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ALSO IN THIS ISSUE: Chemical tagging and star histories 100 years of activated sludge Chlorpyrifos problems in Vietnam in Australia chemistry Dec 2014/Jan 2015 Coffee beans and the perfect brew chemistry Coffee beans and the perfect brew

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Page 1: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

ALSO IN THIS ISSUE: Chemical tagging and star histories • 100 years of activated sludge • Chlorpyrifos problems in Vietnam

in AustraliachemistryDec 2014/Jan 2015

Coffee beansand the

perfect brew

chemistryCoffee beansand the

perfect brew

Page 2: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

www.raci.org.au/chemaust

TO DO:Stay in touch with my professional society.

Aim for that paperless office.Check out news and eventsat raci.org.au

Don’t turn the page yet!Keep in touch with RACI by checkingwe have your latest details, and cut backon the clutter by accessing Chemistry inAustralia online.

1 Visit raci.org.au and log on to yourmembership page.

2 Choose Update Your Details.3 Check that we have your correct

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Four simple steps and you’re up to date. Do it today!

Page 3: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

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raci.org.au/chemaust

cover story

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news & research5 Your say6 On the market7 News8 Research42 Events42 Cryptic chemistry

members4 From the President27 RACI awards29 RACI milestones31 New Fellows33 RACI people

views & reviews35 Books36 Technology & innovation38 Education39 Grapevine40 Sustainability41 Letter from Melbourne

16 Galactic chemistry and the GALAH surveyA new multi-object spectrometer means we no longer have to quantifygalaxies one star at a time.

20 Chlorpyrifos: a global health problemOne of the world’s most widely used insecticides, chlorpyrifos poses healthproblems for agricultural workers where regulation is lacking.

24 Special treatment: Australia’s pioneering wastewater plantThe centenary of activated sludge inspired Bronwyn Kent to research theGlenelg Wastewater Treatment Plant, the oldest of its type in Australia.

The perfect roast reactionForget caffeine – following your favourite barista around town is all about thechemicals in the flavours and aromas of a great coffee.

20

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Page 4: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

I have been part of the Working Group for the inaugural DecadalPlan for Chemistry, an initiative of the Australian Academy ofScience’s National Committee of Chemistry, which is supportedby the RACI. At dozens of open ‘Town Hall’ meetings during2014, chemists from all sectors have given their opinions onthe best way ahead for chemistry in our country. The initialfindings and recommendations are currently being assembledand a Green (consultation) Paper will appear in early 2015 forpublic comment (see http://chemistrydecadalplan.org.au).Every meeting I’ve attended has brought out new issues andideas.

The Decadal Plan project focuses on two questions: ‘Wheredo you want chemistry to be in 2025?’ and ‘How will we get itthere?’ In Australia, we have not tackled these questions beforeand the current generation of newly educated chemists inparticular need to buy into them.

Most at the meetings agreed on the need for improvement inthe public’s perception of chemistry. The word ‘chemical’ is usedpejoratively and the loosely phrased expression ‘chemical free’pervades non-chemistry-literate society. Even young childrenare warned of the dire consequences of going near the (usuallylocked) cupboard with the ‘chemicals’ in it. Some of thesechemicals, which could be anything from cleaning products topharmaceuticals, are potentially harmful if ingested, but we allrely on them, or why did we buy them? Chemists know how tosafely live with chemistry – we survey the information andassess the potential hazards. We don’t fear the chemical.

Organic produce is an interesting example of ‘chemicals’being given a bad name in spite of the longstanding successesof agrochemicals. The organic food industry is based on thepremise that produce grown without (or with a minimum of)(synthetic) chemicals is inherently better for you. The exclusionof synthetic chemicals in favour of ‘natural’ products is apeculiar distinction – synthetic pesticides are generally at oddswith the principles of organic farming yet ‘natural’ pesticidesmay be allowed. A natural product is not intrinsically lessharmful than a synthetic product – a point that is rarely made,

leaving society with a distorted view of the worth of chemicalsand chemistry in general.

The Organic Federation of Australia (OFA) acknowledges thatobtaining accord on the criteria for organic produce in Australiaremains a challenge and there is still no mandated regulatorysystem for organic products. So there are currently variousdegrees of ‘organic’ produce on the market. The term ‘organicchemistry’ must have members of the organic produce industryperplexed. Perhaps it’s seen as an oxymoron. Where does‘inorganic chemistry’ sit (a double whammy)?

The word ‘chemical’ (and ‘chemistry’) needs advocates insociety. You can help by pointing out to friends and relationsthat nothing on Earth is actually chemical-free (in spite ofcountless examples to the contrary – Google ‘chemical-free’ ifyou dare). Although nobody denies the damage that has beendone to the chemistry ‘brand’ by past unregulated andirresponsible handling of some harmful compounds, we shouldpoint out that this does not represent a balanced view ofchemistry. All around, we can see evidence of chemistry’spositive impact. To go (synthetic) chemical-free would limitmuch of what we currently do.

The Chemistry Decadal Plan open meetings also highlightedthat the ‘grand challenges’ are harder to define for chemistrythan for biology or physics (e.g. origin of life, unification of thelaws of physics). However, chemistry will continue to permeatethe other sciences and will share the accolades and rewardsthat come from its interactions on the fringes, although theseboundaries are even more diffuse than ever. The challenges weface in energy, food and water supply and materials for a rapidlygrowing world population will involve chemistry and chemistsat the forefront.

Can we please have our word back now?

EDITOR Sally WoollettPh (03) 5623 [email protected]

PRODUCTION EDITORCatherine Greenwood [email protected]

ADVERTISING SALES Gypsy Media & Marketing Services Marc Wilson, ph 0419 107 [email protected]

PRODUCTIONControl Publications Pty Ltd Ph/fax (03) 9500 0015/0255 [email protected]

GENERAL ENQUIRIESRobyn TaylorRACI National Office, 21 Vale StreetNorth Melbourne VIC 3051 Ph/fax (03) 9328 2033/[email protected]

PRESIDENT Paul Bernhardt FRACI CChem

MANAGEMENT COMMITTEESam Adeloju (Chair) [email protected] Hügel, Alan Jones, Amanda Saunders, Colin Scholes, Curt Wentrup

CONTRIBUTIONSContributors’ views are not necessarily endorsed by the RACI, and noresponsibility is accepted for accuracy of contributions. Visit the website’sresource centre for more information about submissions.

© 2014 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproducedwholly or in part without written permission. Furtherdetails on the website. ISSN 0314-4240 e-ISSN 1839-2539

www.raci.org.au/chemaust

Chemistry in Australia4 | Dec 2014–Jan 2015

from the raci

From the President

Paul Bernhardt FRACI CChem ([email protected]) is RACIPresident. He was educated at the University of Newcastlewhere he joined RACI as a student in 1986. After postdoctoralfellowships in Basel and at ANU, he joined the University ofQueensland where he is currently Professor of Chemistry.

Page 5: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

your say

Chemistry in Australia 5|Dec 2014–Jan 2015

Viability of warm-bloodednessI refer to the June 2013 article ‘When the going gets hot’ (p. 20) wherein Ronald Clarke explains a mechanism wherebywarm-blooded mammals, which include humans, will havetrouble living in warmer climates, a circumstance that herelates to climate change.

Whilst I think that he may be being a bit tongue in cheek, ahighlighted statement in the article says ‘… if global warmingcontinues, warm bloodedness will eventually become unviable…’, but he does not tell us at what temperature and when thismay occur.

Without any quantification of his hypothesis, his statementis unworthy of publication in our journal. Any figures that Ihave seen on global warming are quite minute, being of theorder of tenths of a degree over decades; in fact, over the lasttwo decades the records show cooling, if any change at all.Australians, with their fine warm blood, have no problem livingin Melbourne or Brisbane with an average temperaturedifference of 5°C.

There is no scientific case for claiming that current globalwarming predictions will threaten human life. We live in theArctic and the tropics, and such a proposition should not beperpetrated in our journal without valid evidence.

As an organic chemist, I find this article interesting in termsof the importance of environment upon mammals, but theglobal warming inference is just plain offensive.

Richard Corbett MRACI CChem

Mr Corbett objects to the statement ‘If global warmingcontinues, warm-bloodedness will eventually become unviable…’. However, this statement is simply a logical application ofthe laws of thermodynamics, to which the Earth as a whole andevery human being on it are subject. If the rate of heat inflowto an object remains constant, but the rate of heat outflow isinhibited, as it is in the case of the Earth via the greenhouseeffect, then the undeniable consequence is an increase intemperature of the object concerned, i.e. in the Earth’s case anincrease in the average global temperature. If the temperatureof the Earth increases, this naturally inhibits the ability of allanimals on it to dissipate body heat to their surroundings.Thus, if the rate of heat dissipation is reduced, just as in thecase of the Earth, body temperature must eventually rise, thusimpacting on an animal’s viability.

Of course, this is all based on the hypothesis that globalwarming is occurring, which Mr Corbett doubts. In contrast, hestates that records (uncited) show that the Earth is actuallycooling. However, this is in clear disagreement with theconsensus of results published by the International Panel onClimate Change (established by the United Nations EnvironmentProgramme and the World Meteorological Organization) in their2013 Climate Change Report, which show an increase in theglobally averaged combined land and ocean surface temperatureof 0.65–1.06°C over the period 1890–2012 and an increase inthe average decadal temperature for every decade since the

1970s. It is clear that Mr Corbett is correct that Australianshave no problem in living in Melbourne or Brisbane. However,what is equally true is that in France, a country in which air-conditioning is much less widespread in homes than inAustralia, almost 15 000 heat-related deaths were recorded inthe summer heatwave experienced there in 2003.

Of course, this author hopes that global warming never getsto the stage that the survival of the human species or any otherwarm-blooded animal is threatened. But rather than wait andtake the gamble that it never happens, I would suggest it beadvisable for the world community to take concerted action toensure that it doesn’t.

Ronald J. Clarke MRACI CChem

Swelling jelly babiesThe illustration of Smarties immersed in water in the Novemberissue (p. 39) reminded me of some work of my own from adecade ago (Jones J.C. ‘Looking swell, baby’, Phys. Educ. 2004,vol. 39, p. 25). I published a similar illustration of jelly babiesimmersed in water. We were interested not in colour effects butin swelling. This was part of a program of work in which theswelling of polymers in organic solvents was investigated, andwe also made the brief study of the water-induced swelling ofgelatinous foodstuffs.

A reader performing the Smarties test might care to considerswelling as well as the migration of colouring agents. Swellingof the jelly babies was quite sufficient for visual detection. Itcould of course have been measured quantitatively by use of atravelling microscope.

J.C. Jones FRACI CChem

‘Your say’ guidelinesWe will consider letters of up to 350 words in response tomaterial published in Chemistry in Australia or aboutnovel or topical issues relevant to chemistry. Lettersaccepted for publication will be edited for clarity, space orlegal reasons and published in print and online. Full nameand RACI membership status will be published. Pleasesupply a daytime contact telephone number (not forpublication).

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].

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6 | Chemistry in Australia

Climate change: chemistry + cofactors =complexity + chaotic confusion‘Carbon dioxide reduction’, the climatologists’/physicists’ slogan for reversing the claim of climatechange, but where are the chemists? In my opinion,the world’s chemists must join the discussion todemonstrate that climate change is not resolvablewith a simple one-factor solution.

The chemistry involved in any chemical reaction,which includes every single process in the entireworld, is rarely if ever the result of reactingsubstances creating a new entity without any otheroutside influences/cofactors.

The background to this personal opinion was acomment by Ben Selinger in a climate change article(December 2010) in which I, surprisingly, discoveredthat, as opposed to media information/hype, carbondioxide and methane were not the only ‘greenhouse’gases contributing to ‘climate change’ – water vapourwas the most abundant and equally important, whilenot being mentioned in the public media and rarely inclimate change scientific literature.

The greenhouse gas ‘water vapour’ can betransformed into highly unpredictable/difficult-to-model clouds; hence the demise of the 1980’s ‘nuclearwinter’ panic.

Virtually each drop of rainwater in clouds containsa ‘seed’, aka generic ‘dust’, in the atmosphere due tounpredictable cofactors, e.g. wind, volcanoes,bushfires, earthquakes, aerosols, human activities.

Other natural, unpredictable cofactors involved inclimate change, and of which humans have limitedknowledge and even less control, include oceans, seasand currents, sun cycles, sunspots, solar winds, theroiling Earth’s core etc. which are rarely mentioned,as they are not attributable to humans and thenpolitically taxable.

I agree humans can do a lot to improve or changeour outputs to reduce any generated minor effectsthat actually affect ‘climate change’, if it is reallyoccurring, but it is mostly due to a complex mixtureof non-human induced/uncontrollable cofactors.

This is a call to RACI members to contemplatecofactors and discuss with colleagues, friends andfamilies. Chemists possess the education andexpertise to rationally influence this debate; it is notas simple as the media and pressure groups portray.The truth is more complex than just human outputs;cofactors must be elucidated and included ineducation curricula.

Tony Zipper FRACI CChem

New CAMSIZER® P4 particle size andshape analyserThe new CAMSIZER® P4 is the systematic enhancement andoptimisation of the well-proven CAMSIZER system for thedetermination of particle size and particle shape with Dynamic ImageAnalysis. Based on the unique dual-camera technology, the newgeneration offers improved performance and extendedfunctionalities.

Compared to the previous model, the CAMSIZER® P4 boasts fastercameras with higher resolution, a stronger light source and newsoftware features, resulting in even faster measurements and anextended measuring range. The improved resolution allows for moreprecise particle characterisation, particularly of small particles.

Both hardware and software have been revised. The softwareoffers additional evaluation possibilities, such as separate storage ofall particle images in a database or 3D display of measurementresults as scatter plots (3D cloud). New shape parameters forroundness and sphericity allow for optimised shape characterisation.

Well-proven functions such as the certified calibration standard,the automated air flow in the measurement zone, and the motorisedfunnel height adjustment have been preserved in the CAMSIZER® P4.The obtained measurement results are accurate and reliable, even ifoperated 24/7, and can exactly reproduce existing sieving results.

Better performance, more functions: • Higher resolution of cameras and objectives permits more precise

measurements of particle size and particle shape (20 mm –30 mm).

• Faster hardware and software record more particles per second andprovide more detailed information.

• 3D cloud: easy evaluation of particle morphology thanks to 3Ddisplay of measurement parameters.

• Particle library: direct storage of images of individual particles;convenient administration of new particle library.RETSCH Technology offers instruments for optical particle

characterisation from 0.3 mm to 30 mm. By applying differenttechniques, particle size and particle shapes of wet and dry samplescan be determined accurately.

For more information, please contact MEP Instruments on (02) 9878 6900 or [email protected] or visit www.mep.net.au.

your say on the market

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The Earth’s protective ozone layer is ontrack to recover by the middle of thecentury, the United Nations reported inSeptember, urging unified action totackle climate change and curbcontinued fluctuations to thecomposition of the atmosphere.

That is according to the assessmentof 300 scientists in the summarydocument of the Scientific Assessment ofOzone Depletion 2014, published by theUN Environment Programme (UNEP) andthe UN World MeteorologicalOrganization (WMO).

‘International action on the ozonelayer is a major environmental successstory,’ WMO Secretary-General MichelJarraud said. ‘This should encourage usto display the same level of urgency andunity to tackle the even greaterchallenge of climate change.’

The ozone layer, a fragile shield ofgas, protects the Earth from the harmfulportion of the sun’s ultraviolet rays, thushelping to preserve life on the planet.Its recovery, according to the scientists,is attributed to the collective actionthrough the Montreal Protocol, whichsince 1987 has led countries to carry outpolicies to reduce and then phase outtheir use of ozone-depleting chemicals.

Without the Montreal Protocol andassociated agreements, atmosphericlevels of ozone-depleting substancescould have increased tenfold by 2050,according to the report. ‘However, thechallenges that we face are still huge.The success of the Montreal Protocolshould encourage further action not onlyon the protection and recovery of theozone layer but also on climate,’ saidUNEP Executive Director Achim Steiner.

Secretary-General Ban Ki-moonrecently hosted, at UN Headquarters inNew York, a summit in an effort tocatalyse global action on climate change.

‘The Montreal Protocol community,with its tangible achievements, is in aposition to provide strong evidence thatglobal cooperation and concerted actionare the key ingredients to secure theprotection of our global commons,’Steiner added.

Among the key findings of the report,the authors noted that what happens tothe ozone layer in the second half of the21st century will largely depend onconcentrations of carbon dioxide,methane and nitrous oxide – the threemain long-lived greenhouse gases in theatmosphere.UNITED NATIONS

news

Chemistry in Australia 7|Dec 2014–Jan 2015

Ozone layer recoveringbut remains threatened

The deepest ozone ‘hole’occurred in 1994, whenconcentrations fell to just73 Dobson units on30 September. Purple anddark blue areas are part ofthe ozone hole.NASA Earth Observatory

Mexican plant couldhelp ‘green’ perfumeindustry The mere whiff of a dreamy perfume canhelp conjure new feelings or stir alonging for the past. But the creationof these alluring scents, from the high-end to the commonplace, can also incuran environmental toll. That couldchange as scientists, reporting inSustainable Chemistry & Engineering,examine a more sustainable way toproduce a key perfume ingredient andsupply it to fragrance makers aroundthe world.

José M. Ponce-Ortega and colleaguesexplain that out of the three mainingredients in perfumes, the fixatives,which allow a scent to linger on awearer’s skin rather than quicklydissipate, are often pricey. Aparticularly coveted fixative comes froma rare whale digestive excretion calledambergris. Not only is its costexorbitant, but its use in perfumes inmany countries is illegal. That’s whymany perfumeries long ago turned to asynthetic version. Although not ascostly, the substitute still commands ahigh price, and requires considerabletime and energy to make. A simpler wayto make synthetic ambergris exists, butthe catch is that the starting materialis a flowering plant found in Mexico.That means the plant would have totake a fuel-consuming, environmentallyunfriendly journey across the ocean toEurope, where many perfumes are made.So Ponce-Ortega’s team wanted to seewhether the process would be worth it.

To find out, the researchersconducted a supply-chain analysis. Theyfound that producing the fixative usingthe Mexican plant would generateconsiderable local profits to the tune of$20 million per year and createhundreds of jobs along the supplyroutes. They did find an environmentalcost to the process, but that could bemitigated by using renewable energysources to produce the fixative.AMERICAN CHEMICAL SOCIETY

Page 8: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Helping hand forcrystallography

Cyclic disulfide-rich peptides have beenthe subject of intense scrutiny over thepast decade because of their exceptionalstability and potential as drug designscaffolds. Despite this interest, obtaininghigh-resolution X-ray data on theirstructures has been challenging becausecrystallisation of disulfide-rich peptidesis notoriously difficult. The team ofProfessor David Craik, at the University ofQueensland, has explored the use ofracemic crystallography, in which crystalsare grown from a mixture containing apeptide and its mirror image, to facilitatecrystal formation (Wang C.K., King G.J.,Northfield S.E., Ojeda P.G., Craik D.J.Angew. Chem. Int. Ed. 2014, 53, 11236–41). L- and D-forms of three prototypiccyclic disulfide-rich peptides – SFTI-1(14-mer with one disulfide bond), cVc1.1(22-mer with two disulfide bonds), andkB1 (29-mer with three disulfide bonds)– were synthesised and the racemicmixtures were crystallised, allowing theirstructures to be solved at resolutionsranging from 1.25 Å to 1.9 Å. Theracemic crystallography approach iscurrently being further explored at theUniversity of Queensland.

C60 fullerenes are cage-molecules thatresemble soccer balls, which can trapatoms or small molecules inside the cage.In contrast, electrons are usually trappedwithin the molecular p-system on thesurface of the fullerene. Professors PaulKeller and Stephen Pyne, from theUniversity of Wollongong, in

collaboration with scientists from theUniversity of Erlangen, Germany,

have now discovered thatfullerenes can accept electronsfar more readily when they arenon-covalently in contact witha second fullerene molecule

(Shubina T.E., Sharapa D.I.,Schubert C., Zahn D., Halik M.,

Keller P.A., Pyne S.G., Jennepalli S.,

Guldi D.M., Clark T. J. Am. Chem. Soc.2014, 136, 10890–3). The resultingmolecular ion corresponds to a (C60)2-vander Waals dimer: a stable arrangement ofthe two molecules held together by anelectron between the two C60 molecules(i.e. two fullerenes can form a ’bond’using the extra electron). The figureshows the electrostatic potential on thesurface of such a dimer. The stronglynegative (blue) potential caused by theelectron is clearly visible between thefullerenes. This research should havemajor impact in the understanding offullerenes as n-type semiconductors,which can be used, for instance, tofabricate flexible transistors with verylow power requirements on plastic sheet.

Electrons trapped between fullerenes

Mapping atoms in bimetallic nanoparticles To be able to correlate the catalytic properties of nanoparticles with their structure,detailed knowledge about their make-up on the atomic level is required. The teams ofProfessors Thomas Maschmeyer and Julie Cairney, from the University of Sydney, have,for the first time, demonstrated how atom-probe tomography (APT) can be used toquantitatively determine the three-dimensional distribution of atoms within a Au@Agnanoparticle with near-atomic resolution (Felfer P., Benndorf P., Masters A.,Maschmeyer T., Cairney J.M. Angew. Chem. Int. Ed. 2014, 53, 11190–3). They revealthat the elements are not evenly distributed across the surface and that thisdistribution is related to the surface morphology and residues from the particlesynthesis. The technique allows the determination of the role and influence onperformance of the ‘spectator species’, such as the anions used in the synthesis of theparticles. The effect of curvature and general morphological features on the assemblyof the growing particle can also be addressed. Application of this research will providea basis for the rational design of (multi)metallic nanoparticles to generate a spread ofdesirable reactive sites.

research

Chemistry in Australia8 | Dec 2014–Jan 2015

Page 9: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Radical approach to reversible M–C bond formationThe forming and breaking of metal–carbon bonds by facile oxidativeaddition/reductive elimination processesis the cornerstone of numerous transitionmetal-catalysed transformations. Incontrast, such chemistry is extremely rarefor main group metal systems. As part ofan ongoing collaboration between thegroups of Professors Cameron Jones(Monash University) and Simon Aldridge(Oxford University), the first stable group13 metal(II) radicals (see May issue, p. 13) have been shown to react withdimethylbutadiene, via oxidative M–Cbond formations, to give metallo-butenediyl complexes (see figure). Thesesystems can undergo subsequentreductive elimination under mildconditions, yielding B–C bonded products(Protchenko A.V., Dange D., Blake M.P.,Schwarz A.D., Jones C., Mountford P.,Aldridge S. J. Am. Chem. Soc. 2014, 136,10902–5). In one instance, the

eliminated indium(I) fragment, In(Boryl)Boryl = B(diazabutadienediyl), undergoespartial disproportionation to give theremarkable mixed valence ‘metalloid’cluster, In19(Boryl)6. The ‘naked’ metallicIn13 core of this cluster exhibits anidealised cubic close-packing structure,similar to that found for nanoparticulate

indium metal. The ‘transition metal-like’reactivity displayed by the group 13metal radicals highlights the potentiallow-valent p-block complexes hold foruse as catalysts in organictransformations. This potential continuesto be developed by Jones’ team.

Is bigger always better? Depends how you use itLanthanoid complexes bearing the bulkypentaphenylcyclopentadienyl (C5Ph5)ligand are difficult to synthesise due toreactivity and purification problems.However, redox–transmetallation/protolysis (RTP) reactions carried out intetrahydrofuran (thf) between ytterbiummetal, HgPh2 and C5Ph5H afforded thesolvent-separated ion pair[Yb(thf)6][C5Ph5]2, which can bedesolvated to yield [Yb(C5Ph5)2].Although the latter complex is

structurally intriguing, its poor solubilityhinders reactivity studies. In order toimprove solubility, researchers at Monashand James Cook Universities have turnedtheir attention to the tetraphenyl -cyclopentadienyl (C5Ph4H) ligand (DeaconG.B., Jaroschik F., Junk P.C., Kelly R.Chem. Commun. 2014, 50, 10655–7). RTPreactions yielded the first divalentoctaphenylcyclopentadienyl lanthanoidcomplex, [Yb(C5Ph4H)2(thf)]. Given thatreactions with HgPh2 can be sluggish,the use of Hg(C6F5)2 was explored,

unexpectedly leading to the isolation ofthe first heteroleptic divalent lanthanoidfluoride complex, [Yb(C5Ph4H)(μ-F)(thf)2]2 (see figure). This complexforms from reduction of the C6F5Hgenerated during the RTP process byytterbium metal, rather than from[Yb(C5Ph4H)(C6F5)(thf)2] (an impliedintermediate), which is reluctant to formthe fluoride species even after prolongedheating. 19F and 171Yb NMR studies showthe dinuclear fluoride-bridged speciesmaintains its integrity in solution.

9|Dec 2014–Jan 2015 Chemistry in Australia

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research

Chemistry in Australia10 | Dec 2014–Jan 2015

Why salty Grignardreactions failThe mystery of why water and saltcontaminants destroy organometallicreagents has been solved thanks to newresearch conducted by scientists at theUniversity of Melbourne (Khairallah G.N.,da Silva G., O’Hair R.A.J. Angew. Chem.Int. Ed. 2014, 53, 10979–83).Organometallic compounds, such as theubiquitous Grignard reagents, arepowerful tools used to help create neworganic molecules both in the laboratoryand in commercial chemical plants,although careful management by thechemist is required to avoidcontaminants in the reaction. Theresearch team of Professor Richard O’Hair,Dr George Khairallah and Dr Gabriel daSilva has used a powerful combination ofelectrospray ionisation coupled withmultistage mass spectrometry andtheoretical simulations to study howsimple magnesium and lithium acetylides

react with water when isolated underidealised near-vacuum conditions, andtracked the effect of adding individualsalt molecules (e.g. a MgCl2 ion trio (top)or LiCl ion pair (bottom) in the figure) onthe reaction rate. This approach allowedthe researchers to clearly see that theaddition of an individual salt molecule to

an organometallic reagent dramaticallyenhances its reactivity towards water.Interestingly, theory showed how the saltmolecule provides a second metal centre,which plays an active role to alter thefundamental chemical transformationstaking place when water attacks theseorganometallic compounds.

The importance ofchannelling your energyResearchers from the Centre for OrganicPhotonics & Electronics, University ofQueensland, have shown that themechanism of charge generation inorganic solar cells (OSCs) can besignificantly different depending on thecombination of active materials used(Armin A., Kassal I., Shaw P.E., HambschM., Stolterfoht M., Lyons D.M., Li J., ShiZ., Burn P.L., Meredith P. J. Am. Chem.Soc. 2014, 136, 11465–72). Theconventional picture of photocurrentgeneration in bulk heterojunction (BHJ)OSCs containing a blend of a conjugatedpolymer donor and fullerene acceptorinvolves photoexcitation of the electrondonor, followed by electron transfer tothe acceptor – the Channel I mechanism.Less well studied is the mirror-imageprocess of acceptor photoexcitationfollowed by hole transfer to the donor –the Channel II mechanism. The teamshowed that a BHJ layer comprising anarrow optical gap polymer (DPP-DTT)mixed with PC70BM (see figure) showed

two distinct spectrally flat regions in theinternal quantum efficiency (IQE),consistent with the two channelsoperating with different efficiencies. Hot

excitons or other exotic processes are notin play, with differences in efficiencybeing due to the energetics and excitondynamics.

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Dec 2014–Jan 2015

research

CSI M1132_tit_adv_TitrationExperts201403_076275CS6.indd 1 13/05/2014 16:01

Compiled by Matthew Piggott MRACI CChem ([email protected]). This section showcases the verybest research carried out primarily in Australia. RACI members whose recent work has been published in highimpact journals (e.g. Nature, J. Am. Chem. Soc., Angew. Chem. Int. Ed.) are encouraged to contribute generalsummaries, of no more than 200 words, and an image to Matthew.

New frontier in solar energy conversionThin-film photovoltaics (PVs) based on alkylammonium lead iodide perovskite lightabsorbers have recently emerged as a promising low-cost solar-energy-harvestingtechnology. To date, the perovskite layer in these efficient solar cells has generallybeen fabricated by either vapour deposition or a two-step sequential depositionprocess. A team from Monash University, headed by Professors Leone Spiccia, Yi-BingCheng and Udo Bach, has now demonstrated that uniform CH3NH3PbI3 thin films canbe deposited by using an easily scalable one-step procedure, which involves spin-coating of a DMF solution of CH3NH3PbI3, followed immediately by exposure tochlorobenzene to induce rapid crystallisation (Xiao M., Huang F., Huang W., DkhissiY., Zhu Y., Etheridge J., Gray-Weale A., Bach U., Cheng Y.-B., Spiccia L. Angew.Chem., Int. Ed. 2014, 53, 9898–903). The resulting perovskite films consist of largecrystalline grains with sizes up to microns. Planar heterojunction solar cellsconstructed with these films afforded a maximum power conversion efficiency of16.2% and an average efficiency of 13.9±0.7% under standard AM 1.5 conditions.This simple low-temperature solution process is fully compatible with theconstruction of tandem devices applying existing photovoltaic technologies, such assilicon PVs and polymer solar cells. In addition to aiding the development ofperovskite-based PVs, it will also bring new possibilities to perovskite-based hybridoptoelectronic devices, such as field effect transistors and light-emitting diodes.

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research

Our colleagues in Japan have long had the custom to publishaccounts of their work in Bull. Chem. Soc. Japan whenever theyget an award from the Chemical Society of Japan. Taking a leafout of their book, Aust. J. Chem. reached agreement with theRACI to publish accounts from recipients of research-relatedRACI medals and awards. The current October and Novemberissues contain papers from some of the 2012 and 2013 RACIaward winners.

Michael Kelso and co-workers (University ofWollongong) compared theantibacterial activity ofberberine together withsynthetic NorA multidrugresistance pump inhibitors

(2-phenylindoles) versus hybrid compounds, where these twomolecules are covalently linked. The conclusion, reported in theOctober issue, is that the activity of the hybrid molecules is notjust the sum of the two parts: the mechanism(s) ofantibacterial action of the hybrids must be different from themechanisms at play when berberine is co-administered with 2-phenylindoles as separate compounds. Dr Kelso was therecipient of the 2013 Biota Award for Medicinal Chemistry.

David McGuiness and co-workers (University ofTasmania) describe atheoretical model for theindustrially importantconversion of ethylene tohigher alpha-olefins, usinghomogeneous Cr-PNP catalysis(PNP = Me2P-NMe-PMe2). DFTcalculations suggest a CrI–CrIII

mechanism involving spinsurface crossing from sextet to quartet states. The Cr complexshown with a PNP ligand and two ethylene molecules is a likelyintermediate in the first step, the dimerisation of ethylene. DrMcGuiness was the recipient of the 2013 OrganometallicChemistry Award.

Keith A. Stubbsand coworkers(University ofWestern Australia)report on thesynthesis ofcarbohydrate-based

natural products from the herb Leonurus japonicus as well as abiological evaluation of these compounds as anti-oxidants. Thisgenus contains numerous species that can be found throughoutEurope and Asia, as well as in some regions of the Americas andAfrica, where they also feature in traditional medicine. Threecarbohydrates, including leonoside F pictured, were synthesised

and shown to have the capacity to reduce oxidative stress. DrStubbs was the recipient of the 2012 Rennie Memorial Medaland the 2013 Athel Beckwith Lectureship.

Junming Ho was the winner of 2012 Cornforth Medal for bestPhD thesis (at the ANU, supervised by Michelle Coote). In theOctober issue, he reports a review on computational predictionof pKa values as an alternative to experimental measurement.Reliable prediction of pKa is important in many areas of science,including chemical synthesis, structural biology, and thedevelopment of drugs and functional materials, and this isachievable for many species ranging from small monoproticacids to larger and conformationally flexible polyprotic acids.This paper is freely available on the RACI website as theOctober Aust. J. Chem. paper.

Max Crossley and co-workers (University of Sydney) describesyntheses of steroid–porphyrin conjugates from the naturalsteroids estradiol, estrone and lithocholic acid in the Novemberissue. Four different construction motifs are explored by usingtwo different strategies for forming the requiredalkylidenepyrrole–steroid linkages, i.e. pre- or post-porphyrinsynthesis. It was found that the best method involves lateintroduction of the steroid component by means of anucleophilic substitution reaction. This paper is freely availableon the RACI website as the November AJC paper. ProfessorCrossley was the recipient of the 2013 Leighton Memorial Medal.

Leone Spiccia (Monash) was a recipient of both the BurrowsMedal (2013) and the H.G. Smith Memorial Award (2012). Anarticle, ‘Fluorescent analogues of NAMI-A: synthesis,characterisation, fluorescent properties, and preliminarybiological studies in human lung cancer cells’, with S. Antony,J.C. Morris, T. Bell, T. Brown and Hugh H. Harris as co-authors isavailable ‘Online Early’ on the Aust. J. Chem. website and willbe published in the December issue.

Aust. J. Chem. looks forward to a series of excitingcontributions from the 2014 RACI National Award winners.

The November issue also contains a series of nine papers onmolecular magnetism resulting from a Southampton–Australia–New Zealand Workshop held in Sydney in February. ThisResearch Front is guest-edited by Suzanne Neville, University ofSydney.

Chemistry in Australia12 | Dec 2014–Jan 2015

Aust J Chem

Curt Wentrup FAA, FRACI CChem ([email protected]),http://researchers.uq.edu.au/researcher/3606

N, blue; P, orange; Cr, pale blue.

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Chemistry in Australia 13|Dec 2014–Jan 2015

Coffee is one of the world’s favouritebeverages because of caffeine, an alkaloidthat so many of us find addictive. But wedon’t choose our coffee on strength alone.

As any coffee devotee knows, bean type has longbeen associated with coffee quality. The best beans,cultivated in the right location, soil conditions andclimate, come at premium prices. However, it is theroasting process that really sets up the organicchemistry to produce so much of the flavour andaroma.

During the high-temperature roasting (greater than140°C), a complex series of reactions occurs within thebeans, largely between the amino groups of aminoacids and the carbonyl groups of carbohydrates. Thehundreds of compounds produced then undergofurther chemistry or break down under the hightemperature and oxidation conditions of the roast. Theresult is hundreds more organic compounds, all ofwhich elicit taste and smell responses.

Forget caffeine – following yourfavourite barista around town is allabout the chemicals in the flavoursand aromas of a great coffee.

BY COLIN A. SCHOLES

The perfectroast reaction

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Collectively known as the Maillardreaction, these reactions describe thefood chemistry of many high-temperature food processes. Forexample, the Maillard reaction causescrust formation during bread bakingand gives baked potatoes theirdelicious crispy brown coating. Manyof the organic groups formed duringthe roasting Maillard reaction can beassociated with certain flavours.Furans are responsible for the taste ofsweet caramel, while pyraines registeras nutty, and diacetyl butanedionegives us butterscotch flavour.

To date, around 500 flavourcompounds have been identified incoffee, of which around 60 haveimportant roles in taste. This issignificantly different from other foods,such as apricots and strawberries,which have only 20–30 flavourcompounds. The brown colour ofcoffee is the result of the formation ofmelanoidins during the Maillardreaction.

The higher the temperature and thelonger the roasting process, the moreextensive the Maillard reaction and themore the beans’ organic chemistry isaltered. This is why high-quality beansare only lightly roasted, to limit theextent of the Maillard reaction andretain the original flavours. Poorerquality beans undergo longer roasts,more commonly known as darkerroasts, which convert much of thebean’s original organic chemistrythrough the Maillard reaction. Thismakes it more difficult to distinguishthe origins of the bean, and,importantly, can be used to hide thepoorer quality of the bean.

One of the most common myths ofroasting is that it alters the caffeinecontent of the bean. However, caffeineis a stable alkaloid and has a highersublimation temperature than thatreached during roasting. The othermajor alkaloid, trigonelline, whichprotects the bean from insects andfungal attack, is less stable andundergoes degradation duringroasting. The products supply coffee’s

earthy caramel aromas as pyridinesand your daily requirement (in justover a cup) of vitamin B3 (nicotinicacid).

The bitter taste of coffee is due to acombination of these alkaloids andorganic acids, chlorogenic acid beingthe most prevalent. During roasting,some of the chlorogenic aciddegrades into quinic and caffeic acids,which are responsible for the bolderflavours of good coffee. Citric acid isalso present in the bean and willsurvive the roasting. Too much citricacid will linger as a sour taste in themouth, and is often an indicator of

poorer quality beans. Thetriglycerides, fatty acidsand other lipids in thebean are relativelyunaffected by the roastingprocess, but they have animportant role to play in the taste of agood brew, especially in espressos.

A whole art of coffee preparation isdevoted to achieving the correct

coffee grounds size for the type ofbean and coffee beverage. The coffeebeans are ground to increase thesurface area of the beans exposed tothe water and to ensure faster transferfor the leaching of the organiccompounds during extraction of theorganic compounds into the coffee.

Hot water is the most commonsolvent for extraction: the hightemperature ensures a high extractionrate as well as high solubility. For mostcoffee brewing, water temperaturesaround 90°C are needed to ensure theorganic compounds leach into thewater fast enough to get a freshlybrewed coffee in your hands inminutes. Compounds that areexceptions to this rule are the bitteracids, which have a stronger affinity forthe coffee grounds. Near-boiling wateris needed to overcome theirhydrophobic association and leachthem into the water. If these organiccompounds are extracted into thewater, the change to a highly polarenvironment and high temperatureleads to their further breakdown,

Chemistry in Australia14 | Dec 2014–Jan 2015

Caffeine and trigonelline, coffee’s two main alkaloids. Both have insecticidal and fungicidal properties.

To date, around500 flavourcompounds havebeen identified incoffee, of whicharound 60 haveimportant roles intaste.

iStockphoto/azschach

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Chemistry in Australia 15|Dec 2014–Jan 2015

producing further flavours. The smallerand more volatile of these compoundswill rapidly vaporise and leave thebrew in the steam. These volatiles areregistered by our noses as the freshlybrewed smell. However, these volatilesare quickly lost, and this is whyreheated coffee never regains itsoriginal flavour, and coffee left brewingin the pot always has a poorer taste.

The cold brew process gets aroundthe loss in volatile organics. Cold wateris poured through the coffee groundsand they are left to steep for more thaneight hours. Hot water is added later tocreate the finished drink. Using coldwater minimises volatile organic lossesand limits the breakdown of otherorganic compounds. The coldtemperature also limits the solubility ofthe bitter acids, and they are retainedin the ground bean. For this reason,cold-brew coffee is said to have asmoother taste and fewer boldflavours.

Espressos take the extractionprocess further and apply the hotwater to the finely ground beans atpressures of 8–18 atmospheres. The

high pressure ensures a highersolubility of organic compounds in thehot water, and therefore a moreconcentrated brew. The high-pressureshock of the process breaks down theground coffee beans, some of whichbecome suspended in the coffeesolution. This produces theconcentrated hit that is an espresso,and the sharp taste. Interestingly, theactual amount of caffeine and otherorganic compounds within one

espresso is almost always less than aregular coffee, because the volume ofwater used is significantly less.

One of the side products ofespresso brewing is that thetriglycerides, fatty acids and lipidsbecome emulsified and enter thecoffee. This is generally in the form ofthe espresso crema – the tawnycoloured liquid that initially comes outduring espresso formation and settleson top of the darker espresso brew.Residual carbon dioxide in the coffeebeans, left over from the roastingprocess, dissolves in the hot water atthe high pressure and emulsifies thefatty acids and lipids. This forms acolloidal suspension of fatty acids,lipids and carbon dioxide. The fattyacid emulsification is stronglydependent on the fat content of theoriginal coffee bean and the timeperiod between roasting and brewing(residual carbon dioxide slowlyescapes from the bean with time), aswell on as the barista’s skill. Thisaddition of fatty acids and lipids ispart of the reason an espresso is thebasis of many different coffeebeverages, such as café latte and cafémocha.

Next time you visit your local café,try a different brew and compare thechemistry for yourself.

Colin Scholes FRACI CChem is at the University ofMelbourne.

Chlorogenic acid degrades into quinic and caffeic acids during roasting.

iStockphoto/milosljubicic

The crema on an espresso contains emulsified triglycerides, fatty acids and lipids.

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For astronomers interested inthe formation and evolution ofgalaxies, chemistry usuallymeans measuring

spectroscopically the abundances ofelements relative to hydrogen in thestars and in the gas of galaxies.Although a few of the lightest elements(He, D, Li, Be, B) were produced in theBig Bang itself, most of the heavierelements are produced on differenttimescales by nuclear processes indifferent kinds of stars, so we can useelement abundances to work out whathappened as the galaxies were builtup. We derive the elementabundances in stars by using stellarspectroscopy to measure the strengthsof the absorption lines in the spectra ofstarlight.

Stars form and die: each generationof stars enriches the interstellar gas in

heavier elements such as iron, and theabundance ratio of heavy elementsrelative to hydrogen gradually rises. Indisk galaxies like the Milky Way, mostof the stellar mass lies in a thin, flatdisk in which star formation startedabout 10 gigayears ago and has beengoing on steadily ever since. We findthat the inner regions of thin disks areusually more enriched than the outerregions. This happens because thegalaxies start forming from the inside,so the chemical evolution is moreadvanced in the inner regions.

To quantify this abundancegradient, we can compare theabundance of iron in the inner andouter galaxy with the abundance at theSun, which lies at an intermediateradius. In the inner galaxy, theabundance of iron relative to hydrogenis about twice that of the Sun, and in

Chemistry in Australia16 | Dec 2014–Jan 2015

Galactic chemistryand the

GALAH survey

BY KEN FREEMAN

Our galaxy, the Milky Way, stretchesacross the southern sky. Here we can seethe bright regions of the inner galacticstellar disk, obscured in patches by thedark nearby dust clouds.

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the outer galaxy it is only about one-third of the solar value. We use alogarithmic bracket notation to denotethe element abundances relative to theSun. The solar abundance of ironrelative to hydrogen is denoted as[Fe/H] = 0, and an abundance of one-tenth solar has [Fe/H] = –1.

In addition to the dominant thindisk, almost all disk galaxies have asecond more diffuse disk componentknown as the thick disk. It containsabout 10% of the mass of the thin diskand, as its name suggests, it is thickerthan the thin disk. Its importantcharacteristic is that the star formationin the thick disk started earlier (about12 gigayears ago) and ended quiteabruptly only a gigayear or so later.The thick disk appears to be aninevitable step in the process ofbuilding up disk galaxies, but at thistime we do not understand the detailsof what went on early in the life of adisk galaxy: why did its star formationend so quickly?

The short period of star formationfor the thick disk has chemicalconsequences that we can observe.Massive stars have short lives (around10 million years): when they die assupernovae, their nuclear-processedmaterial is returned to the interstellargas from which the next generation ofstars will form. The ejecta frommassive stars are rich in the alpha-elements (Mg, Si, Ca, Ti).

In contrast, the heavier elements inthe iron-peak come primarily from thesupernova deaths of less massive

stars, which take longer to evolve anddie. So the relative abundances ofalpha-elements and iron-peakelements is a measure of the durationof star formation. In the thick disk, itappears that the star formation wasover before these low-masssupernovae had time to explode andenrich the interstellar gas with theiriron and other iron-peak elements. Thethick disk stars are therefore muchricher in alpha elements relative toiron than the stars of the thin disk, inwhich the star formation has beengoing on steadily for many gigayears(see diagram).

In this way, the chemistry of thethick disk gives us an important clueabout how disk galaxies are built up,even though we cannot fully interpret ityet. Most of what we know about theformation of galaxies comes from

Chemistry in Australia 17|Dec 2014–Jan 2015

The distribution of nearby stars in the [Ti/Fe]–[Fe/H] plane. The thick and thin disks of our galaxy overlapin [Fe/H] but the thick disk stars are relatively enriched in the alpha element Ti, because the thin disk hada short history of star formation and chemical evolution. The Sun lies at the intersection of the dottedlines (Bensby T. et al. Astron. Astrophys. 2014, vol. 562, p. 71).

A new multi-object spectrometermeans we no longer have toquantify galaxies one star at a time.

... the chemistry ofthe thick disk givesus an importantclue about howdisk galaxies arebuilt up, eventhough we cannotfully interpret it yet.

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computer simulations, in which gravity,star formation and chemical evolutionare all included. Much of the detailedphysics of these processes is stilluncertain. Although the simulations arestarting to produce galaxies that looklike the ones we observe, we urgentlyneed observations to constrain thesimulations of the assembly ofgalaxies. We would like to know howthe build-up of galactic disks occurred– was it primarily long ago, shortlyafter the Big Bang, or did it take placesteadily or in bursts over the past10 gigayears?

Stellar chemistry can help. Starsmostly form in clusters of typically athousand to a million stars. Theseclusters are loosely boundgravitationally; they usually disruptafter about 20 million years as thecluster loses mass via the evolution ofits massive stars. After the clusterdisrupts, the stars of the cluster quietlydiffuse right around the galaxy andbecome part of the galactic thin disk. A few clusters do survive. In thesesurviving clusters, we find that the starsare chemically identical over all of the

elements heavier than magnesium, atleast to the level of accuracy withwhich their abundances can bemeasured (about 10%). The gas fromwhich the clusters formed must havebeen very well homogenised.

This gives us a way to reconstructthe star formation history of the galaxy.We measure the abundances of about30 elements in each of about a millionstars in the galaxy, and look for familiesof stars of identical composition. Thesestars are very likely to have been borntogether in a common star cluster thatdisrupted and dispersed. In this way,we can chemically reconstructdisrupted clusters, measure their ages,and so build up the star formationhistory of the galaxy. This process iscalled chemical tagging.

Until recently, abundances of starshad to be measured one star at atime. Measuring detailed abundancesof 30 elements in a million stars wastotally out of reach. Over the past fewyears, we have built a multi-objectspectrometer (HERMES) fed byoptical fibres on the Anglo AustralianTelescope near Coonabarabran in

New South Wales. With HERMES, wecan make these measurements for400 stars at a time. Determiningelement abundances for a millionstars is still a very large project, butthat is what we need to do chemicaltagging, and it has become possible.The project is known as GALAH(Galactic Archaeology with HERMES)and involves about 50 astronomers,mostly Australian. The instrument isnow working and has alreadymeasured more than 60 000 stars. Theproject will take about five years tocomplete.

We can think of a chemical space(C-space) of abundances of theelements: e.g. Na, Mg, Al, Ca, Mn, Fe,Cu, Zr, Ba, Eu … With the HERMESinstrument, abundances for up toabout 30 elements will be measurable.Not all of these elements varyindependently from star to star; manyvary together from star to star in near-lockstep. The dimensionality ornumber of independent dimensions ofthis chemical space is 8 to 9 (Ting Y.-S.et al. MNRAS 2012, vol. 421, p. 1231). Inthe C-space, the stars of a dispersed

Chemistry in Australia18 | Dec 2014–Jan 2015

The Na-Ni distribution for globular cluster stars, dwarf spheroidal galaxy (dSph) stars (faint dwarf galaxiescontaining mostly old stars), field stars and stars of the recently discovered Aquarius star stream (blackstar symbols: Wylie de Boer E. et al. Astrophys. J. 2012, vol. 755, p. 35). Stars of the dwarf galaxy are wellseparated from the other kinds of stars. The stars of the Aquarius stream do not appear to be the debrisof an accreted dwarf galaxy. M3, NGC288, NGC362 are the names of globular clusters. For (Fornax), Sgr(Sagittarius), Scl (Sculptor) and Car (Carina) are dwarf spheroidal galaxies.

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The light from each of the 400 stars is transferredfrom the focal plane of the telescope to the fibreslit. The light is then collimated, and is sent off tothe four cameras (blue, green, red and IR) by thedichroic beamsplitters. CCD cameras image the400 spectra in each band. The CCD images arethen passed to the data reduction pipeline, whichextracts the spectra for each star and passesthem on to the chemical analysis pipeline.

cluster will lie in a tight clump. Star formation from interstellar gas

is the main route to building up thedisk of a galaxy, but numericalsimulations of galaxy formationindicate that the infall of small already-formed galaxies into larger galaxies isalso a significant contributor. While theoutcome of numerical simulations ofgalaxy formation from the expandinguniverse work well on scales largerthan galaxies, on galactic scales theybecome progressively more uncertainbecause the physics becomesprogressively more uncertain. Weneed good observational measures ofhow much infalling galaxies have

actually contributed. Again, elementabundances can help to recognise thedebris of small galaxies from amongthe stars that formed within the galaxyitself. For example, the relationbetween [Na/Fe] and [Ni/Fe] insurviving small galaxies is observedto be different from the relation for themore common stars of the disk (seediagram). The million-star GALAHsurvey of element abundances will bean excellent source of data for findingdebris of accreted galaxies.

Ken Freeman is Duffield Professor, Research Schoolof Astronomy & Astrophysics at the AustralianNational University, and wrote this article on behalfof the HERMES/GALAH team. Visitwww.mso.anu.edu.au/galah/home.html.

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We would like to know how the build-up of galactic disksoccurred – was it primarily long ago, shortly after the BigBang, or did it take place steadily or in bursts over the past10 gigayears?

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The world breathed a sigh ofrelief in the 1980s when DDT(dichlorodiphenyltrichloroethane or 1,1,1-trichloro-2,2-

bis(4-chlorophenyl)ethane) wasbanned in most countries. Australiabanned its use in 1985. The Earth wasrid of a dangerous environmentalchemical heavily used in agriculture,but few gave any thought to itsreplacements. The world’s agriculturalchemical manufacturers had a host ofcandidates available, with many

already registered and in use. Theorganophosphate pesticides werestrong candidates and one of these,chlorpyrifos, was available in Australiain the 1970s. Its use has ramped upsince DDT was banned and it is nowone of the most widely usedinsecticides in Australia and on theplanet.

Chlorpyrifos use in Australia hasbeen restricted, but research by theSchool of Environment at GriffithUniversity in Vietnam and worldwide

Chemistry in Australia20 | Dec 2014–Jan 2015

One of the world’smost widely usedinsecticides,chlorpyrifos poseshealth problems foragricultural workerswhere regulation islacking.

ChlorpyrifosA global health problem

BY DES CONNELL

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Getting prepared forspraying a rice cropwith chlorpyrifos inVietnam

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has shown that chlorpyrifos harms thehealth of most farmers from the manydeveloping countries that use it. Evenin countries where use is restricted,there remain concerns about adverseneurological effects on children. Itclearly poses a problem for publichealth of global dimensions(Marasingh J., Yu Q., Connell D. Toxics2014, doi: 10.3390/toxics2020092).

Chlorpyrifos and DDTChlorpyrifos is a broad-spectruminsecticide used in Australia for cropprotection and protection of buildingsagainst termite attack. It is usedextensively overseas in developingcountries to protect rice crops againstinsect attack. It acts by interfering withthe enzyme acetylcholinesterase in thenervous system and causes paralysisof the muscles and ultimately death.WHO considers chlorpyrifos to bemoderately toxic with an LD50 inexperimental animals of 32–1000 milligrams per kilogram of bodyweight. This toxicity to mammals,particularly humans, was one of themain reasons for its limited use in thepast and the preference for DDT, whichhas relatively low toxicity.

DDT was banned principallybecause it forms residues in manyfoods, in humans and in wildlife. It isvery toxic to fish and other aquaticorganisms and bioaccumulates in theeggs of the top predatory birds. Thishad an adverse effect on populationsof eagles in many parts of the world, atrend reversed by the DDT ban.Chlorpyrifos is non-persistent in theenvironment, does not form residuesor bioaccumulate. However, it is verytoxic to most forms of life.

In Australia and other developedcountries, many restrictions controlwhere chlorpyrifos can be used,particularly in the home and garden.But some relatively small occupationalgroups, such as manufacturingworkers and pesticide applicators, canbe exposed to high levels. Non-targetanimals and plants can also beexposed, with consequent adverseeffects.

Chlorpyrifos in developingcountriesThe pattern of global usage haschanged since the DDT ban.Developing countries are now majorusers of pesticides, includingchlorpyrifos, and usage is increasing

rapidly. In Vietnam, the use ofchlorpyrifos, and other pesticides,increased from 14 000 tonnes in 1990to 50 000 tonnes in 2008. This has beennot been accompanied by enhancedregulation and control. WHO hasreported that pesticide poisonings areoccurring more frequently on a globalscale and at a more serious level.WHO estimates that three millionpoisonings occur each year; thisincludes 220 000 deaths, most of which(99%) occur in developing countries.For each acute poisoning case in theUS, about 600 acute poisoning casesoccur among agricultural workers inVietnam. There is widespread concernin the US that even trace residues ofchlorpyrifos are having a detrimental

Chemistry in Australia 21|Dec 2014–Jan 2015

Chlorpyrifos and its biodegradation product TCP. Analysing urine samples for the TCP metabolite is usedto determine exposure to chlorpyrifos.

Measuring out thespraying mixture intothe backpack reservoir

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effect on human mental processes.Recently, a large team of experts fromNorth and South America carried outan extensive review of the publishedresearch. They concluded that low-level exposure leads toneurotoxicological disorders inchildren, such as behaviouralproblems, working memory deficits,abnormal reflexes and many others(Muñoz-Quezada B.B. et al.,NeuroToxicology 2013, doi10.1016/j.neuro.2013.09.003)

One of the major problems withchlorpyrifos in developing countries ishow it is applied. The common methodof application employs a backpackreservoir with a hand-operated pumpand the spraying nozzles on a pipefacing forward. The operators, bothmen and women, are engulfed in amist of pesticide for the sprayingevent. By contrast, in developedcountries the pesticide is often appliedby tractor-mounted boom sprayers, theoperator avoiding exposure in thecabin of the tractor.

Research in Vietnam and globallyOur research team has been involvedwith the human health risk assessmentof a range of chemicals in the

environment, in particular benzene,chlorobenzenes and chlorpyrifos. Aglobal analysis of published data onchlorpyrifos revealed the hazardquotients (HQ) for occupationallyexposed populations to be high insome situations. A median individualfarmer in Vietnam had exposures up to3.9 times the USEPA guideline (HQ3.9), whereas the 5% most exposedamong the manufacturing workersfrom the US had 42 times this value.Hazard quotients greater than unityusually represent a significant hazardto health. A comparison of theexposure to chlorpyrifos in differentoccupations in several countries has

indicated exposure occurs in manycountries throughout the globe.

We collected samples of the urineof farmers in Vietnam before and aftera spraying event. These samples wereanalysed for the TCP metabolite andback calculated to the originalexposure to chlorpyrifos. This data onthe exposure of the applicators wasplotted as cumulative probabilitydistributions showing the wide rangeof exposures that occurred.Surprisingly, the range was about 100-fold from the lowest to the highest withboth the pre- and post-eventexposures. It also demonstrated thatexposure to chlorpyrifos after a

Chemistry in Australia22 | Dec 2014–Jan 2015

Chloropyrifos ADD

(mg/kg

/day)

USEPA guideline for acute exposure

1000

max

median

min100

Vietnam Sri Lanka

10

1

0.1

US manufacturingworker

US termiticiderUS Nicaragua

Chlorpyrifos exposure, as ADD (absorbed daily dose), of farmers and other workers in different countries compared to USEPA guideline for acute exposure

... exposure to chlorpyrifos after a sprayingevent increased by a factor of about 100from the background. Exposure at thislevel represents a major health hazard tothe median farmer in Vietnam – even morecritical considering that the spraying isrepeated several times each year – and forthe farmers’ working lives.

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spraying event increased by a factor ofabout 100 from the background.Exposure at this level represents amajor health hazard to the medianfarmer in Vietnam – even more criticalconsidering that the spraying isrepeated several times each year –and for the farmers’ working lives(Phung D.T. et al. J. Exp. Sci. Env.Epidem. 2012, doi: 10.1038/jes.2012.32; Phung D.T. et al. Risk Anal.2013, doi: 10.1111/risa.12023).

A highly exposed group constitutesthe 5% most exposed at the cumulativeprobability level of 95%. We concludedthat about 30% of the farmingpopulation suffered from pesticidepoisoning, which agrees withepidemiological surveys.

We also evaluated the effectivenessof protective clothing because theextreme discomfort of personalprotective clothing in tropical climatescan mean it is not practical to use. Theuse of long-sleeved shirts reduced theexposure level significantly.

Education and alternativesQuite clearly, chlorpyrifos is a majorglobal health problem. Our work inVietnam has shown that there are waysto reduce exposure in the field indeveloping countries with minimalimpact on the farming operation. But ithas also indicated that the regulationand control of chlorpyrifos and other

pesticides requires urgent action byindividual countries, as well as a globalbasis (Phung D.T. et al. Bull. WorldHealth Organ. 2012, doi:10.2471/BLT.11.096578).

At the very heart of this problem isthe training and education of farmersand all those using chlorpyrifos. Also,the world’s pesticide researchinstitutes need to design and testpesticides that don’t have the humantoxicity properties of chlorpyrifos, butdo have desirable environmentalproperties such as non-persistence.

Research should be directed towardsthe use of alternative, non-chemical,methods of insect control. Hopefully, inmany situations pesticide use can bereduced or avoided. Such measureswill help to reduce the human cost ofthis chemical.

Des Connell FRACI CChem is Emeritus Professor atthe Griffith School of the Environment, GriffithUniversity, Brisbane. His research has been on thebehaviour and effects of organic chemicals in theenvironment for which he was awarded a DSc andmade a Member of the Order of Australia. In recentyears, he has focused on the evaluation of the healthrisk of chemicals in the environment.

Chemistry in Australia 23|Dec 2014–Jan 2015

Online indexesThe latest Chemistry in Australia indexes are now online.Browse or search our archived back issues from 2003onwards.

To view the latest indexes, visit www.raci.org.au/resourcecentre/further-information/indexes.

iStockphoto/Onur Döngel

Using the backpack sprayer with the hand-operated pump and spraying wand with a rice crop in Vietnam

Dun

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Page 24: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

In April this year, the centenary ofthe creation of the activated sludgeprocess was celebrated at aconference in Manchester, UK. One

of Adelaide’s most popular and affluentseaside suburbs is the home of theGlenelg Wastewater Treatment Plant,Australia’s first activated sludge plant.

In 1928, after much research andhealthy debate, and faced with agrowing population, the SouthAustralian Government embarked onthe design and construction of theGlenelg Wastewater Treatment Plant.The process was successfullycommissioned in December 1932.Since then, other major additions havebeen made to the plant, withextensions in the 1940s, 1950s, 1970sand 2000s. Through these upgrades,the plant, serving a connectedpopulation of more than 200 000,remains committed to the activatedsludge process and is a plant capableof a high level of wastewater treatment,continuing to reduce the nutrient load

discharged to the sea and enabling therecycling of effluent for dualreticulation and irrigation purposes.

In 1928, the Public WorksCommittee in South Australia beganhearing reports from the Engineeringand Water Supply Department on there-organisation of the seweragesystem of Adelaide and suburbs and,importantly, the need for an up-to-datesewage treatment works. A new andadvanced treatment works wasrequired at Glenelg for severalreasons: population and industry inAdelaide were growing, local residentsof affluent suburbs were demanding ahigh degree of treatment anddischarge to the sea was increasinglyseen as viable.

The department set about hiring aconsultant specifically experienced inactivated sludge treatment, A. GordonGutteridge (see box). Gutteridge wasassisted in the design of the GlenelgWastewater Treatment Plant by theAssistant Engineer for Sewerage,

Henry Hodgson (see box). Hodgsonwould soon become a leading expertin activated sludge treatment.

Glenelg beach was fashionable inthe 1920s, and remains Adelaide’spremier beach destination. Therefore,a high level of treatment and theabsence of odour were essential in theplant design.

The treatment process incorporateda main pumping station, whichpumped raw sewage under thePatawalonga River (on the easternboundary of the plant) to the newtreatment plant (situated on sanddunes, beach front). From here thesewage passed through a primarysedimentation tank prior to treatmentvia the activated sludge process,which consisted of mixing tanks,aeration tanks and secondarysedimentation tanks. Effluent wasdisposed of via absorption beds intothe sand dunes. The sludge streamwas treated in a digester with thesludge sent to drying beds before

Chemistry in Australia24 | Dec 2014–Jan 2015

Australia’s pioneering wastewater plant

Special treatment:

The centenary of activated sludgeinspired Bronwyn Kent to research theGlenelg Wastewater Treatment Plant,the oldest of its type in Australia.

BY BRONWYN KENT

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removal from site and subsequent landdisposal. This treatment stream was tobe known as ‘A Plant’.

By December 1932, theEngineering and Water SupplyDepartment had the nation’s firstactivated sludge plant fully operationaland functioning well, capable oftreating 10 megalitres per day annualaverage flow for a connectedpopulation of approximately 40 000.

Plant extensionsThe Glenelg catchment expanded atan unexpectedly high rate. Theconnected population for the originalworks was achieved by the secondyear of operation and by 1939 theplant was attempting to treat aconnected population 50% above thedesign capacity. For the next upgradeto the plant, the government decidedthat external assistance fromconsultants was not required and thedepartment set about ensuring theextensive training of the AssistantEngineer for Sewerage, Hodgson, whothrough his work at Glenelg and onother sewage works in the state hadshown considerable ability.

The much-needed extension to theGlenelg plant was delayed whileawaiting the return of Hodgson fromhis US fellowship study tour (see box).

The Public Works Committeedetermined that Hodgson’s design for

Glenelg would not require externalreview – he was now considered themost experienced designer inAustralia on sewage treatment. Theextension was approved andconstruction could begin.

By 1941, the department had asuccessfully commissioned, extendedplant with a winery waste treatmentstream, capable of treating20 megalitres per day for a connectedpopulation of 92 000.

The design population was reachedwithin 10 years, creating the need foranother large extension. By this stage,Hodgson now held the title of Engineerfor Water and Sewage Treatment.Construction began in 1956.

By 1962, the department hadsuccessfully commissioned the B Plantextension, creating a plant capable oftreating 40 megalitres per day (AAF)for a connected population of 175 000.

In 1960, a scheme supplyingchlorinated effluent to nearby playingfields was approved. This schemeproved to be highly successful andprofitable, leading to further recycledwater schemes. In 1961, 1963 and1970, significant expansions occurredto the recycled water network toinclude several local golf courses,sporting ovals, a primary school, localcouncil and the Adelaide Airport. TheGlenelg Wastewater Treatment Plantand the Engineering and Water Supply

Department had become leaders andinnovators in recycled water schemesin Australia.

By 1969, the plant was againreceiving flows above the designcapacity. But this next extension waseasy. In 1966, Henry Hodgson hadretired from the department as theAssistant Director of EngineeringServices; however, his designemployed in the construction of thesuccessful B Plant extension couldessentially be copied.

By 1975, the Glenelg ActivatedSludge Plant was capable of treating60 megalitres per day annual averageflow for a connected population of250 000.

The EPA began a series of licencechanges in the late 1990s, imposing onSA Water (now corporatised) the needfor an Environmental ImprovementProgram at Glenelg. The aim of thiswas to reduce the total nitrogendischarge to the sea to ≤10 milligramsper litre, and reduce the impact ofeffluent discharge on seagrasses. Noincrease in capacity was required;instead the activated sludge processwas changed to incorporate biologicalnutrient removal. Construction beganin 2000 with commissioning in 2002.

The success of the recycled waterplant was so great and customer

Chemistry in Australia 25|Dec 2014–Jan 2015

Simple schematic of the activated sludge process– a process that uses air and microorganisms tobreak down sewage into carbon dioxide, waterand other compounds

Gutteridge, GHD and GlenelgGorden Gutteridge studied engineering at the University of Melbourne and latercompleted a Masters at Harvard University. In 1928, following his work asDirector of the Commonwealth Division of Public Health, he formed a privatepractice specialising in the design of water and wastewater schemes. In 1939,Gutteridge merged his practice with Gerald Haskins and Geoffrey Davey to formGHD, a large, international engineering consultancy.

In his role as Director of Public Health Engineering, Gutteridge was known forhis ‘zeal, knowledge, learning, industry, discretion and ability’ (Arneil 1988). Heinsisted on high standards, and quality of workmanship was an obsession. Hiswork on the Glenelg plant was so successful that he won commissions for otherschemes in Victoria and Tasmania. GHD quickly became one of the largestconsultancies in its field in Australia. Gutteridge was an impressive character,whose influence would forever define the work culture at Glenelg.

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demand so high that in 2009 a new35 megalitres per day recycled waterplant was commissioned at Glenelg,providing effluent for dual reticulationand irrigation purposes for theexisting customers as well as newcustomers reaching from the westernto the eastern suburbs of Adelaide,including the central business district.This plant incorporates ultrafiltrationmembrane filtration followed by UVdisinfection and chlorination.

Gutteridge and Hodgson are theheroes of this story, but Hodgson

clearly stands out. He was involvedwith the plant from its conception in1928 through to 1966 when he retiredfrom the department after 42 years ofservice. Hodgson was describedthroughout his career as an innovator,a teacher, a modern engineer and anexpert in his field. He was also avisionary: not only did he put intoplace strategic plans for water andwastewater systems in South Australia,he was responsible for the formation ofthe Australian Water Association in1961. He was its federal president in

1964 and in 1973 he was the firstperson to receive honorary lifemembership to the AWA. The work ofHenry Hodgson has stood the test oftime, and you can’t get much better thanthat. We in South Australia couldn’t bemore proud of this plant and its history,and I like to think that Henry Hodgsonwould be pretty proud today too.

Bronwyn Kent ([email protected]) is atSA Water Corporation, South Australia. A list ofreferences is available from the author.

Chemistry in Australia26 | Dec 2014–Jan 2015

Hodgson and hisHarvard studyHenry Hodgson (1901–92) received aBachelor of Civil Engineering from theUniversity of Melbourne in 1923 andwas appointed to the Engineering andWater Supply Department in SouthAustralia in 1924. In 1935, Hodgsonreceived the Commonwealth FundFellowship, New York, which involved a15-month study tour in the US,studying at Harvard University. Thisfund still exists today and focuses onpromotion of health-based research andthe fostering of relationships betweenthe US and the British Empire.

In addition to his study, Hodgsontoured activated sludge plants in theUS, Germany, Holland and GreatBritain. He visited more than150 sewage treatment works. On hisreturn to South Australia, Hodgsonwrote and had printed a book calledSewage and trade wastes treatment,providing exquisite detail of his travels.This was published in 1938, within12months of his return from overseas,and was very quickly recognised as acomprehensive assessment of sewagetreatment practices around the worldand later used as a university textbookin the US.

Glenelg Wastewater Treatment Plant: top – A Plant, 1933; bottom – the plant in 2009.

Primary tank

Digestion tank

Absorption beds

Sludge drying beds

Secondary sedimentation

tanks

Aeration tanks

Main pump station

DAFT plant, 2002

35 ML/day Glenelg to

Adelaide recycled water plant

commissioned 2009

Conversion of B and C Plants

with IFAS, 2002

1 ML/dayrecycled

water plantcommissioned 2002

D Plant streamcommissioned 2002

DecommissionedA Plant, 2002

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from the raci

Chemistry in Australia 27|Dec 2014–Jan 2015

Applied Research Award

Professor David Lewis FRACI CChem joinedFlinders University in 2009 to becomeProfessor of Materials Science and thefounding Director of the Flinders Centre forNanoScale Science and Technology. Thisfollowed a 21-year career in industrialresearch at IBM in the US and researchmanagement at SOLA Optical/Carl Zeiss inAustralia.

During his career, David becameinternationally recognised for work in

microwave processing of polymers, and had key roles in thedevelopment of the first ‘copper wire chips’, multichip modulesfor mainframe computers, Transitions Velocity photochromiclenses and a range of high-index ophthalmic lens materials andcoatings. With a focus on translational research and assistingcompanies to become more competitive, David createdNanoConnect, a mechanism to allow companies to explore thepotential of nanotechnology on their businesses since joiningFlinders.

David has delivered over 20 plenary and invited papers atinternational meetings, edited two conference proceedings,authored or co-authored over 50 papers and has 50 grantedpatent families; he has been recognised by professional bodiesfor technical and professional leadership. He has also beenactive in professional societies, such as the RACI, being aformer Chair of the Polymer Division and SA Branch President aswell as taking on a number of roles internationally.

Citation: Contributions to Chemistryand the Profession

Dr Brian J. Smith FRACI CChem is acomputational chemist and molecularmodeller with extensive experience inprotein X-ray crystallography and structuralbiology. His research is directed towardsunderstanding biochemical processes, drugdiscovery and the development of newtreatments for diseases of globalimportance. He has served on the VictoriaBranch committee for more than 10 years,and was the President of the Victoria Branch2011–12. He has co-authored more than130 scientific publications.

Brian graduated from the University of Melbourne with a PhDin 1987, after which he took up a postdoctoral position at theAustralian National University. Returning to Melbourne in 1991,he held a research scientist position at the BiomolecularResearch Institute, and later moved to the Walter & Eliza HallInstitute of Medical Research. In 2011, he was appointed theinaugural LIMS Principal Research Fellow at La Trobe University.

Dr Anthony O’Mullane MRACI CChemgraduated from University College Cork,Ireland, in 1997 and completed a PhD atthe same university in 2001 in the field ofgold electrocatalysis under the supervisionof Professor Declan Burke. He undertookpostdoctoral fellowships at TechnischeUniversität Darmstadt, Germany, Universityof Warwick, UK, and then in Australia atMonash University with Professor AlanBond. In 2008, he worked briefly as aresearch scientist at CSIRO before taking aposition at RMIT University where he was then awarded a ViceChancellor Senior Fellowship. In 2012, he was awarded an ARCFuture Fellowship and in 2013 continued this fellowship andstarted a senior lectureship at Queensland University ofTechnology.

Anthony’s research interests are the electrochemicalsynthesis and characterisation of nanostructured materials;electrocatalysis; catalysis; organic semiconductors; metaloxides; Li batteries; and in particular the application ofelectrochemical methods to various aspects of physical,chemical and biological science. He combines innovative (butsimple) synthetic methods with state-of-the-artcharacterisation to develop new insights into both old and newelectroactive materials. In these areas he has published onebook chapter, 97 articles and 15 conference papers.

Anthony has also made strong contributions to his disciplineas RACI ambassador for RMIT during his time there and as thesecretary (2010–13) and now Chair of the ElectrochemistryDivision of the RACI.

2014 RACI National Award winners

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Cornforth MedalDr Ganna (Anya) Gryn’ova MRACI (Student)graduated with a Master’s degree inchemistry summa cum laude fromDnipropetrovsk National University inUkraine. She then moved to Australia topursue her interest in applyingcomputational chemistry to study reactionmechanisms and predict physical andchemical properties of the molecules. In2013, she completed a PhD at the AustralianNational University under the supervision of

Professor Michelle Coote. Her thesis, entitled ‘Understandingand Manipulating the Reactivity of Nitroxides and Other StableFree Radicals’, is highly multidisciplinary and contributes to abetter understanding of the role of free radicals in thedegradation of industrial materials and biomolecules, as well tofundamental aspects of free radical chemistry and the nature ofthe polar effects.

Ganna’s PhD research led to, among other contributions,clarifying a realistic mechanism of materials protection byhindered amine light stabilisers, designing a redox mediatorthat doubled the light conversion efficiency of a dye-sensitisedsolar cell; and uncovering previously unappreciated, surprisinglylarge through-space electrostatic effects on delocalised freeradicals. The latter discovery has been reported in the NatureChemistry and resulted in a patent application. During her PhD,Ganna presented her research at numerous Australian andinternational conferences, published 14 research papersincluding seven first-author papers in high-profile internationaljournals such as JACS and received a number of awards,including the Postgraduate Student Researcher Award from theAustralian Research Council Centre of Excellence for Free RadicalChemistry and Biotechnology. Currently, Ganna is employing thefindings of her PhD to design new organic molecules formolecular electronics applications in the Ecole PolytechniqueFédérale de Lausanne in Switzerland.

Fensham Medal: OutstandingContribution to Chemical Education

Professor Simon Pyke FRACI CChem hasover 20 years’ experience in highereducation at the University of Adelaidewhere he is currently Associate Dean(Learning & Quality) in the Faculty ofSciences. Simon is highly regarded as ateacher and has been recognised withnumerous awards including the D.R. StranksMedal for Excellence in Chemistry Education,an ALTC Citation for OutstandingContribution to Student Learning and the

University of Adelaide’s Stephen Cole the Elder Award forExcellence in Teaching (he is the only person in the history ofthis award to have received it twice).

His interests in science educational research encompasscurriculum design, construction and assessment (with particularfocus on threshold learning outcomes); facilitating developmentof skills (discipline related and generic); and studentengagement through classroom practice. He has been a memberof numerous CAUT/ALTC/OLT-funded project teams and hasrecently led a working party of ChemNet, the OLT-fundednational Chemistry network, focused on development andimplementation of threshold learning outcomes in Chemistry.He is also an active contributor to senior secondary educationin South Australia through a long-standing relationship withthe SACE Board.

H.G. Smith Memorial AwardProfessor Martin Banwell FRACI CChemwas born and educated in New Zealand.In 1979, he completed his PhD inorganic chemistry at the VictoriaUniversity of Wellington where heworked under the supervision of BrianHalton. After a postdoctoral period withLeo Paquette at the Ohio StateUniversity, he took up a senior teachingfellowship at the University of Adelaidein South Australia. In 1982, he movedto a lectureship at the University ofAuckland in New Zealand and then to an equivalent position atthe University of Melbourne in 1986. He was promoted to areadership in Organic Chemistry at the same institution in 1993.In 1995, he moved to the Research School of Chemistry (RSC) atthe Australian National University and, at that time, held theposition of senior fellow. In 1999, he was appointed Professorof Chemistry and served as Director of the RSC from thebeginning of 2008 until mid-2013.

Martin’s research interests are in synthetic organic chemistry,particularly the development of new methodologies and theirapplication to the total synthesis of biologically active naturalproducts. He is the author or co-author of some 300 journalarticles in this broad area. A particular emphasis has been theexploitation of strained organic compounds and the products ofwhole-cell biotransformations for such purposes. In recognitionof his work, Martin has received a number of awards, includingthe Rennie and Birch Medals of the RACI. In 2003, he receivedthe Royal Society of Chemistry (UK) Award in Synthetic OrganicChemistry, and he was elected to the Fellowship of theAustralian Academy of Science in the following year.

from the raci

Chemistry in Australia28 | Dec 2014–Jan 2015

Page 29: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Chemistry in Australia 29|Dec 2014–Jan 2015

Le Fèvre Memorial Prize – AustralianAcademy of Science

Associate Professor Richard Payne MRACICChem graduated from the University ofCanterbury, New Zealand, in 2002. In 2003,he was awarded a Gates Scholarship toundertake his PhD at the University ofCambridge. After 18 months as a LindemannFellow at The Scripps Research Institute (LaJolla), he began his independent career (inJanuary 2008) as a lecturer in organicchemistry and chemical biology at theUniversity of Sydney.

Richard’s research focuses on utilising the power ofsynthetic organic chemistry to interrogate biological systemsand address problems of medical significance. As a result of hisresearch endeavours, he has been the recipient of severalprestigious awards including the RACI Biota Medal in MedicinalChemistry (2008), a NSW Young Tall Poppy Science Award(2010), the Rennie Memorial Medal (2012), the Athel BeckwithLectureship (2013), the Tregear Award for Peptide Science(2013) and an ARC Future Fellowship (2013).

Leighton Memorial MedalProfessor Robert O. Watts FAA, FTSE,FRACI CChem, was Vice PresidentTechnology & Chief Scientist for BHPBilliton, where he was responsible fortechnology development throughout theBHP Billiton Group. He managed teams todevelop and transfer research findings toindustry, including establishing feasibilitytrials and taking results through tocommercialisation. Bob joined BHP in 1997and was responsible for ensuringtechnology standards across the company,

including new capital projects and interaction with universities,CSIRO and other external R&D providers.

During a research career spanning some 40 years Bobacquired extensive experience in computational chemistry,modelling of complex molecular systems, experimental atomicand molecular physics, R&D in an industrial setting, problemsolving in the resource industry, and management issues incomplex commercial settings. Before joining BHP, he hadextensive experience in research and teaching roles inuniversities in Canada, the US and Australia.

Over the years, Bob has served on many review and advisorybodies in the US and Australia, including the AustralianResearch Council. He has served the RACI in several capacities,including chair of the Physical Chemistry Division in the early1980s, and as Vice-President then President of the nationalbody from 2007 to 2010.

Bob’s contributions to research and industry have beenrecognised through his election to the Australian Academy ofScience, the Academy of Technological Sciences andEngineering, the RACI and as a Fellow of the American PhysicalSociety.

Pearson Education/RACI ChemistryEducator of the Year Award

Dr Daniel Southam MRACI CChemcompleted his bachelors and PhD degreesin chemistry at the University of Tasmania.It was there that a passion for educationwas sparked, both from opportunitiesoffered in Chemistry during his degrees andwhile tutoring at a residential college.While completing a postdoc at CurtinUniversity, he was offered the opportunityto ‘do a bit of teaching’. Surrounded bycolleagues who value and supportteaching, he has been able to build a portfolio based oninnovative pedagogical practice and research into its efficacy.He is now Senior Lecturer (Teaching Focused) and Director ofFirst Year Studies in the Department of Chemistry.

Daniel has an interest in the dynamic relationship betweenscience education research and its application to practice,especially in large first year classes. Daniel is a passionateadvocate of active learning in large classes, where he craftsengaging social environments that support student success. Hisbroad aim is to improve students’ perceptions and to developcapacity for real change in the depth of their understandingand enjoyment of science. To achieve these aims, his researchalso includes exploring issues of educational measurement indifferent sociocultural contexts, and in interdisciplines such asforensic science and nanotechnology. He has received over$1 million in teaching- and learning-related grants to explorethe efficacy of such environments.

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

Page 30: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Rennie Memorial MedalDr Deanna D’Allesandro MRACI CChemreceived her BSc (Hons) in 2001 and herPhD in Chemistry from James CookUniversity in 2006 under the supervision ofEmeritus Professor Richard Keene. She held abrief postdoctoral position at the Universityof Sydney before venturing to the US toundertake a postdoctoral position withProfessor Jeff Long at the University ofCalifornia, Berkeley from 2007 to 2009 as aDow Chemical Company Fellow of theAmerican–Australian Association and a Royal

Commission for the Exhibition of 1851 Research Fellow. Deannareturned to Australia in 2010 as a University of Sydneypostdoctoral research fellow and L’Oréal for Women in ScienceFellow in the School of Chemistry.

In 2011, she received an Australian Research Council QEIIFellowship, which allowed her to start building her ownresearch group exploring electronic and optical properties ofinorganic materials, along with their applications in energy-related fields.

from the raci

Chemistry in Australia30 | Dec 2014–Jan 2015

RACI membership milestonesThe RACI congratulates the following members forachieving their 50 years of membership. Congratulationsalso to members who have achieved 40- and 25-yearmembership milestones (see www.raci.org.au/raci-news/membership-milestones-414 for details).

RACI Post Graduate Student TravelBursary The RACI Post Graduate Student Travel Bursary was introducedto assist students to attend an overseas conference or researchfacility. The following students have won a Travel Bursary:Briana Davie, Georgina Sauzier, Bradley Stringer, Carol Hua,Deborah Sneddon and Michelle Gazdik.

Carol Hua Deborah Sneddon Michelle Gazdik

Briana Davie Georgina Sauzier Bradley Stringer

NSWDavid St Clair BlackGraeme Julian BurgessJohn Kingsford HakenRobert William JonesDonald Harold Napper

QldRaymond Walter YerburyGeorge AlexanderBrothertonMary Leona CarseldinePaul Wie Tat OhPeter George Wright

SAConstantin ParouchaisTzvetanka Parouchais

Vic.David Howard StrongAnthony Trevor HicksonJohn LawsonRobert John LeydonBryan Clarence LoftHarry MantellIan Maxwell MarshallPatrick William McIlvenaNorman AlexanderMcWhinneyWilliam StarkPeter Richards Terry

WANeville Victor Blesing

Merry Christmasand best wishes for 2015

From the staff of RACIand Chemistry in Australia

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Associate Professor Bayden Wood is anAustralian Research Council Future Fellowworking at the Centre for Biospectroscopylocated in the School of Chemistry, MonashUniversity. He completed his PhD in 1999under the supervision of Professor DonMcNaughton, pioneering new ways toanalyse cells and tissues using infraredmodalities. His research now focuses onapplying vibrational spectroscopictechniques to solve a range of biomedicaland biological problems, including malaria

diagnosis and treatment, cancer diagnosis and testing noveldrugs for cancer treatment, assessing oocyte competence for invitro fertilisation (IVF), stem cell research, heart disease, liverdisease, phytoplankton studies, aquatic wetland studies andfundamental studies into how light interacts with cells andtissues.

Wood is one of the founding members of the Centre forBiospectroscopy, which was established in 2002 after theinaugural Austral-Asian Biospectroscopy Conference held atSuranaree University of Technology in Korat, Thailand, whichattracted over 180 international scientists and introducedbiospectroscopy into South-East Asia, placing the Centre forBiospectroscopy on the world stage.

Wood’s career highlights include developing a new diagnostictool for malaria using a simple infrared-based technique. Thepaper published in Analytical Chemistry was awarded theAmerican Chemical Societies Editor’s Choice in 2014 andreceived widespread media coverage, including television andradio. This has led to a clinical pilot study to trial thetechnology in Thailand in December 2014. As a HumboldtFellow working in Germany at the Institute for AnalyticalSciences in Dortmund with Professor Volker Deckert in 2008, heapplied tip-enhanced Raman spectroscopy, a near-fieldtechnique capable of achieving a spatial resolution of 10 nm, toanalyse biomolecules in single malaria-infected cells andinvestigate the oxidation from the surface of haemoglobincrystals.

He has received a number of awards, including he 2011Kowalski Prize for best applied paper in Journal of Chemometricsfor 2009–2010 and was the 2009 winner of Monash UniversityScience Faculty Early Career Research Award. He has over 100publications, including 10 book chapters with an h-index of 30.Wood teaches in analytical chemistry and has recentlydeveloped a biospectroscopy course for undergraduate studentsat Monash University.

Dr Chris Fellows is a polymer chemist anda senior lecturer at the University of NewEngland. Dr Fellows attended PimlicoState High School in Townsville, NorthQueensland. He majored in chemistry andbiochemistry at James Cook Universityand obtained a BSc(Hons I) and PhD inthe mechanism of alternating radicalcopolymerisation at the same institutionunder the supervision of AssociateProfessor Ernie Senogles, graduating in1998. After a brief period working on thedevelopment and testing of flocculants in Chemical Engineeringat the University of Sydney, he worked as Scientific Projects andEducation Officer with Professor Bob Gilbert at the University ofSydney’s Polymer Centre/Key Centre for Polymer Colloids. In2000, he was appointed as a half-time fixed-term lecturer inhydrocolloids at the University of Sydney, and in 2004 heobtained a permanent academic position as a lecturer inchemistry at the University of New England, where he waspromoted to senior lecturer in 2008. Dr Fellows has had alongstanding involvement with the RACI’s Polymer Division,serving as Treasurer of the Division from 2002 to 2009.

As well as the fundamental kinetics and mechanisms ofradical polymerisation, Fellows’ research is primarily inapplications of polymers in processes where they modifybehaviour at interfaces – flocculation, modification of crystalgrowth, transport through membranes – and instructure/property relations of carbohydrate foods. Fellows haspublished 65 peer-reviewed journal articles in journals rangingfrom Dental Materials to Cereal Chemistry to MacromolecularTheory and Simulations.

Fellows lives in a state of continuous total amazement at thecomprehensibility of the universe and is a passionate proponentof the value of a scientific education. Engraved on his heart arethese words attributed to Max Planck: ‘Experiments are the onlymeans of knowledge at our disposal. Everything else is poetry,imagination.’ He is not, however, dismissive of poetry andimagination and writes fiction together with his wife, Amanda,under the name A.C. Fellows. They have two children, Caillanand Elena, who outshine them as the sun outshines the fixedstars.

Fellows is a contrarian, a theist, and was born in the shadowof the Santa Catalina Mountains in Tohono O’odham country.

Chemistry in Australia 31|Dec 2014–Jan 2015

New Fellows

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from the raci

Chemistry in Australia32 | Dec 2014–Jan 2015

Dr Neale Jackson obtained both his BSc(Hons – Chemical Sciences) and PhD inInorganic Chemistry from LeedsUniversity, his thesis title being ‘TheChemistry of Binary non-AqueousSolvents Containing Carbon Halides withTransition Metals’. While at LeedsUniversity, the late Professor NormanGreenwood was one of his mostsignificant mentors. On leavinguniversity, Jackson undertook positionswith a number organisations, including

Cussons (UK) Ltd as Product Development Manager andLaboratory Health and Safety Coordinator. In 1991, he moved toAustralia after accepting a position with CSIRO Division ofForest Products as a research scientist, where he researchedtimber preservatives. He then joined Gibson Chemicals as aProduct Development Manager and Health and Safety Co-ordinator.

After years in industry, Jackson transitioned to an academicsetting, first at Swinburne University of Technology where helectured for five years and then in the School of AppliedSciences, RMIT University, where he has worked as the ProgramLeader – BSc Applied Sciences (Multi Major) and as a seniorlecturer in occupational health & safety for the past 16 years.

As a chemist, Jackson became involved in health and safetyin a number of roles, this experience becoming a pathway tobecoming a lecturer in OHS and in the development of the verysuccessful three-day, Safety in Laboratories (AS/NZS 2243 andAS/NZS 2982). He has delivered the course across Australia andoverseas, including China and India.

More recently, Jackson has been involved with thedevelopment the Chemical Safety Laboratory (SNET) virtuallaboratory safety CD as a collaborative project between theChemistry Schools of Melbourne, Monash and RMIT Universities.SNET today forms part of the teaching resources forundergraduates in RMIT’s Degree in Applied Sciences.

He is an active researcher into safe work practices forworking with engineered nanomaterials, sponsored by SafeWorkAustralia. More recently Jackson has worked with AssociateProfessor Helmut Hügel in the area of Chinese herbal medicinesand their effectiveness as dietary supplements and potentialmedications. He has 23 peer-reviewed publications and has hadfour research grants.

Aside from his career, Jackson and his partner Lisa enjoy arange of activities, including stamp collecting, photography andsailing.

Dr Nial Wheate completed both his BScand PhD (2002) through the AustralianDefence Force Academy campus ofUniversity of New South Wales whileserving as an officer in the RoyalAustralian Navy. He completed anotherthree years of military service before hewas appointed a senior fellow at theUniversity of Western Sydney, followedby a lectureship at the University ofStrathclyde in Scotland. In 2012, Nialreturned to Australia to take up a seniorlecturer position in the Faculty of Pharmacy at the University ofSydney. In 2013, he was appointed Head of Cancer Researchwithin the faculty. Wheate has a strong service commitmentboth to the RACI, as a member of the NSW PharmaceuticalSciences Group, and in other charitable causes, including as afounding committee member of the Ellie a’Beckett Bowel CancerResearch Trust.

Wheate’s research interests are in the field of cancer and hehas established an international reputation in the field ofplatinum anticancer drug design and drug delivery. He is bestknown for his work in examining the interactions betweenplatinum drugs and DNA and as the first person to demonstratethe medical applications of the macrocycle family of moleculescalled cucurbiturils. Over his career, he has published 65 journalarticles, two book chapters and two international patents.Previously he was an associate editor of the Australian Journalof Chemistry and is currently an editor of the Source Journal ofPharmaceutical Sciences.

Wheate believes strongly in the importance of sciencecommunication and has written numerous articles for Chemistryin Australia, Australasian Science and the news analysis andcommentary on-line newspaper The Conversation. Recently hewas appointed a member of the community council of TheConversation, a body of academics and lay readers who overseecommentary standards of the newspaper.

In his spare time Wheate is heavily involved in volunteeringactivities. Since 2012 he has been a member of the NSW StateEmergency Service and in 2014 started as a St John’sAmbulance volunteer in the Glebe division. He also enjoysreading and has recently taken up salsa dancing.

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Sometime late in 1963, amarried couple joined RACItogether. They were recentmigrants from EasternEurope, escaping theoppression of a Communistsystem and hoping to start anew life. When their 50-yearmembership certificatesarrived, the chance for astory could not be passed.

Constantin Parouchais(Con) was born in 1934 andcompleted his early andsecondary education inVarna, Bulgaria. Thatsecondary educationinvolved two years in a high

school and three years in the Technical College of IndustrialChemistry. He successfully completed matriculation andseparate special university entrance examinations to enter theUniversity of Sofia, Bulgaria, in 1953, to study chemicalengineering. That degree course took six years to complete. Thefirst five curriculum years comprised 12 chemistry subjects,22 engineering subjects, two foreign languages and foursubjects of a political nature; the final year was devoted topostgraduate work culminating in a thesis and dissertationbefore a State Commission consisting of university lecturers andexternal technical experts. On the face of it, this seems to befairly normal for the times.

Meanwhile, also in Eastern Europe, Tzvetanka (Ceci) led amuch less stable life. Her father was an Eastern Orthodox priestwho was posted to Pecs, Hungary, to establish a church. Thetown of Pecs, fifth largest in Hungary, boasted a largecongregation of Bulgarian expatriates, students, itinerants andseveral Slavic minorities. He was busy; additional to his pastoralcare he was advising on legal and consular matters, so, tofacilitate that work he undertook and graduated in law andsociology studies at Pecs University. During World War II hehelped persecuted Jews in their attempts at avoidingconcentration camps: his work eventually put him in adangerous political position and he fled West using hisdiplomatic passport. His wife and two young daughters thenfollowed, using the ruins of a heavily bombed railway system togradually find their way across wartorn Europe. They rejoinedand the priest, his traumatised wife, an older daughter andlittle seven-year-old Ceci joined the throngs frantically fleeingthe advance of the armed forces of the USSR.

After much danger, misery and hunger, they reached theAltotting district of Bavaria, Western Germany, where they later

celebrated the capitulationof the Duetsche Wermachton 8 August 1945. Therepatriation of refugees fromthe devastation was alengthy process, duringwhich Ceci’s mother pinedfor her homeland.Disregarding warnings of anuncertain future and herability to manage life with asmall child in a country witha now well-establishedCommunist regime, shedecided to return and tookten-year-old Ceci. The fatherand older sister did not go,and they eventually choseAustralia for their home. Ceci and her mother returned to Sofia,Bulgaria, in the spring of 1946 and were immediately isolatedto a holding camp for processing and interrogation by InternalSecurity personnel. Because of their connection with a high-ranking priest and envoy who was a former member of thediplomatic community serving pre-Communist governments,there was intense interest in them. Her mother was subjected tolong hours of interrogation over weeks, and upon release wasstripped of her permanent citizenship of Sofia and classified asan ‘unreliable element and potential enemy of the State’. Thisdenied her the right to apply for permanent residence oremployment in Bulgarian towns and forced her into a life ofpermanent exile in the country. Her daughter, young Ceci,shared this status, and it stayed with her until she left thecountry in 1963.

Ceci’s education had been severely fragmented by the war –she had attended German schools using the Gothic alphabet,and she was multilingual. Despite this and fighting acurriculum, cultural and language catch-up, she completed theremaining grades to Year 7 in a village school of NorthernBulgaria. The local Communist apparatchicks warned her to bemodest in her goals, to never aspire to a higher education andto resign herself to a life in the fields of the local cooperative.To escape this, young Ceci left for Sofia, where an aunt took herin and arranged attendance at an elite high school for girls.

Barely a month into her first year at this school, Ceci wassummoned to the Headquarters of State Security in Sofia. Thisunusual request was quite distressing; it involved a lost schoolday for no apparent reason, so her uncle accompanied her. Hewas turned away at the door, and she was met and interrogatedby two strangers, one in the uniform of lieutenant, and theother plain-clothed (but later addressed as ‘Colonel’). They were

raci people

Chemistry in Australia 33|Dec 2014–Jan 2015

Con and Ceci: 50-year members with an extraordinary story

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raci people

Chemistry in Australia34 | Dec 2014–Jan 2015

seeking information of her family and her father’s work duringthe war, but she was unable to enlighten them. Her lack ofknowledge frustrated them and after 12 hours of shouting andabuse, they released the frightened 13 year old at 1.00 am.

This treatment firmed her resolve to succeed, and sheperformed at straight ‘A’ level throughout her school years,including her matriculation examinations. This performancegranted her a medal from the Ministry of Education,circumventing the need for a political reference to enteruniversity and giving her a choice of study discipline. Herlifetime political classification would have otherwiseendangered any chance of university entrance, but her well-deserved medal cleared the way.

She chose the discipline of ‘Technology of Liquid and SolidFuels’ at the faculty of Chemical Engineering. Her university lifewas not easy – she struggled through first year studies with nofinancial support – but after good results, she was granted asmall stipend and some aid for basic accommodation. Along theroad, she had regular security interrogations and warnings thatshe was under constant observation but she somehow avoidedbeing included in the lists designed to remove potentialenemies of the State from students’ ranks.

Despite the hardship, she graduated at the same time as Con.Ceci’s first job as a graduate was that of shift manager at an

antiquated explosives factory remote from Sofia. This positionhad been unfilled and reasons soon became apparent. Thefactories used mixtures of TNT and nitrates of ammonia,potassium and sodium, along with powdered aluminium and‘ferro-siliconTM’ to produce bombs and cartridges of varyingsizes and potency. Unsafe equipment, antiquated technologyand shocking conditions resulted in many ill workers andconstant breakdowns in operations, and the shift manager wasresponsible to the State for these. During her time there, shewas under the constant scrutiny of State Security and after twoyears the position became untenable and she resigned.

Her aunt assisted her to find her work as a chemist in theFilm Processing Laboratories of the Bulgarian Cinecentre. Thiswas very challenging but rewarding, but her background lack ofpermanent citizenship of Sofia, essential to holding apermanent position, ended it.

Meanwhile, she had married Con and they managed tobecome sponsored by her older sister for a visit to Australia.Neither could speak English, and an interview at the Universityof Adelaide was facilitated by Ceci’s sister, who attended asinterpreter. The outcome was good, the qualifications wereacknowledged and they found employment, albeit of ‘temporary’state until their Australian citizenship could be established.

They joined RACI as Junior Graduate Members, eventuallybecoming full members (Associate in those days) in 1967.

Con eventually settled in to work in the South AustralianGovernment Department of Chemistry starting at first in theCereals and Explosives Sections, later joining the Food andDrugs Section to specialise in pesticides analysis. In his firstfive years, he published in pesticides residues analyses, one of

which became a recommended procedure in the US Food &Drugs Administration Manual for Pesticides Residues. Hesuccessfully completed wide-ranging surveys of pesticideresidue levels in food supplies and the environment and theformation and establishment of the Pesticides Residues Section.He progressed to become Assistant Senior-Analyst in theAgricultural Chemicals Section (including Plant & Soil Nutrientsand Minor Constituents Sections) of the Agricultural ChemistryBranch, Chemistry Division of the SA Department of Servicesand Supply, where he continued his good work.

He was also involved in the design, specification andinstrumental set-up of the laboratories in the Forensic ScienceCentre.

From 1983 to 1993 Con held the position of Head of theTrace Elements Laboratory of the Chemistry Division – SADepartment of Services and Supply. Con proposed this serviceand it rationalised all trace element and metal analyses withinthe department. It operated successfully as a stand-alonebusiness unit.

Meanwhile, Ceci was suffering the social and economicrestrictions of the sexist sixties, but became a mother andestablished herself as a good professional chemist. She heldpositions from Analyst through to Head of Blood Alcohol, IllicitDrugs and Horse/Dog Doping Laboratory, Head of Food &General Laboratory, then Head of Pesticides Residues Laboratoryof the Chemistry Division of the SA Department of Services andSupply, and, eventually, 1986–1994, became Senior ForensicScientist in the State Forensic Science Division of the SADepartment of Services. She published in the fields of forensicscience and environmental pollution, and presented atnumerous conferences related to drug analysis, control of theuse of drugs in horses, analytical chemistry, forensic scienceand mass spectrometry.

Con and Ceci retired and travel extensively, often regalingthe local Retired Chemists Group with tales of far-away lands.Ceci’s mother died under suspicious circumstances in a trafficaccident in 1968. During a visit to her homeland in 2006, shewas unsuccessful in establishing the details of this incident andwas warned to stop trying.

John Mason FRACI CChem, with thanks to Con and Ceci Parouchais for sharingtheir story.

PTYLTDRowe Scientific

www.rowe.com.au

ADELAIDE08 8186 [email protected] BRISBANE07 3376 [email protected] HOBART03 6272 [email protected] MELBOURNE 03 9701 [email protected] PERTH08 9302 [email protected] SYDNEY02 9603 [email protected]

Pledge to Chemists

This is not a “subtle” attempt to obtain more

R.J. Rowe (FRACI)

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The five editions of Chemistry in the marketplace provide animperfect record of the changing social interests and concernsrelating to chemistry. Its contents tried to respond to feedbackfrom a variety of sources over many years.

In the 1970s, product labelling was non-existent and productor safety information from industry or government was like pullinghen’s teeth. Our words of wisdom generally came from older-styletextbooks such as Noller’s Organic chemistry and references such asKirk–Othmer Encyclopedia of chemical technology, and H. Bennett’sThe chemical formulary series.

Today, it is about infotainment, and slipping in materialimportant for a chemical education needs to be more subdued.Besides, there is so much good straight chemistry in the internet.

The school and university chemistry syllabuses have movedfrom the practical to the theoretical, from the colourful H2Squalitative analysis and borax beads, to s, p and d orbitals andcurly arrows. However, it is the descriptive and applicable chemistrythat answers community questions.

The public understanding of science becomes the scientists’understanding of the public. While Science weeks have been anoutstanding success. named lectures preach to the converted andthere is no public lecture aimed specifically and public concerns.Perhaps the internet has replaced this but it is not monitored forquality and balance.

In the 21st century, the most dramatic change has been theinternet and the search algorithms developed by Google andothers. A result revealed by a non-representative survey of theless-affluent greater western Sydney local libraries is thedisappearance of science books in general and Dewey 540(chemistry and allied sciences) in particular. In one of the largermunicipalities, the only Dewey 540 book was The idiots’ guide tochemistry. Popular science, Dewey 500, does better.

Talking of old, the Lifeline book fairs throw up what librariesthrow out, and I nostalgically picked up Alex Boden’s 1940sschool text An introduction to modern chemistry. Library turnovercan be slow; modern is a dangerous word to use in a title!

And as for old, the section ‘Chemical Attractions’, at Sydney’sPowerhouse Museum (which replaced the original Museum ofScience and Technology) was launched on St Valentine’s Day 1996.This chemistry section (partly sponsored by the RACI) hasn’tchanged one iota in almost 20 years. The exhibits are dated, andthere are no visitors in sight, in spite of the crowds ofschoolchildren elsewhere. Some exhibits are not working (inparticular the highlight – the chocolate chemistry-cum-dispensingmachine).

Chemical information from government sources can be just asdated. For example, The National Chemical Gateway(https://apps5a.ris.environment.gov.au/pubgate/cig_public/!CIGPPUBLIC.pStart) was last updated on the day it was launched –10 February 2004.

Magazines are the great survivors of the internet mediamassacre. Articles appear that make chemists wish they had neveradopted the word ‘organic’, which is now used to clobber us atevery opportunity. What can be our response?

During a sabbatical in Europe in 1991 I toured with a lecture called‘Chemistry for Tourists’. It struck me that what I wanted as a touristwas for someone else to have done all the hard work, used theirexperience to sift through the totality, and extract a sample of whatmight be of most use and interest. The choice had to appeal to me,as well as to many other people of diverse interests and backgrounds.So the aim for the later editions was to be a ‘Tourist Guide toChemistry’. I’m taking you through a foreign country pointing out andexplaining landmarks I hope will interest you; giving the culturalsetting, telling a few funny stories, helping you with the shopping,and explaining that the natives (the chemical industry) are nowquite friendly. Then I’ll leave you to explore further. I will also warnyou against new age snake oil salespeople who will try to strip yourwallets with pseudo science.’Chemistry in the Marketplace 5th edition 1998

So, we need to throw another non-organic chemical on theBunsen.

Ben Selinger FRACI CChem ([email protected])

For more information, contact theEditor at [email protected].

Love toread?Why not reviewa book for us!

books

Chemistry in Australia 35|Dec 2014–Jan 2015

‘Fifty shades of litmus?’Chemistry in the marketplace 40 years on

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technology & innovation

When eating, I am often guilty of a slightly heavy-handed useof salt. This activity ionically attracts unsolicited advice fromfriends, family and strangers – the core of which is that salt is‘bad’ for me. When quizzed for details, my educator usuallymakes vague reference to blood pressure and heart disease. Myblood pressure and markers for heart health are much betterthan average for my age, and my life-long disdain for popularopinions on health matters remains.

I have always argued back to the salty nay-sayers that mybody contains around half a kilogram of salts and that the fewmilligrams I am about to ingest hardly merits consideration. Ialso note that without salt in our diet we don’t survive very long.Indeed, migration patterns of ancient humans usually followedcoastal regions where salt was readily available and onlyextended inland when either salt deposits were discovered ortrading allowed reliable supply from coastal regions. That is, saltis a necessary input into our diet without which we cannot live.

Before the advent of technology, humans got their saltthrough ingestion of seafood or the use of dried ‘rock’ saltfound in naturally available deposits. By dry weight, sea salt isusually (it varies in coastal regions, near rivers for example)55.03% chloride, 30.59% sodium, 7.68% sulfate, 3.68%magnesium, 1.18% calcium, 1.11% potassium and trace levelsof bicarbonate, bromide, borate, strontium and others. Due tothe sequential precipitation in evaporating salt water bodiesthat form rock salt deposits, sodium chloride levels in rock saltsare typically 90–98%, the remainder being the usual sea saltminerals but in lower relative quantities.

But of course, humans being humans, we started playingwith these compositions as soon as we had the nous to do so.Driven by supply issues, and later on by food aesthetics as wellas productivity and profit motives, we have over a few thousandyears managed to reduce food salt to (almost) pure sodiumchloride plus a bunch of unnatural additives; more on this later.

In ancient times, humans either mined rock salt or extractedsalt from sea water by filling a ceramic pot with sea water(which is only around 2.5% total salts) and boiling it until itwas dry. This netted a greyish, somewhat hygroscopic salt withthe full gamut of trace minerals. The rest of the history of saltproduction can be summarised by three major innovations.

Firstly, humans started using concentration ponds toprecipitate and dry salt water, either brine from mines or seawater, whereupon careful removal of the layers of dried saltprecipitates resulted in various grades, including the preferredsodium chloride-rich evaporate (halite) for table salt use.

Later on, concentration ponds were used in series so thatunwanted and less soluble salts were first crystallised in onepond and then the pure sodium chloride brine was pumped intoits own pond to allow precipitation of a more pure saltproduced by a higher yielding process. Modern salt works havevery complex interdependent pond systems, so this is an over-simplification of what they are really up to. Chemical additives

are often added at each stage to help precipitate or floatunwanted impurities.

For over a hundred years, salt production facilities havebeing using a process in which the concentrated sodiumchloride brine from the pond system is thermally evaporatedunder near-vacuum conditions in a series of tanks. The resultingslurry is dried by centrifuge and a fluid bed drier, and containsvery pure sodium chloride cubic crystals of near-uniform andcontrollable dimensions – the perfect table salt. Salt productionfacilities, by extracting and purifying all the salts separately,can sell various salt types and grades for different consumerand industrial applications.

Common table salt is so ubiquitous that is viewed by healthauthorities as a useful carrier for a number of food additives,including iodide, fluoride and folic acid. These are variablyadded to salt to help combat common health issues associatedwith the deficiency of these chemicals in the average diet. Theaddition of iodide also requires the addition of a stabiliser, suchas sodium thiosulfate, sodium bicarbonate, basic phosphates ordextrin (yes, there may be sugar in your salt) to preventoxidation of the iodide to iodine.

Sodium chloride crystals are cubic and their flat surfaces aresusceptible to fusing together, especially in the presence ofwater. Anticaking agents are added at around 0.5% by weight toprevent this issue and can include desiccants such as sodiumalumina silicates, calcium silicates, calcium carbonates, calciumphosphates and magnesium carbonates. These desiccants areadded as very fine powders (relative to the sodium chloridecrystals) so they also act to physically inhibit the interactionsof sodium chloride crystals. Sometimes salt precipitation ismanipulated by using ferrocyanide salts to produce non-cubicsalt crystals that are less prone to caking.

Of late I have noticed the emergence of ‘sea salt’ as ahealthy alternative to ‘table salt’. Some salt is even labelled as

Chemistry in Australia36 | Dec 2014–Jan 2015

A very large grain of salt

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Salt stock pile at Dampier, Western Australia.

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‘organic’! This is another example where common terminologycan confuse the chemically trained. All the salt that weconsume originates from the sea and yet some is confusinglyand proudly labelled as ‘sea salt’. What we normally don’t knowas consumers is how a particular ‘sea salt’ has been processed.It could be from some natural deposit or from a brine pondsystem, and in both cases it might contain more sodiumchloride than we imagine. The odd thing is that sea salts areusually much less processed than table salt and yet cost muchmore, a reflection of the efficiencies of industrial scaleproduction and also of a little price gouging of health-consciousconsumers by niche operators and retailers.

Does our level of salt consumption actually matter? Notaccording to Scientific American (8 July 2011 and 26 September2012). In these two articles, the author does a very good job ofdeconstructing the arguments and evidence that have beenused to drive the ubiquitous public health messages related tothe risks of high salt consumption. If true, this has frighteningramifications for the faith people might place in our so-calledhealth authorities. In 2013, the US Centers for Disease Controland Prevention retracted their previous advice to Americansthat they keep sodium consumption to less than2300 milligrams a day because a new study found no evidenceto support this previous advice.

Other commentators have taken a different approach andsuggested that natural sea salt, with its wonderful balance of

salts and minerals, can be consumed with abandon but that‘industrial’ table salt is in fact the real culprit that drives healthissues. The evidence supporting this argument is very tenuousbut nevertheless appealing to many. The most likely reality isthat an over-reliance on pure sodium chloride might result in adeficiency of certain minerals if these are not otherwise presentin a diet. In addition, a diet that is rich in industrial table saltis also possibly correlated to processed and fast foods, whichhave other negative health consequences.

For me it is simply a case of consuming carefully chosen and(to me) much tastier ‘sea salt’ – the grey version with salt inthe same proportions to salt in the sea and not the more purerock salt. This way I dodge all the xenobiotic additives inindustrial salt (which may or may not do harm) and get all thetrace elements (which I may or may not need). I tend to usesalt up to a quantitative level that is limited by my body’sreactions (yuk, too salty!). With routine trips to my doctor, Ialso intermittently monitor the key heart-health indicators,which one does anyway. However, the more processed or pre-prepared food I eat, the more industrial table salt that Iunwittingly ingest. If this matters enough to me, or if I everdevelop suspicious health issues, I will know what do.

Chemistry in Australia 37|Dec 2014–Jan 2015

Ian A. Maxwell ([email protected]) is a serial (andsometimes parallel) entrepreneur, venture capitalist and AdjunctProfessor in Electrical and Computer Engineering at RMITUniversity, who started out his career as a physical polymerchemist.

ALSO IN THIS ISSUE: Great minds behind the humble battery • Splendid science reading • Why wines taste di�erent in the sky

in Australia

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EEDDIITTIIOONN

chemistryNovember 2014

The marvellousworld of molecules

Tatts: a novelty thatwon’t wear off

Chemistry at themovies

Your member magazineand other great reads Read the latest issue of Chemistry inAustralia, or a featured article from theAustralian Journal of Chemistry.

Free archive accessBrowse or search our index of issuesfrom 2003 onwards. Tell friends andcolleagues about free access to backissues of the magazine.

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education grapevine

Students look forward to summer because usually it means abreak from formal and non-formal education. Formal educationrefers to education in formal educational institutions, such aspreschools, primary, secondary and tertiary educationalinstitutions, and other registered training organisations. Non-formal education refers to organised educational activityoutside the established formal system that is intended todeliver a defined set of learning objectives to an identifiablegroup of learners (see October issue, p. 33). Informal educationrefers to all learning outside the formal and non-formaleducational system, and is often associated with life-longlearning as it can include reading non-fiction books andscholarly articles, viewing documentaries and other informalprofessional development.

Informal education can also include travel to other countriesand climates. Social constructivist theory maintains thatlearning occurs in social settings; conversely, most learners arelimited by their cultural experiences. For example, Australianstudents have little first-hand experience of sublimation, butthis is commonly observed in very cold climates when frost, iceor snow apparently ‘disappears’ as it sublimes to water vapour,without passing through the liquid state.

Food spoils more quickly in summer than in winter becausehigher temperatures increase the rate of (bio)chemicalreactions. This Arrhenius behaviour is also why bacterial andinsect activity is increased in summer.

Ice is often used to cool food and drinks. The presence ofcondensation on containers of iced drinks illustrates transfer ofheat energy from warmer objects to cooler objects. Astemperatures exceed 30°C and approach or exceed normal bodytemperatures, the ability of mammalian bodies to lose heat tothe environment becomes ineffective because there is lesstemperature difference between the body and the environment:hyperthermia.

The warmer weather provides incentive to make cold foodssuch as ice cream, an activity which in turn is full of learningopportunities. Salt–ice slush is an example of the colligativeproperty of freezing point depression. The rate of coolingaffects the size of the solid particles in ice cream, which affectsthe texture and taste. Rapid cooling gives smaller ice particles,and a smoother, creamier taste. This is analogous to thegeochemical formation of igneous rocks, in which more rapidcooling produces rocks with smaller grains, while slower coolingproduces larger grains.

A favourite summertime activity is to go to the movies,especially in air-conditioned cinemas on a hot day or night.Watching movies are a form of virtual travel, and manyeducators make use of movies to illustrate chemistry concepts.

Some movie producers want a sense of authenticityand work hard to get the details right, even thoughthose details might be incidental to the main plot.For example, in Centurion, Roman soldiers fail in arescue attempt, and are taunted by the Picts forstupidity – they would have succeeded if they hadonly realised that metal become brittle in the cold.Another favourite example comes from The Lord ofthe Rings: The Two Towers, when Bilbo, Samwiseand Gollum are crossing the Dead Marshes and seelights that appear to float over the marshes. Thesewill-o-the-wisps have been known for centuries,and were the subject of a debate between GeorgeWashington and his officers. Washington andThomas Paine, ‘the Father of the AmericanRevolution’, believed that the lights were due to aflammable gas released from the marsh, whileWashington’s officers believed that the lights were

due to a flammable liquid on the surface of the marsh. On GuyFawkes Night, 5 November 1783, the Washington–Paineexperiment showed that when mud at the bottom of a river wasdisturbed, bubbles of flammable gas rose to the surface of thewater. (Unknown to Washington and Paine, Alessandro Voltahad performed a similar experiment in 1776.)

A problem with informal education is that it is oftenunguided. Students may find it difficult to discern thedifference between scientific reality and an artistic distortion ofreality in novels and movies. Educators have an important rolehere. If we only teach facts and concepts, learners will bedependent on a teacher. If, however, we foster students’curiosity and ability to exercise judgement, they will be able tolearn for themselves, not just during the summer, but also inevery season of every year.

Chemistry in Australia38 | Dec 2014–Jan 2015

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Summer is a good time for informal education

Kieran F. Lim ( ) FRACI CChem([email protected]) is an associate professor in the Schoolof Life and Environmental Sciences at Deakin University.

Page 39: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

The festive season is celebrated in many different climates aroundthe world. In Australia, viticulturists and winemakers contemplatewhat the heat load may do to the development of grapes for thefollowing harvest, while their counterparts in some northernhemisphere countries gear up for the production of Icewine.Icewine (Eiswein) is an intriguing curio, being made from frozengrapes; hence the name. Variations on the traditional style can befound in many other wine-producing countries, including Australia(bit.ly/1nyNnL7).

Dr Marc Bradshaw, a former doctoral student of mine, has nowestablished a highly successful career in cool-to-cold-climatewinemaking in the Niagara region in Ontario, Canada. It was Marcwho introduced me to Icewine. Winemaking practice in Ontario iscontrolled by the Vintners Quality Alliance (VQA Ontario). ForIcewine, there is a requirement that the grapes be harvested aslow as –9°C. Many winemakers actually prefer –12°C or lower.Freezing the water in the grape berry results in an increase in thesugar concentration by ‘removal’ of the water. This harvesttemperature requirement necessitates a few rather complex andphysically demanding practices, including grape picking at nighttime and when the vines are under snow. The image illustratesworkers hand-harvesting grapes at night under floodlights. Iunderstand that it is a major challenge to cut frozen bunchesusing secateurs while wearing protective gloves. The image alsoshows the netting used to cover the vines up to harvest. The netscatch grapes that fall off the bunch under the weight of snow aswell as protecting against bird attack and from coyotes prowlingthe vineyards, seeking the sweet grapes to satiate their hunger.

After harvest, the frozen berries are pressed at up to about6 atmospheres. This is where some good physical chemistry comesinto play. The harvest and pressing conditions are below the triplepoint for water, so operations are performed when most water isin its solid state. Some obviously remains in the sugar solution.The Clapeyron equation for the solid–liquid line indicates that forevery increase in 1 atmosphere pressure, the freezing point ofwater will decrease by 0.0074°C. A 6 atmosphere increase duringpressing will lower the melting point by 0.044°C, a negligiblechange ensuring that there will be little melting of the frozenwater although some will melt due to friction and local‘mechanical’ heat.

Pressing results in 150–170 litres per tonne of grapes, muchlower than the 700 litres in regular wine production. Inoculationof the pressed juice that may be at 350 gram/litre sugar or moreinduces considerable osmotic stress in the yeast. Dr Debra Inglisat Brock University, Ontario (bit.ly/1DCz3p5), has shown that theimpact of this osmotic stress is the production of acetic acid andmaybe also ethyl acetate, both quality defects. Fermentationusually takes 6–8weeks. If longer, stress in both the yeast andwinemaker can occur.

The fermentation is stopped when the sugar concentration isbetween 100gram/litre (regulation) up to about 170 gram/litre(market preference) with an alcohol concentration between

10 and 12%. The sweetness from the sugar and alcohol is to someextent balanced by the relatively high acidity of the finished wine.Aroma descriptors include apricot, raisin and honey, withlusciousness and viscosity describing the palate. A sparklingIcewine, made by the tank fermentation process to trap thecarbon dioxide, has the added dimension of bubbles, which tendto reduce the sensation of sweetness.

Icewine can be made from Riesling and Chardonnay as well asVidal (a hybrid variety). Red varieties include Cabernet Franc(winemaker preferred) and Shiraz. Tasting a red Icewine is anexperience to behold, not one that holds much joy for me, butclearly it does for others. Pillitteri’s Shiraz Icewine, put togetherby Marc Bradshaw, was named in the top ten at the 2008 Syrah duMonde competition (bit.ly/1tdDHGJ).

Donald Ziraldo (bit.ly/ZNxSE9) has led the charge forinternational marketing of Niagara Icewine. The major markets arein Asia, especially China and Japan. Presentation of the wine inbottle is one of the keys to market success. Generally, the wine isavailable in 375milliltre bottles, although some 50millilitrebottles can be found. Donald’s book, Icewine – extremewinemaking, co-authored with Karl Kaiser, gives more detail onproduction practices, a flavour wheel, and recipes for matchingIcewine and food.

Finding Niagara Icewine in Australia is a challenge. Inniskillinand Ziraldo wines can be found at around $100 per 375millitrebottle. Or you may care to try something from Australia. AndrewHood initiated Icewine making in Tasmania by using cryo-extraction. Here, the harvested grapes are frozen in tanks andthen pressed and the juice fermented as described above. A quickGoogle search will identify several local wines made by this cryo-extraction approach: Frogmore Creek is one that can be purchasedfor around $20 for a half-bottle. You might wish to decide whetherthe cryo-extraction method is the ‘real thing’ or not.

Chemistry in Australia 39|Dec 2014–Jan 2015

education grapevine

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.

The festive season and Icewine

Night Icewine harvest in Niagara

Mar

c Br

adsh

aw

Page 40: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

sustainability

Waste. Most people will associate this wordwith something they want to get rid of,something without value. Butelectronic waste, or so-called e-waste, still contains vast amounts ofscarce metals and valuableelements.

E-waste is the most rapidlygrowing type of waste all over theworld, as the first generations of mobilephones and computers are reaching therecyclers. In 2012, 14.2 kilograms of e-waste was discarded on average by everyperson on Earth (www.step-initiative.org/index.php/WorldMap.html).The potential of this type of waste as asustainable resource for scarce elements isenormous because e-waste is already aconcentrate of gold, palladium, silver, rareearths etc. For example, a mobile phonecontains about 305 milligrams of silver and30 milligrams of gold which is 40–50 times moreconcentrated than in the ores from primary mining(www.oeko.de/oekodoc/1375/2012-010-en.pdf; K. Binnemanset al. J. Clean. Prod. 2013, vol. 51, pp. 1–22).

In addition, the recycling of e-waste also regenerates therequired metals in the ratios needed to manufacture thesedevices again. The amount of useless side products is thereforereduced to a minimum compared to ordinary mining.

Closed loop productionThe biggest bottleneck at this moment is the efficient collectionof this type of waste. Surveys show that every Americanconsumer holds two unused cell phones on average at home,because 60% cannot be bothered to turn in their old devices –even though the recycling value of modern smartphones caneasily reach $100 (www.prweb.com/releases/2013/2/prweb10432797.htm). It is estimated that US consumers aresitting on $33.8 billion in used mobile phones. More effectivemarketing and financial incentives could motivate people tobring their unused electronic equipment to collection points.

Several encouraging examples exist, such as shops offeringdiscounts for a new mobile phone when an old one is handedin.

Fluorescent lights and batteries have an advance comparedto other electronic equipment because they contain toxicelements that have to be dealt with accordingly, to avoid themending up in the wrong places. Governments therefore put inplace efficient collection methods and urged the public to bringin their used batteries and energy-saving lightbulbs, usingadvertising campaigns to raise public awareness about thisissue.

These strategies were initially put inplace to deal with the toxic elements they

contained, but very soon differentcompanies started to developrecycling schemes to retrieve thevaluable elements from this new type

of feedstock. Several successfulexamples exist such as the recycling of

computer circuits, rechargeablebatteries, mobile phones, high-end

magnets and energy-saving light bulbs bychemical companies such as Umicore and

Solvay (K. Binnemans et al. op cit.) Thesecompanies have developed a profitable

business around this idea of urban mining,where waste is no longer considered a problem

but a solution!With over $21 billion worth of gold and silver

used in electronic gadgets every year, and only15–20% of that being recycled, it is not

surprising that green tech was the most rapidlygrowing industry of 2013 (http://thediplomat.com/2013/11/the-potential-of-urbanmining).

The rapidly growing amount of e-waste is therefore receivingincreasing attention as the feedstock of the future. TheEuropean Commission and the United Nations have identifiedthe recycling of e-waste as a top priority for the development ofa sustainable high-tech industry and the safeguarding of scarceresources (http://ec.europa.eu/enterprise/policies/sustainablebusiness/sustainable-industry/forums/index_en.htm;www.unep.org/pdf/Recycling_From_e-waste_to_resources.pdf).Reusing the valuable elements trapped inside these devices isthe key to a ‘closed loop’ sustainable manufacturing of theelectronic gadgets we are all so keen on.

The burden on the environment often associated withprimary mining would become too large if the upcomingeconomies started consuming high-tech products as we do. Butin a closed-loop system, very few of these rare elements are lostand a completely new innovative industry can even emerge totry and retrieve them as efficiently as possible – transformingpiles of mobile phones into fresh new bars of gold, silver,palladium, cobalt and all the other elements needed tomanufacture these amazing devices that connect us to theworld. The way we think about waste is changing rapidly!

Chemistry in Australia40 | Dec 2014–Jan 2015

David Dupont is a PhD student in chemistry at the University ofLeuven, Belgium. His research focuses on the recycling of rareearths and valuable metals. YourFormula.eu is an online platformand multimedia magazine, powered by Cefic (The EuropeanChemical Industry Council), where young chemistry enthusiastsblog about chemistry’s role in a sustainable world.

First published at www.yourformula.eu and reproduced inChemistry International, 2014, vol. 36(4), pp. 10–11.

iStockphoto/bakalusha

Let’s not waste our e-waste

Page 41: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Alfred W. Stewart (1880–1947) was a physical chemist who helda chemistry chair at Queens University in Belfast (1919–44)where he managed to combine chemical research with thewriting of 27 crime fiction novels under the nom de plumeJ.J. Connington. By then, he was well into reviewing chemicalliterature, beginning in 1908 with Advances in OrganicChemistry, followed the next year by Advances in Physical andInorganic Chemistry. Both series ran to nine editions, but hisbiographer, George Kauffman, felt that in the end it was clearthat he was not keeping up with developing ideas in chemistry.For example, I found him questioning the validity of the Debye–Hückel theory of strong electrolytes long after it had passedinto the chemical lexicon.

I have a number of Stewart’s Advances volumes on myshelves, the earliest being the third edition (1919) of RecentAdvances in Physical and Inorganic Chemistry. Sir WilliamRamsay had contributed an introduction, which must have beenprepared for an earlier volume since Ramsay died in 1916. Itmakes interesting reading.

Ramsay began by proposing that scientific problems shouldrank among the great questions facing society, such as thedivine right of kings and the question of women’s suffrage. Thefirst of his scientific examples was quite high-flown – an ‘all-absorbing theme which (sic) exercised the minds of men ofscience as regards the true nature of phlogiston’. He also wroteof a contemporary problem, ‘the present contest regarding thestructure of the cobaltammines’ and went on to claim thatproblems in science are more easily solved than those inpolitics, since (a) experiments could be devised to decideknotty questions, and (b) it is not in the interests of scientiststo conceal the truth. Curiously, I found no mention of thecobaltammines in this edition of Advances, but on the third-lastpage, in a short section on stereochemistry, I found ‘thetetrahedron was used ... by Werner in his explanation of theisomerism of complex salts’. I learned about them from J.S. Anderson’s brilliant third-year lectures at the University of Melbourne.

Ramsay assured readers that Stewart, in his Recent Advancesin Physical and Inorganic Chemistry, was dealing with ‘subjectswhich (sic) are at present prominent in the minds of chemists’.Although Stewart had presented rival theories in cases wherethere was contention, he had ‘not scrupled to express his ownopinion where he holds a decided view’. Ramsay reflected thatalthough the present problems represented the current state ofknowledge, they were likely to be succeeded by others thatwould engross chemists. It was also possible, he wrote, that theold problems would be re-examined from time to time, withknowledge gained by incessant experiment, enabling or causingrevisions to be made.

Ramsay drew attention to the enormous mass of chemicalliterature, which was making it impossible for the chemist to domore than take a quick look at the titles of the papers,although it was recognised that every paper ‘represents muchpatient and careful work’ by other researchers and it was sad tothink that it could be so easily passed over by a busy reader.Looking more broadly, Ramsay wrote that there were manypeople not actively engaged in scientific research butnonetheless possessed of some chemical knowledge and with‘neither the leisure nor inclination to sit down and read theTransactions of the Chemical Society or the Zeitschrift fürAnorganische Chemie’. Dr Stewart’s work will be a boon to them,he said, because it provides readable and up-to-date accountsof the main lines of chemical development in ways that are notto be found in a typical textbook. Thanks to him people nowhave the opportunity of ‘having their chemical food preparedfor the table instead of trying to assimilate indigestible massesof what is often very crude material. Dr. Stewart may be likenedto a skilful cook, who has trimmed his joint, rejecting allinnutritious and redundant excrescences, and has served it upto table in a palatable form’.

Ramsay elaborated on his distinction between important andunimportant research. ‘Nothing is so sad’, he wrote, ‘as to seemuch time and labour spent, with patience and devotion, in theinvestigation of some matter which possesses no realimportance. It may be retorted that every true statement is ofimportance, but this is not so. It is only statements which holdforth some prospect of contributing to an organic whole whichcan be held valuable. There may, perhaps, be a little more meritin ascertaining to hundredth of a degree the boiling point ofsulphur than of measuring the area of the wings of someparticular butterfly; but the difference is barely appreciable.One is as likely to prove useless as the other.’ Stewart’s Advanceswas the ideal place for ‘those imbued with the spirit ofinvestigation to make a happy choice of a subject of research.Should this hope be realised, Dr. Stewart will have done a mostuseful work’.

And to close the year on a personal note, I should like tothank the readers who paid me compliments on my 30+ years ofLetters. I get great pleasure from researching and writing themand from the correspondence that is often generated. Just keepreading!

letter from melbourne

Chemistry in Australia 41|Dec 2014–Jan 2015

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.

Dr Stewart trims the joint

Page 42: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

Chemistry in Australia42 | Dec 2014–Jan 2015

cryptic chemistry

Across1 Ultra fast laser spectroscopy comes back

with inclusion of ionic compounds. (5)4 React acetal? Nod when the story is

told. (9)9 Perhaps a thermostat makes rules. (9)10 Presents man at NASA over inclusion. (5)11 Resin sales talk. (5)12 Similar helipad daredevil centres little

animal. (9)13 Started new dietitian. (9)16 3365353 character-encoding scheme.

(1.1.1.1.1.)18 Called for phosphorus getting on. (5)19 Undecided in the grid adjustment. (9)20 Contamination: actively confine it. (9)23 Punts for thrills. (5)25 A profit repeated. (5)26 Locating and using it at interchange. (9)27 Centred py complex needs to be

decoded. (9)28 New Age is protection. (5)

Down1 Undress band. (5)2 Spooner’s evening fish flashes. (9)3 Fairy is shapely without vowels

changing. (5)4 Tried unkempt matted pet. (9)5 Put your name down to go back to a

Victorian seaside town. (5)6 Dry out drunken diet cases. (9)7 Perhaps past being stressed. (5)8 Yeast, for example is going to hold

ethylenediamine. (9)13 Tip maleic reaction to show

involvement. (9)14 It’s an obscenity! Cyanide centre drops

rate when mixed. (9)15 Set off diethyltryptamine on a spread for

drying. (9)17 Spooner’s lower face stick conclusive. (9)21 98876 in old money. (5)22 A picture in a picture in firm. (5)23 Cuddly animal under vehicle according to

Spooner. (5)24 Wise guys’ mixture of gases. (5)

11th Australasian Aluminium Smelting TechnologyConference6–11 December 2014, Dubai, United Arab Emirateshttp://11aastc.com

RACI National Congress7–12 December 2014, Adelaide, SAwww.raci.org.au/events-awards/raci-national-congress-2014Early Bird registration closes 1 August 2014

Advanced Materials & Nanotechnology (AMN7)8–12 February 2015, Nelson, New Zealandwww.amn-7.com

35th Australasian Polymer Symposium13–15 July 2015, Gold Coast, Qldwww.35aps.org.au

IUPAC 201548th General Assembly 6–13 August 2015, 45th World Chemistry Congress 9–14 August 2015,Busan, Koreawww.iupac2015.org

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

RACI events are shown in blue.

Coming up• Medicinal chemistry explained

• Chlorophyll, carotenoids and otherautumnal pigments

• Transporting sodium cyanide

• Molecular deuteration inoptoelectronics

iSto

ckph

oto/

lest

yan4

events

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

Page 43: Coffee beans brew€¦ · chemicals in the flavours and aromas of a great coffee. 20 13. I have been part of the Working Group for the inaugural Decadal Plan for Chemistry, an initiative

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iStockphoto/Jirkab