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ALSO IN THIS ISSUE: John Monash and the Battle of Hamel • The catch-22 ofenergy storage • Pharmaceuticals in urban sewage

in Australia

International Yearof Crystallography

chemistryAugust 2014

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cover story

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news & research9 News13 On the market15 Research42 Cryptic chemistry42 Events

members34 RACI news36 New Fellows37 Obituary

views & reviews4 From the president6 Guest editorial7 Your say38 Education39 Grapevine40 Environment41 Letter from

Melbourne

18 The inner space raceThe emergence of X-ray crystallography is the story of an earnest dash to the then-elusive double helix.

22 The catch-22 of energy storageRenewable energy sources pose the problem of intermittency. Is storage the answer?

26 Lieutenant-General Sir John Monash: an engineer on the battlefieldThe Battle of Hamel on 4 July 1918 was the first operational task planned andexecuted by John Monash as a Corps Commander. It broke conventional militarywisdom and demonstrated that with new tactics the static nature of trench warfarecould be overcome.

30 Does urban sewage have a drug problem?To most of is, out of sight is out of mind for anything that goes down the toilet, butsome environmental scientists are giving it serious thought.

In recognition of the importance of crystallography, the UN has declared 2014the International Year of Crystallography. Read more in this month's guesteditorial and in our page 18 feature.

22

Diffraction pattern, electron density map and molecular structure of a minor product from the degradation of 1-(ethylcarboxymethylene)-2-(1-pyrazolyl)benzimidazole in dilute aqueous nitric acid, sent to the Cambridge Crystallographic Data Centre(deposition no. 955573) as a private communication. The data was used as a tutorial at the 2013 Australasian CrystallographySchool as an example of the elucidation of an unknown small molecule structure based on high-quality diffraction data.

18

EDITOR Sally WoollettPh (03) 5623 [email protected]

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Chemistry in Australia4 | August 2014

The federal government announced itsbudget priorities for the coming years inMay. Considerable commentary hasappeared in the media on the impact ofthe budget proposals on the conduct ofscience in Australia. The RACI President-Elect, Professor Paul Bernhardt, and Iwrote an open letter to the PrimeMinister and Treasurer in June in defenceof the role that chemistry plays in oursocioeconomic fabric. This letter wasemailed to members on 16 June, and isreproduced below.

An open letter to the Prime Ministerof the Commonwealth of Australia,the Honourable Tony Abbott MP,and the Treasurer of theCommonwealth of Australia, theHonourable Joe Hockey MP, fromthe leadership of the RoyalAustralian Chemical Institute.

9 June 2014

Dear Prime Minister and Treasurer,

The Royal Australian ChemicalInstitute (RACI) is concerned aboutthe potential negative impact onthe conduct of the chemicalsciences in Australia as a result ofthe recent federal budgetannouncements.

Chemistry is an enabling science;chemists and those educated in thechemical sciences make substantivecontributions to Australia’s

socioeconomic performance. Thereare more than 60,000 peopleemployed in the Australian chemicalindustry, which comprises oursecond largest manufacturing sector.The chemical industry contributesover $11.6 billion to our GDP perannum (PACIA ‘Adding Value –Strategic Roadmap’, 2011).Australia’s future growth in buildingand construction, mining andagriculture are fed by materialssupplied by the chemical industry;chemicals and plastics alone supply109 of Australia’s 111 industries.

Chemists work collaboratively withscientists from a range of disciplinesspanning the physical, biologicaland mathematical sciences – as wellas engineers and technologists – todeliver innovative and practicalsolutions to a diverse range ofproblems. Chemists provide tangibleinnovation, productivity, efficiencyand education outcomes whichunderpin Australia’s economicdevelopment.

The future of chemistry in Australiastarts with its young. The RACI isdeeply concerned that thegovernment’s proposed changes tothe fee structure charged touniversity students may have anadverse impact on theattractiveness of undergraduatescience degrees. Australia needshighly trained chemistry (andscience) graduates. A structuraldisincentive, in the form ofsignificant university fee increases

for science degrees, is not in thenational interest.

Similarly, the government’sunprecedented proposal to introducefees for domestic research higherdegree (RHD) students will have asignificant impact on our country’sfuture capacity for innovation. RHDstudents already make a significantfinancial sacrifice by committing toa further 3-to-4 years’ universityeducation beyond theirundergraduate study. Remunerationat the level of an AustralianPostgraduate Award ($25,392 p.a.or $488.31 per week in 2014) iswell below the National MinimumWage ($640.90 per week; Fair WorkAustralia 2014) so RHD graduatesare typically in their mid-20s beforethey have the opportunity to earnan income appropriate to their levelof training and expertise. Theproposed additional impost on topof an existing HELP debt from theirundergraduate education can onlyfurther discourage prospective RHDstudents from following a careerpath towards innovation. Our nationdesperately needs scientists trainedto the highest internationalstandards to lead the science-drivenadvances of tomorrow.

The 2012 Excellence for Research inAustralia (ERA) evaluation hasshown that chemistry is punchingwell above its weight. Whenexamined at the sub-discipline level(e.g. inorganic chemistry, physicalchemistry, etc.), 78 out of a total of

from the raci

From the President

August 2014

82 chemistry units of assessmentwere rated at, above, or well aboveworld standard (95%). Thisexceptional level of performanceacross Australia’s universities hasbeen due to the efforts ofgenerations of researchers (inparticular, RHD students) and thesupport of successive governments.

This long-standing investment andsupport of Australian science byboth sides of Australian politics isbeing jeopardised. Australia’sability to foster the nextgeneration of innovators and toenable them to fulfil their researchand problem-solving potential inthe global marketplace is put atrisk by the federal government’sproposals to reduce funding to keyscience and research agencies byapproximately $425 million (DSTO,$120m; CSIRO, $114.8m;Cooperative Research Centres,$80m; Australian ResearchCouncil, $74.9m; ANSTO, $27.6m;Australian Institute of MarineSciences, $7.8m).

The Government’s planned $20 billion medical research futurefund is a bold proposal. However,the RACI is concerned thatquarantining such a largeproportion of Commonwealthresearch funding at the exclusionof the other sciences will becounter-productive in the longterm. Without breakthroughs inthe enabling chemical, biologicaland physical sciences, progress indisease prevention, diagnosis andtreatment is put at serious risk offoundering.

A sustainable, bipartisan vision forscience is urgently needed fromAustralia’s political leaders.Fundamental research in thechemical, physical and biologicalsciences underpins our nation’sfuture prosperity and capacity todeal with pressing challenges inenergy, food, health and advancedmanufacturing. The RACI isconcerned that the current focuson biomedical research with anaim to pick research ‘winners’ doesnot address the bigger (long term)picture. Major scientific advancesalso stem from serendipitous,curiosity-driven inquiry. There isno better example than CSIRO’sdevelopment of WiFi technology; aproduct of researchers overcomingthe challenge of sharing largevolumes of astronomy data. This isa telling case study of Australianinnovation that has had deepimpact on a global scale, but onewhich would never have beensupported by a biomedicalresearch fund.

The RACI calls on the federalgovernment to reconsider decisionsthat will have an adverse impacton Australian science and thenation’s future prosperity. Wewould welcome the opportunity toengage with the Government in ashared vision for the Australianchemistry community.

Mark Buntine FRACI CChem([email protected]) is RACIPresident.

M1165 IC Strip 275x76 DLe.indd 1 20/06/2014 14:30

Australia’s ability to foster the nextgeneration of innovators and to enablethem to fulfil their research andproblem-solving potential in the globalmarketplace is put at risk by the federalgovernment’s proposals to reducefunding to key science and researchagencies ...

6 | August 2014Chemistry in Australia

Crystallography is the most powerful technique for obtainingdetailed information of the three-dimensional structure ofmolecules (in the solid state). No fewer than 29 Nobel Prizeshave been associated with this technique, and it has beeninstrumental in our understanding of chemistry, biology andmaterials science. To quote one of those Nobel Prize winners,Max Perutz (Chemistry, 1962):

Why water boils at 100° and methane at –161°, why blood is red and grass

is green, why diamond is hard and wax is soft, why glaciers flow and iron

gets hard when you hammer it, how muscles contract, how sunlight makes

plants grow and how living organisms have been able to evolve into ever

more complex forms … the answers to all these problems have come from

structural analysis.

In recognition of the importance of crystallography, 2014has been designated by the United Nations as the InternationalYear of Crystallography (IYCr). This year represents thecentenary of the awarding of the Nobel Prize in Physics to Maxvon Laue ’for his discovery of diffraction of X-rays by crystals’. Itis also 50 years since Dorothy Hodgkin was awarded the NobelPrize in Chemistry for her determination of the structures of anumber of important biochemical compounds, including the firststeroid structure (cholesteryl iodide), insulin (finally solved in1969, five years after her Nobel), penicillin and vitamin B12.

However, while IYCr had a lavish launch at UNESCO House inParis earlier this year, Australia started their celebrationsconsiderably earlier, with a special Bragg CentennialSymposium, held in Adelaide in December 2012 in conjunctionwith meetings of the Asian Crystallographic Association (AsCA)and the Society of Crystallography in Australia and New Zealand(SCANZ). This Symposium marked the centennial of W.L.(Lawrence) Bragg’s discovery of Bragg’s law, to my mind stillone of the most elegant equations in science (nl = 2dsinq),and the foundation upon which crystallography is built. For thisdiscovery, as well as for the solving of the first crystalstructures, Lawrence shared the 1915 Nobel in Physics with hisfather (W.H. (William) Bragg), and is still the youngest everwinner of a Nobel (only 25!).

The hosting of this event in Adelaide was no accident; whilethe key discoveries were made after the Bragg family returnedto the UK, Lawrence was born in Adelaide and obtained hisundergraduate degree at the University of Adelaide, where hisfather was professor of physics at the time. The Australianconnection, however, runs even deeper; Lawrence’s mother(William’s wife) was the daughter of Charles and Alice Todd.Charles Todd oversaw the building of the Overland Telegraph,completed in 1872, which was Australia’s first direct connectionto the rest of the world. Thus, Alice Springs and the Todd Riverare named after Lawrence Bragg’s grandparents.

Crystallography has, of course, come a long way since thoseearly days. Structures that would take months, even years, tosolve a few decades ago (or were simply too difficult to solve at

all) can now be done routinely in a matter of hours. In the localcontext, the early self-styled ‘bush crystallographers’ of the1970s have evolved into SCANZ, and we now host not only thelatest X-ray diffractometers in many chemistry and biochemistrydepartments, but also have large national facilities, namely theAustralian Synchrotron and the OPAL research reactor, whichhave multiple beamlines dedicated to diffraction techniques.

Australia therefore has much to celebrate during IYCr, andthere are numerous activities planned or underway around thecountry, many with the support of the RACI, SCANZ or theAustralian Academy of Science (AAS). Notably, all three aresupporting the RACI’s crystal growing competition, run inschools all around the country. Other things to look out forinclude:• the fascinating Crystallography365 blog (a crystal structure a

day – crystallography365.wordpress.com)• displays of crystallographic artwork, including pictures and

three-dimensional models, at galleries (including the VergeGallery, University of Sydney, 16–23 August) and otherpublic spaces around the country

• a ‘Crystallography in Everyday Life’ photo competition andtravelling exhibition

• special issues of CrystEngComm (Asia–Pacific region issue)and Aust. J. Chem. celebrating IYCr

• a national lecture tour in August by Professor Stephen Curry(Imperial College); for a sneak peak, have a look atStephen’s excellent public lecture on crystallography oneither YouTube or the Royal Institution’s website

• the Science at the Shine Dome Minerals to Medicines event inMay 2015 at the AAS. While after the IYCr, this will mark thecentenary of the Braggs’ 1915 Nobel Prize.So keep an eye out for these activities, have a look at the

fantastic resources on the official website (www.iycr2014.org),or celebrate like one research group is by havingcrystallography-themed cakes at their group meetings this year.And remember that the real power of crystals is not theirfictitious healing properties, but their ability to reveal thethree-dimensional structures of molecules, and to explain theproperties of matter.

Stuart Batten FRACI CChem is President of the Society of Crystallographers inAustralia and New Zealand.

International Year of Crystallography

guest editorial

MOOCs and moreThank you for another great edition (June). Kieran Lim’s articleabout MOOCs is spot on. To take the matter further, this methodcould very well be an integral part of most Australian universityaward courses in the future. Indeed, I believe that Deakin alreadydoes this. Despite laboratories being the ‘signature pedagogy’ inchemistry education, there is a possibility that this componentcould be done on a week ‘block basis’ as it is now done for off-campus learning enrolled students. The major problem is thegeographic spread and large numbers of participants that MOOCsattract. I’m sure a solution will be found, if one doesn’t alreadyexist.

For any members who have not had a look at the offerings,then perhaps visit www.coursera.org. You will find a large list(about 80) of participating institutions including the University ofMelbourne and Stanford University. You will also find anastounding range of subjects on offer. Type ‘chemistry’ into thesearch engine and hold your breath. At the moment, I have almostfinished an eight-week course on epigenetic control of geneexpression, run free on Coursera, badged by the University ofMelbourne and presented by Dr Marnie Blewitt, who is head ofmolecular genetics at WEHI. At last count, the course has 22 000participants globally, with participant levels from undergraduateto postdoc. I think MOOCs might also be used as a means ofprofessional development.

Thanks also to Oliver Jones for the cover story ‘Using yourLoaf’. I was very interested in the matter of coeliac’s disease as wehave a daughter-in-law who suffers from the problem. I have beenbaking bread now for about 12 years and have never thoughtmuch about its history or chemistry. It really isn’t that difficult anart, and one is amply rewarded with the rich aromas of freshlybaked bread, not to mention better flavour and texture made toyour own taste. You also know exactly what is in it. For those whowant to have a fling, try the book that I have been using for allthese years – The bread bible by Rose Levy Beranbaum, publishedby W.W. Norton & Company (ISBN 9780393057942). Her materialsand methods work. The only warning that I give is that I havebroken two domestic mixers over the past 12 years and havemoved to a small commercial mixer. It, however, will not whisk acouple of egg yolks as it is a bit big for the normal domesticchores.

Denis McCann MRACI

Hake’s over ambition?Was Cecil Hake being overly optimistic about cordite output forVictoria’s cordite factory (150 tpa) or did annual productionactually reach this target at some point (June 2014, p. 16)? Inote that monthly output for the initial six months was 5.5 tonnes(66 tpa), well below Hake’s goal. As the article proffered nofurther production values, I was left to wonder whether Hake’s‘ambitious’ annual cordite total was ever achieved or not.

I really enjoyed Dave Sammut’s road test of the continuumsource atomic absorption spectrometer (June p. 24). I think an

occasional review of an instrument, tool or some other chemistry-related equipment or technique would be a worthwhile addition tothe magazine. Book reviews have been a staple magazine featuresince inception, so maybe it’s time to consider including someother kinds of reviews by members too.

Damien Blackwell MRACI CChem

It appears that the theoretical maximum amount of corditeproduced by the Maribyrnong factory was 150 tpa if three shiftswere implemented, though I can’t find any reports that this wasever attempted. The Sydney Morning Herald (Monday, 24 April1911, available via Trove.nla.gov.au) reports on ‘interesting facts’in Hake’s final report that had been delivered on his resignationthe previous week. ‘The output of the factory is based at 50 tonsannually, but should it be necessary to double the output at anytime, it can be done with the same plant by working two shiftsinstead of one. The plant erected is capable of manufacturing guncotton and nitro-glycerine, the two main ingredients of cordite,also nitric acid, and it can recover and concentrate waste acids.Large cordite for the guns can be easily manufactured at thefactory with a few additions to the plant, but this would involvethe equipment of proof grounds also. The factory will be capableof manufacturing either cordite Mark 1 for rifles, or cordite markMD for guns, up to 150 tons per annum, by working three shifts.Raw materials, such as nitrate of soda, cotton waste, acetone, andmineral jelly, will have to be imported.’

Apparently poor Defence planning in the following decadesmeant that cordite production was insufficient at the outbreak ofthe World War II. A document lodged at the Australian WarMemorial (http://static.awm.gov.au/images/collection/pdf/RCDIG1070363—1-.PDF) states that the cordite production line atthe factory had ramped up to 1500 tpa by 1935. However, it statesin Chapter 16 ‘Ammunition and Explosives’ that ‘Calculations basedon the assumption that the defence forces should be prepared fora “minor scale of attack” – the officially-accepted view – revealedthat the capacity of the government factories for producingcordite and TNT (which was at the rate of 1500 and 600 tons perannum respectively) fell short of requirements.’

Four days before the outbreak of World War II Australia’sMinister For Supply and Development (Mr Casey) approved aproposal for decentralising the manufacture of these explosives.The Imperial Chemical Industries Australia and New Zealand(ICANZ) would build an annexe to its Deer Park factories (laterknown as No. 5 Government Explosives Factory, Albion), whichwould be designed in the first instance for an annual output of2000 tons of TNT, 1000 tons of cordite, and 250 tons of carbamite(used in the production of cordite).

David Kilmartin

your say

7|August 2014 Chemistry in Australia

your say news


A comment on RACI’s open letterIt is pleasing to see the RACI lifting its head above the parapet tochallenge some of the nonsense of the federal budget, and ingeneral terms I agree with what has been said in the open letterto the Prime Minister and the Treasurer (see p. 4).

However, it is deeply disappointing that the letter makes noattempt at all to correct the budget’s (and more generally thegovernment’s) irresponsible attempts to trivialise anthropogenicglobal warming. Just as chemistry is an enabling science formedical research, so too does it inform most aspects of climatechange research – a subject in which spectroscopy,thermodynamics, aqueous carbonate chemistry and many otherbranches of chemistry play major roles.

Why is the RACI so reticent to mention this elephant? Like itor not, it is in the room, stomping about and threatening tocharge. It must be confronted, and preferably with science ratherthan wishful thinking. Chemists can help.

Jim Bonham FRACI CChem

Tribute to KatritzkyThank you for sending me a copy of Chemistry in Australia, June2014, with the obituary of my husband, Alan R. Katritzky.

Several of his students and collaborators went on to positionsin Australian universities and it was a great privilege to visit themthere on several occasions, and to forge new links and refreshlongstanding ones with chemistry in Australia. Among them‘Kappa’ Cornforth, who like Alan took his PhD with Sir RobertRobinson. So the article on him (p. 5) brought back happymemories with him and his admirable wife Rita.

I am very touched by the tribute paid to my husband’sendeavours and have already thanked Dr Peter Lehman. He hasremained a life-long friend, like so many others, who have workedwith my husband.

With thanks and many good wishes …

Linde Katritzky

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Got something to say?As your RACI member magazine, Chemistry in Australiais the perfect place to voice your ideas and opinions, andto provide feedback on chemistry issues and recentlypublished articles.

Send your contributions (approx. 400 words) to theEditor ([email protected]).

Chemistry in Australia 9|August 2014

your say news

The Earth’s interior could contain more than three times theamount of water in all our oceans combined, existing withinthe structures of silicate materials that are stable at theprevailing conditions deep inside the Earth. New research fromETH Zürich has helped to elucidate exactly how deep water getstransported into the Earth’s interior.

Water is fundamental for processes that occur at the Earth’ssurface, but also plays a critical role in many geologicalprocesses occurring deep inside of it that shape its evolution.Small amounts of water incorporated into the structure ofminerals have a major effect on their stability, behaviour andphase equilibria. Global processes such as mantle convection,plate tectonics and naturally occurring catastrophic events suchas earthquakes and volcanic eruptions are strongly influencedby the activity of this water.

Water is reintroduced into the Earth’s interior by hydratedtectonic (oceanic) plates that return into the mantle insubduction zones, and released when hydrous minerals/phasesare decomposed due to the high pressure and temperature ofthe Earth’s interior. Much of this water returns to the surface byvolcanism, but a large fraction is retained in newly formedhigh-pressure hydrous phases that are stable at much higherdepths, opening the possibility for water to recirculate deeperinto the mantle beyond 400 km depth. However, the exactamount of water stored in the solid Earth, and how (and howmuch) of this water is recycled back to the surface, remainsobscure.

Carmen Sanchez-Valle, assistant professor of experimentalgeochemistry and mineral physics at the Swiss Federal Instituteof Technology, Zurich, has worked with her team to developseveral novel analytical techniques to investigate thisenvironment. ‘Through learning about the Earth’s interior, webecome more aware of what actually occurs on the surface,’ sheexplained.

A group of dense hydrous silicate phases discovered inlaboratory experiments in the mid-1960s, the so-calledalphabet phases (phase A, E, D and superhydrous B), areplausible candidates for the transport of water at depth due tothe large stability field. The physical and chemical properties ofthese materials, obtained through mineral physics studies, arefundamental to revealing the deep water cycle.

A device called a diamond-anvil cell is the primary tool usedby researchers to replicate extreme conditions that exist at theEarth’s interior, and explore how hydrous phases behave. Bypowerfully compressing micrometric-size samples between theflat surfaces of quarter-carat diamonds, the apparatusauthentically simulates pressure conditions down to the Earth’score. To recreate the infernal temperatures present in theserealms, heating elements or infrared lasers are introduced tothe tests.

‘Crucially, the diamonds are transparent, which means thatbrilliant X-rays produced by synchrotron sources and laser

analysis can be used to probe the physical and chemical stateof samples while they are submitted to extreme pressure andtemperature conditions,’ added Sanchez-Valle. ‘Theseexperimental simulations provide us with a virtual window intothe deep Earth.’

Fortunately,seismic waves canbe simulatedwithin the team’sfacilities. Using aunique laserspectroscopy calledBrillouin scatteringspectroscopy, thespeed of seismicwaves andelasticity ofmaterials can bemonitored underpressure, divulgingtheir water-bearing

qualities. The team also use the brilliant X-rays produced atsynchrotron sources to monitor the development of textures inhydrous materials deformed at conditions that mimic those ofsubducting slabs penetrating in the lower mantle.

Set-up for Brillouin scattering spectroscopy

‘Our combined studies on hydrous phases has allowed us forthe first time to interpret seismic anomalies observed in deepsubducted slabs,’ said Sanchez-Valle. ‘The work has shown thathydrous slabs penetrating below the transition zone in areassuch as Tonga could contain at least 1.2% in weight of waterbound to dense hydrous phase D. The dehydration of phase D atgreater depths is a potential mechanism to activate very rare(and less damaging) deep focused earthquakes, and the waterreleased into the lower mantle has important consequences forthe geodynamical and geochemical evolution of the deep Earth.’INSIGHT PUBLISHERS

Journey to the centre of the Earth

A diamond-anvil cell

news


Metal crystals from a single atomResearchers have announced the first ever method forcontrolling the growth of metal crystals from single atoms.

Published in Nature Communications and developed at theUniversity of Warwick, the method – nanocrystallometry –allows for the creation of precise components for use innanotechnology.

Professor Peter Sadler from the University’s Department ofChemistry commented that: ‘The breakthrough with

nanocrystallometry is that it actually allows us to observe anddirectly control the nano-world in motion’.

Using a doped-graphene matrix to slow down and then trapatoms of the precious metal osmium, the researchers were ableto control and quantify the growth of metal crystals. When thetrapped atoms come into contact with further osmium atoms,they bind together, eventually growing into 3D metal crystals’

‘Tailoring nanoscopic objects is of enormous importance forthe production of the materials of the future’, said Dr Barry fromthe University’s Department of Chemistry. ‘Until now theformation of metal nanocrystals, which are essential to thosefuture materials, could not be controlled with precision at thelevel of individual atoms, under mild and accessible conditions.’

Sadler said: ‘Nanocrystallometry’s significance is that it hasmade it possible to grow with precision metal crystals whichcan be as small as only 0.000 000 15cm, or 15 Å, wide. If ananodevice requires a million osmium atoms, then fromone gram of osmium we can make about 400 000 devices forevery person on this earth. Compared to existing methods ofcrystal growth, manocrystallometry offers a significantimprovement in the economic and efficient manufacture ofprecision nanoscopic objects.’

The researchers argue that the new method possesses arange of potential uses. ‘We envision the use ofnanocrystallometry to build precise, atomic-level electroniccircuits and new nano-information storage devices. The methodalso has significant potential for use in the biosensing of drugs,DNA and gases as well for creating unique nano-patterns onsurfaces for security labelling and sealing confidentialdocuments. Nanocrystallometry is also an innovative method forproducing new metal nano-alloys, and many combinations canbe envisaged. They may have very unusual and as yetunexplored properties’, commented Barry.

‘The advances have been made possible thanks to our use ofa state-of-the-art aberration-corrected high-resolutiontransmission electron microscope, the only microscope of thiskind in the UK, that has the potential to image individualatoms in this way. We know that things are made of atoms, butit is really rare to see them dancing in front of your eyes’, saidDr Richard Beanland from the University’s Department ofPhysics.

Commenting on the commercial potential fornanocrystallometry, Andrew Lee, Business Development Managerat Warwick Ventures said: ‘We think that the team’s techniquecould be a real break-through in terms of offering the capabilityfor micromanipulation and derivatisation of a graphene surface;seeing multiple commercial opportunities arising in the future.We have put a patent application in place and we are activelyseeking industrial partners with whom to collaborate in thefuture.’UNIVERSITY OF WARWICK

3D projection of the crystal growth

Osmium atoms forming the crystal on the graphene matrix

University of W

arwick

University of W

arwick

Although Australia continues to be a world leader in lead metalmining, smelting and processing, international scientists haveraised urgent concerns in a new Environment International paperabout a lack of understanding on the hazards of theseoperations.

‘The lead pandemic is not a problem of the past,’ said leadauthor Professor Mark Taylor.

‘There is now an overwhelming body of evidence showingthat Australia’s lead level for children is too high. We’re askingwhy would it take Australia’s leading public health body, theNational Health and Medical Research Council (NHRMC) so long– from 2012 to 2014 – to undertake what appears to be areview of reviews. Are they anticipating that they mightconclude something different from other global experts?’

In their report, Taylor, Professor Chris Winder and ProfessorBruce Lanphear show how childhood blood lead levels havefallen sharply across the world’s developed countries in recentdecades, as a result of work by the WHO and Food andAgricultural Organization (FAO) of the United Nations.

However, Australian policy responses have stalled, despite‘the incontrovertible evidence that adverse neurocognitive andbehavioural effects occur at levels well below the currentnational goal of 10 mg/dL’, the paper reports.

‘This delayed response is happening when blood lead levelsare actually rising by some measures in two of Australia’s threeprimary lead mining and smelting cities: Port Pirie, SouthAustralia, and Broken Hill, New South Wales,’ said Taylor.

The authors argue that urgent changes are required to bothstate and national policy approaches, to bring them in line withcontemporary international standards.

They recommend a lower blood lead intervention level of nomore than 5 mg/dL, with a national goal for all children underfive years of age to have a blood lead level of below 1 mg/dL by2020.

The scientists warn that procrastination on this issue will be‘the thief of an equitable and healthy start to life for Australia’slead-exposed children.’MACQUARIE UNIVERSITY


Push for lower blood lead levels in children

news

Broken Hill is one of two lead mining and smelting cities in Australia where lead levels are rising.

iStockph

oto/trigga

74th IChemE presidenttakes officeGeoff Maitland, professor of energyengineering at Imperial College London,has become the 74th president of theInstitution of Chemical Engineers(IChemE).

A graduate in chemistry from OxfordUniversity, Maitland is a Fellow ofIChemE, Royal Society of Chemistry,Energy Institute and the Royal Academyof Engineering.

During a distinguished industrial andacademic career, Maitland enjoyed spellswith Bristol University, Imperial CollegeLondon, ICI and Schlumberger beforereturning to Imperial College London in2005.

He is a vocal advocate of low-carbon,renewable energy and technologies suchas carbon capture and storage (CCS) tomitigate what he describes as ‘sleep-walking into a catastrophic climatechange future’.

Maitland replaces Judith Hackitt CBE,chair of the GB Health and SafetyExecutive. Current honorary treasurer,Andrew Jamieson OBE, has beenappointed IChemE deputy president.

Maitland said: ‘During this year I willplace particular emphasis on celebratingthe contributions chemical engineeringis making to the quality of life acrossthe world.

‘Today, I am launching my campaign,ChemEng365, which will feature 365chemical engineering successes andachievements throughout my year-longpresidency. I will be encouraging myfellow members to visit my bloggingwebsite and contribute to a celebrationof our profession.

Joining IChemE’s Council in 2014, thegoverning body for the Institution’s40 000 members worldwide, are KenRivers, former chief executive ofRefining NZ; Iain Martin, divisionaltechnology director for the ProcessTechnologies Division at JohnsonMatthey PLC; and Dr Jarka Glassey,reader in chemical engineeringeducation at Newcastle University, UK.INSTITUTION OF CHEMICAL ENGINEERS

news on the market

Professor Donald Bruce Dingwell is thewinner of the 13th Otto Schott ResearchAward, valued at €25 000. The Canadianexperimental volcanologist has headedthe Department of Mineralogy andPetrology at the Ludwig MaximilianUniversity (LMU) in Munich since 2000and is Director of the Department of Earthand Environmental Sciences. Dingwellreceived the award for his many years ofresearch in the field of physical andchemical properties of volcanic glasses.‘His work on glass formation underextreme conditions like those that occurduring volcanic activity provide us withvaluable insights for use in industrialglass melting,’ noted Dr Hans-JoachimKonz, Chairman of the Board of Trusteesof the Ernst Abbe Fund and Member of theBoard of Management of SCHOTT AG,during the award ceremony that was held

at an international conference on glasstechnology in Aachen.

Dingwell’s research centres on therole of melts and glasses in geologicprocesses. He succeeded in documentingthe central role that the glass transitionplays in explosive volcanism. This makeshim a pioneer in the quantification ofthermodynamic and transport propertiesof molten silicates of both simple andcomplex compositions.

The Otto Schott Research Award ispresented every two years by the ErnstAbbe Fund to recognise outstandingachievements in the area of fundamentalresearch and technology development inthe fields of glass and glass-ceramicsciences for the areas of applicationoptics and electronics, renewableenergies, health and lifestyle.SCHOTT AG


Geoscientist recognised forpioneering work on volcanic glasses

Professor Donald Bruce Dingwell (second from left) receiving the Otto Schott Research Award 2014from Dr Hans-Joachim Konz (second from right), member of the Board of Management of SCHOTT AGand Chairman of the Board of Trustees of the Ernst Abbe Fund. Also present, member of the Board ofTrustees and laudator Professor Carlo Pantano (Penn State University) (right), and member of the Boardof Trustees Professor Reinhard Conradt (RWTH Aachen) (left).

news on the market

Stronger, lighter, tougher – creatingbetter carbon fibre for the futureDeakin University researcher Linden Servinis is using cleverchemistry to change carbon fibre surfaces, in a bid to makematerials stronger and lighter with better crash-resistance.Servinis is using chemistry techniques to add ‘chemical arms’to sections of the fibre surface previously thought to beunreactive.

Carbon fibre composites are solid materials made up ofweaved carbon fibres covered in a layer of plastic resin.Servinis said when these materials were subjected to highimpact, the fibres often pulled away from the resin, causingfailure.

‘This research seeks to prevent composite failure byadding new chemical arms with reactive chemical hands atthe ends. These hands can then grab onto the resin in achemical reaction, and prevent failure, making a strongermaterial,’ Servinis said.

‘Carbon fibre composites are looking to be the nextaluminium, with incredibly strong and light-weight propertiesthey have incredible potential to maximise fuel efficiency.’Servinis said recent interest in large-scale production ofcarbon fibre for automotive and aerospace had highlightedthe importance of investigating the interaction between fibreand resin to maximise composite performance.

‘This and other research at Deakin is providing a betterunderstanding of the subtle molecular interactions which canhave a large impact on composite performance,’ Servinis said.

‘Current carbon fibre production includes an electrolyticoxidation process, which introduces oxygen functional groupsto the surface, and roughens the fibre, which improvesbonding between fibre and resin.

‘While the oxidation helps bonding, it does not introducethe “reactive chemical hands”, which can hold onto the resinlayer the same way our chemical arms can.’

Servinis, whose project is part of a PhD she is undertakingwith Deakin’s Carbon Nexus research facility, said not onlyhad three separate chemistry techniques been shown toeffectively graft these arms onto the surface, but they couldalso be designed to react specifically with each resin systemchosen.

A combination of X-ray photoelectron spectroscopy,single-fibre testing, and single-fibre fragmentationtechniques are used to validate each new technique, toensure chemistry doesn’t degrade the fibres, while improvingperformance. Servinis said the research was part of acollaboration with the Australian Future Fibres Research andInnovation Centre and the CSIRO. She said her presentationas a finalist at the FameLab competition, which is designedto find, develop and mentor young science and engineeringcommunicators, provided a valuable national platform toarticulate the benefit of carbon fibre research.SCIENCE IN PUBLIC


Abbemat juice station – precise Brixmeasurement of beveragescontaining pulp

Fruit juices are natural products with many ingredients. Toensure the expected product quality, these beverages have tomeet the defined product specifications.

One of the most important quality analysis parameters injuice production is °Brix (°Bx), which represents the sugarconcentration as well as the composition of the juice. Abbematrefractometers are fast and reliable instruments commonly usedfor °Brix measurements. However, many juices, especiallyorange juices, contain pulp, which remains in the beverage.

During measurement with a conventional refractometer, thispulp starts to deposit on the measuring prism, leading tounstable readings. The vertical set-up of the Abbemat juicestation avoids the sedimentation of particles on the prism andensures reliable and stable measuring results.

Abbemat juice station refractometers are easy to operate.The attached filling funnel allows fast and simple serialanalyses: cleaning of the measuring prism is not requiredbecause the next sample flushes out the previous one. Theautomatic temperature control of the sample assures accuratemeasuring conditions.

For more information, please contact MEP Instruments on(02) 8899 5200 or [email protected] or visit www.mep.net.au.

Turning miningwastewater intorainwaterA new cost-effective technology to treatmining wastewater and reduce sludge byup to 90% has been used for the firsttime at a commercial mine.

The technology, called Virtual Curtain,was used to remove metal contaminantsfrom wastewater at a Queensland mineand the equivalent of around 20 Olympicswimming pools of rainwater-qualitywater was safely discharged.

Sludge is a semisolid by-product ofwastewater treatment and reducing theamount produced has huge environmentaland economic benefits.

‘Our treatment produced only afraction of the sludge that a conventionallime-based method would have andallowed the mine water to be treated in amore environmentally sound way,’ CSIROscientist Dr Grant Douglas said.

‘Reducing the amount of sludge isbeneficial because the costly and timelysteps involved to move and dispose itcan be reduced.’

Given the Australian mining industryis estimated to generate hundreds ofmillions of tonnes of wastewater eachyear, the technology opens a significantopportunity for companies to improvewater management practices and be moresustainable.

‘The technology can produce amaterial high in metal value, which canbe reprocessed to increase a miner’soverall recovery rate and partially offsettreatment costs,’ Douglas said.

Virtual Curtain utilises hydrotalcites,which are minerals sometimes found instomach antacids, to simultaneously trapa variety of contaminants – includingarsenic, cadmium and iron – in one step.

Douglas and his team developed thetechnology after discovering thathydrotalcites could be formed byadjusting the concentrations of common

wastewater contaminants aluminium andmagnesium to an ideal ratio and then byincreasing the pH.

‘By using contaminants alreadypresent in the wastewater we haveavoided the need for expensiveinfrastructure and complicated chemistryto treat the waste,’ he said.

‘If required, the treated water can bepurified much more efficiently via reverseosmosis and either released to theenvironment or recycled back into theplant, so it has huge benefits for mining

operators in arid regions such asAustralia and Chile.

‘It is a more efficient and economicway to treat wastewater and is enablingthe global mining industry to reduce itsenvironmental footprint and extractwealth from waste.’

The licensed technology, which can beapplied to a range of industrialapplications, is available throughAustralian company Virtual CurtainLimited.CSIRO


(Top) The new treatment in progress to remove a range of metal contaminants. (Bottom) The mine pit following the release of the treated water

news research


Cooperativity in an ion-pair host:Ca2+ switches ‘on’ Cl– bindingCooperative interactions play a very important role inboth natural and synthetic supramolecular systems, asexemplified in the allosteric regulation of metabolicenzymes and oxygen binding to haemoglobin.Fundamental questions regarding cooperativity continueto challenge and fascinate researchers, and simplesupramolecular systems provide an excellent platform foraddressing these questions. The Thordarson group at theUniversity of New South Wales has reported a tetratopic ion-pair host (receptor) that can bind up to two anions and twocations simultaneously, showing a rich collection of cooperativebinding properties (Howe E.N.W., Bhadbhade M., Thordarson P.J. Am. Chem. Sci. 2014, 136, 7505–16). Anions and cations ontheir own (i.e. with a non-binding counterion such as

tetrabutylammonium or perchlorate) show negativecooperativity towards this host, and in a protic solvent mixture,anion binding is completely inhibited. However, in that sameprotic solvent, the addition of Ca2+ switches ‘on’ Cl– binding,with Cl– now showing positive cooperativity towards the host!The insight that this work gives into cooperativity could allowbetter design of cooperative synthetic supramolecular systemsfor information transfer and catalysis.

AgelessseparationsIndustrial separationsare responsible for upto 40% of the world’senergy demands.Membranes, withtheir continuousmode of operation,are one of the mostenergy-efficientoptions for reducingthis demand. Due totheir internalporosity, stemming from low-density chain packing, super-glassypolymers deliver prolific transport pathways, and are most attractive foruse in membranes. Unfortunately, they age badly over time, the chainspacking to a denser and hence less permeable state, making themunattractive for long-term application. Researchers at CSIRO inMelbourne, in collaboration with Monash, ANU and the University ofColorado, have discovered that a specific ultraporous framework knownas PAF-1 can prop open the polymer chains and stop ageing, while alsotripling the gas permeability in the system (Lau C.H., Nguyen P.T., HillM.R., Thornton A.W., Konstas K., Doherty C.M., Mulder R.J., Bourgeois L.,Liu A.C.Y., Sprouster D.J., Sullivan J.P., Bastow T.J., Hill A.J., Gin D.L.,Noble R.D. Angew. Chem. Int. Ed. 2014, 53, 5322–6). The bulky sidechains of polyacetylenes, or bulky chemical moieties on polymers withintrinsic microporosity, are physically tethered within the pores of PAF-1;consequently, polymer chain relaxation is prevented. The study hasimplications for carbon capture, dye removal, natural gas purification,hydrocarbon separations and biofuel purification.

Cyclic peptides have great potential as therapeuticagents because they can mimic larger proteins andthereby modulate protein–protein interactions.However, synthesising cyclic peptides is often aninefficient process and, furthermore, it is difficult tofine-tune the precise shape of the macrocycle in order

to optimise the biological potency. Researchers at theUniversity of New South Wales have nowdemonstrated, for the first time, that stereoselectivefluorination chemistry can overcome these limitations(Hu X.-G., Thomas D.S., Griffith R., Hunter L. Angew.Chem. Int. Ed. 2014, 53, 6176–79). A team led by DrLuke Hunter has efficiently synthesised several vicinaldifluorinated analogues of the natural cyclicheptapeptide unguisin A. Remarkably, it was foundthat alterations to the configuration of the fluorine-bearing carbons had a profound effect on the peptidesecondary structure, even at distant parts of themacrocycle. This discovery opens up futurepossibilities for optimising the properties of manyother cyclic peptide drug leads.

F-tuning the shapes of cyclicpeptides

news research

research


Biometals are important in thepathogenesis of neurodegenerative braindisorders. However, limited resolution ofcurrent analytical approaches tomeasuring metal biodistibution has ledto a roadblock in our understanding ofthe disease process. Bulk tissue metalanalysis often masks important subtlechanges at the subcellular level. To

address this problem, the groups ofAssociate Professor Anthony White and DrPaul Donnelly, University of Melbourne,together with Australian Synchrotronscientists, and collaborators in the USand Finland, have applied X-rayfluorescence microscopy (XFM) to neuronsgrown from an animal model of thechildhood brain disease neuronal ceroid

lipofuscinosis (Grubman A., James S.A.,James J., Duncan C., Volitakis I., HickeyJ.L., Crouch P.J., Donnelly P.S., KanninenK.M., Liddell J.R., Cotman S.L., de JongeM.D., White A.R. Chem. Sci. 2014, 5,2503–16). Bulk biometal analysis byinductively coupled plasma massspectrometry revealed no changes tooverall metal levels in the neurons.However, XFM revealed majordisturbances to subcellular biometalhomeostasis, with a critical loss ofcorrelation between nuclear and cytosoliczinc and calcium levels in diseased cells.These defects could be largely rectifiedby application of a cell-permeable zinc-complex (bis(thiosemicarbazone)) to thecells. The researchers are now probing athigher resolution to determine where thesubcellular biometal changes are mostprominent and how homeostasis isrestored by metal complexes.

The unique hydrocarbontetravinylethylene (TVE), featuring bothcross- and through-conjugation, firstsuccumbed to total synthesis some50 years ago. Surprisingly, this milestonein hydrocarbon chemistry provided littleinformation about its chemical andphysical properties, presumably due todifficulties associated with accessingsignificant quantities of material from itslow-yielding synthesis (


The July issue is dedicated to the chemistry of guanidine, guanidiniumand guanidinate derivatives. Leo Fohlmeister and Cameron Jones(Monash University) synthesised and investigated the reactivity of low-valent FeI–FeI complexes stabilised by a bulky guanidinate ligand, suchas the Fe=Fe compound shown, which has a very short Fe–Fe distance.Its reaction with CS2 led to reductive C=S bond cleavage and theisolation of the {[(Pipiso)Fe]2(m-S)(m-CS)} compound.

Carlos A. Murillo (Texas A&M) describes ‘A Magic Equation: Delta Bonds Plus Bicyclic Guanidinates EqualsStrong Reducing Agents’. Reactions of bicyclic guanidinates with dimolybdenum and ditungsten precursorspossessing quadruply bonded dimetal units with s2p4d2 electron configuration generated very strong reducingagents. Analogous rhenium compounds led to the formation of dimetal species in unusually high oxidationstates. The properties of these compounds are attributed to the interaction of the p electrons of the C(N)3

-

guanidinate core with the electrons in the delta bond of the dimetal units.

Kazuo Nagasawa and co-workers (TokyoUniversity of Agriculture and Technology)report on a new class of bifunctionalguanidine–bisurea organocatalysts such as4d, with chiral centres located outside theurea groups. With these catalysts, a-hydroxylation of b-keto esters is achievedin yields up to 99% and ee up to 51%.

Frank T. Edelmann et al. (University of Magdeburg, Germany) report on thefirst aziridinyl-guanidinates as new precursors for potentially volatile metalcomplexes. The lithium–aziridinylamidinates, Li[(C2H4N)C(NR)2] shown wereprepared by addition of N-aziridinyllithium, C2H4NLi, to dialkyl carbodiimides.The cyclohexyl derivative was obtained in the form of crystalline solventadducts {Li[(C2H4N)C(NR)2]S}2 (S = THF or Et2O). X-ray crystallographycharacterised them as ladder-type dimeric molecular structures. The chemistryof guanidinate anions is of significant current interest in terms of thesynthesis of homogeneous catalysts and volatile metal precursors.

Scott Bunge et al. (Kent State University) reportsynthesis and characterisation of group 11 guanidinatecomplexes derived from dicyclohexylcarbodiimide. Theaddition of lithium dialkylamides todicyclohexylcarbodiimide yielded lithium 2,2-dialkyl-1,3-dicyclohexylguandidinates. Further reaction with agroup 11 halide (CuCl, AgBr and AuCl) generatedoligonuclear complexes with the general formula{M[CyNC(NR2)NCy]}n where M, R, and n are respectivelyCu, CH3, 2 ; Cu, CH2CH3, 2; Ag, CH3, 3; Ag, CH2CH3, 3;Au, CH3, 2; and Au, CH2CH3, 2 (examples shown). Group11 guanidinate compounds are of interest because or their potential to have closed shell d10–d10 metal interactions, as reagents foratomic layer deposition, and for their luminescent properties.

Aust J Chem

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

This year is the InternationalYear of Crystallography, anarea of science important tome due to my own family ties

(see box p. 20). Given the connection, Ihave been keen to write something toacknowledge the celebration.

I initially thought along the lines ofAustralia’s Bragging rights to thescience, most particularly becauseWilliam Lawrence Bragg was born andraised in Adelaide. It is, after all, agrand Australian tradition to lay claimto its share of the accolades of its sonsand daughters, no matter how far flung

their exploits. Indeed, the tradition canstretch to our country’s nephews andnieces, and any immediate neighbourswho have ever resided here, no matterhow fleetingly (I’m looking at you,Russell Crowe).

However, as I continued to read, Ifound myself utterly compelled by thegreat race that took place following theinitial establishment of the science.The competition between researchhouses, between the great luminariesof the day, and between the internalfactions and personalities makes for asimply thrilling story.


BY DAVE SAMMUT

iStockphoto/Magnilion


THEINNERSPACERACE

The emergence of X-ray crystallography is the storyof an earnest dash to the then-elusive double helix.

William Lawrence Bragg (1890–1971) was born into the Australiancolonies at a time of great change. Justmonths before, Henry Parkes haddelivered his Tenterfield address, andthe colonies were wrangling with theformation of a new nation. Within justfour years, the South Australianparliament would be only the secondin the world to grant women the vote.Shortly after his tenth birthday, the firstelectric lights would appear on thestreets of Adelaide.

Before Lawrence was even ateenager, new discoveries hadrevolutionised physics. In 1895,Wilhelm Roentgen discovered theexistence of X-rays, although at thatpoint they were still considered aparticle. Henri Becquerel and MarieCurie had both made key discoveriesin the radioactive properties ofuranium and other elements. Indeed,

the first recorded surgical use of X-rays in Australia was by William HenryBragg (Lawrence’s father and futureco-recipient of the Nobel Prize),investigating five-year-old Lawrence’sbroken arm after he fell from histricycle.

A brilliant young man, Lawrencegraduated at age 18 from theUniversity of Adelaide; then, movingback to England with his family, hewent on to graduate with honours fromCambridge at age 22. He was juststarting as a research student atCambridge when it was announcedthat Max von Laue had observed thediffraction of X-rays by crystals, forwhich he won the Nobel Prize just twoyears later in 1914. The rapidity of theawarding of this honour shows just howevident was the importance of thisdiscovery. And after just three years ofwork, the two Braggs published the

seminal work X rays and crystalstructure in 1915, for which they wereawarded the Nobel Prize the sameyear.

… the firstrecorded surgicaluse of X-rays inAustralia was byWilliam HenryBragg …investigating five-year-oldLawrence’s brokenarm after he fellfrom his tricycle.

From there, Lawrence Bragg’s rise was meteoric. Hebecame the professor of physics at Manchester Universityin 1919, and the head of the Cavendish Lab in 1938 –succeeding Ernest Rutherford in the role.

Across the Atlantic, a rival was emerging – Linus Pauling(1901–94). Inspired by the Braggs’ book, Pauling hadconducted his own first determination of molybdenitecrystal structure in 1922. On a Guggenheim Fellowship,Pauling studied revolutionary quantum mechanical theoryunder Niels Bohr and Erwin Schrodinger. Returning to the

USA, he spent five prolific years to 1932, during which hepublished approximately 50 papers, was awarded theLangmuir Prize by the American Chemical Society for themost significant work in pure science by a person 30 yearsof age or younger, and produced the seminal work ‘TheNature of the Chemical Bond’, published in the Journal of theAmerican Chemical Society.

During this time, both Pauling and Bragg developed setsof rules for interpreting X-ray diffraction patterns from morecomplicated crystals. But to Bragg’s chagrin, Paulingpublished first, and a rivalry was established that would lastfor another 20 years.

In the years that followed, X-ray crystallography wasapplied to increasingly complex molecules. Newdiscoveries were being compared against theoreticalconsiderations – in some cases as sophisticated as cuttingpieces of paper into the shapes of molecular subunits (suchas the amino acids that make proteins) and then pushingthem around to consider and eliminate alternatives. Incombination, these pieces of information were being usedto elucidate the structures of the molecular building blocksto life itself.

The British took the lead in the 1920s, with WilliamAstbury working in Bragg’s group at the Royal Institute toprovide the first X-ray diffraction pictures of fibrous protein.By the 1930s, Astbury had correctly showed that globularprotein modules such as haemoglobin are made up of long-chain proteins (polypeptides) that are folded to make balls.

However, the Americans were not to be outdone. Caltechresearchers Roscoe Dickinson (doctoral adviser to Pauling)and Albert Raymond definitively showed in 1923 that


Bragg’s group published firstin 1950, but their model wasshown to be flawed, and hewas once again trumped byPauling’s team with thecorrect solution in 1951 – thehelical structure of fibrousprotein.

A crystallography careerMy late father-in-law, Don Craig (1936–2009), will have been known to many RACI members through his 54-year career incrystallography at the University of New South Wales, stretching right back to the days when it was still the TechnicalInstitute. The UNSW School of Chemistry wrote that Don ‘will always be linked with crystallography at UNSW. His tireless work,enthusiasm and encyclopaedic crystallographic knowledge benefited many UNSW postgraduate students over his 51 years ofservice to the University, resulting in over 400 peer-reviewed articles.’

Don is remembered at the university through the Don Craig Memorial Prize to honour the very significant contributions thathe made to the School and the field of crystallography. The prize was won in 2014 by PhD student Matthew Gyton, with theprize presented by Don’s long-standing friend, Emeritus Professor Brynn Hibbert.

As a loving family member, I would add that Don had the rare gift of being able to recognise what he loved doing in life,and the determination to stick with it. He didn’t want promotion or wealth. For the love of science, he just did his research,raised a family and a social ‘cleansing ale’, and was content with his life. He will always be missed.

molecules have a three-dimensionalarrangement and that within a crystalthese molecules are discrete andseparated by distances greater thanthe molecular covalent bonds.

In the mid-1930s, Pauling struck outfrom his early interest in inorganicmolecular structures to biological,citing Astbury’s work in hisconsiderations.

Both sides were severelyinterrupted by the war, but by the late1940s, both were actively workingtowards the problem of coiling apolypeptide in three dimensions.

Bragg’s group published first in1950, but their model was shown to beflawed, and he was once againtrumped by Pauling’s team with thecorrect solution in 1951 – the helicalstructure of fibrous protein. TheCaltech team published no fewer thanseven papers in the May 1951Proceedings of the National Academy ofSciences, laying out the detailedchemical structure of hair, feathers, silkand other proteins.

The obvious next step was DNAitself, first identified in the 1940s. Therace was in full swing, but politics andpersonality came to play a critical role.Both of the facilities in Britain capableof conducting the research werefunded by the Medical ResearchCouncil. With limited funding available,a gentleman’s agreement was madethat the team at King’s College underMaurice Wilkins would get the first goat the DNA problem. But within theKing’s team personalities, andapparently also misogyny, meant thatthe gifted young researcher RosalindFranklin was being frozen out byWilkins.

It therefore fell to an interloper team– US chemist James Watson and Britishphysicist Francis Crick, with the latterworking unofficially from a deepinterest in the issue. Indeed, Crick wasreportedly twice told by Bragg to leaveDNA to the King’s team andconcentrate on his own PhD. Accordingto my reading, Bragg only came tosupport the work when in late 1952

Pauling claimed in a letter to his son (atCambridge) that his team was comingclose to solving the problem.

X-ray diffraction photographs werecritical to this work, but the onlyimages available were those fromAstbury from 1938. The images werenot improved until Franklin took up thesubject, and Watson’s work washampered by the lack.

Watson attended a talk given byFranklin at King’s, which by his ownlater account (The double helix) he didnot fully understand, but based uponwhich he and Crick came up with afirst model of DNA that was presentedto Franklin and Wilkins. This was soroundly criticised as to leave the pairthoroughly chagrined.

Serendipitously, in 1952 the pairchanced to have two criticalconversations. Discussing the issuewith mathematician John Griffith, Crickfirst raised the idea that nucleotidebases might somehow fit together tohold the DNA molecule. And in achance discussion with biochemistErwin Chargaff (inventor of Chargaff’srules, of which Watson was ignorant), itwas noted that samples of DNA alwayscontain equimolar base ratios ofadenine and guanine, thymine andcytosine. Together, this pointed Watsonand Crick to a DNA structure involvingpairs of long-chain molecules, linkedby A–G and C–T.

Armed with an advance copy ofPauling’s paper incorrectly proposinga three-stranded DNA model, Watsonvisited Wilkins at King’s, whoresponded by showing him (withoutFranklin’s knowledge or permission)one of Franklin’s best X-rayphotographs. The photo was thecritical piece of missing evidence, andin combination with the informationfrom Griffith and Chargaff, Watson andCrick were able to finish their work.

This major breach arguably costFranklin her due recognition and hershare of the ensuing Nobel Prize. Justone day before the event, she hadfinished the first draft of her ownpaper, which appeared alongside that

of Watson and Crick, and a third paperby Wilkins and his colleagues in the 25 April 1953 issue of Nature. Franklindied of cancer in 1958, neverreceiving her due acknowledgementin the 1962 awarding of the NobelPrize in Physiology or Medicine(awarded to up to three recipients peryear; Nobel Prizes were rarely givenposthumously), which went to Crick,Watson and Wilkins. Had Franklin lived,would she have received a NobelPrize? Watson was only to come cleanon the matter in his autobiographicalaccount in 1968.

This was neither the firstcontroversy in the relentless advanceof science, nor was it the last, but whocould fail to be inspired by the race todiscover our inner space?

Dave Sammut MRACI CChem is principal of DCSTechnical, a boutique scientific consultancy providingservices to the Australian and international minerals,waste recycling and general scientific industries.


William Henry Bragg’s X-ray spectrometer as usedby him and his son William Lawrence Bragg toinvestigate the structure of crystals

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Pick up a research paper onbattery technology, fuel cells,energy storage technologiesor any of the advanced

materials science used in these fields,and you will likely find somewhere inthe introductory paragraphs athrowaway line about applications tothe storage of renewable energy.Energy storage makes sense forenabling a transition away from fossilfuels to more intermittent sources suchas wind and solar, and the storageproblem presents a meaningfulchallenge for chemists and materialsscientists.

Or does it? Several recent analysesof the inputs to our energy systemsindicate that, against expectations,energy storage cannot solve theproblem of intermittency of wind or

solar power. Not for reasons oftechnical performance, cost or storagecapacity, but for something moreintractable: there is not enough surplusenergy left over after construction ofthe generators and the storage systemto power our present civilisation.

The problem is analysed in animportant paper by Weißbach et al.(Energy 2013, vol. 52, p. 210) in termsof energy returned on energyinvested, or EROI – the ratio of theenergy produced over the life of a

power plant to the energy that wasrequired to build it. It takes energy tomake a power plant – to manufactureits components, mine the fuel, and soon. The power plant needs to make atleast this much energy to break even.A break-even power plant has an EROIof 1. But such a plant would bepointless, as there is no energy surplusto do the useful things we use energyfor.

A minimum EROI, greater than 1, isrequired for an energy source to be


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BY JOHN MORGAN

Renewable energy sources pose the problem of intermittency.

Is storage the answer?

iStockphoto/jntvisual

able to run society. An energy systemmust produce a surplus large enoughto sustain things such as foodproduction, hospitals, transport,construction, universities to train theengineers to build the plant, and all theelements of the civilisation in which itis embedded.

For countries like the US andGermany, Weißbach et al. estimate thisminimum viable EROI to be about 7.An energy source with lower EROIcannot sustain a society at those levelsof complexity, structured along similarlines. If we are to transform our energysystem, in particular to one withoutclimate impacts, we need to pay closeattention to the EROI of the end result.

The EROI values for variouselectrical power plants aresummarised in the figure on page 24.The fossil fuel power sources we’remost accustomed to have a high EROIof about 30, well above the minimumrequirement. Wind power at 16, andconcentrating solar power (CSP, orsolar thermal power) at 19, are lower,but the energy surplus is still sufficient,in principle, to sustain a developedindustrial society. Biomass, and solarphotovoltaic (at least in Germany),however, cannot. With an EROI of only3.9 and 3.5 respectively, these powersources cannot support with theirenergy alone both their own

fabrication and the societal serviceswe use energy for in a developednation.

These EROI values are for energydirectly delivered (the ‘unbuffered’values in the figure). But things changeif we need to store energy. If we wereto store energy in, say, batteries, wemust invest energy in mining thematerials and manufacturing thosebatteries. So a larger energyinvestment is required, and the EROIconsequently drops.

Weißbach et al. calculated theEROIs, assuming pumpedhydroelectric energy storage. This isthe least energy-intensive storagetechnology. The energy input is mostlyearthmoving and construction. It’s aconservative basis for the calculation;chemical storage systems requiringlarge quantities of refined specialtymaterials would be much more energyintensive. Carbajales-Dale et al.(Energy Environ. Sci. doi:10.1039/c3ee42125b) cite dataasserting batteries are about ten timesmore energy intensive than pumpedhydro storage.

Adding storage greatly reduces theEROI (the ‘buffered’ values in thefigure). Wind ‘firmed’ with storage,with an EROI of 3.9, joins solar PV andbiomass as an unviable energy source.CSP becomes marginal (EROI ~9) with

pumped storage, so is probably notviable with molten salt thermalstorage. The EROI of solar PV withpumped hydro storage drops to 1.6,barely above break even, and withbattery storage is likely in energydeficit.

This is a rather unsettlingconclusion if we are looking torenewable energy for a transition to alow-carbon energy system: we cannotuse energy storage to overcome thevariability of solar and wind power.

In particular, we can’t use batteriesor chemical energy storage systems,as they would lead to much worsefigures than those presented byWeißbach et al. Hydroelectricity is theonly renewable power source that isunambiguously viable. However,hydroelectric capacity is not readilyscaled up as it is restricted by suitablegeography, a constraint that alsoapplies to pumped hydro storage.

This particular study does not standalone. Closer to home, Springer havejust published a monograph (G.Palmer, Energy in Australia: peak oil,solar power, and Asia’s economicgrowth, 2014) that contains anextended discussion of energysystems with a particular focus onEROI analysis, and draws similarconclusions to those of Weißbach. Thestudy by Carbajales-Dale et al. is moreoptimistic, ruling out storage for mostforms of solar, but suggesting it wouldbe viable for wind. However, thisviability is judged only on achieving anenergy surplus (EROI > 1), notsustaining society (EROI ~ 7), andexcludes the round-trip energy lossesin storage, finite cycle life, and theenergetic cost of replacement ofstorage. Were these included, windwould certainly fall below thesustainability threshold.

It is important to understand thenature of this EROI limit. This is not aquestion of inadequate storagecapacity – we can’t just buy or makemore storage to make it work. It is nota question of energy losses duringcharge and discharge, or the number


Origins of EROI The concept of EROI was introduced by US fisheries ecologist Charles Hall, whonoted that the energy a predator gained from eating prey had to exceed theenergy expended in catching it. In 1981, Hall applied this net energy analysis toour own power generation activities, charting the decline of the EROI of US oilas ever more drilling was required to yield a given quantity, and suggesting thepossibility that oil may one day take more energy to extract than it yields. Halland others have since estimated the EROI for various power sources, a difficultanalysis that requires identification of all energy inputs to power production.

EROI is a fundamental thermodynamic metric on power generation. Net energyanalysis affords high-level insights that may not be evident from looking atfactors such as energy costs, technological development, efficiency and fuelreserves, and sets real bounds on future energy pathways. It is unfortunatelylargely absent from energy and climate policy development.

iStockphoto/jntvisual

of cycles a battery can deliver. Wecan’t look to new materials ortechnological advances, because thelimits at the leading edge are those ofearthmoving and civil engineering.The problem can’t be addressedthrough market support mechanisms,carbon pricing or cost reductions. Thisis a fundamental energetic limit thatwill likely only shift if we find lessmaterially intensive methods for damconstruction.

This is not to say wind and solarhave no role to play. They can expandwithin a fossil fuel system, reducingoverall emissions. But without storage,the amount we can integrate in thegrid is greatly limited by thestochastically variable output. Wecould, perhaps, build out a generationof solar and wind and storage at highpenetration. But we would be doing soon an endowment of fossil fuel netenergy, which is not sustainable.

Without storage, we could smooth outvariability by building redundantgenerator capacity over largedistances. But the additionalinfrastructure also forces the EROIdown to unviable levels. The best wayto think about wind and solar is thatthey can reduce the emissions of fossilfuels, but they cannot eliminate them.They offer mitigation, but notreplacement.

Nor is this to say there is no value inenergy storage. Battery systems inelectric vehicles clearly offer potentialto reduce dependency on, andemissions from, oil (provided theenergy is sourced from clean power).Rooftop solar power combined withfour hours of battery storage canusefully timeshift peak electricitydemand, reducing the need forpeaking power plants and gridexpansion. And battery technologyadvances make possible many of our

recently indispensable consumerelectronics. But what storage can’t dois enable significant replacement offossil fuels by renewable energy.

If we want to cut emissions andreplace fossil fuels, it can be done, andthe solution is to be found in the upperright of the figure. France and Ontario,two modern, advanced societies, haveall but eliminated fossil fuels from theirelectricity grids, which they have builtfrom the high EROI sources ofhydroelectricity and nuclear power.Ontario in particular recently burnt itslast tonne of coal, and each jurisdictionuses just a few per cent of gas-firedpower. This is a proven path to adecarbonised electricity grid.

But the idea that advances inenergy storage will enable renewableenergy is a chimera – the catch-22 isthat in overcoming intermittency byadding storage, the net energy isreduced below the level required tosustain our present civilisation.

John Morgan is Chief Scientist at Pooled Energy,developing smart grid and grid-scale energy storagetechnologies. He is Adjunct Professor in the Schoolof Electrical and Computer Engineering at RMIT, holdsa PhD in physical chemistry, is an experiencedindustrial R&D leader and is an inventor on over 80patents.


Energy returned on energy invested with and without energy storage (buffering). CCGT is closed-cycle gasturbine. PWR is a pressurised water (conventional nuclear) reactor. Energy sources must exceed the‘economic threshold’, of about 7, to yield the surplus energy required to support an OECD level society.Reprinted from Energy, vol. 52, D. Weißbach, G. Ruprecht, A. Huke, K. Czerski, S. Gottlieb, A. Hussein,Energy intensities, EROIs (energy returned on invested), and energy payback times of electricity generatingpower plants, pp. 210–221, Copyright 2013, with permission from Elsevier.

The best way tothink about windand solar is thatthey can reducethe emissions offossil fuels, butthey cannoteliminate them.

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August 2014

Sir John Monash, c. 1919 (photograph with hand colouring)State Library of Victoria

Lieutenant-GeneralSir John Monash

An engineer on the battlefield

BY FRANK EASTWOOD

The Battle of Hamel on 4 July 1918was the first operational taskplanned and executed by JohnMonash as a Corps Commander.It broke conventional militarywisdom and demonstrated thatwith new tactics the static natureof trench warfare could beovercome.

John Monash (1865–1931) joinedthe militia in 1887 at the age of 22and was commissioned into theGarrison Artillery, responsible for

the Victorian coastal guns. In 1914, atthe age of 49 and with the rank ofMajor, he was chosen to command the4th Infantry Brigade.

Monash had degrees in arts,engineering and law and had decidedto make his career in engineering andin the military. He had learnt chemistry,physics and mathematics and hadtrained for years in the artillery. Hisknowledge of the explosives beingdeveloped by Alfred Nobel for use inmunitions, quarrying and mining andthe shift from muzzle-loading smooth-bore cannons to breech-loading rifledartillery with new propellants, and thechanges from muskets to rifles andmachine guns, made him moreknowledgeable than his peers aboutweaponry and he kept abreast of allsuch developments throughout hiscareer. His practice in law gave him aremarkable ability to expound asubject and to write unambiguousorders, and he was renowned for hisattention to detail.

Senior officers in the militia or thepermanent army had no way ofexperiencing wartime command.Inexperienced men were led byinexperienced officers. At Gallipoli,commanding the 4th Brigade (4100men), Monash was learning his tradeand was promoted to Brigadier andthen Major General. The men wereequipped to fight open warfare buthad to fight in trenches, which weretotally outside anybody’s experience –all had to learn quickly. Throughout hislife, Monash welcomed any chance tobroaden his knowledge,understanding and experience, and heshowed he could withstand theimmense strains of command inwarfare.

In 1916, Monash moved with the 4thBrigade from Egypt to Flanders, butafter a short time on the front went toEngland to train the newly formed 3rdAustralian Regiment (27 000 men),

which he led in Flanders under thecommand of superiors in 1917.Monash could demonstrate leadership,expertise and ability but, while underorders from senior commanders, nothis own creative originality.

On 21 March 1918, with his troopsresting near Boulogne in France,Monash was ordered to create adefensive line east of Amiens, to helpstop the German spring offensive.Then, most of the Australians makingup the Australian Corps were broughttogether under the command ofGeneral Sir William Birdwood. Monashtook command of the Australian Corps(166 000 men) on 31 May as part of the4th British Army under the commandof Lord Rawlinson and began hisperiod of leadership with the battle ofHamel, 20 kilometres due east ofAmiens, to remove a German intrusivestrong point and straighten his frontline.

Monash’s career as a projectengineer building railways andbridges convinced him of the need tocomplete work on time and withinbudget, and of the need to care for hisworkforce and maintain their numbers.He had seen the terrible waste of menon the battlefields. Monash expressedhis view that:

The true role of the infantry was not toexpend itself upon heroic effort, not towither away under merciless machinegun fire, not to impale itself on hostilebayonets but, on the contrary, to advanceunder the maximum possible array ofmechanical resources, in the form ofguns, machine guns, tanks, mortars andaeroplanes; to advance with as littleimpediment as possible; to be relieved asfar as possible of the obligation to fighttheir way forward.

A.G. Serle, John Monash. A biography,Melbourne University Press, 1982, p. 386.

The job of the infantry was to mopup all resistance and consolidate thegains. There had been no Alliedoffensive since the Passchendaelefighting in autumn 1917 and Monashwas ambitious for the Australians to

show the way in pushing back theGermans. His thinking at Hamel wasbased on the arrival of new Mark Vtanks, which were greatly superior toearlier models with which theAustralians had had bad experiences.The tanks and their crews and the menwere introduced well to the rear wherethe men could climb over and in thetanks, watch them being driven and trytheir hand at driving. What Monashinsisted on was that each tank had onejob to perform and took orders fromthe infantry officer commanding thetroops it was accompanying. The tankswould flatten the barbed wire andeliminate the machine guns bypirouetting on the emplacements.

Monash said the starting line for amajor attack should be straight so thatthe artillery could move the barrage insteps in front of the advancing tanksand troops. Errors in ranging andsighting the guns, which changed withwear, were measured on a specialrange in the rear so that ranging shotswere not needed. At intermediateobjective lines, troops halted to ensurecommand systems were in order andto permit fresh men to lead theadvance. The final line must not be


Monash’s careeras a projectengineer buildingrailways andbridges convincedhim of the need tocomplete work ontime and withinbudget, and of theneed to care forhis workforce andmaintain theirnumbers.

overrun by the men so that thedefences could be consolidated whilethe barrage protected them fromcounter-attack.

Two men, whose job it was toprovide small arms ammunition, wererequired to carry one box of 1000rounds, which a machine gun mightuse in five minutes, and they were

vulnerable on the battlefield. Monashused supply tanks and aeroplanes todeliver such ammunition, the planesdropping two boxes with parachutesfrom bomb racks. This allowed themachine guns to be used offensively.Aircraft were also used to harry theenemy by bombing gunemplacements and disrupting supply

systems in the rear, for observation toassist the artillery and by strafing(attacking ground targets from low-flying aircraft) German troops.

Monash had instituted the practiceof, in general harassing fire, artilleryfiring both smoke and gas shells. Thismeant that the Germans always puttheir gas masks on when they saw thesmoke and smelt the gas. On themorning of an attack, only smokeshells would be fired, which gave theAustralians an immediate advantagebecause they did not have to wearmasks. Smoke bombs, which wereintroduced for mortars, made itpossible to blind a single machinegun.

The most dangerous period in abattle was at the start, when the menwere concentrated; secrecy wasparamount both for surprise and toavoid a German artillery barrage. Allpreparatory movements were at nightand reconnaissance planes inspectedthe Australian positions each day toensure there were no visible changes.On the morning of the attack at Hamel,the day started normally withharassing fire beginning at 03:02 tomask the noise of the advancing tankswith which the infantry appeared out ofthe mist and surprised the Germans.Later, Monash used patrolling heavybombers to mask the noise of thetanks.

Monash’s method of warfaredepended on a continuous stream ofinformation from the battlefield to thecentral command. Reconnaissanceaircraft were used to note the positionof the foremost troops and theinformation was recorded anddropped, using a weighted colouredstreamer, near headquarters where itwas collected and delivered within atotal time of 10 minutes.

In a renowned simile Monashexplained:

A perfected modern battle plan is likenothing so much as a score for anorchestral composition, where the variousarms an

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