as the worldcelebrates the International Year of Light in 2015.’AUSTRALIAN NATIONAL UNIVERSITY AND UNIVERSITY OF ADELAIDE

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New era of astronomy as gravitational wave hunt begins

LIGO vacuum chambers.

ANU lock acquisition system being installed.

LIG

O

LIG

O

One of science’s unresolved questions – where all of theantimatter at the origin of the universe went – may now beexplored with the help of Curtin University research.

Professor Igor Bray, Head of Curtin’s Department of Physicsand Astronomy, said the university’s theoretical physics researchgroup utilised supercomputers at the National ComputationalInfrastructure (NCI) and the Pawsey Supercomputing Centre tolook at ways to create neutral antimatter in a laboratory to helpresolve the long-standing problem of matter–antimatterasymmetry in the universe (Physical Review Letters doi:10.1103/PhysRevLett.114.183201).

‘Laws of physics predict equal amounts of matter andantimatter at the origin of the universe, but it appears thatpresently this is not the case. In order to explore this,scientists require an adequate amount of antimatter in thelaboratory, something that is currently not available,’ Brayexplained.

Scientists hope to measure how antimatter behaves undergravity, and its various energy levels to the same precision as ispossible with ordinary matter. Antimatter must be in a neutrallycharged state in order to be used in such experiments.

‘The simplest neutral antimatter is the antihydrogen atom,

which is a bound state of an antielectron, also called apositron, and an antiproton. The challenge for scientists todate has been to find a way to create the antihydrogen in alaboratory in enough quantity to be a viable material source forexperiments,’ Bray said.

‘In our research, we looked at ways to create a suitableamount of antihydrogen atoms. One mechanism is to collideslow antiprotons with positronium, a bound state of an electronand a positron. Our calculations discovered that whenpositronium is in a laser-prepared excited state, the number ofantihydrogen atoms created can be enhanced by a factor of1000.

‘The competitive mechanism for creating antihydrogen thatthis research has uncovered will be used at CERN, the EuropeanOrganisation for Nuclear Research, where three different groupsare in a race to make antihydrogen in sufficient quantities.’

The calculations for this research required overone million CPU hours following a decade of computer codedevelopment.

‘This discovery would not have been possible without themodern supercomputers now available in Australia,’ Bray said.CURTIN UNIVERSITY

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Making antimatter: research provides foundation forfuture experiments

news


Non-metallic mesoporous structures have already demonstratedpotential for applications in gas storage, separation, catalysis,ion-exchange, sensing, polymerisation and drug delivery. Metalmesoporous films could have fascinating and useful opticalproperties as they are effectively the inverse of nanoparticlearrays. Now for the first time a collaboration of researchers inJapan, Turkey, Korea and Sweden demonstrate a simpleapproach for producing metal films with regular tuneablemesopores, and show their potential for high-sensitivity opticaldetection (Nature Communications doi: 10.1038/ncomms7608).

When light is incident on nanostructures of noble metalssuch as gold, the electrons oscillate collectively – a so-calledplasmon – and this greatly enhances the electromagnetic fieldclose by. According to Babinet’s principle in optics, the inversestructure – a mesoporous film – should lead to similar localelectromagnetic field enhancements, but as Yusuke Yamauchiand his colleagues point out in their report, controlling goldcrystal growth well enough to produce mesoporous films has sofar been difficult.

The success of their approach relies on electrochemistry and

micelle self-assembly. They dissolve hydrogen gold chloride (or chloroauric acid, HAuCl4) and polystyrene-block-poly(oxyethylene) in a solution of tetrahydrofuran, which leadsto the formation of micelles with a polystyrene core andpolyoxyethylene shell. The micelles reduce the AuCl4

– ions sothat gold deposits on the micelles. The result is highly regulargold mesopores with a size that can be tuned by varying theconcentrations of the HAuCl4 and polystyrene-block -poly(oxyethylene).

Calculations showed that hotspots of high electric fieldenhancement indeed exist in the pores of the structure, and theplasmon resonances can be tuned by changing the pore size.Further experiments confirmed the surface enhancement ofprotein spectral signatures, known as surface enhanced Ramanscattering. The researchers conclude, ‘The electrochemicalapproach is widely applicable to embed uniform mesopores inother metal and alloy systems, which are generally difficult tobe synthesised.’INTERNATIONAL CENTER FOR MATERIALS NANOARCHITECTONICS (WPI-MANA)

Holes in gold enhance molecular sensing

Avoiding chocolate ‘bloom’Chocolate is one of the world’s mostpopular foods, but when a whitishcoating called a bloom appears on theconfection’s surface, it can makeconsumers think twice about eating it.The coating is made up of fats and isedible, but it changes the chocolate’sappearance and texture – and not forthe better. Now scientists report in ACS Applied Materials & Interfaces(doi: 10.1021/acsami.5b02092) newinformation that could help chocolatiersprevent blooms from forming.

Svenja K. Reinke and colleaguesexplain that baked goods andconfectionery products, includingchocolate, contain a mix of componentsthat don’t always stay in place. Fatblooms, for instance, occur when lipids

from within a chocolate product wanderto the surface. They’ve long been ascourge of chocolatiers, but no one fullyunderstood what caused them. Reinke’steam wanted to find out what factorswere contributing to their formation.

The researchers investigated themicroscopic structural changes thatoccur when chocolate blooms. Theyfound that the lipids that areresponsible move through pores andcracks in the chocolate. Along the way,they soften and dissolve solid cocoabutter into a liquid form. Theresearchers say reducing the number ofpores and the liquid cocoa buttercontent of chocolate could helpminimise blooms.AMERICAN CHEMICAL SOCIETY

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on the market


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ATA Scientific are now the local distributor for MicroCalITC/DSC products. These systems are in use in over 1000 labsworldwide, both for R&D and commercial applications and

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research


Many recent studies have been performedto understand how the physicochemicalproperties of particles (such as size, shapeand surface chemistry) are correlated withtheir biological interactions. In particular,particle stiffness has been shown toinfluence in vivo circulation and in vitrocellular interactions. However, mostreported studies have used particles withseveral differing properties, making itdifficult to determine the influence ofparticle stiffness alone. By using thetechnique of atom transfer radicalpolymerisation mediated continuous

assembly of polymers (CAPATRP) to controlthe wall thickness of hollow polymerparticles called polymer capsules, aresearch team led by Professor Greg Qiaoand Professor Frank Caruso at theUniversity of Melbourne has preparedhyaluronic acid (HA) capsules with tunablestiffness while keeping other parametersconstant (Sun H., Wong E.H.H., Yan Y.,Cui J., Dai Q., Guo J., Qiao G.G., Caruso F.Chem. Sci. 2015, 6, 3505–14). The effectof capsule stiffness on cellular interactions(surface binding, association andinternalisation) and intracellular

distribution was then systematically andquantitatively investigated. Theresearchers found that the softest HAcapsules interacted more strongly andrapidly with cells than stiffer capsules andthat cellular uptake was stiffnessdependent. But regardless of capsulestiffness, all internalised capsules weredeformed and accumulated in lysosomes.These findings highlight the importance ofcapsule stiffness on cellular processingand provide useful information for therational design of polymer capsules forbiomedical applications.

Cells have a soft spot for soft particles

Earlier this year, researchers at theUniversity of Melbourne showed that thecell walls of mushrooms and yeastconsumed in our diet can be broken downby our gut microbiota (Nature 2015, 517,165−9; see Chem. Aust. June 2015, p. 13).The gut microbes use enzymes called GH76endomannanases to metabolise fungal cellwall glycans to short-chain fatty acids thatmodulate our immune systems and nourishthe endothelial cells of our distal gut. Now,in collaboration with groups from the UKand Spain, the group of Associate ProfessorSpencer Williams has clarified at amolecular level the catalytic mechanism bywhich the same highly specialised GH76endomannanases in a soil bacterium,Bacillus circulans, metabolise fungal cell

walls (Thompson A.J., Speciale G., Iglesias-Fernández J., Hakki Z., Belz T., Cartmell A.,Spears R.J., Chandler E., Temple M.J.,Stepper J., Gilbert H.J., Rovira C.,Williams S.J., Davies G.J., Angew. Chem.Int. Ed. 2015, 54, 5378−82). Usingchemically synthesised enzyme inhibitorsand substrate analogues, they were able todetermine X-ray structures ofenzyme−substrate complexes that mimickedthe ground-state and transition-statebound forms of the enzyme. Supported bycomputational studies, the authors wereable to identify the amino acid residuesthat are essential for catalysis and theconformational changes of the substratethat occur during the endomannosidase-catalysed reaction.

X-ray structure of mannopentaosebound to GH76 enzyme from Bacilluscirculans. The protein is colouredaccording to amino acid sequenceconservation. Red = highly conserved.

Mushroom munchers: how bacteria metabolise thefungal cell wall

August 2015

M955_TwindriveRheometer20150622_275x76-CC14.indd 1 22/06/2015 17:42

The structure and mechanism of thecatalytic Mn4Ca cluster in photosystemII, which oxidises two water moleculesinto molecular oxygen and protons,remain among the most challengingproblems in bio-energetics. The reactionin nature exhibits unrivalled chemicalefficacy and is the ‘benchmark’ forefficient electrolytic hydrogen productionfrom water. Recently, great progress hasoccurred in characterising this water-oxidising complex (WOC), with a 1.9 Åresolution X-ray diffraction structure andnow a 1.95 Å X-ray free-electron laser(XFEL) structure. However, apparentconflicts with other data have challengedthese achievements. The earlier 1.9 Åstructure disagreed with extended X-rayabsorption fine structure (EXAFS) data,suggesting that the Mn centres in theWOC had suffered from X-ray

photoreduction. For the latest 1.95 Åstructure, Mn photoreduction was not anissue, but poor agreement withcomputational models, which commonlyassumed a ‘high’ Mn oxidation state,again suggested that the structure wascontaminated with ’reduced’ WOC forms.However, new density functional theorymodelling at the Australian NationalUniversity shows that the distinct 1.9 and 1.95 Å WOC geometries can bestraightforwardly explained if the Mnoxidation states are actually lower thancommonly supposed (Petrie S., Pace R.J.,Stranger R. Angew. Chem. Int. Ed. 2015,54, 7120−4). Remarkably, the twostructures are simple tautomers, relatedby a single proton relocation from the O5water group to the His337 amino acidresidue.

Resolving differences between photosystem IIcrystal structures

research


The cost of growth factor required tosupplement cultures of human cells iscurrently a prohibitively large expense intranslating promising laboratory-scalescience to the clinical scale. In solution,growth factors are rapidly internalisedinto the cell and degraded. Binding theseproteins to a solid substrate inhibits thisprocess, but surface binding canpotentially affect growth factor activity.Researchers at the University of SouthAustralia have come up with a novel wayto determine the minimum surfacedensity of nerve growth factor (NGF)needed to induce differentiating mouseembryonic stem cells to form neurons, byconstructing a gradient of immobilised

NGF on a cell culture surface (Delalat B.,Mierczynska A., Rasi Ghaemi S.,Cavallaro A., Harding F.J., Vasilev K.,Voelcker N.H., Adv. Funct. Mater. 2015,25, 2737–44). Underlying the NGFgradient is a polymer film prepared byplasma polymerisation containing avarying density of aldehyde functionalgroups, onto which NGF is covalentlycoupled by amination. Plasma polymer

coatings can easily be scaled up andtransferred onto porous scaffolds ortissue cultureware; thus this work aidsthe design of advanced nerve tissueengineering scaffolds and tissue culturesurfaces for neural cell expansion. Theimmobilised biomolecule gradient can begeneralised to other cell culture scenariosas a tool to develop affordable bioactivematerials.

The research group of Professor CurtWentrup at the University of Queensland,together with co-workers in Germany, hasdeveloped an automated falling-solidflash vacuum pyrolysis technique (FS-FVP) that allows the rapid, efficient andhigh-yielding synthesis on a multigramscale of arylacetylenes 3 from aldehydesvia 4-arylmethylidene-5(4H)-isoxazolones1 with vinylidenes 2 as key intermediates(Wentrup C., Becker J., Winter H.-W.,Angew. Chem. Int. Ed. 2015, 54,5702−4). The innovative centrepiece ofthe apparatus is a spinning brush (E)that acts as a vertical conveyor for thefinely powdered solid starting material.Aryl- and heteroaryl-acetylenes,naphthylacetylenes and p-diethynylbenzene are readily obtained.The new method is advantageous in otherapplications. For example, 5-substitutedtetrazoles are convenient startingmaterials for arylcarbenes but are oftentoo involatile to be practical for FVP.Nevertheless, 1-azulenylcarbene 4 wasgenerated from tetrazole and aldehyde

tosylhydrazone precursors by FS-FVP andrearranges to cyclobuta[de]naphthalene 5and cyclopenta[cd]indene 6.Furthermore, 2-azulenylcarbenerearranges to 1-azulenylcarbene. FS-FVPhas also been used to generate 4-, 3- and 2-quinolylcarbenes 7, which allrearrange to 1-naphthylnitrene 8, whichwas observed directly by ESR

spectroscopy prior to ring contraction to1-cyanoindene. In related work, 1,4-naphthoquinone-2-ylnitrene 9 hasalso been characterised by ESRspectroscopy as the first directlyobserved vinylnitrene (Sarkar S.K.,Sawai A., Kanahara K., Wentrup C.,Abe M., Gudmundsdottir A.D. J. Am.Chem. Soc. 2015, 137, 4207−14).

Arylacetylenes in a flash

Brain-on-a-slide: gradient surfaces to optimise neural differentiation

Compiled by David Huang MRACI CChem ([email protected]). This section showcases the very best research carried out primarily in Australia. RACI memberswhose recent work has been published in high impact journals (e.g. Nature, J. Am. Chem. Soc., Angew. Chem. Int. Ed.) are encouraged to contribute general summaries,of no more than 200 words, and an image to David.

In the July issue of Aust. J. Chem., Craig Francis(CSIRO, Clayton), Michael Perkins (FlindersUniversity) and co-workers report severaltransformations of the pyrazolo[1,5-b][1,2,4,6]thiatriazine ring system. Thesemolecules possess four nucleophilic sites (N2, N4,C5 and N7) and undergo alkylation predominantlyat N4 and N7. Novel reactions include ringexpansion of the pyrazole ring to yield a new ringsystem, pyrimido[1,6-b][1,2,4,6]thiatriazines.Catalytic amounts of acid caused extrusion of SO2

to produce pyrazolyl-guanidines.James Crowley and co-workers (Dunedin) have

used the copper(I)-catalysed azide-alkyne ‘click’reaction (CuAAC) to synthesise a family of tripodaltetramine ligands incorporating two pyrazolyl andone 1,2,3-triazolyl donor arm. Mono-, bis- and tris-tripodal ligand scaffolds were readily generated bythis method. The coordination chemistry,spectroscopy and crystallography are described.

Flavanoids are widely consumed in food and formedicinal purposes as they possess importantbiological properties, including anticancer, anti-inflammatory, antimicrobial and antiviral. Nhu,Hawkins and Burns (Walter and Eliza Hall Institute)now report an efficient oxidative synthesis offlavones under phase transfer conditions.

A photovoltaic application of coumarinderivatives is reported by Guo, Wang et al.(Tianjin, China), who synthesised 7-coumarinoxy-substituted zinc and cobalt phthalocyanine dyesand demonstrated a through-space electrontransfer from the dye to TiO2 films. The zinccomplex achieves a higher conversion efficiencythan reported for other, similar complexes becauseof its slower charge recombination rate and fasterelectron injection from the dye to the conductionband of the conducting glass.

Darryl Nguyen (University of Western Sydney)has developed a synthetic antibacterial 3D softtissue with applications in wound healing. Theartificial tissue is prepared from a mixture ofcollagen type I, the most abundant type ofcollagen in the dermal layers of skin, andsimulated wound fluid (50% foetal calf serum and50% physiological NaCl in 0.1% peptone), which ispolymerised at 35°C. The tissue allows in-vitroassays of the potency of potential antimicrobialdrugs under conditions that mimic the in-vivoenvironment of biofilm infections.


Aust J Chem

Curt Wentrup FAA, FRACI CChem ([email protected]),http://uq.edu.au/uqresearchers/researcher/wentrupc.html?uv_category=pub


Beer consists of just four basicingredients – water, malt,hops (flowers of the Humuluslupulus plant) and brewing

yeast (Saccharomyces cerevisiae,Saccharomyces pastorianus). Soundsimple? Definitely not! Brewing is avery complex and delicate series ofchemical reactions that are measuredand controlled within specificconditions to ensure a high-qualityfinal product. To the initiated, brewingis a microcosm of uniqueterminologies, tradition and somepretty serious chemistry. Brewersworldwide produce beer at anadvanced technological level, yetalways keep in mind the importance oftradition.

Before brewing begins, there iswork to be done at the malthouse toprepare malted barley, which is thesource of carbohydrates forconversion to alcohol. Unmalted starchsources such as wheat, barley, rice,corn and sorghum as an adjunct(additional carbohydrate source) aresometimes used regionally, except inGermany where the Reinheitgebotpurity law allows only malted barley.Most beers produced globally containa high proportion of malted barley.

Brewing barley contains mainlystarch, protein, cell wallpolysaccharides, and a smalleramount of fats and minerals. Themodification of barley begins withsteeping the grains in water to initiate

germination in which enzymes breakdown the cell walls and some of theprotein in the starchy endosperm.Enzymes (amlyases) are produced thatare utilised later in the mashingprocess. The partially germinatedgrains are then kilned at hightemperatures to halt germination anddevelop the desired biscuity and maltyflavour and aromas. The level of kilningproduces specialty malts that deliver arange of colour and flavourcharacteristics from amber malty lagerto rich dark caramel-like stouts.

Off to the brewhouse where malt ismilled to ‘grist’ and mashed in a tunwith other prepared materials(adjuncts, salts or supplementaryenzymes). A carefully controlled

Chemistryof beerWhether you’re mashingin a tun, boiling the kettleto make wort, pitchingyeast or hopping a brew,the brewing of beer isboth art and science.

BY MELINDA CHRISTOPHERSEN


amount of liquor (water) is added at aset temperature. During the mashingprocess, polysaccharides areenzymatically broken down by theamylases to simpler sugars. The mashis filtered through the bed of grainhusks and the liquid known as ‘wort’(pronounced wert) is collected into akettle for wort boiling. This is wheresome of the most important chemistrytakes place.

Heating the wort sterilises theliquor, resulting in colour developmentby ‘non-enzymatic browning’, via aMaillard reaction between amines, oramino acids, and carbonylcompounds, in particular reducingsugars. The pigments are melanoidinsand the final product is caramel.Melanoidins have also been shown toexhibit antimicrobial and antioxidativeeffects, complexing with hydroxylradicals, which in turn improves shelf-life stability. Wort boiling contributes tothe final physical stability of the beerby coagulation of proteins, which areremoved, clarifying the wort andpromoting colloidal stability.

Hops are added to the wort kettleas cones or pellets (a compressedpelleted hop flower). It is the alpha-acids in the hops that are extractedinto the wort and isomerised duringthe boil to the more soluble iso-alpha-acids, which provide the characteristicbitterness. A series of hop additionsare made to the kettle, which ismaintained as a rolling boil. Thisprocess depends on temperature andconcentration since the hopcompounds are barely soluble. Inaddition to alpha-acids, hops alsocontain essential oils, contributing tothe sensory characteristics, such ashoppy, resinous, floral, fruity and spicyaromas to name a few. Most of thesecompounds are highly volatile and cantherefore be lost by evaporationduring wort boiling. In order to obtaina suitable compromise betweensufficient boiling to coagulate protein,isomerisation of the hop acids, andretaining aroma, the brewer may addpart of the hop addition later to the

whirlpool (late hopping) or even muchlater during the maturation process(dry hopping).

Hop varietals used in the beer havebecome of increasing interest asconsumer’s interest in raw materialprovenance grows. For the brewer andthe brewing chemist, the addition ofhops opens up a plethora of chemicalreactions that determine not only thecharacteristic bitterness of the beerand beer foam improvement, but alsothe flavour profile and quality of thesensory bitterness achieved. It isimportant to note that the aromatics ofthe raw hop may not necessarilydirectly predict the final aroma in beer.Aroma hop compounds (ppt–ppbrange) can be analysed during thebrewing process or in beer itself bygas chromatography with solid-phasemicro-extraction. In our laboratories,analytical profiles of raw hop pelletslurries have revealed very differentessential oil and thus olfactory profilesfrom those present in the final product.However, each hop variety willproduce specific flavour profiles infinished products that are somewhatrelated to the original compositionwhen considering expected losses ofvolatiles and more importantly theaddition point of the hops. This is a

complex process, and often hops areadded at several stages duringbrewing, further complicating theelucidation of the origin of thearomatic contributions produced.Besides addition point, one must alsoconsider the effect of yeastfermentation on the production of hoparoma, where aroma compounds arebio-transformed during fermentationby yeast.

Wort boiling fulfils many otherfunctions like stripping of undesirablevolatiles such as dimethyl sulfide,which can produce a corny, vegetalaroma. Dimethyl sulfide is continuouslyproduced in hot wort from the sulfur-containing amino acidS-methylmethionine, which originatesfrom the malt. Wort is chilled as quicklyas possible after the boil to preventfurther dimethyl sulfide productionand prepare the wort for fermentation.

The unique character of beer asopposed to other alcoholic fermentedbeverages is due to the subtleinteraction between carefully selected‘brewing strains’ of yeast and the maltand hops that come together as wort.Beer fermentation involves theconversion of sugars, derivedprimarily from malt, into ethanol by theyeast. Cooled and aerated wort is

The brewing process: where tradition meets technology


mixed rapidly with yeast (‘pitching’)and the cells multiply, take up sugarand produce ethanol, carbon dioxideand energy. Fermenters may be openor closed. The temperature offermentation determines the rate andamount of the side reactionsgenerating small quantities of

hundreds of compounds such asdiacetyl, higher alcohols and estersthat contribute to the beer’s flavour,some desired and others not so. Thelevel of higher alcohols or ‘fusel oils’produced are monitored as thesecompounds can negatively affectflavour. One important family of

compounds produced are the esters,which strongly influence theorganoleptic properties of beer due totheir presence at thresholdconcentrations, and therefore smallchanges in concentration have a largeimpact. The main representatives areethyl acetate (solventy) and iso-amylacetate (fruity). Lager beers,fermented at low temperature withbottom-fermenting yeast, usually havelow ester concentrations, producing acharacteristic clean flavour. Ales,which are fermented at highertemperature with top-fermenting yeast,often have the fruity or flowery notescharacteristic of esters. This is a clearexample of the diversity of beer styles.Flavours that are appropriate anddesirable in one style of beer may beconsidered defects in another style.

During fermentation, the pH of thebeer drops, which inhibits infection. Asubsequent maturation period allowstime for any residual sugars to befermented while non-desirablecompounds such as aldehydes and

Isomerisation of isohumulone

Key hop aroma compounds

The author and analytical chemist Ian McInerney at the GC-MS.

Chemistry in Australia 19|

sulfur compounds are removed by thecarbon dioxide produced. Maturationalso serves to degrade diacetyl (2,3-butanedione)) and a-acetolactate(the precursor). Diacetyl and related2,3-pentanedione are known as vicinal diketones (VDKs). Diacetyl ischaracterised by a butterscotch aromaand flavour and is consideredundesirable in lager beers. VDKs aregenerated by yeast as it synthesisesthe amino acids valine and leucine, thereaction accelerated by highertemperature and lower pH. Diacetyl islater converted to 2,3-butanediol bythe yeast, which has a lower flavour

impact. The presence of sufficienthealthy yeast during maturationpromotes diacetyl removal. Thus,diacetyl is a key parameter monitoredduring maturation and it must reachthe desired level before chilling andfiltration of the matured beer cancommence.

A key challenge for the brewer isthe physical and chemical stability ofthe product. Matured beer is filtered toremove turbidity due to the presenceof residual yeast and colloidal haze,and stabilised to promote flavour andfoam stability. Final pasteurisation orsterile filtration ensuresmicrobiological stabilisation.

Beer is best consumed fresh withvery few exceptions. As consumerpreferences shift towards packagedproducts and away from on-premiseconsumption, an understanding of thestability of the product and how tocontrol and lengthen its shelf life isessential. The main catalysts fordevelopment of aged characteristicsare oxygen and temperature.Packaging of beer must be carefully

controlled to avoid oxygen pick-up.Initially, chemical reactions developfruity flavours (fruity ‘ribes’), butprogress to papery (trans-2-nonenal)and waxy characteristics, as bitternessdecreases.

As a chemist or microbiologist inbrewing all processes are closelymonitored from raw materials topackaged products. When I startedworking as a chemist in brewing, oneof the first things I noticed was the highlevel of analytical technology andcomplex chemistry that was beinginvestigated. From dissolved gases,flavour and aroma profiles to sugarspectrums, there are always problemsto solve, new varieties of hops todiscover and processes to improve.Sensory evaluation is requiredthroughout and tasters undergorigorous sensory training of flavourand aroma attributes with continualassessments and re-familiarisation tomaintain accreditation and alignmentin scoring. For a brewer, theinterdependencies of the variouschemicals derived from the naturalingredients, as well as those producedduring the different stages, and theirsubsequent interaction with yeast andeach other is what makes brewing sofascinating and technically challenging.Yet, at the end of the day, the sheervariety of delicious, thirst-quenchingand wholesome beers that can beproduced makes all the effortworthwhile.

Dr Melinda Christophersen is Analytical ServicesManager at Carlton and United Breweries, where shemanages the National Laboratory function andsupport services to the production breweries. Thelaboratory specialises in flavour and aroma analysesfor brewing and beverages.

pyruvate

YEAST CELL WALL WORT

2,3-butanediol

readsorbtiondiacetyl diacetylleucine,

valine

a-acetolatate a-acetolatate

Diacetyl formation and removal by yeast.

The foam head of a lager contributes to itsaromatic qualities.


Citizen scienceThe New

EnlightenmentBY DAVE SAMMUT

Riding on the ICTrevolution,recruiting publichelp for research ison the rise, bringingbenefits for bothscientists and non-scientists.

In the wave of scientificadvancement through theRenaissance, through theEnlightenment and extending into

the 19th century, independent sciencewas an inspiring movement. Ourhistory is replete with men and women– for example Antoine Lavoisier, HenryCavendish, Mary Anning and CharlesDarwin – whose innate curiositytranslated to their direct dedication toscientific endeavour, using whateverresources were available to them at thetime.

As the 19th century progressed, theincreasing complexity and cost ofresearch saw the process becomemore institutionalised, and by the

20th century independent science wasvirtually extinct.

It might be argued (albeitsimplistically) that by taking scienceand sequestering it behind ivy-covered walls, we have done it adisservice. By reserving scientificadvancement and recognition largelyto an academic elite, perhaps we havedisenfranchised a significant portion ofthe population. In a recent article (Mayissue, p. 18), I wrote about the directconsequences of poorcommunications of science prior to theL’Aquila earthquake, which is at leastpartly a consequence of disparity inunderstanding and expectation.

iStockphoto/higyou


In the past 5–10 years, an emergingparadigm – citizen science – isshowing promise in bridging the gap.Its participants are different from theearlier independent scientists becausethe former were scientists first, byinclination and training. By contrast, theparticipants in the modern citizenscience or crowdsourcing projectscome from as wide a range ofbackgrounds as can be imagined.

As with any relatively new field, theterminology is evolving, but a goodworking definition of citizen science isprovided by Dr Philip Roetman of theAustralian Citizen Science Association.He describes citizen science asprojects where scientists work with thecommunity to conduct research.Roetman emphasises that a goodcitizen science project must includethree key components: research,engagement and education.

Perhaps the biggest driver in therapid growth of citizen scienceprojects in the 21st century has beencomputing and communicationstechnology, which has become cheap,rapid and ubiquitous. Information hasbecome democratised, readily

available to all, in a manner in whichthe creation and distribution ofinformation is no longer ‘top-down’,but much more shared. Roetman notesthat the IT revolution has been ‘thecatalyst for the explosion of citizenscience around the world.’

Earlier citizen science projectsinvolved the sharing of computationalresources as ‘distributed computing’,particularly for intensive calculationssuch as astronomy. However, inRoetman’s opinion, this lies at the edgeof the field, because it can lackparticipant engagement. More recentprojects such as those withinZooniverse (www.zooniverse.org)provide better examples withinastronomy. Among these projects,amateurs were encouraged to assist inlaborious tasks such as examiningastronomical images for galaxies andundiscovered planets. Moving beyondastronomy, zooniverse has a range ofinteresting projects, such as ‘OldWeather’, which asks volunteers totranscribe the weather observationsfrom historical ship logs, valuable datathat could help us understand how theclimate has changed. Critically, it wasfound that not only did amateursenthusiastically participate in therequested work, but they also formedforums in which they interacted witheach other to conceive and contributetheir own hypotheses to carry theresearch forward.

A good Australian example is theExplore the SeaFloor project(exploretheseafloor.net.au). Nearly10 000 citizen scientists are helping toanalyse nearly 400 000 images, initiallyto spot a northern sea urchin speciesinvading Tasmanian waters as part ofan investigation into the effects ofclimate change on local kelp andseaweed ecosystems. Participants aregiven online tutorials and support toidentify urchins in images captured bya robotic underwater vehicle, so thatresearchers can then assess thedepths and locations of the urchins,their number and range. There isfeedback on the progress, and the

opportunity to win a small prize asreward.

In the National Koala Count,selected and trained citizen scientistsare provided with a mobile phone app,and in a ten-day annual program theylocate and photograph koalas across awide geographical distribution.Importantly, these photos areautomatically geo-tagged using thephones’ GPS location features, so thatthe data can be verified and analysedfor bias (such as a predominance ofsightings along roads).

One of the key advantages of citizenscience is that it offers the potential togather significantly greater quantitiesof data, numerically, spatially andtemporally, than would be achievableusing paid field staff. It therefore lendsitself particularly well to environmentaland ecological studies, where thegreater sampling also increases thechance of capturing rare or sporadicevents.

Ornithology is particularlybenefitting from citizen science,drawing on a substantial establishedresource of enthusiastic hobbyists.However, flora and fauna studies andecology more generally also gainsubstantial participation, and it isnotable that such studies offer greatexamples of the multiple models forcitizen science. In ‘Contributory’models such as the Koala Count, theresearch is designed and conductedby scientists, with data input from thepublic. In ‘Collaborative’ models, thepublic may help refine the projectdesign, analyse data or disseminatefindings. In ‘Co-created’ models, thepublic are active in all phases of theresearch from initiation. This isparticularly the case for localecological projects such as studyingcontaminated aquatic ecologies.

Across all of these models (mostobviously the co-created projects),engagement is a crucial component.This extends beyond the choice ofresearch topics and emphasis toengage the interest of the participants,but also to the use and sharing of the

One of the keyadvantages ofcitizen science isthat it offers thepotential to gathersignificantlygreater quantitiesof data,numerically,spatially andtemporally, thanwould beachievable usingpaid field staff.


interim and final results. As such, thisalso shows the importance of goodproject design and clear definition ofgoals, because in a local ecologicalproject, for example, the community’semphasis might be on gathering datato support or precipitate early actionor intervention, whereas the scientists’emphasis might instead be on longer-term evaluation and/or analysis in awider context.

The educational component ofgood community science is similarlyimportant. The integrity of the datacaptured by citizen scientists is forpreference verifiable, and the use oftechnology has been of significantassistance in this regard. However,proper training and support for citizenscientists is important to minimiseobserver bias or sampling error, most

particularly as the degree ofcomplexity in field work increases.

As noted by Janis Dickinson et al.(Front. Ecol. Environ. doi:10.1890/110236), ‘A critical componentof this effort is the creation ofeducational materials, includingbackground information that allows theparticipants to understand the theoryand ideas behind the research, acomprehensible description of theresearch questions, and clearlydescribed, tested protocols for how tocarry out observations.’

This reliance on technology meansthat citizen science can’t simply beassumed as a source of ‘free data’. Thegrowing literature on the subjectroutinely emphasises the importanceof good project infrastructure design,including the website for engagement,

Other citizen science projectsIf you are interested in the opportunities, practiceand successes in Australian Citizen Science, checkout the Australian Citizen Science Associationwebsite (www.citizenscience.org.au), which will becelebrating the success of its July 2015 inauguralconference.

Links to various projects here andinternationally include:• Streamwatch (bit.ly/1C9LmHb)• Who's Living on My Land? (bit.ly/1ej29Tj)• Weather Detective (bit.ly/1MY1Ybo)• Donating computer downtime

(stanford.io/1QzTywn)• National Geographic citizen science

(bit.ly/1GoZ39c)• scistarter.com

Current citizen science projects in chemistryseem to be relatively scarce. The RACI is spreadingthe word among chemists by sharing the ABC’s callfor citizen science project proposals for NationalScience Week in August (bit.ly/1K8zVqd).

... proper trainingand support forcitizen scientists isimportant tominimise observerbias or samplingerror, mostparticularly as thedegree ofcomplexity in fieldwork increases.

iStock

pho

to/fotostorm


interaction and easy data entry, and (ifappropriate) a mobile phone app forfield use.

The establishment costs for acitizen science project may beappreciable, and it is important tofactor in the costs of the appropriatesupport, oversight andengagement/education resourcesthroughout the tenure of the project.However, the answer to this may atleast partially lie in the crowdsourcingmodel itself. Already there arespecialist sites through whichresearchers can pitch their ideas forcrowdsourced funding, often in returnfor project trinkets or outputs.

In an era when academicinstitutions are under increasingpressure for funding, citizen sciencemay be an opportunity for efficiency inlarger projects, particularly where

these involve certain types of labour-intensive data input (such as weatherobservations or image analysis), orexpensive field trials. However, moreimportantly than just projectefficiencies, I believe that the inclusionof the wider public in scientificendeavour can only lead to improvedoutcomes for the communication andgeneral understanding of sciencemore generally.

By participating in the scientificprocess, community members canbecome more familiar with the rigoursof the scientific method, theimportance of repeatable experimentover anecdote, the importance ofuncertainty and the timeframes of thedevelopment of knowledge. They willsurely become more alert to scientificnews, and more receptive to informeddiscourse.

By engaging more directly with thepublic, we as scientists should alsobecome more adept at explaining ourwork, more inclusive in our thinkingand (perhaps most importantly) betterat the art of listening, regarding andadapting to the needs of thecommunity that supports us. After all,that hasn’t always been our strong suit.

Dave Sammut FRACI CChem is Principal of DCSTechnical, a boutique scientific consultancy,providing services to the Australian and internationalminerals, waste recycling and general scientificindustries.

Citizen science duringtimes of warIn World War II, decoding of the Enigmamachine, one of the notable successes atBletchley Park, was a massive group project,involving hundreds of codebreakers(contrary to the story in the recent film onthe topic), including civilian amateurs whohad been recruited through a newspapercompetition. Although necessarily secret atthe time, this is an example of success incitizen science.

However, citizen science hasn’t alwaysbeen successful. In 1941, actress HedyLamarr conceived an approach to protectwireless communications from jamming by‘frequency hopping’, synchronised betweenthe transmitter and receiver. The idea wasrejected by the US Navy, who told her thatshe could better serve the war effort byusing her status as an actress to sell warbonds. But it was eventually taken upduring the Cuban Missile Crisis in 1962, andthe idea has served as a basis for themodern spread-spectrum communicationtechnology, used in Bluetooth and otherwireless communications. She was inductedinto the Inventor’s Hall of Fame in 2014.

iStockphoto/Mouse-ear


Science is undergoing asignificant transformation,moving away from thetraditional silo-style research

laboratories to larger consortia-style‘conglomerates’ that operate more likesmall companies than smallbusinesses. Group leaders haveevolved into group coordinators whopull in the funding, sell the product atinternational meetings, liaise withmultiple collaborators and manageseveral teams led by postdoctoralfellows. Postdocs too have greaterresponsibilities – supervising students,managing lab administration,balancing budgets, serving oncommittees, writing papers andleading their own projects – akin togroup leaders of small laboratories20 years ago.

Convergence, collaboration andcommunication are the latest buzzwords. Today’s scientists are urged todevelop interdisciplinary cross-sector

collaborations, attract industrypartners, patent and translate theirbasic discoveries, diversify theirfunding portfolios, contribute to policydevelopment and effectivelycommunicate their research topoliticians and the public.

With all of this change, it can bechallenging to plan ahead and knowyour next move.

There are certain milestones everyscientific researcher is expected toachieve – and the bar gets higherevery year. There will always be asmall percentage of ‘high flyers’ whogo far and above such expectations todizzying heights, where Nature andScience papers abound, and fundingand awards are plenty.

Failing to make strategic moves,however, can leave you stranded in aholding pattern or ‘pushed out’ – atany stage. Exciting opportunities canarrive at any time, so how can you bestprepare yourself to recognise them?

Our working livescan seem simplerwhen we have acareer plan – atimeline with goalsand outcomes. Inreality, the path canbe far from clear.

Your science careerMaking a strategic planBY MARGUERITE V. EVANS-GALEA iStockphoto/GlobalStock

Even a team of one. Develop your leadership style by being the change you want to see.While you do not need to become Gandhi, visionary leaders with a strong ethical compassattract followers in droves. Be consistent in your approach. Praise in public and critiquein private – with one critical exception (bit.ly/1M6JVzb). Disrespectful behaviour orcommentary should be called out diplomatically and promptly. Fully acknowledge thosewho did the work. It is common to see a group leader’s presentation consistently use theroyal ‘we’. Particularly in smaller group meetings or in media releases, be inclusive andtake the time to say ‘well done’. Respect and reward your team with simple acts: check inwith them occasionally, ask how you can help move their work forward, spend time withthem and say goodbye at the end of the day. Support their professional development – bea leader of leaders.


But don’t lose sight of the big picture.Defining your mission will help you towork harder and stay focused on yourgoal(s). As a graduate student, yourgoal was to get a PhD. Goals are lessblack-and-white as we progress,especially in science where the careerstructure is undefined for most of theresearch workforce. Our goals can blurto ‘doing good science’ or ‘contributingto the greater good’ – still excellentgoals, but much less defined. Only asmall percentage of researchers willexperience the linear academic careerpath to professor. If that is yourprimary goal, however, it is importantthat you keep this in mind during theday-to-day grind of negative data,failed funding applications andrejected manuscripts.

1STAYFOCUSED

Personal and professional. No one is anisland. As much as we think we areinvincible and can do it all ourselves,this is an unrealistic view. A researchcareer is rewarding, but it is alsohighly demanding. Do not be afraid toask for help and guidance. Our familyand friends celebrate our successes,commiserate our failures and cheer uson. A team of mentors, includingsenior investigators and/or peermentors, can share their experiencesand provide advice on different aspectsof your research and career. A strongsupport network, at home and at work,will make the tough times lesschallenging and enhance your abilityto perform at your best.

3SEEKSUPPORT

‘It’s not what you know, it’s who youknow’. In science, this is a falsestatement because if you do not knowyour stuff (see point 2), you will not berespected. This does not mean who youknow is unimportant. It is critical toextend your professional network bygetting out and meeting people. Thiscan include attending social events inyour organisation, sitting next tosomeone new at the next seminar,speaking with presenters at a postersession or working the room at aninternational meeting. Social media hasadded another layer to networking sinceit is an excellent tool for connectingwith people anywhere in the world.Networking enhances our skills, exposesus to new people and professions, andensures we are always thinking ‘outsidethe box’ and ready for opportunities.

4GETCONNECTED

Consistently. Like your research,develop an ‘operational mode’ that isreproducible and consistent. Tick theboxes routinely on your list. If youagree to meet with someone, be there.Follow up with emails and stick todeadlines. Know your stuff – and getknown for it. Instead of brushing overthe abstracts, actually read theliterature. Try not to spread yourselftoo thin. Become a productiverecognised expert in your researcharea. While ‘publish or perish’ is theacademic’s mantra, publish quality overquantity. A highly cited paper ofsignificance carries more weight thanone that gets lost in the noise. Makefirst- or senior-author papers yourpriority, but demonstratecollaborations with ‘other author’papers as well. Speak wheneverpossible – this is great experience andalso gets you and your research known.Importantly, be financially responsible.Be strict with your budget and a goodsteward of funds – public and private.If you perform consistently anddevelop good habits, you will bereliable – and people will be moreforgiving when you need to divert yourefforts for unexpected reasons.

2TICKBOXES

5BUILD AWINNING TEAM

iStockphoto/devseren


Let’s face it, scientific research can be a roller-coaster ride. You need to have confidence, bepersistent and know you can do it. Researchersare typically self-motivated individuals with ahunger for success. Eureka moments are few andfar between, and high-achieving researchers cansometimes struggle with these long periods. Finda way to ride the wave. This is different foreverybody: keep a ‘good moments’ folder on yourdesktop (filled with acceptance letters, awardsand friendly emails), practise mindfulness, dokick-boxing or go for a walk. Ensure your innervoice speaks kindly. Imposter syndrome(bit.ly/1BGupnv) and negative self-talk are bothcommon, especially in women, but both areunhelpful. Work on strengthening the skills youneed to develop, but have confidence in what youdo well.

Collaboration (bit.ly/1eMPOGM) is at the heartof research. So is healthy competition. Withdwindling funds, research has become hyper-competitive. Funding bodies and the public arekeen to see researchers collaborating more –young researchers want to work this way too.Collaborating is also a plus in a tight fiscalenvironment since sharing resources and talentreduces cost. We can encourage collaborationwithin our own team, but importantly withinour own organisation. Do a quick assessment ofthe research teams on your floor. How many doyou know? How many do you collaborate with?Does your team know the other teams – dothey know what techniques and equipmentthey have? Consider co-supervising a student orfellow on a novel project. Cross-fertilise ideasby hosting joint group meetings. These aresimple ways to extend your research capacityand network in-house. Beyond your institute,reach out to colleagues with similar over-arching research goals even if they are in adifferent discipline or field. Find commonground and work towards a shared goal bycomplementing and utilising each other’sexpertise.

6SYNERGISE

8BUILDRESILIENCE

But be prepared for anything. Develop a strategy to achieve your goals. Thiswill involve breaking things down into smaller bite-size triumphs. When weaim high, we are setting ourselves aspirational goals – and these can seemfar off, and on a bad day, unattainable. By mapping things out and settingachievable goals, like planning a long-distance road-trip, these goals becomemore realistic.

Imagine that you want to build your international profile. Sounds big, buta good way to move towards this goal is to speak at an internationalmeeting. Plan backwards and set realistic achievable goals that lead up toabstract submission and the meeting itself. This could include presentingyour research within your institute and seeking feedback on both the qualityof your work and your presentation. You are then in a stronger position todevelop a high-impact publication. Promote your work through a blog,attend a national meeting and do a ‘speaking tour’ in different institutes.Speak with your colleagues, collaborators and mentors often – and considertheir counsel. Importantly, revise your research plan as you go to increasethe quality of your work. Once your paper is ready, it is time to submit yourabstract, and click ‘oral presentation preferred’. This obviously takes time, butbefore you know it you will be the invited speaker.

This strategy can be applied to almost any goal. If you want a promotion,then research the requirements for the next level and work at or above thislevel. If you want to increase your public profile, write a blog every time youpublish and share it via social media. Work with your organisation’s publicrelations team to engage positively with the media.

Looking five years ahead is constructive and motivating. Have anindividual development plan (http://myidp.sciencecareers.org). Revisit whatis important to you both personally and professionally, then map it out –while expecting the unexpected.

7PLANAHEADiStockphoto/TAGSTOCK1


We now tell students that a PhD providesexcellent training and skills for any career,and the UK Royal Society recentlydeveloped guidelines for doctoral studentcareer expectations (bit.ly/1KAz8fM). Sowe must inherently believe and practisethis ourselves. Attend workshops tonurture, update and polish these skills,which include critical-thinking, problem-solving, trouble-shooting, projectmanagement, public speaking, leadershipand management, finance, writing anddebating skills. Develop a teachingphilosophy, write a teaching statementand teach or tutor whenever possible. Staycurrent with your techniques andexpertise, and accept opportunities tocontribute beyond the research sector.This will develop new skills and networksthat may be needed and useful when youleast expect.

9CREATEOPTIONS

Today’s scientific research environmentrequires an element of entrepreneurialsavvy. So as with any good business plan,there must be an exit strategy. Have a back-up plan (bit.ly/1dIMIU0). This is where allof the elements in the previous nine pointscome together to provide you the skills andknow-how of transitioning to a differentorganisation or another professional career(in or out of science) if required, or ifdesired. We all have limits and over time weget firmer on where those limits lie – on ourtime, expertise, finances, heart, body andmind. You will know when you are close toreaching your limits. It is up to you whatyour exit plan looks like and when it needsto engage, but at least look beyond thebench to what else is out there. You don’twant to miss any exciting opportunities.

10HAVE ANEXIT PLANSo can you really ‘strategically plan’ a career in science?For success in any career, it is perhaps less about having a plan andmore about ‘being strategic’. Of course timing and luck also play arole. Developing the skills and applying the strategies outline here willstrengthen your ability to never run low on fuel, avoid holding patternsand take flight to succeed in science!

Dr Marguerite V. Evans-Galea is at the Bruce Lefroy Centre for Genetic Health Research,Murdoch Childrens Research Institute and the Department of Paediatrics, the University ofMelbourne. She is co-founder of Women in Science Australia.

iStockphoto/4774344sean

PTYLTDRowe Scientific

www.rowe.com.au

Reference materials from all major worldwide sources including:NIST (USA), CANMET (Canada), SABS (South Africa), BAS (UK), Standards Australia, BGS (UK), BCR (Belgium), NWRI (Canada), NRCC (Canada), Brammer (USA), Alpha (USA), Seishin (Japan)

Suppliers of:

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CERTIFIED REFERENCE MATERIALS

books


My life in the golden ageof chemistry: more funthan funCotton F.A., Elsevier, 2014, hardcover, ISBN9780128012161, 344 pp. + appendices, $77

Though not an avid reader ofautobiographies, I jumped at theopportunity to review My life in the goldenage of chemistry. Every inorganic chemistover the past 60 years has heard ofFrank A. Cotton. I have often referred tohis books and papers, but knew little abouthim, so was eager to learn more.

Frank Albert (‘Al’) Cotton was one of inorganic chemistry’sgiants. His research output exceeded 1600 publications in bothcoordination and organometallic chemistry, he was co-author ofthe standard textbook on inorganic chemistry for well over twodecades (I have three editions) and he authored Chemicalapplications of group theory. He also supervised119 postgraduate students and nearly 150 postdocs (all listedin the appendices), many of whom went on to distinguishedacademic positions.

Sadly, Cotton passed away on 20 February 2007, while thisbook was being prepared, as a result of injuries sustainedduring a brutal assault while walking near his house.

The timeline of the book traces Cotton’s periods at highschool, then as an undergraduate in Philadelphia andpostgraduate at Harvard, followed by his academic career at MITand then Texas A&M University.

Cotton arrived at Harvard in 1951 and decided to work witha new assistant professor, Geoffrey Wilkinson. Shortly thereafter,Kealy and Pauson published their seminal paper on thesynthesis of bis(cyclopentadienyl)iron(II), now known asferrocene (so named by Mark Whiting, a postdoc of RobertWoodward). Wilkinson and Woodward’s deduction of ferrocene’scorrect structure and their discovery that E.O. Fischer in Berlinwas working in the same area led to a veritable frenzy ofactivity in the nascent area of organometallic chemistry.

Following his PhD, Cotton transferred to MIT where the years1955–71 were spent rising from instructor to full professor. Hesubsequently joined Texas A&M University to occupy theRobert A. Welch Chair.

Part of this book’s fascination is that Cotton’s careercoincided with the renaissance of inorganic chemistry, to whichhe made fundamental contributions concerning both itssynthetic and theoretical aspects. Many of these were ‘firsts’,such as:• application of group theory to metal carbonyl compounds• application of crystal field theory• X-ray crystallography• metal–metal bonds and clusters• dynamic NMR spectroscopy and fluxional molecules• agnostic interactions.

Cotton knew and interacted with all the big names of theépoque; some are mentioned in the book’s various sections andothers are grouped in a separate chapter near the end (thisincludes his thoughts on Geoffrey Wilkinson).

The appendices include details about Cotton’s publications,postgraduate students and postdoctoral fellows. Particularlygermane to the present dire research climate is Appendix D,which contains the text of his presentation for the 1998 PriestlyLecture, entitled ‘Science Today – What Follows the Golden Age’.I concur with his sentiments expressed therein, namely that thedays of curiosity-driven research are over. Nowadays, theobsession is with applications or usefulness. Funding is tightand controlled by administrators with short-term perspectives.You need look no further than the proliferation of journals tosee that everybody is riding on the same few bandwagons.Academics spend much of their time chasing their next grantinstead of focusing on and enjoying the chemistry.

I find the book’s title especially apt. The ‘golden age’ ofresearch is well and truly over, golden in this context meaningthe period of generous funding for pure research.

The style is easy to read. Naturally, as Cotton was a chemist,there is a solid amount of chemistry among his reminiscences.This gives him the opportunity to acknowledge those whocontributed to the research.

I highly recommend this book without any hesitation toanyone with an interest in inorganic chemistry.

Franz Wimmer FRACI CChem

Solid state chemistryand its applications(student edition)West A.R., John Wiley and Sons, 2nd edn, 2014, paperback, ISBN 9781119942948, 556 pp.,$77.95, ebook $62.99

The first edition of Solid statechemistry and its applications byAnthony West appeared in 1985. Youcan still buy it from the publisher inprint-on-demand format for a mere$964.95! This 2014 version is aslimmed-down, student edition of the eponymous book, whichis scheduled for re-publication in 2015/2016. Essentially, it isan update on West’s related work Basic solid state chemistry,first published in September 1988 with a second editionpaperback published in May 1999. If you are confused, then soam I. It appears the aim is to meld two titles into one,distinguished by the term ‘student edition’. This book is not the‘real deal’, but an abbreviated version of the yet-to-appearmajor work. Either way, it is an impressive work with a wide andup-to-date coverage.

Solid state chemistry is an interesting ‘beastie’ and a very,very important area both economically and intellectually. Yet,


perhaps because the teaching of chemistry traditionally dividesinto four main segments (physical, organic, inorganic andanalytical), while the solid state spans the field (and so belongsto none), it is probably under-studied, under-appreciated andlargely unloved in undergraduate chemistry courses. Westadvances a cogent argument, slightly tongue-in-cheek, fordividing chemistry into two areas, molecular (liquids and gases)and non-molecular (solid state). Though probably a good idea, Ican’t see it happening any time soon. Meanwhile, materialsscientists, chemical engineers, geologists and sundry other‘apostate chemists’ have largely claimed this section of ournoble chemical heritage!

This book is very well written and logically developed. Afterdeveloping crystal structures and crystal chemistry, thenbonding in solids, very interesting sections on synthesis andfabrication of solids and techniques for analysing them ensue.This is all really well done, but if I have to single out one bitfor special mention, then the discussion of defects in solidswould be it.

The book’s concluding chapters concentrate on the electric,magnetic and optical properties of solids, bringing the readerup to speed on areas including superconduction, fibre optics,phosphors, photodetectors and solar cells. Much of this is verytopical and directly relevant to our lives today. Theexplanations are clear and the book is splendidly colour-illustrated. Since crystal structures are usually threedimensional and bits of paper essentially two, the use of colourto illustrate structures is superbly beneficial, although I don’tknow whether a phase diagram gains all that much. Theaccompanying website (www.wiley.com/go/west/solidstatechemistrystudent) is a mine of freely available anduseful information, including a downloadable CrystalMakerviewer program (Windows and Mac) and a library of 100 or socrystal structures to access and manipulate on your computer.The website also hosts PowerPoint slides of diagrams from thebook, answers to questions and so on.

So what is missing? The earlier ‘full’ edition containedchapters on glass, cement and concrete, refractories andorganic solid state chemistry. These topics receive minimalcoverage in this edition but will, presumably, be treated in thenew ‘full’ version. They are, after all, major areas of solid statechemistry, albeit perhaps lacking the glitz of the more recentdevelopments discussed.

If you read this book (and it is a very good book), then youwill ensure you have a very fine grounding in all the fundamentalaspects of the chemistry of solids, plus a good grasp of some ofthe more recent developments in the field. If you lecture and seeka good book to underpin a course in solid state chemistry, thenyou have found it! All in all, I recommend this book most highlyas a well-thought-out, well-written tome, pitched atundergraduate to postgraduate level, about a fundamentallyimportant area of chemistry and materials science.

R. John Casey FRACI CChem

Open-source lab: how tobuild your own hardwareand reduce researchcostsPearce J.M., Elsevier, 2013, hardback, ISBN 9780124104624, 271 pp., $65

Open-source lab is a very enthusiasticbook. Using open-source microcontrollers(the book concentrates on one variety,Arduino, costing US$20-50*) and 3Dprinting (using a RepRap, or self-replicating rapid prototyper), plus freelyavailable software, author Joshua Pearce claims you canconsiderably cut research costs. He’s probably right. However, ifyou do decide to DIY, the time spent sourcing the hardware andsoftware you need, fathoming out whether you need to adaptthe latter and, if so, how (these devices operate on a LINUXplatform and a bit of programming knowledge in C++ is also

useful), or using your 3D printer to produce bits of hardware,again from downloadable open-source software, could make theeconomics less favourable. You will probably also need to be aproficient at soldering (and this can take practice too!).

The notion that there are all these goodies on the internet,freely available to share and develop in an evolutionary way soyou can re-share anew with others, is very appealing. The ideaof building your own lab-jack, spectrophotometer, reactionvessel or Buchner funnel using software someone else is happyto give you is also very exciting, particularly if you think it willsave you money too. But it gets better! The 3D printer is oneyou have made yourself. The text devotes a lot of effort todescribing exactly what parts are needed, where to buy them,and how to assemble your RepRap for about US$600.Intriguingly, the RepRap is capable of making over 50% of itsown parts. Well, I guess the moral is ‘don’t be first’, or at leasthave a friend with a 3D printer.

You can see, I hope, that Open-source lab is for enthusiastswho like tinkering about with clever devices, enjoy a bit ofprogramming and know a bit about assembling circuitry. Theyalso quite enjoy soldering components onto circuit boards

*Australian enthusiasts may be more familiar with, for example, Raspberry Pi.

... Open-source lab is forenthusiasts who like tinkeringabout with clever devices,enjoy a bit of programmingand know a bit aboutassembling circuitry.

(made with their RepRap?) and are looking for cheap ways tofacilitate their work. To build your own RepRap is a greattemptation, but it does mean backing your own ability to thetune of US$600 odd. What if it doesn’t work? Well, there’splenty of help out there on the internet, but for not a lot moreyou could buy a commercially available printer (although I haveno idea of performance comparisons) which is, more or less,guaranteed to work. If you do want to build your own, thenPearce’s text looks like a good guide to follow.

I think you could have a lot of fun with your Arduino,without (even) blowing the petty cash budget. There are lots ofinteresting bits and bobs you can build, some of which could bevery useful in teaching laboratories where you might be lookingat ‘class sets’. There are big savings to be had in making yourown pH meter, potentiostat or fluorimeter (to name three I’veseen in action) and getting them to work. While costing labourinto the mix might turn your savings ephemeral, if it is fun,then enjoy. In a research environment, the possibilities arelimited only by your own imagination. Like the TV program YesMinister, if you want the answer to your problem, then you haveonly to ask. If you don’t know what questions to ask, then Iguess you buy this book, grub around the web, buy yourself anArduino and have a play. It just might pay off big-time.

I can see a role for 3D printing in chemistry, but my vision islimited. It may be more productive to take your ideas to alaboratory craftsman to realise than to reinvent the wheel.Again, if it is fun, then applications will surely follow.

Overall, I enjoyed this book. It is enthusiastic andencouraging and will point you in the right direction if youenjoy tinkering. As a burnt finger survivor, my advice is festinalente. Treat the exercise as good fun, but don’t expect miracles.

R. John Casey FRACI CChem

Sittig’s handbook ofpesticides andagricultural chemicals Pohanish R.P., Elsevier, 2nd edn, 2015,hardcover, ISBN 9781455731480, 973 pp. (including 105 pp. of synonymsand 124 references), $531.95

When I agreed to be a book reviewerfor the RACI, I expressed a preferencefor the traditional hardcopy ratherthan the new e-book format. Havingsince received this 2.6 kg reference,perhaps I should have considered myrequest more carefully! However, despite its relative mass,Sittig’s handbook of pesticides and agricultural chemicals wascertainly easier to ‘use’ than if it were in electronic format.Being able to thumb quickly to other pesticides and betweencross-references is best performed with a hardcopy, rather thanthe cumbersome scrolling demanded by the ‘newer’ electronicformat.

As an environmental chemist of more than 30 years’experience, it has been a long time since I actually needed toread the ‘How to Use this Book’ section of a reference work likethis. But with a complex reference tool like Sittig’s handbook,such reading is mandatory. The 14 pages of ‘how to use’ detailsthe systematic methodology applied to organise and describethe more than 450 pesticide and agricultural chemicals includedin the handbook. Some 40 sections describe key informationsuch as chemical name, use type (of which there are 28,including fertiliser and fungicide), CAS number, formula andsynonyms (which proves especially useful for pesticides)through to regulatory and advisory agency trigger values,physical properties and, importantly, incompatibilities andstorage recommendations. Personal protective equipment(including respirator selection), medical surveillance, first aid,

Online indexesDid you know that Chemistry in Australia indexes areavailable online? Browse or search our archived backissues from 2003 onwards.

To view the indexes, visit chemaust.raci.org.au and goto Other resources.

iStockphoto/Onur Döngel

books



John Wiley & Sons books are now available to RACI members at a20% discount. Log in to the members area of the RACI website,register on the Wiley Landing Page, in the Members Benefits area,search and buy. Your 20% discount will be applied to yourpurchase at the end of the process.

Receive 25% off Elsevier books at www.store.elsevier.com (usepromotion code PBTY15).

points of attack on the human body and (finally!) disposalmethods round out the range of information sections presented.

As noted in the preface to this second edition (hopefullywith no pun intended), the handbook is described as animportant tool for ‘all who come in contact with pesticides andagricultural chemicals at work or at home’. Sittig reports thatthe world’s top ten pesticides consumed in 2007 (based onmass used) in an agricultural market dominated by the US werethe herbicides glyphosate, atrazine, metolachlor-S, acetochlor,2,4-D and pendimethalin; and the fumigants metam-sodium,dichloropropene, methyl bromide and chloropicrin. Sittig alsonotes that an estimated 80% of all US pesticide usage in 2007was in agriculture. Between 2000 and 2007 (the most recentyear reported in Sittig for this data), the world’s total mass ofpesticides consumed was reported to have actually decreasedby 8%, from 1.2 billion pounds to 1.1 billion pounds (thoughstill more than 500 000 metric tonnes!), commanding a value ofmore than US$12.5 billion.

As a reference, Sittig’s handbook of pesticides andagricultural chemicals has considerable value. I wouldrecommend it to those chemical industry practitioners whoneed quickly accessible data at their fingertips.Notwithstanding today’s electronic database society, suchhardcopy references still remain a much more user-friendly and accessible means for complex data inquiry (or am I justgetting old?).

Ross McFarland

Online magazine discountThe quality of our monthly magazine Chemistry inAustralia has never been better thanks to theprofessionalism of the editorial team, the many regularcolumnists and guest authors. Unfortunately, the costsof printing and posting hard copies of the magazinehave continued to rise and they are placing increasingpressure on the RACI’s finances and thus membershipfees. Compounding the problem is the increasing trendof advertisers moving away from in-print advertising toonline advertising. For these reasons, it has beennecessary for the RACI Board to put in place a strategyto address the results of declining advertising incomeand rising printing and postage costs.

To ensure that the quality of the magazine continuesto improve and that all members continue to haveaccess, we have recently established a dedicatedwebsite (chemaust.raci.org.au) for Chemistry inAustralia. All members are encouraged to visit thewebsite to appreciate the work that has gone intomaking this magazine even more accessible. The onlineissue is also available earlier than the printed copy.

Many RACI members are already choosing the onlineversion of Chemistry in Australia but they have notreceived any financial incentive for this until now. The Board has decided to introduce a membership feedifferential where members taking the online onlyversion of Chemistry in Australia will receive a $15discount from their membership fee from the nextrenewal cycle.

Those members who wish to continue receiving theirhard copy will still be able to do so at the standardmember rate.

Honorary life members, who pay no subscription, willcontinue to receive the hard copy free of charge if theywish.

Paul Bernhardt FRACI CChem, RACI President

Memoir: Stephen AngyalUnder the auspices of the Australian Academy ofScience, a biographical memoir that will be of interestto chemists was published in the latest issue ofHistorical Records of Australian Science (vol. 26, no. 1,pp. 84–91): ‘Stephen John Angyal 1914–2012’. Manymembers will have access to the journal via institutionalsubscriptions. Others can obtain a pdf copy bycontacting the author at [email protected] the online publication is a completepublication list for this important Australian chemist.

plants & soils


This is a true story.There once a lovely gentleman who was so old that he had

been one of the Rats of Tobruk. He was, and still is, a gardener,a storyteller and a poet.

Just before his 100th birthday, he reluctantly moved into anursing home, where he arranged for one of the raised gardenbeds in the courtyard to become a vegetable garden, partly fortherapy for the other ‘sick’ people in the home. He planted someseeds and sat in the Perth autumn sun and waited. All hisrelatives arriving for his birthday celebrations waited with him.

And chemistry happened, down in the soil where no onecould see.

Dry seeds are in a state of quiescence, maintaining aminimum (but not zero) level of metabolic activity. Everythingis there ready for them grow, but there are also hormones suchas abscisic acid that inhibit the initiation of germination. Thisis just a common example – there is a wide variety of inhibitorycompounds in different plants.

When the seed ‘feels safe’ – usually where it is damp anddark, there is a Goldilocks (‘just right’) temperature for thatparticular species, there is adequate oxygen circulation and nottoo much carbon dioxide – then water penetrates thesemipermeable membrane of its hard coat. Since proteins arezwitterions, they have a high affinity for water, so seeds withhigher protein content will imbibe more water than thosewhose major energy-storage compounds are starch or lipids.(This is neither good nor bad, it is just something else thatdiffers between plants.) Once the critical water concentrationhas been achieved for that particular seed, germinationproceeds and the process cannot be turned back.

Water deactivates (or sometimes washes away) the inhibitorsand activates other hormones such as gibberellic acid A thatmodulate chromosomal transcription and initiate some of theenzymes that break down the nutrients stored in the seed intosimpler sugars and amino acids. All the other metabolicprocesses that ensure the development of the seed into a plantare also stimulated. Giberellic acid concentrations typically riseas abscisic acid concentrations fall.

Eventually the hard seed coat ruptures and the little radicle(root) emerges. At the same time, the developing embryo takesin even more water and increases its respiration rate. The rootshuns light, and, under the influence of gravity, it moves downthrough the soil. The gardener could not see this, but from hislong experience he knew it was happening. He sat and waitedsome more.

After this phase, when nutrients are being metabolised andATP produced like mad, the epicotyl (shoot) pushes out of theground, moving towards the light and away from the force ofgravity – as each generation of primary-school studentscontinues to affirm. Each plant is now an autotrophic organism… the process of ‘germination’ is complete. Hormones called

Chemistry happens underground where no one is looking

Since proteins arezwitterions, they have a highaffinity for water, so seedswith higher protein contentwill imbibe more water thanthose whose major energy-storage compounds arestarch or lipids.

Your advert could be here.For further information about advertising here or on our website, contact:Marc Wilson ◆ Gypsy Media Services ◆ 0419 107 143 ◆ [email protected]

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auxins, such as indole-3-acetic acid, promote cell growth incertain ways, and cytokinins (such as zeatin) influence celldivision and shoot formation in other ways.

But more chemistry needs to happen before the vegetablesgrow and can be harvested. The first leaves to appear are thecotyledons (seed leaves). Dicotyledons and monocotyledonsdiffer in both physiology and biochemistry, and there are alsosome plants whose cotyledons stay beneath the earth. But allthese fat little leaves have a reserve of partially hydrolysednutrients, a source of quick energy for the newly growing plantto use before the real leaves develop and can startphotosynthesising.

And the day that our gardener’s vegetables first showedtheir beautiful little green shoots to the onlookers was 1 April– my Uncle Colin’s 100th birthday. This was not one of his usualpractical jokes, nor was it an April Fool’s prank played back onhim. This really is a true story.

Dr Deidre Tronson FRACI CChem used to be a mad scientist, but isnow the Good Little Banksia Lady who, in retirement, is anenthusiastic member of Scientists and Mathematicians in Schools ata local primary school. She has proudly raised three sciencegraduates. She has had separate careers in research and teaching,culminating in a position as part-time senior lecturer at the

University of Western Sydney, Hawkesbury campus. (PS. My previous article (May issue, p. 40) was about plant communication. If youwant to follow that up and see that I was not totally talking through my hat, seethe set of Smithsonian (US) videos at bit.ly/1cXv1yM.

Uncle Colin next to his raised vegetable garden bed.

technology & innovation


Inherency is a complex issue that often arises in patentsrelating to the life science technologies. In the appeal decisionin Bristol-Myers Squibb Company v. Apotex Pty. Ltd. [2015]FCAFC 2, the issue of whether or not a particular chemicalproperty of a particular drug was inherently disclosed in a priorart document was considered.

Brief background of the inventionAustralian Patent No. 2002334413 in the name of OtuskaPharmaceutical Co. Ltd. and assigned to Bristol-Myers SquibbCompany (BMS) is titled ‘Low hygroscopic aripiprazole drugsubstance and processes for the preparation thereof’. Theclaimed invention relates to a chemical compound, genericallycalled aripiprazole, in a crystallised form. Aripiprazole is anatypical antipsychotic drug useful for treating schizophreniaand is the active ingredient in Abilify, which is supplied by BMS Australia. This crystalline form of aripiprazole was shownto have low hygroscopicity. Such an improved form ofaripiprazole would allow ease of handling during manufacture,improved shelf life, and improvements in the preparation ofaccurate dosages.

The patent claim under consideration recites:

Anhydrous Aripiprazole Crystals B wherein said crystals have lowhygroscopicity wherein said low hygroscopicity is a moisture content of0.40% or less after placing said drug substance for 24 hours in a closedcontainer maintained at a temperature of 60°C and a humidity level of100%; have a powder x-ray diffraction spectrum which is substantiallythe same as the following powder x-ray diffraction spectrum shown inFigure 5; have particular infrared absorption bands at 2945, 2812, 1678,1627, 1448, 1377, 1173, 960 and 779 cm–1 on the IR (KBr) spectrum;exhibit an endothermic peak near about 141.5°C in thermogravimetric/differential thermal analysis (heating rate 5°C/min); and exhibit anendothermic peak near about 140.7°C in differential scanningcalorimetry (heating rate 5°C/min).

Prior artOne of the prior art documents, which was also discussed in thepatent specification, detailed in its examples how one form ofanhydrous aripiprazole crystals can be made. This prior artexemplified recrystallisation of aripiprazole from ethanol toform anhydrous aripiprazole as a specific type of crystal,designated as Type-I.

The prior art further exemplified that aripiprazole wassubsequently used in pharmaceutical testing on mice, but thedocument did not state the form of the chemical used.

Apotex’s submissionsApotex made several submissions. These included that:1 a particular crystalline form (a polymorph) was claimed2 the crystalline form was not limited to any particular

environment3 the crystalline form was not limited to any particular process

of manufacture

4 hygroscopicity is an inherent property of a polymorph andthe claim refers to a single unique polymorph

5 the skilled person would remove ethanol as a matter ofroutine from the crystals when following the proceduredescribed in the prior art.

Inherent disclosure?Apotex’s position was that the prior art disclosed a method ofmaking a crystal form of aripiprazole as claimed in the patent.In order to demonstrate its position, Apotex directed its expertwitness to follow the experimental procedure as outlined inExample 1 of the prior art document. Apotex’s expert completedthe experimental procedure, but he additionally dried thecrystals at between 80°C and 100°C overnight in an oven toremove ethanol bound within the crystals of aripiprazole.Ethanol was removed in line with the motivation to preparearipiprazole suitable for pharmaceutical testing. Apotex’sexpert’s procedure resulted in the formation of the claimedcrystals, having the specified hygroscopic property.

BMS similarly instructed its expert witness to follow the priorart method. However, its expert did not dry the crystals formed.The crystals formed by BMS’s expert did not have the specifiedhygroscopic property.

It was submitted by Apotex that a drying step would be aroutine step conducted by any chemist at the priority date andwould have been done as a matter of course.

Australian inherency – the devil is in the detailaripiprazole

This decision confirms that adocument would beconsidered to inherentlydisclose a feature if theskilled person would, as aresult of following theinstructions, inevitably obtainthe claimed invention.

A question to be considered by the Court was whetherExample 1 of the prior art inherently disclosed the lowhygroscopic crystalline form of aripiprazole, when the skilledperson followed the instructions, even though a drying step wasnot disclosed.

What causes the low hygroscopic nature ofaripiprazole?The experts were questioned on the role of the crystal structureon hygroscopicity. The evidence suggested that crystal structurewas not the sole contributing factor and that other physicalproperties, such as crystal size and the surface properties of thecrystal, also played a role. BMS’s evidence suggested that aspecific drying step, as disclosed in the patent, resulted inmodifying the physical characteristics of the crystal surface,which in turn, resulted in reduced hygroscopicity. Thisreasoning was approved by the Court and it agreed that theunique surface properties of the crystal structure were impartedas a result of the drying step.

The evidence also showed that a broad range of dryingprocedures was available as options for removing ethanol. SinceApotex failed to show that a different drying step to thatconducted by its expert would also result in crystals withreduced hygroscopicity, it did not show that any drying stepwould result in the claimed hygroscopic property. Therefore, theFull Court determined that the skilled person, in following theexperimental procedure, might have obtained the claimedcrystals serendipitously, but it was equally possible that theywould have obtained conventional crystals without the reducedhygroscopicity. Since there were no clear and unmistakabledirections to do what the patentee claimed to have invented,the Court considered that the prior art did not inherentlydisclose the low hygroscopic feature.

Take-home messageThis decision confirms that a document would be considered toinherently disclose a feature if the skilled person would, as aresult of following the instructions, inevitably obtain theclaimed invention. Although Apotex had shown that drying acompound was a routine step, it did not show that other dryingmethods would result in aripiprazole having low hygroscopicity.

Elizabeth Houlihan FRACI CChem ([email protected]) and Jim Y. Onishi([email protected]) are patent attorneys at Houlihan2, Patent & Trade MarkAttorneys.


Chemistry in Australia’s diverse readership representsall major fields of chemistry – in research, education, manufacturing, business, minerals, food, pharmacy andmore.Chemistry in Australia is the flagship publication of TheRoyal Australian Chemical Institute Inc., the qualifyingbody for professional chemists in Australia. For over 30 years, the magazine has served its readers in thebroad discipline that is chemistry. To present your product or service to this specialist market, contact Gypsy Media Services: Marc WilsonDirectorPh. 0419 107 143 [email protected]

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economics


In a chemical process, if by-products have no or little value,then processes should be refined to minimise their productionand eliminate waste disposal costs. For many processes, by-products are a significant outcome that cannot be eliminated.The essence of many a successful chemical business ismaximising the sales revenue from such by-products.

The impact of the value of by-products is well illustrated inthe production of biodiesel from vegetable oils and fats.Biodiesel is a mixture of fatty acid methyl esters (FAME)produced by the trans-esterification of oils and fats usingmethanol. The by-product is glycerine (glycerol).

Regional agricultural considerations tend to determine thesource of FAME. In the US, soybean is a major source, in Europeit is rape (canola) and in our region palm oil is a majorfeedstock. Many other seeds can be used if available. Anothersource in our region is tallow (beef and lamb fat) produced frommeatworks.

From seeds, the first step in the process is milling (crushing ofthe seed) to produce the vegetable oil and a by-product meal usedas cattle feed. So at this first stage, the ultimate production costof the biodiesel depends on three variables – the cost of the seeds(farm economics, seasonal influences), the value of the vegetableoil and its alternative use as a foodstuff, and the value of cattlefeed. Clearly the processing margin at the mill will influence theprice paid for the vegetable oil for biodiesel.

Oils and fats are triglyceride esters of fatty acids. Althoughmany enthusiasts use these oils as diesel fuel, the highviscosity and contaminants make them unsuitable for use asquality biodiesel. The oil produced is trans-esterified withmethanol to produce FAME and glycerine. The process removesimpurities and reduces the viscosity, making the producedFAME a suitable diesel fuel, especially when blended withconventional diesel to produce a blend such as B5 or B20 (5% and 20% blend of biodiesel and petroleum dieselrespectively). Higher blends are possible but the use of highlevels of FAME is generally not recommended by vehiclemanufacturers without changes to engine components such aspumps and injectors.

The inputs are oil and methanol and the outputs are FAMEand crude glycerine. Methanol prices are sometimes quitevolatile and this volatility has to be accommodated in theprocess economics.

Refined glycerine has a large demand in food, cosmetics andother high-added-value industries. There are several grades,with some grades such as kosher being exclusively producedfrom vegetable oils. In the early days of biodiesel production,glycerine was a by-product of quite significant value. However,as the biodiesel industry has expanded, so has the productionof glycerine and this has seen the relative price of glycerinefall.

Biodiesel and by-products – glycerine

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Palm oil is derived from the fruit pulp of oil palms, predominantly Elaeis guineensis.


The fall in the price of glycerine has had a major impact onthe production cost of FAME. This is illustrated in the graph,which takes account only of the feedstock (in this case canolaoil at $500/t) and methanol costs ($300/t); operating andcapital costs are not included.

This graph illustrates the dramatic dependence of the cost ofbiodiesel production on the achieved value of the by-productglycerine. At current oil prices, diesel is traded at about 50c/L,which requires crude glycerine prices in excess of $800/tcompared to recent prices below $500/t.

The declining profit of biofuel operations in the face ofdeclining glycerine prices and the glut of glycerine on themarket has sparked research into alternative uses for glycerine.One is the selective hydrogenation to produce 1,2-propanediol,which is a highly valued product produced from propyleneoxide. This is having some impact on the 1,2-propanediolmarket but it is not a perfect substitute, with preference forsome uses still favouring the relatively expensive propyleneoxide route. Another idea is the selective hydrogenation to 1,3-propanediol, another highly valued chemical.

A consequence of poor FAME economics is the promotion ofan alternative approach to biodiesel, so-called ‘green’ diesel. Inthis process, the vegetable oil or tallow is treated at hightemperature and pressure with hydrogen over a catalyst tohydrogenate and decarboxylate the glycerol esters to produceparaffins and propane. For example, a C18 fatty acid ester

produces a mix of C17 and C18 paraffins and propane. Theseproducts are completely compatible with mineral diesel and LPG(propane). This route avoids the compatibility issues of FAMEand conventional diesel as well as avoiding the production ofcrude glycerine.

Green diesel can be produced in small-scale plants producing100% biofuel for blending or use. It can also (with a bit ofadaption) be utilised in a conventional refinery hydro-treater,producing diesel and directly produce a blend of biodiesel andmineral diesel; for example, B5 can be produced by hydro-treating conventional gas-oil with 5% vegetable oil or tallowadded to the hydro-treater feed. Using a conventional oilrefinery process unit avoids the capital cost of building andoperating a bio-fuel facility. The economics are almost entirelydetermined by the price of the vegetable oil relative to that ofdiesel and LPG.

This route can also be used to produce bio-jet fuel bychoosing oils with high C14 and C15 ester content such ascoconut oil.

The concept of green diesel has gone further to the conceptof bio-refinery in which vegetable oils and tallow are hydro-treated to produce 100% bio-jet, biodiesel and bio-LPG.

As various jurisdictions legislate for the inclusion of morerenewable fuel in the conventional fuel mix, the concept of abio-refinery is of increasing interest. For example, the Italiancompany ENI has converted its refinery near Venice to producemore that 300 000 t/year of 100% renewable fuel.

The major downside for this process is the source of thefeedstock. The preferred feed (because of relatively low price asa consequence of high crop yields) is palm oil. This is nowbeing shipped in large parcels to bio-refineries in Europe andaround the region for the production of bio-fuels so as toachieve government-legislated mandates. This is addingconsiderably to the demand for palm oil, leading to thedestruction of tropical rain forests for increased oil production.

The declining profit of biofueloperations in the face ofdeclining glycerine pricesand the glut of glycerine onthe market has sparkedresearch into alternative usesfor glycerine.

500 600 700 800 900 1000 1100 1200 1300

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80

70

60

40

30

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F AME ( c/ L)

Glycerine ($/t)

Effect of price of glycerine on price of FAME.

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Duncan Seddon FRACI CChem is a consultant to coal, oil, gas andchemicals industries specialising in adding value to naturalresources. He is indebted to CRU International Limited(www.crugroup.com) for market information on bauxite, alumina,anode carbon and metal prices.

environment

Renewable energy and energy policy have been in the news lately.Just before writing this, the federal government and oppositionwere engaged in negotiations over the revised Renewable EnergyTarget (RET). The RET was intended to, among other things,encourage the generation of electricity from renewable resourcesand reduce greenhouse gas emissions. However, the negotiationshave refocused to a reduction of the target. Once again, the‘policy’ debate has been mainly about a very large number, whichcan’t be comprehended by most people, and is measured in unitsthat many in the media seem unable to get right.

The RET was adjusted because, although the previous GWhnumber had been set at 20% of anticipated electricity productionin 2020, reduced electricity demand meant that the previousfigure would likely be 23% of production. For some reason thiswas not acceptable to the federal government. Perhaps this wasdue to the perception that renewable energy was causing anincrease in electricity prices. However, this perception iscountered by the findings of the RET Review, which concluded thatthe RET was exerting some downward pressure on wholesaleelectricity prices. This begs the question of why the governmentwasn’t happy with the previous target.

However, just when it seemed that an agreement was possibleto allow the new RET to be implemented, the idea was floatedthat electricity generation from burning wastes from native forestlogging should be included in the amount of electricity generatedto count towards meeting the target. While the timber industryhas long used wastes and off-cuts to provide heat and electricityfor its own operations, it would be hard to argue that nativeforests are a renewable resource. Certainly, plantation timber isrenewable within a period of less than about 20 years, butselectively harvesting a native forest takes out the largest treesthat have been growing for some 30 years or more, and these can’tbe ‘renewed’ within an economic time period. In any case, theamount of electricity generated this way is likely to be small. Theelectricity industry recognised in the late 1800s that coal was abetter fuel than wood.

Recent media debate has also cast light on the performance ofthe coal-fired electricity industry. Newspaper reports havecommented that in the absence of a price on CO2 emissions, theproportion of electricity generated by burning brown coal has

increased, mainly at the expense of black coal. Almost perversely,brown coal, which has a lower energy density than black, andwhich we probably couldn’t give away, has an advantage in thedomestic market. The explanation is that black coal is pricedaccording to the world price, and local buyers have to competewith export customers. To someone like me who has been exposedto the process industries, this is a contradiction. But life can bestranger than fiction.

Turning our attention back to renewables, recent debates inthe press have discussed the role of solar-generated electricity.Several state-based schemes provided generous feed-in tariffs toencourage the uptake of solar power, and the industry hasblossomed. One school of thought says that subsidies spent onthese schemes have resulted in very expensive CO2 abatement. Forexample, I have heard that Germany spent some €70billionsubsidising solar power and yet replaced only 1.5% of theirgenerating capacity. I thought it was bad news, personally, toread that all mainland capitals, except Melbourne, are well placedfor household solar electricity. That may be the case, but I haverecently established that at home we are on track to achieve theseven-year payback we were told to expect when we installedsolar panels in 2011.

In contrast to the federal government, the New South Walesand Victorian state governments have been keen to promote thebenefits of emerging battery technology to boost solar generation.Both governments have been talking up the Tesla battery from theUS, produced by the maker of electric cars of the same name. ThePowerwall battery is just that, a unit about the size of a suitcasemounted on the outside of a house. However, the governments’timing seems to be unfortunate. Within days of the Victorianpronouncements on this topic, an online discussion group forenvironmental professionals carried a report that even Teslaconsidered the Powerwall not up to the task for which the localministers were advocating. It seems that Tesla’s domestic unitsare intended mainly as back-up to the grid, and are designed foronly about 50 charge cycles a year. They aren’t yet up to the taskof daily charge and discharge needed by household solarinstallations. Back to the drawing board for the ministers.

All of this focus on renewable energy and battery storagereminded me of a neighbour when we arrived in Melbourne in1992. He had a small wind turbine above his house, and thebasement was filled with batteries. He installed this unit to supplyall his electricity needs because, when he built his house, it wasgoing to cost him nearly as much to connect to the grid as toinstall the turbine and batteries. It sounds like there is really isnothing new under the sun (or in the wind).


Almost perversely, browncoal, which has a lowerenergy density than black,and which we probablycouldn’t give away, has anadvantage in the domesticmarket.

Is the answer blowin’ in the wind?iStockphoto/CDH_Design

Paul Moritz MRACI CChem ([email protected]) isa Principal Contaminated Land Consultant with Douglas Partners,and an EPA-appointed Environmental Auditor in Victoria, New SouthWales and the Northern Territory. He acknowledges the assistance ofhis colleague, Alan Lee, in the preparation of this article.

A vast body of research has attempted to identify thecompounds in a food or beverage that contribute to theastringent response. Consumers generally do not like highlyastringent beverages: adding milk to tea is a good example of‘softening’ the mouthfeel. On the other hand, polyphenoliccompounds are often claimed to show health-promoting effects.Perhaps the rhesus monkey that chooses food based on itsphenolic content has a better understanding of astringentresponse than we do and I wonder if a new fad, the rhesus diet,could be established!

In wine research, two general strategies have been used totry and understand what compounds contribute to astringency.One involves adding a compound to a wine or model wine andthen assessing the change in astringency. This process is slow,simply due to the large number of compounds that are involved,but it does generate a lot of data for doctoral programs.

The second strategy involves size fractionation of the winefollowed by tasting the reconstituted fractions or taste dilutionanalysis of the fractions. Taste dilution analysis involvessequential dilution of the fractions, each sub-fraction beingtasted to identify which sub-fraction contains the mostastringent compounds. Chemical analysis of each fraction orsub-fraction is then used to identify compounds that appear tocontribute to the astringent response. The limitation to thissecond approach is that the tasting is no longer occurring inthe wine matrix so that any important molecular interactionswill be missing.

Not surprisingly, the two approaches give different results.The ‘compound addition’ method has shown that the monomericflavan-3-ols, (+)-catechin and (-)-epicatechin, contribute toastringency. This has not been observed in wine fractionationstudies. Rather, hydroxybenzoic acids and hydroxycinammic

acids together with polymeric compounds have been seen to beimportant. More detail on these studies is set out in our reviewon red wine astringency (Trends Food Sci. Nutr. 2012, vol 27,pp. 25–36).

In addition to perturbation of the wine matrix in theseexperimental approaches, the fascinating conformationalchemistry of phenolic compounds makes astringency assessmentdifficult. The flavan-3-ols readily polymerise through the C4 toC8 or C4 to C6 positions. The dimer shown here is (−)-epicatechin-(4b→8)-(−)-epicatechin, usually abbreviated toprocyanidin B2. There are three other C4–C8 isomers, dependingon the arrangement of catechin and epicatechin in the dimer.Further, there are four C4–C6 isomers, giving B1 to B8, all ofwhich have the same molecular mass, which makes identifyingthem in a wine matrix a challenge.

Stereoselective synthesis allows some isomers to beprepared. Isabelle Pianet and her team from the University ofBordeaux have looked at the dimers B1 to B4 as well as thetrimer C2 (three catechins linked C4 to C8) using diffusionalNMR (DOSY). Aggregation or self-association of the flavan-3-olmonomers is efficient, much more than for the procyanidindimers. This high affinity for monomer self-association wassupported by dynamic simulations (see Langmuir 2008, vol. 24,pp. 11 027–35). These results imply that the monomers aremore likely to form hazes or precipitates and not interact withproteins.

To assess the potential interaction between procyanidins andproteins, the interaction between B1 to B4 and C2 with theproline-rich peptide, IB714 (14 amino acid residues), wasexamined by the Bordeaux team using DOSY and otheranalytical techniques. C2 was found to have the highest affinityfor IB714, followed by B2 > B4 > B1 > B3 (Carla et al., FASEB J.2010, vol. 24, pp. 4281–90). Extending this work, the Bordeauxgroup (Planta Med. 2011, vol. 77, pp. 1116–22) found that theprocyanidin’s conformation played a critical role. One canimagine the dimer to be like a pair of tweezers, hinged at theC4–C8 bond. The lowest energy conformation for B2 is an opentweezer, while B3 is closed. The open-tweezer structure allowsbinding to two proline-rich peptides, whereas the closedstructure, with a significant degree of intramolecular binding,interacts with only one proline-rich peptide.

While the implications of these results for astringencyassessment are still to be evaluated, it is now clear that there ishighly specific chemistry affecting the tannin-protein response.I confess that I would never have imagined isomer andconformer chemistry to be so exciting!

grapevine


Astringency and phenolic conformations

Geoffrey R. Scollary FRACI CChem ([email protected])was the foundation professor of oenology at Charles SturtUniversity and foundation director of the National Wine andGrape Industry Centre. He continues his wine research at theUniversity of Melbourne and Charles Sturt University.

As the new semester begins, public transport gets clogged andcarparks on campus disappear. As we drown in the deluge ofstudents, I often parry my colleagues’ complaints about thecrowds with: ‘Yeah, this would be a great university if it wasn’tfor all the students.’

The truth is that I consider students an essential part of thelife of an academic researcher. If funding is the lifeblood thatkeeps the group running, then students are the heart throughwhich this blood pumps. So although many of my colleagueslook at taking on part-time students as a hindrance to theirworkflow, I welcome the challenge of training up a newbie andenjoy watching them grow into a competent researcher. I’d liketo talk about a few of my students here, just to illustrate thegreat experiences I’ve had and all we’ve accomplished together.

The first student I mentored was Christian. Christian hailedfrom Germany and I designed a perfect research project for him.It was simple, but he could work on it independently and itwould generate useful data for the group. My supervisor insistedthat we dial down the skill level required for the projectbecause we’re never sure of the ability of short-term visitors.Christian turned out to be amazing in the lab. He quicklyworked out that my idea was less solid than I’d originallythought and he had a much better one. His idea turned out tobe so good, that a postdoc took over the project and weeventually published the paper in the Journal of the AmericanChemical Society (no small feat for a simple visiting student).

After Christian came Hedi. Hedi was from Tunisia and hadn’treally spent any time in a chemistry lab so I couldn’t expectChristian-level work from him. I designed a project for himbased on polymerisation kinetics with an emphasis on 1H NMRanalysis. I spent the first few weeks teaching himpolymerisation methodology, how to operate the NMRspectrometer and interpret the data. Then I left him to hisdevices. Hedi promptly went and broke his foot that weekendplaying football. So all those NMR spectra that I wanted him torun would no longer be run (the NMR spectrometer is a 10-minute walk from the lab). I wanted to re-design theproject, but Hedi would have nothing of it. He insisted onworking and corralled me into walking to the spectrometer forhim. In the end, he completed his project and we published thework this year after running 121 1H NMR spectra!

At the same time as I was running NMR spectra for Hedi, Ialso started mentoring Seb. Seb came from Italy, looked at the

project I proposed and suggested we do something entirelydifferent. I wanted him to work on polymer functionalisationreactions, but he said he’d rather work with cancer cells. Sotogether we learned about culturing cells and measuring theirproperties using flow cytometry. As Seb analysed the cells, morequestions were raised so we planned more and moreexperiments, which he ran with ever-increasing adroitness.Every time we planned an experiment, he ended up analysing690 000 cells. Eventually we analysed enough cells to tempereven Seb’s seemingly boundless enthusiasm. He collapsed into aseat in the office and begged me never to plan anotherexperiment again. I agreed and he breathed an audible sigh ofrelief.

Despite my apparent taskmaster-like attitude, Seb still popsinto my office every now and then to find someone to grab abeer with. He even gave a glowing report of me as a supervisorto Muriel (a Swiss-German). Muriel took over where Seb had leftoff. She scoured the literature, optimised procedures, plannedexperiments and executed them flawlessly (Swiss precision andGerman efficiency, I guess). Five months after she saw her firstcell (and her first Erlenmeyer flask) she was engaged in avigorous debate with my supervisor, gallantly defending herresults. That and the 1 350 000 cells she analysed earned herthe best grade in the class.

I could go on about the great students I’ve encountered, likeMichael (who did about four times the amount of work I wantedhim to do while sorting out his future internship at MIT), orHenri (the second-year student who was so pleased with histwo weeks in the lab that he begged to come in in his sparetime and continue his tinkering), or Joan (who somehowmanaged to make amazing polymer brushes while learningSpanish so that he could volunteer in Ecuador). But at thisstage you get the point: students have absolutely been thehighlights of my research career and I have been in greatuniversities because of them.

postdoc diary

Chemistry in Australia| August 201540

If funding is the lifeblood thatkeeps the group running,then students are the heartthrough which this bloodpumps.

iStockphoto/A-Digit

Of thee I sing (part 1): students

When I was a third-year student in the late 1950s, Professor‘Old Bill’ Davies lectured on heterocyclic chemistry. It wasmostly about the syntheses of nitrogen heterocycles that camewith the names of their authors – pyrroles by Knorr,isoquinolines by Bischler–Napierelski and by Pictet andSpengler, and indoles by Fischer (yes, it was Emil, he of thesugars). Curiously, none of these heroes is memorialised inOrganic chemistry: the name game (Nickon and Silversmith,1987), but the names dot the pages of innumerable texts onheterocyclic chemistry.

Davies never lost his strong Yorkshire accent, nor the limpthat derived from some childhood illness, but it was his lectureperformance that sticks most strongly in my memory. Drawingstructures on the blackboard, he would speak about thechemical change taking place in the next step, pull down thesleeve of his jacket and use it to erase part of the structure,and then chalk in the new atoms. It made note-taking adifficult task, which most of us managed by scribbling in thenew bit and leaving space so that the whole structure could bewritten in later. Good revision, I suppose, although I didn’tthink of it that way at that time.

Davies spent quite a while on indole chemistry and inparticular on indole-3-acetic acid and its action as a planthormone, showing pictures of growing plants and speaking ofwhat I heard as ‘decapilated oat coleoptile’. ‘Coleoptile’ wasclearly a technical term but since I judged that the materialwas probably not examinable, I never looked up its meaning.Likewise, I accepted that ‘decapilated’ might have meant somekind of trimming of the plant tissue. When I came to write thisLetter I found that what he said was probably ‘decapitated’ so Iwas more-or-less correct, albeit uninformed. And as for thecoleoptile, it is the sheath covering the growing shoot.

What none of us students realised at the time, and what Ihave only recently discovered, is that Davies had done researchin this field, in conjunction with his student Philip Hudson, andGeorge Atkins, a tutor in Philosophy and ‘researcher in Botany’at the university. Their work was reported in a short note toNature in 1936 and a full paper the following year in Annals ofBotany. In the few years before and after 1930, Kögl, Erxlebenand Haagen-Smit had extracted from human urine threesubstances that exhibited plant growth-promoting activity andwere known generically as auxins. The most potent of them,heteroauxin, was shown to be identical with indole-3-aceticacid. This started a hunt for other auxins, and in 1933 othersreported that the juice of oranges and lemons promoted plantgrowth in oats (Avena sativa) and speculated that ascorbic acid(vitamin C) might be the active principle. Experiments over thenext few years produced mixed results, and that is where theDavies team began their work.

Davies and his collaborators found that indole-3-acetic acidpromoted root growth in willow shoots. Ascorbic acid in lowconcentrations did, too, but stronger solutions caused

retardation, and that was puzzling. The researchers purchasedtheir ascorbic acid but synthesised the indoles they used intheir experiments. Indole-3-acetic acid was synthesised fromthe anion of indole by reacting it with chloracetonitrile beforehydrolysing the nitrile group to COOH. The Fischer indolesynthesis was used to prepare indole-3-propionic acid, as wellas the corresponding malonic acid and 3-ethylindole. All weretested as very dilute aqueous solutions but olive oil was usedas solvent for more concentrated solutions. In a series ofexperiments, the substances were applied to one side of thepetioles (stalks connecting leaf blades to the stems) oftomatoes and castor-oil plants (Ricinus communis). Only forindole acetic and propionic acids was the petiole ‘curved readilydownwards’ – that is, gave positive results. Ascorbic acid wasineffective but the researchers went to extraordinary lengths toconfirm this negative result. As well as simply wiping thesolution onto the petiole, they tried with small pads of cottonwool soaked in the test solution and renewed frequently.Worrying that the ascorbic acid might have been destroyed byaerial oxidation, they tried excluding air by coating the padswith paraffin wax, and even administered ascorbic acid mixedwith adrenalin, which was expected to preferentially absorboxygen. It was possible, they concluded, that there was noeffect or, alternatively, that translocation of ascorbic acid wasso rapid that differential action could not be observed.

Auxin A and auxin B were supposed to be cyclopenteneswith short, hydroxylated side chains, but they probably neverexisted. Instead, they belong to a series of natural productstructures identified in Kögl’s laboratory that were fantasies ofsomeone’s imagination. It is widely believed that Erxlebenproduced the evidence confirming Kögl’s hunches and that heuncritically accepted these ‘proofs’ of structure.

Davies’ co-workers subsequently went on to interestingcareers. After wartime work for the defence industries, Hudsonworked in chemical industry and spent some years withMonsanto in Melbourne. Atkins, who already had his MA at thetime of the plant research, went on to earn his MSc, thenworked at Defence Standards Laboratories in Maribyrnong as amycologist investigating attack on fabrics by a range ofmicroorganisms and fungi.

letter from melbourne


Decapilated oat coleoptile

Ian D. Rae FRACI CChem ([email protected]) is a veterancolumnist, having begun his Letters in 1984. When he is notcompiling columns, he writes on the history of chemistry andprovides advice on chemical hazards and pollution.

Auxin A and auxin B ...belong to a series of naturalproduct structures ... thatwere fantasies of someone’simagination.


cryptic chemistry

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with no boron. (6)17 Lymphocyte immune globulin initiates

and forms a complex. (6)19 50% of the all AFL seconds. (4)20 Production facilities with reference to

great duds. (10)22 Indicates scores. (6)23 Remove charge discharge. (8)25 Unconnected specific. (8)26 Tight limit. (6)

Down1 Stage walk. (4)2 Recurrent 639636. (6)3 Exact detail about it. (8)4 It causes reactions about a bloke. (7)5 Oil Spooner’s eye valley. (6)6 Looking at hitting the books. (8)7 Dance cut-in riot by which an

electromotive force is created. (10)13 Lutetium comes back with cast iron

breaking up above 20 kHz. (10)16 Liking similarity. (8)17 Rant: lens rotates lights. (8)18 Property results. (7)20 Frankincense and myrrh, perhaps,

feature in stores in summer. (6)21 Give back soak boiler. (6)24 Instrument to sort out Be/O2 reaction. (4)

events

Graham Mulroney FRACI CChem is Emeritus Professor of Industry Education at RMIT University.Solution available online at Other resources.

Southern Highlands Conference on HeterocyclicChemistry30 August – 1 September 2015, Bowral, NSWwww.chemistry.unsw.edu.au/news-events/latest-news/conferences-and-workshops/2015-southern-highlands-conference-heterocyclic

13th Conference on Laser Ablation (COLA-2015)31 August – 4 September 2015, Cairns, Qld http://cola2015.org

13th Annual UNESCO/IUPAC Workshop andConference on Macromolecules and Materials7–10 September 2015, Port Elizabeth, South Africahttp://academic.sun.ac.za/unesco

22nd International Clean Air and EnvironmentConference 20–23 September 2015, Melbourne, Vic. http://casanz2015.com

4th Federation of Asian Polymer Societies –International Polymer Congress5–8 October 2015, Kuala Lumpur, Malyasia www.4faps-ipc.org.my

2015 Sustainable Industrial Processing Summit andExhibition9 October 2015, Turkeywww.flogen.org/sips2015

Pacifichem 201515–20 December 2015, Honolulu, Hawaiiwww.pacifichem.org

RACI events are shown in blue.

Coming up• The delectable chemistry of

chocolate

• Using apps in chemistry teaching

• Salmon and their strontiumsignatures

• Petrichor: the smell of rain

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a balanced brew of technology and tradition - Chemistry …chemaust.raci.org.au/sites/default/files/pdf/2015/CiA... · 2018-02-27 · List $1831.72 SALE PRICE $987.69 ... TARSONS