chemistryPlan draft document highlighting Australia’s current position ... ph 0419 107 143 [email protected] PRODUCTION Co ntrol Publications Pty Ltd Ph/fax (03) 9500 0015/0255

• A new mindset about mining metals • Game thinking and good chemistry apps • Facing commercial challenges of early career research

in Australiachemistry

September 2015

chemistry

Chemical pathways to perfectchocolate

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news & research6 News13 Research42 Cryptic chemistry42 Events

members4 From the President28 Obituary

views & reviews5 Your say29 Books32 Technology & innovation34 Pondering petrichor36 Economics38 Plants & soils39 Grapevine40 Education41 Letter from Melbourne

20 Groundbreaking work: smart ways to seek metals. Part IWe need to look at metals in new ways and in new places, to see whatcommodities are there for the taking, says Dave Sammut.

24 A new element in teaching: using apps in chemistryeducationUni students are rarely without a tablet or smartphone. Although they candistract from learning, mobile devices can be useful educational resources.

Chocolate: a moveable feastThe next time you snap a piece off a chocolate bar for afternoon tea, considerthe polymorphic behaviour of cocoa butter.

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The inaugural Decadal Plan for Chemistry (being coordinated bythe Australian Academy of Science’s National Committee ofChemistry in partnership with RACI) has been underway for morethan a year. The initial phase involved an enormous amount ofdata collection throughout 2014. Twenty-six open ‘Town Hall’meetings were held all over Australia, which were very wellattended by RACI members. In addition, many one-on-oneinterviews and online surveys were held. All sectors of thechemistry community have been involved. This data has now beenassembled and distilled, and a draft version of the Decadal Planfor Chemistry is available for public comment (http://chemistrydecadalplan.org.au). It’s vital that we have as muchfeedback on this document as possible so the more people whoare able to read and comment on it, the better it will be.

The Decadal Plan literally maps out the road ahead forchemistry as a discipline over the next 10 years, and makingaccurate predictions of where chemistry will be and how it will fitinto the world in 2025 is more difficult than ever, given the rapidtechnological, scientific, economic and political changes that weare experiencing. The Decadal Plan must capture what is mostimportant to us all and deliver strategies that will lead tosignificant improvements across all sectors. The Decadal Planworking group is only a very small subset of the Australianchemistry community. We don’t have all the answers andsolutions. We need your input!

Many findings came out of the consultation process. One of theclearest messages is the disconnection between many parts of thechemistry community such as academia and industry, and thesecondary and tertiary education interface. Another issue is thegeneral lack of awareness in society (and in politics) of whatchemistry is and how reliant we have been on chemistryinnovation over recent decades and over centuries before that.Getting our message out to the public is paramount and thechemistry community must take responsibility for this; it isn’tgood enough to say that ‘nobody understands what we do.’

The timeline of the Decadal Plan clearly spans that of severalfuture terms of government, so we dearly need a bipartisanagreement between the major political parties on how chemistry(and science for that matter) relate to our education system, andinnovation (and economic prosperity). A long-term policy is

needed that will not simply be reversed by an incoming newgovernment. There are some sobering statistics in the DecadalPlan draft document highlighting Australia’s current positionamong OECD nations on the score of innovation and alsoinvestment by industry in academic research. Australia is, on manyof these measures, ‘holding up the table’. There is no reason whywe should be in this position unless we accept (and I don’t) thatAustralia is incapable of doing things as well if not better thancomparable OECD nations in terms of translation of chemistryinnovation into high-value technology.

The final (and most important) issue that remains, when theDecadal Plan for Chemistry document is tabled, is implementation.How can we ensure that the recommendations from this report aretaken up by policymakers and the public? There are manyexamples of similar documents gathering dust after being written.We cannot repeat the same mistakes here.

RACI is obviously the largest representative organisation forchemistry in Australia and it will be doing all it can tocommunicate the virtues of this report to those who can helpimplement these recommendations. At the July 2015 SpecialGeneral Meeting of RACI, the Constitutional changes proposed bythe Board were overwhelmingly accepted. A key change was theability to recruit up to two Board members from outside thechemistry sector. RACI, an Institute, restricts full membership(with voting rights) to those who hold a recognised chemistrydegree (or equivalent). This formerly excluded the involvement ofanyone on the RACI Board who did not have a formal chemistrytertiary qualification, yet there are many areas, beyond knowledgeof chemistry, that require the RACI Board to make informed andstrategic decisions. This restriction is now gone and the Boardmay appoint up to two non-members (non-chemists) who bringexpertise that may not available to the Board at that time. Thiswill be an exciting opportunity for the Board and may also proveimportant in the communication and implementation of theinaugural Decadal Plan for Chemistry.

EDITOR Sally WoollettPh (03) 5623 [email protected]

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

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PRESIDENT Paul Bernhardt FRACI CChem

MANAGEMENT COMMITTEESam Adeloju (Chair) [email protected], Michael Gardiner, Helmut Hügel, Alan Jones, Amanda Saunders, Colin Scholes, Madeleine Schultz, Julia Stuthe, Richard Thwaites, Curt Wentrup

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

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


Chemistry in Australia4 | September 2015

from the raci

From the President

Paul Bernhardt FRACI CChem ([email protected]) is RACI President.

your say

Chemistry in Australia 5|September 2015

Neville CurreyI read the June 2015 issue with interest. Ian Rae’s columnconcerning little-known chemist Neville B. Currey was intriguingand I decided to do a little further searching of my own usingtrove.nla.gov.au. Trove is a valuable resource for lovers of early20th-century Australian history.

Several entries indicate that he was a businessman andmanufacturing chemist, active in the social scene of inter-warMelbourne. Exactly what business he was in is less clear.

It appears that he ran a business using his own name andalso the ‘Twilight Shoe Dressings Pty Ltd’ company. In 1926, heapplied for a trade mark, number 43 930, covering Twilight as a‘cleaner for evening shoes and all other forms of footwear’,which was granted and renewed up to 2006, so perhaps a readermay recall the brand. In 1930, another application number54 498 was made regarding ‘heel pads for boots and shoes madeof velvet, rubber solution and cotton, in which velvet (orcotton) predominates. A poster design displaying a comfortshoe grip’. In 1935, he exported a case of shoe cleaner to HongKong, presumably to build his business.

It seems reasonable to conclude that Currey’s principalbusiness was boot and shoe polish maker with a sideline inshoe accessories, rather than as a professional chemist of thestature of Professor Masson and the others mentioned by Ian.

Bruce Leary FRACI Hon Life Member

CSIRO’s futureIan Maxwell’s analysis of CSIRO (July, p. 18), prompted by hismeeting with new CEO Larry Marshall, will no doubt interestmany readers of Chemistry in Australia. Ian admits to someconfusion regarding CSIRO’s role and its struggle to ‘findrelevance’. He sees a leadership seemingly desperate to makeCSIRO more profitable or at least generate enough positivepublicity to secure government funding. He wonders about itscomplicated structure and whether all parts suit the Australia of2015. He suspects that future commercial income growth willbe problematic as the market approaches saturation. Mostsignificantly, he questions the emphasis on science when thereal growth is in engineering and IT. According to Ian, LarryMarshall is still thinking about future strategy.

Yes, CSIRO can be confusing. It’s old and big and carries lotsof baggage. The National Flagship structure conveys its currentfocus easily but also suggests rigidity and excessive coverage.But I spent 30 years in CSIRO and am confident that it still hasa role. Larry’s challenge is to inject an agile element whileensuring the stable framework that R&D, a notoriously long-term human activity, requires.

CSIRO’s strategic purpose should remain as the creation ofnew knowledge. The tests it should apply are deceptivelysimple. Does Australia need the new knowledge? Can CSIROacquire and exploit that knowledge? Is it all worth the cost?But these are hard questions to answer. The results will befuzzy. Judgements must be made. That’s the nature of thebusiness.

Structure follows strategy. Predetermining CSIRO’s fields ofactivity through structures like flagships, or prejudging them asscientific or technological or engineering, can reduce flexibilityand responsiveness, though I do acknowledge the need forfocus.

Ian describes Larry Marshall as a serial entrepreneur, venturecapitalist and private investor. That’s a useful background forgenerating the discipline needed to guide CSIRO’s future.Indeed, he may well see every CSIRO project as a kind ofpersonal investment, a risk-laden venture for the funding hecontrols or can gather. That would be a great starting point butextremely difficult to apply consistently. I wish him luck.

Tom Biegler FTSE FRACI CChem

New coal chemistryI greatly enjoyed Duncan Seddon’s ‘New coal chemistry’ (July, p. 36). He gives interesting perspectives on the production ofchemicals from synthesis gas and related issues, includinggreenhouse gas emissions.

Duncan mentions the release of carbon dioxide from theproduction of hydrocarbons from coal. This of course is due tothe water gas shift reaction, to which he refers and for whichhe gives the chemical equation. Carbon dioxide fromgasification can be sequestrated, as is currently happening on atrial basis in Alberta, Canada. There, synthesis gas is made byunderground gasification of coal and nearby geological sites forsequestration are being identified (Olateju B., Kumar A. Appl.Energ. 2013, vol. 111, pp. 428–40).

I wish also to draw attention to possible substitution ofbiomass for coal in making the synthesis gas, to whateverextent local availability of biomass makes this feasible. Carbondioxide removed from synthesis gas so made would, like thecarbon dioxide from combustion of biomass fuels, notcontribute to the carbon dioxide level of the atmosphere. Itwould simply be put back where it came from, which is thebasis of carbon neutrality of fuels. It also applies to synthesisgas.

Clifford Jones FRACI CChem

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

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

news

6 | September 2015Chemistry in Australia

Action taken by the National Measurement Institute (NMI) willkeep Australia on time with the rest of the world. You’d beforgiven for not noticing, but every second counts in today’sglobal markets.

At precisely 9:59:59 am (AEST) on 1 July, measurementscientists at the NMI added an extra second to their super-accurate atomic clocks, to account for a very slight slowing inEarth’s rotation. In fact, it’s thought that four billion years ago, aday on the planet lasted only 22 hours.

Observing this leap second at NMI’s Lindfield facility inSydney, Parliamentary Secretary for Industry and Science KarenAndrews said this was another example of how science andtechnology underpin daily life.

For more than a decade, NMI has supplied accurate timingsystems that have linked the atomic reference clocks to industry,defence, government, law enforcement, telecommunications andfinancial markets.

The SI definition of the second is ‘… the duration of9 192631770periods of the radiation corresponding to thetransition between two hyperfine levels of the ground state of the133Cs atom’. NMI’s four commercial primary caesium frequencystandards work to this definition.

The need for a leap second is determined by the InternationalEarth Rotation and Reference Systems Services, which keep trackof time by comparing the Earth’s rotation against an internationalnetwork of atomic clocks. The leap second keeps the timedifference between the two ‘clocks’ to below 0.9 seconds.

The leap second is introduced to the world’s atomic clocks inunison, immediately before midnight on 30 June UTC(Coordinated Universal Time).DEPARTMENT OF INDUSTRY AND SCIENCE

iStockphoto/agsandrew

Leap second keepsAustralia on time

Canberra researcher’s medicaldiscovery heading for marketUS chemical company Strem Chemicals Inc. has signed acommercialisation agreement to market a new syntheticcatalyst developed by University of Canberra researcherAssociate Professor Ashraf Ghanem FRACI CChem that will helpmake the pharmaceutical manufacturing process more efficient.

The deal is the University of Canberra’s first intellectualproperty licence for a chemical product that will be soldworldwide.

The catalyst, discovered by Ghanem, will be useful inpharmaceutical processing, particularly in the production of thedrug Ritalin (methylphenidate), which is used in the treatmentof attention deficit disorder and attention deficit hyperactivedisorder.

Ghanem explained that this synthetic catalyst produces achemical reaction that allows certain molecules to be extractedwith a very high level of purity, reducing the need foradditional processing and diminishing the risk of unintendedside effects.

‘This is important because it can help produce moreeffective pharmaceuticals quickly, at a reduced cost andhopefully in the future that means people are paying less forthe medication they need,’ he said.

Ghanem said the path to commercialising his discovery hasbeen hard work, but rewarding now that his research isdelivering a beneficial outcome to the pharmaceutical field,with great flow-on effects for those depending on theirmedication.

Molecular structure of bis(THF) adduct of the catalysts tRh2(S-PTTL)4. Space-filling representation: (a) top view, (b) bottom view, (c) and (d) side.UNIVERSITY OF CANBERRA

As astronauts embark on increasingly ambitious space missions,scientists have to determine how to keep them healthy for longerperiods far from Earth. That entails assuring the air they breatheand the water they drink are safe – not an easy task given theirisolated locations. But scientists are now reporting in AnalyticalChemistry (doi: 10.1021/acs.analchem.5b00055) a new method tomonitor the quality of both in real time with one system.

Current options for testing air and water for contaminants,including microbes and radiation, require collecting samplesand sending them back to Earth for analysis. But for longmissions – aboard the International Space Station, for example– this approach could take six months before the astronautshave their results. The International Space Station is also

equipped with some real-time hardware for detecting unwantedsubstances, but it has limitations. Facundo M. Fernández,William T. Wallace and colleagues wanted to come up with asystem to conduct real-time, sensitive monitoring.

The researchers outfitted a kind of air quality monitoralready used aboard space missions with a device that canvaporise water samples, turning its contents and anycontaminants, into a gas. The gas can then enter the air qualitymonitor for analysis. Astronauts could also use the sameequipment, with a modification, for testing the air. The teamsays the system could be used in space or for remote locationshere on Earth. AMERICAN CHEMICAL SOCIETY


Keeping astronauts in space longerwith better air and water

Currently, ISS residents such as European Space Agency astronaut Samantha Cristoforetti must collect air and water samples and sendthem back to Earth.

NASA

news


GO Resources and CSIRO sign safflower deal GO Resources Pty Ltd – a new Australian clean technologycompany – has entered into an exclusive worldwide licence withCSIRO to commercialise its technology to produce super-higholeic safflower oil for the high-value industrial oil market.

Super-high oleic oil represents a step in the development ofplant-sourced alternatives to petroleum-based raw materialsand traditional sources of oleic oils. GO Resources’ super-higholeic safflower oil will have direct applications as a raw materialfor bio-based feedstock, with industrial applications includinglubricants, solvents, cosmetics, plastic additives, resins andpolymers, biofuels, coatings, paints and inks.

The estimated value of the worldwide industrial oils andoleochemical market is in excess of $30 billion a year.

GO Resources will give Australian farmers access to safflowerthat produce very high levels of oleic acid (>92%) in the oilextracted from the seed. At the same time, there is a reductionin the levels of less-desirable saturated and polyunsaturatedfats. This level of oleic acid is currently the highest of anycommercially available plant-derived oil worldwide. Oleic acid isa naturally occurring and industrially significant fatty acid,traditionally sourced at much lower levels from palm, tallow andoilseeds.

GO Resources expects Australian commercial production tobegin in 2018 and seeks to expand Australian and internationalopportunities over time.GO RESOURCES

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Researchers have discovered how anabrupt global warming event triggered ahighly corrosive deep-water current to flowthrough the North Atlantic Ocean55million years ago.

The findings, published in NatureGeoscience (doi: 10.1038/ngeo2430), solvea long-running scientific mystery that alsohas profound implications for thesensitivity of our current climate to carbondioxide emissions.

The researchers explored theacidification of the ocean that occurredduring the Paleocene Eocene ThermalMaximum (PETM) period when Earthwarmed 5°C in response to a rapid rise inCO2 in the atmosphere and one of thelargest mass extinctions occurred in thedeep ocean.

This period is considered to closelyresemble the scenario of global warmingwe are experiencing today.

‘There has been a longstanding mysteryabout why ocean acidification caused byrising atmospheric CO2 during the PETMwas so much worse in the Atlanticcompared to the rest of the world’s oceans,’said lead author from the ARC Centre ofExcellence for Climate System Science, Ms Kaitlin Alexander.

‘Our research suggests the shape of theocean basins and changes to oceancurrents played a key role in thisdifference. Understanding how this eventoccurred may help other researchers tobetter estimate the sensitivity of ourclimate to increasing CO2.’

To get their results, the researchersrecreated the ocean basins and landmasses of 55million years ago in a globalclimate model.

At this time, there was a ridge on theocean floor between the North and SouthAtlantic that separated the deep water inthe North Atlantic from the rest of theworld’s oceans. It has been described asbeing like a giant bathtub on the oceanfloor.

The simulations showed this ‘bathtub’filled with extremely corrosive water from

the Arctic Ocean, mixed with dense saltywater from the Tethys Ocean and sank tothe North Atlantic seafloor where itaccumulated. The sediment in this areaindicates the water was so corrosive that itdissolved all the calcium carbonateproduced by organisms that settled on theocean floor.

When Earth warmed as a result of arapid increase in atmospheric CO2, iteventually warmed this corrosive bottomwater. As this corrosive water warmed, itbecame less dense and was replaced bydenser water sinking from above.

The corrosive deep water was pushedup and spilled over the edge of the giant‘bathtub’ and flowed down into the SouthAtlantic.

Determining how the event occurredalso has important implications for today’sclimate and how it might warm in responseto increases in atmospheric CO2. This isbecause if the high amount of acidificationin the Atlantic Ocean was an indication ofglobal acidification, then it would suggestenormous amounts of CO2 are necessary toincrease temperatures by 5°C.

However, these latest findings suggestthat other factors made the Atlanticbottom water more corrosive than in otherocean basins.

‘We now understand why thedissolution of sediments in the AtlanticOcean was different from records in otherocean basins,’ said fellow author of thepaper Associate Professor Katrin Meissnerfrom the Climate Change Research Centreat the University of New South Wales.

‘Using all sediments combined, we cannow estimate that the amount ofgreenhouse gases released into theatmosphere causing a temperature rise of5°C was around the CO2 equivalent of7000–10000gigatons of carbon. This issimilar to the amount of carbon availablein fossil fuel reservoirs today.’

The big difference between the PETMand the alteration to the current climate isthe speed of the change, said Alexander.

‘Today we are emitting CO2 into theatmosphere ten times faster than the rateof natural CO2 emissions during the PETM,’Alexander said.

‘If we continue as we are, we will seethe same temperature increase that took afew thousand years during the PETM occurin just a few hundred years. This is anorder of magnitude faster and likely tohave profound impacts on the climatesystem.’UNIVERSITY OF NEW SOUTH WALES

Solution to corrosive ocean mysterypoints to future climate

In this bathymetric image, surface currents are yellow, deep currents are purple, shadingshows the shape of the ocean floor.

news


The University of Otago/NIWA Research Centre for Oceanographyhas turned a brand-new shipping container into a cleanlaboratory for use on board research vessels – keeping NewZealand on the map internationally for research on marinebiogeochemical cycles of trace elements.

The Centre, which was established in 1996 by a memorandumof understanding signed between NIWA and the University ofOtago, won the Prime Minister’s Science Prize in 2011.

Centre Director Research Associate Professor Sylvia Sander ofChemistry says the Class 100 clean laboratory was fundedthrough the Prime Minister’s Science Prize money.

It recently finished its maiden voyage – a three-weeksampling trip on board the NIWA RV Tangaroa with Dr RobMiddag – taking samples from the Hauraki Gulf and over theshelf to the east as part of a Marsden-funded research project.

Sander says while the Centre has used modified shippingcontainers as onboard laboratories previously, this is the firsttime it has had a new container fitted out professionally and forthis purpose.

‘The benefits are huge, because now we can be absolutelysure our samples aren’t becoming contaminated. We spendweeks cleaning our bottles in acid before the trip, and thensome intense weeks working on board. We don’t want to findthe samples are tainted.’

Preventing contamination is as vital as it is difficult, shesaid. Trace metals are present in the water in such minute

amounts, that any particle from the ship, the container or aircould jeopardise the results. The new container is internallytotally metal-free and the air is fully HEPA-filtered, removing allairborne particles.

Sander said the container laboratory keeps the University ofOtago/NIWA Research Centre for Oceanography at the samelevel as its contemporaries across the globe.

‘This is especially important as we are a partner in theinternational GEOTRACES research program, which aims toimprove understanding of biogeochemical cycles in the oceans,’she said. ‘By mapping the distribution of trace elements andisotopes in the ocean, we can begin to understand theprocesses controlling this distribution – and to establish thesensitivity of these distributions to changing environmentalconditions, such as climate change and ocean acidification. Allresults are rigorously quality controlled and we would not wantto embarrass ourselves with results from contaminated samples.’

The container will be used for coastal as well as open oceanwork on the micronutrients iron, copper and zinc, but also mostother trace elements.

One of the next missions will be to the Kermadec Arc in2016/17 on the German RV SONNE, where the Otago group isleading the trace metal sampling and analysis. Several othervoyages including work in the Southern Ocean and Antarctic arealso likely.OTAGO BULLETIN

On-board laboratory for Otago research centre

The new Class 100 clean laboratory is liftedonto the RV Tangaroa for its maiden voyage.

September 2015

Scientists from the Moscow Institute of Physics and Technology (MIPT) Departmentof Molecular and Chemical Physics have for the first time described the behaviourof electrons in a previously unstudied analogue of graphene, two-dimensionalniobium telluride. In the process, they uncovered the nature of two-dimensionalityeffects on conducting properties. These findings will help in the creation of futureflat and flexible electronic devices.

In recent decades, physicists have been actively studying so-called two-dimensional materials. Andre Geim and Konstantin Novoselov received the NobelPrize for their research on graphene. The properties of such materials, which canbe described as sheets a few atoms thick, strongly differ from their three-dimensional analogues. For example, graphene is transparent, conducts currentbetter than copper and has good thermal conductivity. Scientists believe thatother types of two-dimensional materials may possess even more exotic properties.

A group of scientists from Russia and the US recently conducted research on theproperties of the crystals of one such material, Nb3SiTe6. In their structure, thecrystals resemble sandwiches with a thickness of three atoms (around 4 Å): a layerof tellurium, a layer of niobium mixed with silicon atoms and then another layer oftellurium. This substance belongs to a class of materials known asdichalcogenides, which many scientists view as promising two-dimensionalsemiconductors.

The scientists synthesised Nb3SiTe6 crystals. They then separated them into two-dimensional layers, taking samples for further analysis by transmission electronmicroscopy, X-ray crystal analysis and other methods. Their goal was to investigateelectron–phonon interaction changes in two-dimensional substances.

Quasi particles, quanta of crystal lattice oscillations, are called phonons.Physicists introduced the concept of phonons because it helped simplify thedescription of processes in crystals, and tracking of electron–phonon interaction isfundamentally important for description of the different conducting properties inmatter.

‘We developed a theory that predicts that electron-phonon interaction issuppressed due to dimensional effects in two-dimensional material. In otherwords, these materials obstruct the flow of electrons to a lesser extent,’ said PavelSorokin, a co-author of the study, from MIPT. US colleagues confirmed thisprediction in related experiments.

Full details of the research can be found in an article published in NaturePhysics (doi: 10.1038/NPHYS3321).MOSCOW INSTITUTE OF PHYSICS AND TECHNOLOGY

Transition from three to two dimensionsincreases conduction

The crystal structureof Nb3SiTe6.

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research


The heterogeneously catalysed transformation of synthesis gas(CO/H2) to hydrocarbons and oxygenates, via theFischer−Tropsch (F−T) process, is carried out on an industrialscale. However, such transformations are very energy intensiveand offer low product selectivity. Accordingly, considerableefforts are currently directed towards developing homogeneousd-block metal catalysts that enhance F−T selectivity. Until now,such ‘F−T-like’ reactivity has not been observed for s-blockmetal compounds. In a recent paper, Professor Cameron Jonesof Monash University and his collaborators (Maron, Toulouse;Stasch, Monash) have achieved this for the first time(Lalrempuia R., Kefalidis C.E., Bonyhady S.J., Schwarze B.,Maron L., Stasch A., Jones C. J. Am. Chem. Soc. 2015, 137,8944–7). They showed that the formal hydrogenation ofmagnesium(I) dimers in the presence of CO leads to C−C bond-forming reactions and the selective formation of unprecedentedcyclopropanetriolate or ethenediolate complexes, depending onthe steric bulk of the magnesium reactant employed. A

computational investigation showed the mechanisms of thereactions to be very similar to those previously proposed forrelated processes involving f-block metal hydride compounds.This study highlights the potential of cheap and non-toxicmagnesium compounds for transforming feedstock gases tovalue-added oxygenate products.

Magnesium gets its snout in the Tropsch

A versatile two-step modular process forsite-specific antibody modification andconjugation has been reported inAngewandte Chemie (Alt K.,Paterson B.M., Westein E., Rudd S.E.,Poniger S.S., Jagdale S., Ardipradja K.,Connell T.U., Krippner G.Y., Nair A.K.N.,Wang X., Tochon-Danguy H.J.,Donnelly P.S., Peter K., Hagemeyer C.E.Angew. Chem. Int. Ed. 2015, 54, 7515–19). In the first step, enzymaticbioconjugation with the transpeptidasesortase A is used to incorporate astrained cyclooctyne functional group

into an antibody. Functional moleculesbearing an azide functional group arethen added by an azide–alkynecycloaddition click reaction thatcompletes the site-specificbioconjugation. The team, led byAssociate Professor Paul Donnelly and DrBrett Paterson from the University ofMelbourne and Professor ChristophHagemeyer, Professor Karlheinz Peter andDr Karen Alt from Baker IDI,demonstrated the versatility of the two-step approach by selectivelyincorporating fluorescent dyes and a

positron-emitting copper-64 radiotracerinto a single-chain antibody fragmentthat targets activated platelets. Theresulting constructs could be used forfluorescence or positron-emissiontomography imaging of activatedplatelets and thrombi. This approachcould be readily adapted to incorporate alarge array of tailor-made functionalgroups using reliable click chemistrywhile preserving the activity of theantibody or other sensitive biologicalmacromolecules.

Clicking imaging probes on to antibodies

New zinc supplement The chemistry of compounds containingunsupported post-transition metal−metalbonds has rapidly expanded since thelandmark preparation of the first zinc(I)dimer, Cp*ZnZnCp* (Cp* = C5Me5

–), in2004. Subsequent computational studieshave suggested that extended metalchain analogues of this system would bethermodynamically unstable, and hencenot synthetically accessible. The team ofProfessor Cameron Jones at MonashUniversity has turned this view on itshead, with the synthesis of the firstmixed-valence, two-coordinate, linear tri-zinc complex, L*ZnZnZnL* (Hicks J.,Underhill E.J., Kefalidis C.E., Maron L.,Jones C. Angew. Chem. Int. Ed. 2015,doi: 10.1002/anie.201504818). Thiscompound is kinetically stabilised by a‘super bulky’ amide ligand developed bythe group. It was accessed by firstpreparing a formally zinc(0) complex byreduction of L*ZnBr with a magnesium(I)

dimer, also developed at Monash. Thiszinc(0) species contains the first exampleof a Zn−Mg bond, and was used as an‘inorganic Grignard reagent’ in itsreaction with ZnBr2, yielding the targettri-zinc complex. Computational studiesreveal that this compound is best viewed

as a covalently bonded [Zn3]2+ dication

that is stabilised by two anionic amideligands. The Jones team is currentlyexploring the reactivity of Zn0/I

compounds towards small-moleculeactivation processes.

research


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

Better health can be achieved through personalised medicine.In particular, low-cost and easy-to-use point-of-care devicesthat provide quick and accurate results for on-site therapeuticdrug monitoring would help clinicians to adjust dosingregimens for individual patients. An entirely new way toextract, isolate and concentrate drugs from body fluids suitablefor disposable point-of-care devices has recently beendeveloped by Aliaa Shallan, a PhD student from the Breadmoreand Guijt group in the Australian Centre for Research onSeparation Science (ACROSS) at the University of Tasmania(Shallan A.I., Guijt R.M., Breadmore M.C. Angew. Chem. Int. Ed.2015, 54, 7359–62). An electrokinetic size and mobility trapbased on two sequential nanojunctions with different poresizes is used to capture pharmaceutical targets prior to a rapidelectrophoretic separation for identification and quantitation.Levels of the antibiotic ampicillin were determined in 5 mindirectly from 40 μL of whole blood. The linear-response regimefor the device of 2.5–20 μg/mL covers the recommended levelsfor treating sepsis, a critical condition with 30–50% mortalityfor which treatment is complicated by unpredictable drug

levels. This new method is simple, applicable to a wide range ofpharmaceuticals, and compatible with low-costmicrofabrication, and hence has the potential to bringtherapeutic drug monitoring within the reach of many.

New approach to on-site therapeutic drug monitoring

The August issue contains several papers and accounts by the2014 RACI award winners announced in Adelaide last December.

Dave Winkler (CSIRO, Clayton), the winner of the AdrienAlbert Award for medicinal chemistry, describes newcomputational modelling tools capable of exploring largechemical spaces, extracting meaning from large data sets,designing new bioactive molecules, and making predictive,quantitative models of the properties of materials for use intherapeutic and regenerative medicine.

Martin Banwell (ANU), winner of the H.G. Smith MemorialAward, reports on the use of PdII-catalysed intramolecularAlder-ene (IMAE) reactions of C-, N- and O-linked 1,6-enyne-type compounds in the preparation of various carbo- andhetero-cyclic compounds, including total syntheses of thealkaloids hamayne and galanthamine (see scheme).

Jeff Reimers (University of Technology Sydney), winner ofthe Physical Chemistry Division Medal, elaborates the conceptof reaction coordinate – a well-known quantity used to definethe critical motions in chemical reactions, but many othermotions – often ignored – always accompany it. Spectralmeasurements that one may assume are dominated by thereaction coordinate could instead be dominated by other,accompanying modes. The assignment of the visible absorptionspectrum of chlorophyll-a was debated for 50 years, withprofound consequences for the understanding of light-

harvesting. InReimers’ newassignment, thecentrepiece is thedetermination of thereaction coordinatefor a previouslyunrecognisedphotochemicalprocess. The notionthat spectroscopyand reactivity areclosely connected

follows from Hush’s adiabatic theory of electron-transferreactions. These ideas are applied to isomerisations,hybridisation, aromaticity, hydrogen bonding and understandingwhy the properties of first-row molecules such as NH3 (bondangle 108°) are so different from those of PH3–BiH3 (bondangles 90–93°). In the new approach, all chemical processesare described using the same theory.

Andreas Stasch(Monash), winner ofthe OrganometallicChemistry Award,reviews the synthesisand characterisationof well-defined alkalimetal hydridecomplexes and theprinciples governingtheir generation and stabilisation. The properties of the familiaralkali metal hydrides such as LiH and NaH are dominated byionic NaCl-type structures. Stable, soluble and well-defined LiHand NaH complexes are obtained by metathesis and b-hydrideelimination reactions and by using bulky ligands coordinatingto multiple metal ions. The structure of (DipNPPh2)4Li8H4, whereDip = 2,6-iPr2C6H3, is shown. The reactivities of these novelhydride complexes are higher than, and different from, those ofthe familiar ionic solids.

David Lewis(Flinders), winnerof the AppliedResearch Award,used silicananoparticles toinvestigate theeffect of surfaceroughness ofhydrophobic filmson contact angles and sliding angles for water droplets.Superhydrophobic materials are of much interest due to theirself-cleaning, antifouling, stain-resistant and ice-repellentproperties. On a rough surface, the droplet can reside in one oftwo states, either resting on the surface summits, with smallpockets of air underneath, or filling the grooves and thusgaining direct contact with the solid substrate surface asindicated in the figure. The ‘Cassie state’ (left) is desirable inorder to achieve low sliding angles because a smaller contactarea results in less adhesion. The water contact angle increasesfrom 105° for a smooth surface to 140° for the roughenedsurfaces, and it then remained approximately constant for allnanoparticle-roughened surfaces.

Additional papers by Chris McErlean (University of Sydney),winner of the Athel Beckwith Lectureship (chemistry of thesynthetic strigolactone mimic GR24), Anthony O’Mullane (QUT),recipient of an RACI Citation (electrochemical restructuring ofcopper surfaces using organic additives and its effect on theelectrocatalytic reduction of nitrate ions), and this author,winner of the Arthur J. Birch Medal (acetylenes from aldehydes)complete the awards section.


Aust J Chem

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

Chocolate. Once reservedfor emperors and royalty,this edible luxury is nowwithin the reach of most

people. Legend has it that Aztecwarrior Montezuma demanded50 chalices of choclatl – drinkingchocolate spiced with annatto (anatural colouring agent), which wouldstain the drinker’s lips blood-red –before retiring with his harem of wives.(No word on what his wives thought ofthe brew.)

Chocolate is made from cacaobeans, which are obtained from thepods of Theobroma cacao, a tree thatgrows 20° above and below theequator. When ripe, each pod is slicedopen and its mucilaginous fruit are

removed and fermented, a processthat converts the fruit sugars into asoup of ethanol, acetic acid and lacticacid. At this point, the cacao bean isnot particularly tasty, but it containsflavour precursors with the potential toexpress the chocolate flavour thatmany of us seek. Next, the resultingcacao beans – a misnomer, asbotanically, they’re actually seeds – aredried to a maximum of 8% humidity,and then shipped to a chocolatemaker.

The chocolate maker winnows thebeans to remove their papery husks,and roasts them to transform flavourprecursors into full-blown flavours. TheMaillard reaction creates roastypyrazines, floral oxazoles, and even


Chocolate

A moveable feastBY EAGRANIE YUH

The next time yousnap a piece off achocolate bar forafternoon tea,consider thepolymorphicbehaviour of cocoabutter.

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vegetal pyridines. Other pathways canresult in fruity esters, nutty furans,butterscotchy diacetyls, and more.Depending on the roastingtemperature, acetic and lactic acidscan persist, as do some of the bitteralkaloids that provide chocolate’smuch-touted health benefits.

Once roasted, the cacao beans areground into a paste called cocoaliquor, cocoa mass, or unsweetenedchocolate. Subjected to temperatureand pressure, the paste can beseparated into its two constituentcomponents – cocoa solids and cocoabutter. Cocoa solids are the dryportion of the cocoa bean, much likecocoa powder used in baking. Cocoabutter is a solid fat at roomtemperature and melts just belowbody temperature.

To make high-quality darkchocolate, chocolate makers combinecocoa liquor and sugar, often addingvanilla and lecithin (an emulsifier). Milkchocolate contains the same, plus milkpowder. White chocolate contains nococoa solids, and is a combination ofcocoa butter, sugar and milk powder.A good test for your chocolate’s qualityis a quick scan of the ingredients list: ifsugar comes first, you are buyingcandy, not chocolate. Another cue isthe presence of vegetable fats, whichoffer cheap substitute for the moreexpensive cocoa butter.

In fact, it’s cocoa butter that isresponsible for much of the pleasureassociated with eating chocolate. Inaddition to creating chocolate’sluxurious melt, cocoa butter providesa vehicle for all of chocolate’sestimated 600 flavour molecules toreach our taste and olfactoryreceptors.

Like other fats, cocoa butter is amixture of triglycerides. The primaryfatty acid components are oleic acid,an 18-carbon chain with one cis-double bond; stearic acid, a saturated18-carbon chain; and palmitic acid, asaturated 16-carbon chain. Traceamounts of linoleic acid and arachidicacid can also be found, but typically

comprise less than 5% of cocoabutter’s make-up. An estimated 80%of cocoa butter is of the formsaturated–unsaturated–saturated (SUS)and 5–20% is saturated–unsaturated–unsaturated (SUU). A very minorproportion is composed of the all-saturated (SSS) or all-unsaturatedtriglyceride (UUU).

The relatively simple composition ofcocoa butter belies the complexity ofits crystallisation behaviour. In therealm of edibles, sodium chloride isyour reliable, stalwart friend – barringthe introduction of any interlopingcations, it will always adopt a simplecubic crystal structure. Cocoa butter,then, is a rebellious and rambunctiousstepchild, a polymorphic substancethat can adopt up to six crystallineforms – the melting points of whichnearly overlap. These are, mostoriginally, labelled form I (the leaststable, with a melting point of 16–18ºC) through to form VI (the most stable, with a melting point of 34–36ºC).

Six crystalline forms may bepossible, but only one is desirable:form V, which offers the shiny andsnappy chocolate that is so readilymoulded into bars, bonbons andbarks. The process of obtaining form Vcrystals is called tempering.

The first step to tempering is to heatchocolate over a double boiler, to meltany and all cocoa butter crystals thatmay be present. This may seemcounterintuitive, given that commercialchocolate is already tempered, butunless you are serving your guestschocolate chips, melting is a must. Inculinary school, I was taught to heatthe chocolate to at least 40ºC toprovide a blank slate of liquidchocolate. (There is nothing magicalabout 40ºC, except that it is safelyabove the melting point of all cocoabutter crystals but not so hot that thechocolate will burn.)

Next, transfer one-third of thechocolate to a marble countertop andspread it thinly using a long, offsetspatula. Using a spackle knife (yes, the

kind you would use on a wall), scrapeup the chocolate, then repeat theprocess of spreading and scrapinguntil the chocolate thickens andbecomes slightly pasty, like a nutbutter. Heat transfer from the chocolateto the marble speeds cooling,encouraging the formation of the lessstable crystal forms I and II.Conveniently, these crystals are highlyunstable; form I crystals quickly giveway to form II, which rearrange toform III, and so forth.


In addition tocreating chocolate’sluxurious melt,cocoa butterprovides a vehiclefor all of chocolate’sestimated600 flavourmolecules to reachour taste andolfactory receptors.

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Next, add the thickened chocolateback to the main bowl and stir toincorporate. The crystals created bytable-cooling will propagate throughthe bulk chocolate. Even still, thechocolate will likely be a muddle ofcrystal forms I–V, with its exactcomposition depending on itstemperature and the extent of mixing.(Form VI crystals are formed by asolid–solid rearrangement, and are notobtained from liquid chocolate.)

Finally, re-heat the chocolate to atemperature of 30–32ºC. Thistemperature range is above themelting point of the crystal forms I–IV,but below the melting point of theform V crystal. In short: all the unstablecrystals melt, and only form V crystalsremain. Further stirring and time willencourage propagation of the form Vcrystals through the liquid chocolate,providing you with a bowl of temperedchocolate.

However, as I have learned fromexperience, tempering requires morethan just cycles of heating and cooling.French chefs in towering paper hatstaught me a mnemonic for tempering:TMT, or temperature, movement andtime. Temperature, as we have seen,controls the types of cocoa buttercrystals. Movement and time, however,are equally important. Within the liquidchocolate, fat solidifies onto seedcrystals – in an ideal system, ontoform V crystals – and adopts the sameform, helping the crystals propagatethrough the bulk material. Therefore, itis important to stir the chocolate, inorder to spread the seed crystalsamong as many fat particles aspossible. And while the conversionfrom forms I and II crystals is quiterapid, form V crystals are the slowestto form. Therefore, you must allow timefor the form V crystals to make theirway through the bulk chocolate.

There are other methods fortempering chocolate. The methoddescribed above is the tabletopmethod, but the seeding method isalso widely used. With the seedingmethod, a bowl of chocolate is meltedcompletely and then seeded with asmall portion of form V crystals. Thisis typically in the form of finelychopped or grated commercialchocolate, and some companies nowoffer form V powdered cocoa butterfor this purpose. The principle issimilar to the tabletop method: melt allthe crystals, seed with form V, andhold the temperature at 30–32ºC toencourage propagation of the form Vcrystals. Most chocolate shops useindustrial tempering machines withvarious temperature-controlledcompartments and mechanisedstirrers, but the basic principles ofusing temperature, movement andtime still hold.


The complex tastes, aromas and flavours of chocolate come from a wide range ofchemical compounds.

Chocolate inevitably morphs from form V toform VI crystals. The latter is ugly, but safeto eat.

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The primary fatty acid components ofchocolate.

If this rigmarole seems excessive,consider the consequences of achocolatier not using temperedchocolate. For example, to create ahollow Santa, chocolatiers typically usepolycarbonate moulds: they fill themwith chocolate, tap out the excess andallow the chocolate to set. Here, thecrystal-packing behaviour of cocoabutter comes in very handy. Crystalforms I–IV are more loosely packedthan forms V and VI. Consequently, asproperly tempered chocolate sets, itshrinks by approximately 2% in eachdimension. This shrinkage makes iteasy for a chocolatier to remove theirproducts from a mould. Once thechocolate sets, it’s a matter of a

confident rap on the bench to dislodgeit from the mould. Pity the chocolatierwho has not used tempered chocolate –it will stick to the mould, no matter howhard they try to extricate it.

Properly tempered, plain chocolatehas very low water activity and if storedin a cool, dark place, will keep for atleast a year. Any ‘best before’ dates aremostly for enjoyment, rather than foodsafety. This is due to the slowrearrangement of form V crystals to themore stable form VI, which can result ina more brittle, less melty chocolate Thissolid–solid rearrangement occursslowly, over the course of many months.Because form VI crystals are packedmore closely than form V, the change

causes interstitial liquid cocoa butter tobe squeezed from the interior onto thesurface, resulting in a slightly yellowsheen called fat bloom. The issue isexacerbated in systems with other fats,namely milk chocolate and anythingwith nuts or nut fillings. It can also occurif chocolate is not stored properly – thatis, if it is subjected to variabletemperature or humidity. Notably, whilefat bloom looks like mould, it is not. So,go ahead – that chocolate Santa is stillsafe to eat.

Eagranie Yuh is a freelance writer and editor whoteaches people how to taste chocolate. She waspreviously an organic chemist and a chocolatier. Sheis the author of The chocolate tasting kit (HardieGrant) and lives in Vancouver, Canada. Learn more atthewelltemperedchocolatier.com.


(Top row left to right): Half-melted chocolate in a bowl. Pouring one-third of the liquid chocolate onto marble. Continuing to scrape up the chocolate. The cycles of spreading and scraping continue until the chocolate starts to thicken.(Bottom row left to right): The chocolate has thickened to a point where it can sit on the scraper and not run off; it would feel cool to touch.This is the consistency you want before adding it back to the bowl of chocolate. The different viscosities of the chocolate in the bowl (especially at about 2 o’clock) and the cooled chocolate, pooled on the spatula. Chocolate that has been heated to about 30°C. With more stirring and time, the form V crystals will propagate throughout to result in a bowlof tempered chocolate.

Almost 50 years ago, the Clubof Rome published anotorious text, Thepredicament of mankind,

which made dire predictions about thelimited availability of non-renewableresources, most particularly oil.Subsequent versions – peak oil, peakcopper, peak helium – have beendesperately overblown.

Although those predictions havebeen repeatedly wrong – failing toproperly consider advances intechnology, replacement, and supplyand demand – basic mathematics saysthat sooner or later their underlyingprinciple has to be correct. Perhapsmore critical than the absolute quantaof resources available versus thoserequired to serve the growingpopulation and per-capitaconsumption, the rate at whichresources can be gathered anddistributed is likely to become a key

factor in global geopolitics. Withscarcity comes competition. Whennations compete for resources, war istoo frequently the result.

Crude oil resources are becomingdeeper and more sour (higher sulfurcontent). Miners are increasinglyrequired to turn to deeper, lowergrade, more complex (oftenpolymetallic) resources, often in lesspolitically stable regions. Barringincremental improvements inefficiency and scale, production costsacross many metals industries arerising.

I have spent much of my careerworking on ways to improve theefficiency of metals extraction andprocessing, most particularly in step-change new technology for basemetals (copper, lead, zinc and nickel).Throughout this time, the opportunityfor any new technology has beenclosely linked to the global prices of


Smart ways to seek metals PART I

Groundbreakingwork

We need to look atmetals in new waysand in new places,to see whatcommodities arethere for the taking, says DAVE SAMMUT.

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these commodities, but not always instraightforward ways. It has often beenthat the greatest pressure to bringforward advances has been when theprices were trending downwards, andtherefore when margins were underthreat. Of course, there comes a time insuch a cycle when the innovativemoney simply dries up and allprogress slows or stops, but theunderlying message has always been‘if your new technology can get intothe bottom quartile of the industry costcurve, then it might have legs.’

Clearly, if new technology canextend the life of existing mines, if itcan rework old ground to morethoroughly exploit what has alreadybeen disturbed, then the need to opennew mines to satisfy demand isdeferred.

This is the first of a two-partdiscussion of some clever ideas in thetechnology pipeline that might oneday play their part in the global metalscycle. None is yet truly competitive,but the whole point of the supply–demand equation is that the situationwill always be fluid. As the pressuresshift, one company’s problem willbecome another’s opportunity.

Above-ground resourcesThe best form of metal resource ismetal that is already above ground. Forthis purpose, scrap recycling is athoroughly established ideal. Metalliclead, for example, is one of the mostrecycled metals on Earth, far morethan even copper or aluminium.According to the International LeadAssociation, more lead is recycledeach year than is mined, and usedlead–acid batteries are ‘the world’smost recycled consumer product’, atnearly 100% in North America andEurope.

Reworking old mine tailings isanother established practice. Withadvancements in technologies, oldtailings dumps can be an incrementalsource of metal sitting at-surface(without the costs and impacts of goingdeep). In simple terms, the older the

former mine, the more likely it is thatthe tailings can be usefully re-worked,both because of the improvements inextraction and because older mineswere generally higher grade. Somenew mines being opened have lowergrades than some early tailingsdumps. For example, at the MigoriProject in Kenya, the Macalder tailingshas a grade of 1.7 g/t, while the Mikeishear zone (ore) has a grade of 1.3 g/t.

In a similar fashion, multipleproposals have looked at mining oldmunicipal waste dumps, particularlythose dating from the mid-20th centuryand particularly in North America.Such ‘urban mines’ have oftendecomposed much of the putresciblematerial (making the residue easier toreprocess), but were formed during an

era when the intensity of metalsconsumption had risen sharply andtherefore have high metal grades.

Metals in sewage andwastewater sludge For the past several years, a sewagetreatment facility in the Naganoprefecture north-west of Tokyo hasbeen recovering gold from incineratedsewage sludge. The gold levels in thisash have been world-class, with1890 g/t of gold in the ash, ascompared to <20 g/t for a typical goldmine. The prefecture reportedlyexpected to receive about 15 millionyen from the recovered gold in its firstfiscal year (2009), subject to goldprices … and these went upconsiderably after the GFC.


According to the International LeadAssociation, more lead is recycled eachyear than is mined, and used lead–acidbatteries are ‘the world’s most recycledconsumer product’, at nearly 100% inNorth America and Europe.

Lead–acid batteries continue to play a significant role in the automotive industry, and are a majorsource of metals.

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The gold content in the Nagano ashis somewhat higher than mightgenerally be expected, reportedlybecause of a substantial localpresence of high-tech industry, whichis presumably somehow permitted todispose of metalliferous waste to thesewers (this would attract heavypenalties in most regions of Australia).

More widely, metals are generallyknown to concentrate in sewage. Thisis due to their ubiquitous presence inhousehold products, plus the effluentsof local industry, storm run-offparticularly from roads – which havelevels of platinum group residues fromautomotive catalysts – and anythingelse that gets flushed down the drain.

A recent study (doi: 10.1021/es505329q) estimated that the sewagesludge from a typical US city with apopulation of one million could containmetals worth up to US$13 millionannually, including US$2.6 million ingold and silver.

That metal value is an enticingeconomic ‘pull’ factor for recovery, butsociety should also be applying a‘push’ factor to waste sludge. In manyurban wastewater and sewage plants,including in Australia, the metals thatare contained in the sludge are notstabilised in any way prior to thecurrent disposal routes, often landfill,agriculture or oceanic outfall. Typicalfacilities rely on the greater bulk of the

organic residues to reduce metalcontent to levels deemed acceptableby regulatory regimes – a classicexample of ‘dilution as the solution topollution’. In terms of the otherwise-reusable metals being thrown away, itmakes the waste wasteful. Between thelost opportunity for reuse and theenvironmental effect of disposal, it’s adouble negative.

The key to the metal sludge studieshas been the initial incineration of thesludge, which first removes theorganics that would hinder mostconventional metals extractiontechniques, and second concentratesthe (non-volatile) metals into the ashfor easier recovery.

However, incineration creates its ownpotential problems, both technical andsocietal. Incineration of sewage sludgemay generate limited calorific value, butthe bulk of the energy is lost due to theheat of evaporation of water, so that fuelsare actually added in some cases toincinerate the sludge. Some attention isbeing paid to alleviating this problem,mostly for developing nations. TheBill & Melinda Gates Foundation has, asan example, put its weight behind theOmni Processor, designed by a US firmto treat sewage on a thermally self-sustaining basis to yield clean drinkingwater.

Another obvious problem is thathalogens are ubiquitous in waste and

sewage, through the extensive use ofchlorinated and brominated plastics,and the natural processes that leachand distribute low levels of chlorinequite widely. When incineratinganything with significant organic levelsand even low levels of halogens,persistent organic pollutants (POPs,particularly dioxins and furans) formreadily between 250°C and 400°C.Incinerators may operate at highertemperatures, but the off-gases needto be rapidly quenched to prevent POPformation.

Incineration also has a reputationalproblem. Commonly practised in themid-20th century, incineration ofmunicipal waste was a convenient wayof reducing mass and putrescibleorganic content. This was sometimescoupled to heat utilisation, but withlimited or no emission controls, thosepractices were clearly problematicand were mostly phased out.

So the legislation and regulationsgoverning the recovery of metals andenergy from waste, in the case ofmaterials with high calorific value, stillcarry the legacies of the old problems.Similarly, the social and environmentalgroups that are necessarily involved inthe permitting of proposed waste toenergy and waste recycling facilitiestend to hang on to the negativeconnotations of the old paradigms. Thisis understandable, but it is animpediment to newer, clean facilitiesthat can recover the usefulcomponents of sewage and/or otherorganic sludge.

New frontiersIn the second part of this series, I willexplore seabed mining and asteroidmining as novel ways to address theworld’s future problems with metalssupply. Each is technically fascinating,and both are massively challengingwith potentially global environmental,societal and legislative consequences.

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


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Teachers, you have all beenthere: keen and ready toinspire young minds, you lookout over the classroom only to

see a good proportion of studentsplaying with phones instead of payingattention, and becoming disengagedbefore you have even started talking.

You might take heart to know thatyou are not alone and that, whiletablets and mobile phones may berelatively new, distractions in class arecertainly not. This letter from amedieval father to his son studying atuniversity (amzn.to/1dkqG90) remindsus that procrastination has always beenwith us, both outside and inside theclassroom.

I have recently discovered that you livedissolutely and slothfully, preferringlicense to restraint and play to work and

strumming a guitar while the others areat their studies, whence it happens thatyou have read but one volume of lawwhile your more industrious companionshave read several. Wherefore I havedecided to exhort you herewith to repentutterly of your dissolute and carelessways, that you may no longer be called awaster and your shame may be turned togood repute.

Eh Zaydel (trans), Vagabond verse: secularLatin poems of the Middle Ages, 1966

In 1845, at the insistence of thefamous resident university, the railwaystation in Cambridge was built morethan a mile from the centre of the town(where it is still located). Concernedthat easy access to London woulddistract students from their studies, theuniversity repeatedly blockedconstruction of a more central station

September 2015

Uni students arerarely without atablet orsmartphone.Although they candistract fromlearning, mobiledevices can be usefuleducationalresources.

A new elementin teachingteaching

Using apps in chemistry education

BY OLIVER A.H. JONES AND

MICHELLE J.S. SPENCER

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over the years, and even (many yearsago) restricted undergraduate travel(bit.ly/1KgPWf2). (Some havesuggested that the dons may also havebeen worried that the station wouldspoil the view.)

Distractions are not always a badthing. Railway trips to London enabledstudents from Cambridge andelsewhere to attend public lectures atthe Royal Institution, for example. In the21st century, smartphones and tabletsare not going away, and whiletechnology can be disruptive it canalso be harnessed in the chemistryclassroom to help teach and reinforcekey ideas.

A surprisingly large number ofchemistry-based apps are availablefor university and college students,chemistry professionals and teachers.These range from relatively simple butfun memory-based tests such asAndrey Solovyev’s Molecular Gamesseries (bit.ly/1fLNIaJ), e.g.Hydrocarbons, to extremely advancedsystems, such as SpinDrops

(apple.co/1Hme9jp) for the interactivesimulation of the dynamics of coupledspin systems (see screenshot on p. 26).

Some apps enable chemists topractise their basic skills, access a hugerange of chemistry-related data, sketchand rotate small and large moleculesand search online databases such asChemSpider (apple.co/1RFsQxH).Some of these sorts of apps could beintegrated into practical classes toreplace, say, the SI chemical data book,or to share the results of an experimentwith the entire class (to show variationin replicate measurements, forexample) fairly easily. There are alsoapps to allow students to practisechemistry experiments safely at home.The Chemical Heritage Foundation’sChemCrafter app allows you toencounter fire and smoke, releasevarious gases, and shatter equipment,all from the comfort of your own home(and without increasing your insurancepremiums).

A review covering 30 or so of themore popular (and mostly free apps)

that can be used to learn chemistryand/or serve as reference or researchtools was recently published in theJournal of Chemical Education(bit.ly/1SRFZ9a). A list of ‘top 10’ freechemistry apps for teachers, includingdescriptions, can be found atabt.cm/1Ktj0P5.

While some apps are free, someneed to be purchased and some arefree to download but offer and/orrequire in-app purchases to work, or atleast work at a reasonable speed andallow you to progress through thelevels. Cost can be an important factorto consider with apps and games,particularly for use in a classroomsetting. In-app purchases are asignificant drawback and source ofannoyance in ChemCrafter forexample.

Many chemistry apps provide anexperience similar to traditionaltextbooks and papers, and the use ofconnectivity and interactivity possiblewith mobile devices is usually fairlyminimal. This means that the user still


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has to want to access and read thematerial and to be kept engaged whiledoing so. The lure of Facebook andTwitter are after all just as strong, if notstronger, on a tablet as they are in alecture. How then can we encouragestudents to engage with the material?One approach might be through theuse of gaming principles in appsmeant for teaching.

Gamification is the use of game-thinking and game mechanics toengage users and solve problems.Although not without its critics ineducational circles, if done well it canbe a useful learning tool. Theadvantages of using games forteaching are that learning can bemade active, goal-oriented,contextualised and interesting.Additionally, students tend to be drawnto systems where they can receive


Some popular free chemistry apps; nearly all are available on both Apple and Android operating systems.

Screenshots from the Hydrocarbons (panel A) and SpinDrops (panel B) apps.

rewards for proficiency and/orcompete against their peers, and suchfeatures are easily implemented in agame – via the use of leaderboardsand/or internet connectivity, forexample. Games also have theadvantage of potentially makinglearning fun and so they offer apowerful tool for learning throughdoing and enhancing student interestin the subject as a whole.

Chemistry and science in generalare becoming increasingly popular incomputer games, including bestsellers such as Portal, Portal 2 and theHalf-Life series. However, good gamedesign is not just about having an idea.The idea is probably the easiest part;what counts is making it work. The roleof a game designer is to take the initialidea and work from the earlyprototype stages of the game designthrough to the final product. The markof a good game designer is theirability to attract and keep the attentionof the person playing the game (AngryBirds being a good example).

Many books and university coursescover game design in detail. Goodexamples are Scott Rogers’ Level up!The guide to great video game designand What video games have to teach usabout learning and literacy by JamesGee. David Kushner’s Masters ofDoom: how two guys created an empireand transformed pop culture is alsowell worth reading for the humanaspect. A fun game should have anarrative and consequences, andplayers should be offered meaningfulchoices (e.g. ‘Is doing X a betterchoice than doing Y and if so, why?’)without being afraid to make decisionsor feel as though they’re missing out.Good design can make learninginteractive, provide ongoing feedback,

grab and sustain attention, and haveappropriate and adaptive levels ofchallenge. Bad design will mean thegame is never used. For both videogame makers and educators, failing toengage the user is not an option.

RMIT University’s Trouble Tower isan example of a game that followsgood game design principles and isdesigned to assist students learningoccupational health and safety (OH&S)for construction at RMIT(bit.ly/1CAcz6a). In this game, you areconfronted with increasingly morecomplex OH&S situations related tobuilding sites. Your task is to identifythe hazards and select the appropriatesolution; in doing so you learn OH&Sprinciples and can compete to seewho can work out the solution thefastest. The design team did severalfollow-up studies and found thatstudents who played the game wereengaged, and felt that, through playingthe game, they had learned somethingnew. Trouble Tower is now part of thecurriculum of construction inductioncourses at RMIT. So in this case at least,it is possible to learn and have fun atthe same time.

Of course, no technology is apanacea, and many of the traditionalproblems associated with educatingstudents will remain, no matter howamazing the game or sophisticated thesmartphone. However, educators

shouldn’t shy away from testing theabilities of technology to enhance andencourage learning. Academics are inan ideal situation to help develop thesesystems by incorporating theirbackground knowledge with personalexperiences in lecturing and teachingscience. Trouble Tower is a goodexample of this: it was developed by ateam of people with expertise inelectronic games development as wellas OH&S and construction. Each partof the design team added something; ifthe game designers had not beeninvolved, then it would have been nofun to play, and if the OH&S andconstruction people had not beeninvolved, then the app would not havebeen useful for teaching. This two-party approach should help in thedesign of future game-based teachingapps.

Electronic games and apps havegreat potential for teaching andlearning fundamental chemistryconcepts, particularly if both chemistsand game designers are involved fromthe start. It will be interesting to seehow these systems are furtherdeveloped in the future; in themeantime, happy gaming.

Dr Oliver Jones MRACI CChem and Dr MichelleSpencer MRACI CChem are senior lecturers in theSchool of Applied Sciences at RMIT University inMelbourne, who promise that the science gets doneand they don’t spend all their time playing games ontheir iPads.


Academics are in an ideal situation tohelp develop these systems byincorporating their backgroundknowledge with personal experiences inlecturing and teaching science.

obituary


Jim Shannon’s name is inextricably associated with massspectrometry, as his scientific career was devoted to itsdevelopment and applications to organic, biological andcoordination chemistry. Jim was born in Adelaide on11 July 1926 and studied at the University of Adelaide,graduating in 1949 with first class honours in Chemistry. Aftersome further postgraduate work, in 1952 he went to ImperialCollege London for his PhD, as the recipient of a British CouncilFellowship. He returned to Australia in 1955 to a researchposition at CSIRO in what was to become the Division of CoalResearch in Sydney.

Charged with elucidating the chemical structure of coal, Jimrealised the need for the latest analytical instrumentation,including mass spectrometry and nuclear magnetic resonance.Consequently, a German Atlas CH4 mass spectrometer wasinstalled in Sydney in 1961 and was the first in Australia thatwas devoted to the elucidation of the structures of organiccompounds. Jim was promoted to the level of senior principalresearch scientist in 1963. His generous services to otherchemists around the country were widely used and appreciated,especially as he continued to develop and understand new andvaluable applications.

In 1968, CSIRO transferred the Mass Spectrometry Unit toCanberra. Jim’s stay in Canberra was rather short-lived, as hewas appointed Professor of Chemistry at the University of NewSouth Wales in 1969 and stayed there until his retirement in1986. Jim’s role in the development of the School of Chemistryat the University of New South Wales was immense;furthermore, his wider contribution to the university cannot beoveremphasised. Scientifically, Jim established a strong groupin chemical ionisation mass spectrometry, and successfullymasterminded the transfer from La Trobe University not only ofPeter Derrick, but also of Peter’s grand-scale double-focusingmass spectrometer. The negotiations were significant becausethey resulted in the conversion of substantial areas of teachinglaboratories into state-of-the-art mass spectrometry researchlaboratories. Jim’s scientific output was justly recognised by theaward of the H.G. Smith Medal for 1967 by the RACI. Also in1967, he was awarded the degree of Doctor of Science by theUniversity of Adelaide.

On the administrative side, Jim’s broad vision, unwaveringintegrity, sound judgment and diplomatic skills were quicklyrecognised and highly valued. He served as Head of the Schoolof Chemistry in 1976–7 and again in 1980–4. He served oninnumerable committees of the Professorial Board of theUniversity and chaired the Research and Higher Awards

Committee, and the Board of Studies in Science andMathematics. He was elected to the University Council where herepresented the Faculty of Science.

There are many scientists who have benefited from JimShannon’s innovative science, wise leadership and friendship,and they are deeply indebted to him.

Jim died on 3 May 2015. He is survived by his devoted wifeVois, to whom he was married for 59 years.

David Black FRACI CChem

Jim ShannonMass spectrometrist

Charged with elucidating thechemical structure of coal,Jim realised the need for thelatest analyticalinstrumentation, includingmass spectrometry andnuclear magnetic resonance.

Microwave-assisted samplepreparation for trace elementdeterminationde Moraes Flores É.M. (ed.), Elsevier, 2014,ISBN 9780444594204, 412 pp., $235.95

Microwave-assisted sample preparation for traceelement determination is ably edited by Érico Marlonde Moraes Flores. There are 12 chapters and 36authors, so it must have seemed like herding cats toget them lined up and pointing in more-or-less thesame direction! Many of the authors are associatedwith universities throughout Brazil, a fair sprinklingcome from the University of Aberdeen’s Chemistry Department (TraceElement Speciation Laboratory, TESLA), while the US, Germany, Austria,Poland and Libya are represented to make up the numbers. Ably edited,indeed!

The book is a tour de force of every-which-way you can visualiseusing microwaves to prepare samples and a few more you maybe haven’tthought of. Each chapter concentrates on one aspect and is a complete,stand-alone review with its own comprehensive referencing. If yourinterest lies in the topic of a particular chapter, then you’ve probablyfound a very useful review. If, on the other hand, your interests broadlyrelate to whether you ought to move towards microwave techniques forsample preparation in your laboratory, then you will surely find youranswer in this book, but you’ll have to dig it out.

The strength of this book is its comprehensiveness plus some veryuseful tables in a number of chapters, which will rapidly point you inthe direction of methods for particular analytes. Its weakness is theisolation/segregation of the chapters from each other; there is no cross-referencing and pulling together into the rounded ‘story’ the titleimplies. This is a pity because the book is quite expensive.

The introductory chapter, ‘Introduction to sample preparation fortrace element determination’, is a clear and insightful definition of theprocess and goals of trace elemental analysis. Compulsory reading for alltyro analysts! The quality of the remaining chapters is variable, rangingfrom so-so to very good, mainly at the latter end. For most of theauthors, English is not their mother tongue, so in places the English isnot quite correct, although the meaning is always quite clear. I knowleaping to conclusions based on surnames can be a dangerous game toplay; I have an acquaintance with a lengthy, hard-to (OK, impossible-to)pronounce Polish name and an accompanying Glaswegian accentreflective of his Scottish ancestry! However, I think I’m on terra firmastating this book has a strong Brazilian flavour.

In summary, if you are looking for a series of comprehensive reviewsabout microwaves in trace analysis, or a competent literature reviewabout one of the review topics (as of a couple of years ago), then lookno further. If by contrast you are looking for a rounded review of thearea, then it is mostly here, but you’ll need to work at it and draw yourown conclusions. Finally, if you just want to get a feel for how youmight use microwaves in analysis, then you could do worse than eyeballthe table of contents, but you could probably do better elsewhere.

R. John Casey FRACI CChem

Science in wonderland:the scientific fairy talesof Victorian BritainKeene M., Oxford University Press, 2015,hardcover, ISBN 9780199662654, 227 pp.,$34.95

Science in wonderland explores the curiousintersection of fairy tales and science inVictorian Britain. Author Melanie Keeneillustrates the integration of 18th-centuryfairies, goblins, giants and sundry other

mythical entities into children’s stories, exploring aspects ofthe science that emerged from the Industrial Revolution andassociated era of scientific discovery and reinterpretation.

All societies have their myths and legends. We all striveto make sense of our world and find meaning in existence.In times past, explanations of the unknown were frequentlyrooted in superstition, invoking the influence and agency ofspecially endowed not-of-this-world creatures. Perhapsnothing much has changed. Santa Claus, the Easter Bunnyand the tooth fairy are still very much alive and well,provided, of course, you believe! And sundry importantpeople apparently think the climate-change good fairy willsave our bacon!

Against this pseudo-spiritual world, 19th-century Britainwas engaged with new technology driving the ‘satanic’ millsand a rapid expansion of scientific theory. Fossils were nolonger objects of awe, but merely the remains of long-deadcreatures; tiny species seen under the microscope were seenfor what they were rather than begging arcane explanation;astronomy was starting to make sense to the emergingmiddle classes; and physics, chemistry and microbiologywere directing society away from the magic and make-believe towards evidence-based explanation. Educationstrove to present a strictly rational world view, free fromfairies and the like.

Did this rationalist mechanistic view succeed? No, nottotally. Apparently the love of fairies runs deep. At the endof the 19th century, butterflies were still pretty much seenas fairies; Kingsley’s Water babies melded ‘scientific’ waterwith fairies; and Gilbert and Sullivan had fairies galore,illuminated with twinkling lights no less, courtesy of(chemical) batteries. No danger of tipping out the babyfairy with the bathwater. Children’s authors kept the fairiesand fitted the science round the edges.

Overall, this is a delightful little book. It is interestingand engaging, reasonably inexpensive and good bedtimereading. You’ll enjoy it!

Good gracious! A little fairy has just lightly tripped rightpast my house. I think she is probably on her way to balletwith her mother (apparently a mere mortal).

R. John Casey FRACI CChem

books


The tale of the duelingneurosurgeons: the historyof the human brain asrevealed by true stories oftrauma, madness, andrecoveryKean S., Little, Brown and Company, Hachette BookGroup, 2014, hardcover, ISBN 9780316182348,407 pp., $16.63 (Amazon)

The tale of the dueling neurosurgeons is another exciting bookby Sam Kean. While neurosurgery may not at first sight appearto be strictly chemistry, the book is not bereft of thedevelopment of the chemistry of neurotransmitters, synapses,neurons and prions; and the importance of dopamine and vitamin B1, along with the ‘wiring of the brain’. It is, however,the epic stories of discovery that make the book compellingreading.

The story behind the title covers the tale of FrenchKing Henri II, who was involved in a jousting accident in 1559.The tale is really about two prominent surgeons of the day,Ambroise Paré (of France) and Andreas Vesalius (of Brussels).The former was a barber-surgeon with substantial battlefieldexperience, the latter was initially a self-taught anatomistinvolved in dissecting deceased remains, following the ancientphysician Galen (CE 129). The surgical team could do little forthe dying king, who drifted in and out of consciousness, evengetting up and walking. The underlying philosophy at the timeposited if the skull remained intact, then death was aconsequence of the visible injuries. Indeed, Henri had largesplinters of jousting pole through one eye-socket (which wereremoved), but he ultimately succumbed. Vesalius and Paréconvinced the French Court an autopsy should be performed onHenri. They predicted what they might find, and theirpredictions were confirmed – pools of blackened fluids at therear of the brain ‘antipodal to the blow’ – and the brain itselfhad yellowed and putrefied at the back. They also found thatthe ‘splinters’ at the front of Henri’s head had not entered hisbrain.

This story serves two purposes. First, early neurologicalresearch is based on observing a pattern of ‘misfortune’ as amechanism to study how a victim’s brain may cope (sometimesquite miraculously and at other times not so), followed by apost-mortem analysis of the sites of disorder; and second thebrain is a lump of loosely anchored tissue floating around in asoup of fluids within a solid skull.

Our author cashes in on what Henri’s autopsy shows in today’scontext. Namely, brain trauma can occur even if the skull remainsundamaged, a lesson we still appear to be learning in the domainof our gladiatorial sports such as boxing, football (body and headimpact codes), ice-hockey and even warfare (no blood, no harm?).The recent story of two Australian servicemen in Iraq describes abomb explosion, where one soldier remained relatively unaffected

(although seriously injured) but his colleague with fewer injurieswas designated in an advanced state of Alzheimers – all related todirectional location from the blast.

Another story from 1957 concerns the disease kuru, suffered bythe Fore people and their neighbours (some 40 000 people) in theeastern mountain highlands of Papua New Guinea (PNG). Typicallythe diet of the PNG highlanders was mostly fruits and vegetables,plus a few sweet potatoes gathered from the poor mountain soils.A few villages kept pigs and hunted rats, possums and birds(mostly consumed by the men), but protein for the women andchildren came from so-called ‘funeral feasts’, where the dead werecooked and consumed. Choice bits like genitals, buttocks andbrains were provided to relatives of the deceased first. Thesymptoms of kuru commence with lethargy, headaches and jointpain, and progress through victims stumbling about, flailing theirarms and within months being unable to stand or sit up straightwithout support. Along the way many start to laughuncontrollably. The lucky ones die of pneumonia before theystarve, while the unlucky ones just whittle away.

The neuroscientist and adventurer Carlton Gajdusek wasattracted to the highlands in the late 1950s. From 1957, Gajdusekstarted to gather data on kuru victims and noted it was mainlywomen and children who succumbed to the disease. He foundsome 200 people were dying of the disease each year. Gajdusekalso started to perform autopsies on the brains of victims. Thiswork attracted the attention of other neurologists as well as somenair-do-well local sorcerers. The upshot was the initial damagecaused by kuru was traced to the cerebellum – the brain’smovement centre. It was speculated by some that the diseasemight be genetic but this was dismissed since unrelated adultsoften had the disease.

In the 1960s, Gajdusek’s lab in the US also demonstrated thatthe diseases kuru, scrapie (a similar disease in sheep) andCreutzfeldt-Jacob disease in rodents had some common elements.All resulted in ‘spongyform’ brain damage, which can remaindormant for long periods. Coincidentally, funeral feasts hadbecome rarer in the 1960s because cannibalism was frowned uponby Christian missionaries. Nevertheless, it took until 1975 for kuruto be all but eliminated.

Stanley Prusiner, a San Francisco-based neurologist, thendetected some ‘rough proteins’ at the blood–brain barrier ofvictims of the above diseases, which he called prions(proteinacious infectious particles). Prions prove immune tocooking and digestion and unfortunately cross the brain–bloodbarrier. Prions, consumed by the Fore women and children atfuneral feasts, proved to be the source of kuru disease. Byanalogy, the outbreak of mad cow disease in the 1990s is basicallya case of ‘bovine kuru’. Possible links of prion-type proteins toAlzheimer’s and Parkinson’s disease are currently beinginvestigated.

If I were to be critical of the author, then it would be becausehe mentions the colonial power of Australia in a somewhatdismissive manner, while neglecting the critical contributionsmade to the kuru story by Australian medico Professor Michael

books


September 2015

Alpers. Alpers, who among other things directly collaboratedwith Carlton Gajdusek, has continued to monitor one of thecritical aspects of the disease – its incubation period. Thelast case of what is now called the degenerative priondisease kuru was reported in 2005, not 1975 as suggestedin this book (see www.youtube.com/watch?v=vw_tClcS6To).

Beriberi and vitamin B1 appears to be a worthy place toconclude this review. For as long as people have eaten ricein Asia, doctors there have reported outbreaks of beriberi.This was accentuated in the early days of rice milling whenthe outer husks were removed from rice grains, producingso-called ‘white’ rice. During the Russo–Japanese war alonesome 200000 Japanese soldiers fell victim to beriberi. Thedisease was particularly common in Changi duringWorld War II, where two doctors, de Wardener and Lennox, collected tissue samples from thebrains of beriberi victims. These samples (another story ofintrigue) ultimately enabled the link to be drawn betweenvitamin B1 deficiency, beriberi and Wernicke–Korsakoffsyndrome, which expresses itself through ‘confabulation’(telling plausible lies), and arises from frontal lobe damageof the brain.

The book includes numerous other stimulating storiesthat open our understanding of functional aspects of thebrain, often through dysfunction.

Dr Alan J. Jones FRACI CChem

John Wiley & Sons books are now available to RACImembers at a 20% discount. Log in to the members area ofthe RACI website, register on the Wiley Landing Page, in theMembers Benefits area, search and buy. Your 20% discountwill be applied to your purchase at the end of the process.

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technology & innovation


It cannot be disputed that Australian scientists are facingchallenging times. Perhaps ‘challenging’ is an understatement.Australia is producing an ever-increasing number of scientificPhD students, yet government funding of the sciences is at arecord low. EMCRs – early-to-mid-career researchers who arelooking to take the leap from postdoctoral position to apermanent placement in academia/industry – are arguably themost affected.

Professor Carver, Director of the Research School ofChemistry, ANU College of Physical and Mathematical Sciences,says there is a ‘huge demand or need for trying to encourageEMCRs in the development of their careers … it’s a pretty toughtime at the moment for anyone doing research, particularlypeople in those age brackets’. I doubt that any of us woulddisagree.

Professor Carver has been selected as an Ambassador of theScience Next Collaborative (SNC). Launched in mid-May of thisyear, the SNC is an Australian-first industry initiative, led bySigma Aldrich, that aims to better enable Australian scientiststo successfully translate their research through tocommercialisation.

The initiative will focus on the challenges faced by EMCRs,particularly the transition from basic and promising researchdiscovery to translational research and its commercialisation.

‘A thorough examination of the Australian scientific researchsector uncovered that many researchers are struggling toachieve the final steps in their research continuum: successfulcommercialisation’, that is, according to Ms Reich Webber-Montenegro, Director – Marketing, Inside Sales and SharedServices, Sigma Aldrich Oceania. Ms Webber-Montenegroidentifies the issue as a gap in the knowledge and know-how ofEMCRs as opposed to their more senior colleagues, and that thisis a worthy area for Sigma Aldrich to focus on.

Ms Webber-Montenegro considers that the commercialchallenges faced by EMCRs ‘may discourage them from pursuingmeaningful and ongoing scientific endeavours … If this riskbecomes a reality, Australia may see a huge dip in theinnovation ecosystem and associated returns generated by adynamic research industry.’

Associate Professor Derek Richard, Director of Research,School of Biomedical Sciences, Queensland University ofTechnology, and also an SNC Ambassador, has stated ‘it’s usuallydifficult for young researchers to take their discoveries throughto commercialisation, possibly due to a lack of experience inintellectual property protection, market research, lodgingpatents and gaining working capital, which are all fundamentalsin the commercialisation of research.’

The SNC is led by Ms Webber-Montenegro, who is passionateabout the program and what it can potentially offer to EMCRs.Sigma Aldrich has recruited seven key scientists across

Australia, and together they constitute the SNC ambassadors,also known as the ‘think tank’. Sigma Aldrich became familiarwith each of the ambassadors through their dealings with thecompany, and subsequently approached them for theirexpertise.

Key to selecting the ambassadors was that they must beinfluential opinion leaders in their field, be at a point in theircareer where they can lay claim to having successfullycommercialised research, and, importantly, now be willing togive back to the field and mentor the next generation ofAustralian scientists. Further, it was essential to Sigma Aldrichthat the ambassadors come from a good representation ofAustralian research institutions, in both the chemical andbiological fields.

From my own investigation, it appears that the SNCAmbassadors have vastly varied commercialisation track records.Professor Carver considers that each of the SNC Ambassadorsoffer different areas of expertise. In Professor Carver’s instance,while his commercialisation experience may or may not be asstrong as other Ambassadors, through his leadership roles atboth the University of Adelaide and Australian NationalUniversity, he has mentored EMCRs, encouraging them tofurther their careers in research. His experience in mentoringEMCRs is a strength that he will be bringing to the SNC.

There is often a direct conflict between commercialising andpublishing research, and this is a problem. Research grants areheavily dependent on the number and quality of publicationsproduced, yet commercialising research often requires theinformation to remain out of the public domain. When I spokewith Professor Carver about this, I was reassured to learn thatthe SNC Ambassadors had discussed this competing interest atlength, and that the content of the forums will reflect this.Professor Carver considers that ‘academics are geared to outputsin terms of research publications in prestigious journals’, andconsequently, ‘academics are routinely measured in this way’. Hestates there is ‘little room, in many ways, for people who have adifferent approach’. Quite simply, commercialisation output doesnot fit the standard model that we currently have in place, andthis will need to change.

The initiative will materialise as a series of forums held inBrisbane on 26 August, Sydney on 3 September, and Melbourneon 8 September 2015. There is no cost to attend the forum,though there will be no financial support available for thosewho do not reside in these key cities. The Ambassadors willpresent their commercialisation experience, guiding EMCRsthrough the process. A session on intellectual property and itsrelevance to EMCRs is also on the agenda. At this stage, theforums are not limited to particular EMCRs, and are notexclusive to particular institutions.

The SNC online ‘hub’ (sciencenextcollaborative.com) includes

Science Next Collaborative: a new approach to thecommercial challenges of early career research


information about commercialising research as relevant toEMCRs and will be expanded to include a variety of educationalresources. Forum dates are advertised at the hub and throughmajor institutions. The SNC intends to have the forums postedas videos online, with the opportunity to stream the sessions inreal time for those who cannot attend.

The first of the objectives to be met by the SNC Ambassadorsis the publication of a positioning paper, which is available viathe SNC hub. The paper captures the current situation faced byEMCRs, key challenges, and ways to better enable scientists tosecure economic returns for their research.

The feedback received from EMCRs along the way will beused to direct future SNC efforts. Professor Carver considers it adynamic process in which the program will continue to evolveto meet EMCR needs.

What is the value of the SNC to an EMCR? First and foremost,an EMCR’s commercialisation knowledge will benefit fromparticipating in the SNC. Second, so will their resumé. Would anemployer value an EMCR who has participated in the SNC?Absolutely, according to Professor Carver, who is well versed in

hiring for academic positions. He states that employers are‘looking for distinguishing characteristics … It’s not just aboutthe ability to do research; it’s about the ability to interact, it’sabout the ability to have a variety of skills … this initiativewould be another aspect to that.’

What’s in it for Sigma Aldrich? The answer is ‘stakeholderengagement’. This is highly valued by Sigma Aldrich, and is the‘main goal’ in terms of measurable return; Sigma Aldrich wantsto engage with key leaders in industry and academia, as well asup-and-coming EMCRs. Perhaps I’m naïve, but I believe thisresponse. Australian science is a relatively small communitywhere word spreads quickly. Altruistic acts do not go unnoticed,and the initiative will surely fair favourably for Sigma Aldrich.We should be encouraged to see an industry-led initiative, suchas the SNC, aim to directly address the issues faced byAustralian scientific researchers.

Dr Brittany Howard MRACI completed her PhD in medicinalchemistry at the Monash Institute of Pharmaceutical Sciencesbefore undertaking a postdoctoral position with the NationalInstitutes of Health (US), and has since commenced as a traineeattorney with Watermark Patent and Trade Marks Attorneys.

Attendees at the Science Next Collaborative Think Tank Meeting, 11 May. Back row (left to right): Associate Professor Derek Richard (QUT),Professor Peter Currie (Monash University), Professor Mark Baker (Macquarie University), Professor John Carver (ANU). Front row (left toright): Irfan Beig (Scientific Liaison, Sigma-Aldrich), Arlene Burton (Product Initiative Manager, Sigma-Aldrich), Reich Webber-Montenegro(Director – Marketing, Inside Sales & Shared Services Oceania, Sigma-Aldrich), Associate Professor Kaylene Simpson (Peter MacCallumCancer Centre), Rachael Rose (Marketing Communications Assistant, Sigma-Aldrich), Farhad Shafiei (Product Manager, Sigma-Aldrich).

pondering petrichor


Are you one of those people who can smell when the rain iscoming? Ever wondered then what you’re actually smelling?

Australia’s CSIRO has come up with some pretty amazinginventions over the past 86 years of research, from polymerbanknotes to insect repellent and the world-changing Wi-Fi. Butwe can also lay claim to something a little more esoteric – weactually invented a whole new word.

And no, we’re not talking about one of these new-fangledinternet words like ‘YOLO’, ‘selfie’ or ‘totes’.

The word is ‘petrichor’, and it’s used to describe the distinctscent of rain in the air. Or, to be more precise, it’s the name ofan oil that’s released from the earth into the air before rainbegins to fall.

This heady smell of oncoming wet weather is somethingmost Australians would be familiar with – in fact, somescientists now suggest that humans inherited an affection forthe smell from ancestors who relied on rainy weather for theirsurvival.

The smell of rain: how CSIRO invented a new wordiS

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OriginsEven the word itself has ancient origins. It’s derived from theGreek ‘petra’ (stone) and ‘ichor’, which, in Greek mythology, isthe ethereal blood of the gods.

But the story behind its scientific discovery is a lesser-known tale. So, how is it that we came to find this heavenlyblood in the stone?

‘Nature of Argillaceous Odour’ might be a mouthful, but thiswas the name of the paper published in Nature of 7 March 1964,by CSIRO scientists Isabel (Joy) Bear and Richard Thomas, thatfirst described petrichor.

Thomas had for years been trying to identify the cause forwhat was a long-known and widespread phenomena. As thepaper opened:

That many natural dry clays and soils evolve a peculiar and characteristicodour when breathed on, or moistened with water, is recognised by allthe earlier text books of mineralogy.

The odour was particularly prevalent in arid regions and waswidely recognised and associated with the first rains after aperiod of drought. The paper went on to say:

There is some evidence that drought-stricken cattle respond in a restlessmatter to this ‘smell of rain’.

The smell had actually been described already by a smallperfumery industry operating out of India, which hadsuccessfully captured and absorbed the scent in sandalwood oil.They called it ‘matti ka attar’ or earth perfume’. But its sourcewas still unknown to science.

Joy and Richard, working at what was then our Division ofMineral Chemistry in Melbourne, were determined to identifyand describe its origin.

By steam-distilling rocks that had been exposed to warm,dry conditions in the open, they discovered a yellowish oil –trapped in rocks and soil but released by moisture – that wasresponsible for the smell.

The diverse nature of the host materials has led us to propose the name‘petrichor’ for this apparently unique odour which can be regarded as an‘ichor’ or ‘tenuous essence’ derived from rock or stone.

The oil itself was thus named petrichor – the blood of thestone.

Bring on the humidityThe smell itself comes about when increased humidity – aprecursor to rain – fills the pores of stones (rocks, soil etc.)with tiny amounts of water.

While it’s only a minuscule amount, it is enough to flush theoil from the stone and release petrichor into the air. This isfurther accelerated when actual rain arrives and makes contactwith the earth, spreading the scent into the wind.

According to the Nature paper:

In general, materials in which silica or various metallic silicatespredominated were outstanding in their capacity to yield the odour. Itwas also noted that the odour could be obtained from freshly ignitedmaterials rich in iron oxide, with or without silica.

It’s a beautiful sequence of events, but one that may behard to visualise.

Thankfully, in a testament to the ongoing scientificfascination with this finding, a team of scientists at theMassachusetts Institute of Technology have just this yearreleased a super slow motion video of the petrichor process inmotion.

Using high-speed cameras, the researchers observed thatwhen a raindrop hits a porous surface, it traps tiny air bubblesat the point of contact. As in a glass of champagne, thebubbles then shoot upwards, ultimately bursting from the dropin a fizz of aerosols.

The team was also able to predict the amount of aerosolsreleased, based on the velocity of the raindrop and thepermeability of the contact surface, which may explain howcertain soil-based diseases spread.

Lasting legacyThere’s a small body of research and literature on petrichorthat’s fascinating in its own right, including Thomas and Bear’ssubsequent paper ‘Petrichor and Plant Growth’ a year after theyfirst named the smell.

So what happened to Joy Bear and Richard Thomas?Richard had actually retired from CSIRO in 1961 when he was

First Chief of the Division of Minerals Chemistry. He died in1974, aged 73.

Joy, aged 88, a true innovator and pioneer in her field,retired from CSIRO only in January this year, after a careerspanning more than 70 years.

The joint discovery of petrichor was just part of a trulyremarkable and inspiring career that culminated in 1986, withJoy’s appointment as a Member of the Order of Australia forservices to science.

We are thankful to both for the lasting legacy on giving aname to the smell of rain and to Joy for the role model she hasbeen to so many women in science.

Howard Poynton, Research Group Leader – Materials Characterisation, CSIRO. Firstpublished at The Conversation (www.theconversation.com).


The smell itself comes aboutwhen increased humidity – aprecursor to rain – fills thepores of stones (rocks, soiletc.) with tiny amounts ofwater.

economics


It now seems likely that Australia will be one of the first (if notthe first) major industrialised countries to close all of its oilrefinery operations. An old and outdated refinery in Adelaide(Port Stanvac) closed in the 1990s. The two refineries in NewSouth Wales (Shell at Clyde and Caltex’s refinery at Kurnell)have closed in the past years, BP’s Bulwer Island near Brisbaneis slated to close and there are persistent rumours that the BPrefinery at Kwinana in Western Australia will follow suit. Thisleaves the two refineries in Victoria (Viva Energy, formerly Shell,near Geelong, and ExxonMobil’s refinery at Footscray inMelbourne) and Caltex’s refinery at Lytton near Brisbane.Whether these refineries will survive their scheduled major shut-down and maintenance times over the next few years,when new capital is usually required for upgrades or replacingmajor equipment, is a moot point.

The duty of a refinery is to convert crude oil, which has ahydrogen to carbon stoichiometric ratio of 1.5 or less, intorefined fluids for motor transport, which have hydrogen tocarbon ratios of over 1.8 for gasoline (petrol) and the best-quality diesel. This role is performed in refineries by eitherrejecting carbon in the crude oil or adding hydrogen.

In Australia, carbon rejection is the favoured method viafluid catalytic-cracking (FCC). In this process, hot solid-acidcatalysts react with heavy oils (H/C < 1.5) to form gasoline,olefins and a low-quality diesel with H/C ratios of 1.8 or more.The reaction is very rapid and the catalyst becomes coated incarbon (coke). The catalyst is regenerated by separating it fromthe hydrocarbons and burning the coke off the catalyst to formcarbon dioxide and reheating the catalyst to the requiredreaction temperature.

An alternative to FCC is hydrocracking, which is used at theBulwer Island refinery (and at New Zealand’s refinery at MarsdenPoint). For this operation, hydrogen is required; it usuallycomes from natural gas by the steam reforming reaction:

CH4 + H2O → CO + 3H2

or, as is used for the Bulwer Island operation, by partialoxidation:

CH4 + 1⁄2O2 → CO + 2H2

more hydrogen is made by water-gas-shift:CO + H2O → CO2 + H2

The carbon dioxide is removed and emitted to atmosphere.For completeness, another method for rejecting carbon,

which is not used in Australia, is to form coke by liquid-phasepyrolysis of heavy components. This makes a low-qualitygasoline and diesel, which require further hydro-treatment, andpetroleum coke, which can be used to make anodes for smeltingaluminium.

One of the main effects of increasing the ratio of hydrogento carbon in the products is that the density of the products issignificantly lower than that of the crude oil feedstock. Thisresults in an increase in the total volume and because oilproducts are universally sold on a volume basis, this results in

increased product volumes and sales (the so-called refinerygain).

In modern refineries producing fuels to the latest qualitystandards, more hydrogen is required to hydro-treat diesel fuelsto virtually eliminate sulfur (less than 10 ppm). This is requiredto minimise the tailpipe emissions of particulates from diesel asrequired by the latest vehicle engine technology.

A significant issue is the economy of scale. Refineries have agood response to economy of scale (unit production costs fallwith increasing size of the refinery). Recently in our regionseveral refineries have been built with outputs near orexceeding Australia’s total refinery capacity. Some of the majorexport refineries in the region are given in the table.

These refineries are export-oriented refineries in that theytake crude oil from the Middle East, including Iran, and convertit into products that are exported to the region. These refineriesuse the latest technology to produce high-quality fuels nowbeing adopted throughout Asia. Also they use heavy oil hydro-cracking so that high-density, high-sulfur crude oil (i.e. cheap)can be used rather than the more expensive light crudes thatAustralian refineries require; the graph shows the persistentprice differential between heavy oil (sg < 0.933; APIgravity < 20) and the lighter crude oils (sg > 0.876; API > 35.1).This benefit is increased by a larger refinery gain because of therelatively higher density of the feedstock oil.

Declining refineries

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Closure of Australian refineries has resulted in the facilitiesbeing refurbished as import terminals importing high-qualityspecification fuels from these export refineries.

As well as the smaller scale, one of the major issues forAustralian refineries competing with these facilities is thatcoastal shipping in Australia (cabotage) is very expensivecompared to shipping from foreign ports using foreign flaggedvessels. It is cheaper to service an Australian port fromSingapore (say) than from an expanded refinery somewhere elsein Australia. Also, from the above equations, it is evident thatrefinery operations are major emitters of carbon dioxide. Theenthusiasm for taxing or proscribing such emissions in Australiaincreases the investment risk versus investments in countrieswith little enthusiasm or even hostility to carbon emissiontaxes and the like.

One of the major issues for the chemistry profession is thatas refineries close, there is less opportunity for chemists andchemical engineers both working for and servicing refineryoperations. But it is worse than this because refineries alsosupply many downstream chemical manufacturers withfeedstock. This ranges from propylene for making high-valuedpolymers to sulfur for the fertiliser and agricultural industries.

Compared to the furore over the demise of vehiclemanufacturing, there has been little concern expressed aboutthe demise of hydrocarbon processing in Australia. This is a veryworrying situation as it leaves the country exposed to thevagaries of international supply of high added-value productsand further reduces exports to basic minerals and LNG, whichhave minimal added value.

Duncan Seddon FRACI CChem is a consultant to coal, oil, gas andchemicals industries specialising in adding value to naturalresources.

Major export refineries in the Middle and Far East with output similar to Australia’s total refinery capacityCompany Location Country Capacity (bbl/day)

SK Innovation Ulsan South Korea 840 000

GS Caltex Corp Yeosu South Korea 785 000

S-Oil Corp Onsan South Korea 669 000

Reliance Industries Jamnagar India 660 000

ExxonMobil Jurong/Pulau Ayer Singapore 592 000

Reliance Industries Jamnagar India 580 000

Saudi Aramco Ras Turana Saudi Arabia 550 000

Formosa Petrochem. Maliao China Taiwan 540 000

Kuwait National Petroleum Min Al-Ahmadi Kuwait 466 000

Shell Eastern Pulau Bukom Singapore 462 000

BP PLC Kwinana, WA Australia 136 698

Viva Energy Australia Geelong, Vic. Australia 120 000

Caltex Australia Lytton, Qld Australia 108 600

BP PLC Bulwer Island, Qld Australia 96 850

ExxonMobil Footscray, Vic. Australia 77 000

Total Australian refinery capacity 539 148

Relative cost of oil at varying density.

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)

—— sg < 0.933—— sg 0.876–0.850

plants & soils

In the next few years, it is likely that specific legislation will beintroduced for inorganic arsenic concentrations in rice inAustralia, Europe and elsewhere, with the acceptable levels forinorganic As set at 0.2–0.3 mg/g. This will require producers ofrice in Australia to certify that their rice has acceptableinorganic As concentrations.

Inorganic As is a class one carcinogen and at high exposurelevels causes cancer of the bladder, lung and skin. Worldwide,drinking water and foodstuffs are the two main sources ofinorganic As. In Australia, rice consumption is an exposure

route of inorganic As. Arsenic is a natural component of soilsand when paddocks are flooded, arsenic can become availablefor uptake by plants. Historically, lead arsenate was alsoextensively used in sheep dips and dimethylarsinic acid (DMA)used as an insecticide in orchards. Some of this legacy arsenicwill also be present in rice-growing areas.

A recent survey of arsenic in rice available in Australiansupermarkets (Maher W., Foster S., Krikowa F., Donner E.,Lombi E. Environ. Sci. Technol. 2013, vol. 47, pp. 5821–2) hasshown that rice contains less than 0.4 mg/g arsenic, which is

well below the current maximum levels permissible for arsenicin cereals in Australia (1 mg/g) (Australian and New ZealandFood Standards Code, Standard 1.4.1 Contaminants and NaturalToxicants 2011C). Inorganic As concentrations are below0.2 mg/g.

Measurement of inorganic As in food is difficult. First,inorganic As must be quantitatively extracted and separatedfrom other arsenic species such as monomethylarsenic and DMA,to avoid overestimation of inorganic As. Commonly, HPLCcoupled to inductively coupled mass spectrometry (ICPMS) is

used for this purpose, but care must betaken that co-elution of arsenic speciesand/or losses from adsorption to columnpacking material doesn't occur. Arsenicanalyses by ICPMS can suffer from carbonenhancement in the ICP torch and isobaricinterferences in the mass spectrometer,leading to an overestimation in arsenicconcentration. Precautions must be takento ensure the quality of results.

Accurate measurements of inorganic Asin rice are required because inaccurateanalyses will result in substantialinconvenience, lost production and coststo the rice industry. At the EcochemistryLaboratory at the University of Canberra,we have produced a rice reference materialto assist those undertaking inorganic Asanalyses of rice. Rice flour was sterilisedby gamma irradiation and extracted with2% nitric acid; total arsenic was measuredby ICPMS and inorganic As and DMA byHPLC-ICPMS by a method verified byanalysis of eight international rice flourreference materials and XANES. The riceflour contains 0.192 ± 0.006 mg/g dry masstotal As, 0.040 ± 0.004 mg/g dry mass AsIII,0.068 ± 0.003 mg/g dry mass AsV and0.085 ± 0.004 mg/g dry mass DMA.

Homogeneity tests were conducted using a suite of otherelements present in the rice flour. The analysis of referencematerial and obtaining satisfactory results gives confidence inarsenic concentrations being reported.

The reference material is available, free of charge, bysending a stamped, self-addressed envelope to EcochemistryLaboratory, University of Canberra, Bruce, ACT 2601. For moreinformation, email [email protected].

Professor Bill Maher is at the Institute for Applied Ecology, University ofCanberra.


Measuring arsenic in rice – an Australian reference material

A range of rices ready for analysis. Brown rice normally contains more arsenic than whiterice. Polished rice has less arsenic than rice with husks.

The capacity to predict astringency has been the subject ofconsiderable research. In our review of red wine astringency in2011 (Trends Food Sci. Nutr. vol. 27, pp. 25–36), wesummarised six different approaches that have been used. Inreality, most of these studies were not ‘predictive’. Rather, theysimply determined the correlation between the taster-assessedastringency and a chemical assay for astringency. One approachtowards a predictive model has used the measurement of theturbidity that resulted following the addition of mucin to awine and the consequent formation of a mucin–polyphenolprecipitate. While the authors initially used grapeseed extractto develop their method, they found a high correlation(r2 = 0.95) between the measured turbidity and astringencyrating for 18 wines (Condelli et al., Food Qual. Pref. 2006,vol. 17, pp. 96–107).

Irrespective of the apparent success of some approaches toassess astringency, there are numerous factors that make thelink between prediction and consumption a challenge. First, awine’s phenolic composition can change over time through arange of polymerisation and hydrolysis reactions. Second, theconformation of the phenolic compounds is important indetermining interactions with salivary proteins as I discussed inmy August column. Changes in conformation as a wine ageswould change the perception of astringency.

Third, recent work by Aurélien Furlan and colleagues fromthe University of Bordeaux (Langmuir 2014, vol. 30,pp. 5518−26) has raised new questions relating to phenoliccompound interactions with lipids, particularly oral cavitymembranes. The work used deuterium and phosphorus solid-state NMR to examine the interactions between phenoliccompounds and micrometric liposomes, as a model for oralcavity membranes, and nanometric bicelles to represent foodlipid droplets. Catechin, epicatechin and epigallocatechingallate caused disordering of the membrane’s hydrophobic coreas well as destabilisation of the bicelles. While the authorsrecognise that the models used in their study were somewhatsimplified, the approach provides a new strategy for examiningthe complex interactions that occur in the mouth when wine isconsumed.

For some time, I have been reflecting on the role of what Icall molecular assembly in the structure of red wine and this isa fourth issue that can influence attempts to assess or predictastringency. Molecular assembly is now commonly accepted infoods, but only recently has it started to gain traction in redwine. The concept was first proposed in 1966 by Dr ChrisSomers, then at the Australian Wine Research Institute. Chrissuggested that his gel filtration experiments on red wineimplied that the pigmented molecules were ‘physically and notchemically bound in a three-dimensional tannin structure’.

The procyanidin association studies that I described in myAugust column provide more recent evidence for molecular

assembly and help interpret conflicts in the literature aboutcompounds that contribute to astringency. The flavan-3-olmonomers catechin and epicatechin, as well as someprocyanidin dimers, have been proposed to contribute toastringency. The experimental approach used in the studyinvolved additions of the compounds to a model and thenassessing by taste the increase in astringency. Theconcentrations used in the addition study, however, would haveexceeded the critical micelle concentration for some of theflavan-3-ols leading to molecular aggregates and even colloidalparticles. Some estimates of particle size suggest diameters of300 nm or more can be obtained. Particles of this dimension arelikely to induce friction in the flow of saliva, which couldpossibly be interpreted as astringency.

To add to the complexity of aggregate formation, DrazenZanchi and colleagues (J. Phys.: Condens. Matter 2008, vol. 20,494224; doi: 10.1088/0953-8984/20/49/494224) have shownthat under conditions of high supersaturation, conditions thatmay be achieved when compounds are added to wine, theperturbation of the wine matrix can be significant and lead tothe formation of fractal, rather than spherical, aggregates. Thisthen opens up a new research area of the relationship betweengeometric characteristics and changes in mouthfeel response.

For some time, I have been arguing that the assemblyprocesses in wine could lead to frictional effects as this seemsmore relevant when tasters use terms such as gritty orsandpaper. It would be fair to say that my position has notgained much credence with the traditionalists in wine sensorywork. However, the work of Zanchi and others is suggesting thatlarger fractal aggregates may induce changes in texturalcharacteristics rather than a change in lubrication that wouldbe the traditional view of the astringent response. And in 2013,Gibbons and Carpenter (J. Texture Stud. vol. 44, pp. 364–75)argued that ‘astringent stimuli alter the salivary bulk, salivarheology and the saliva pellicle leading to an increase offriction in the oral cavity’. So, I am not alone!

When next at a wine tasting, if you find your assessment ofastringency differs from the rest of the group, you couldcomment that ‘clearly the combination of my salivary flowtogether with the phenolic conformer interactions with mysaliva as well as the phenolic interactions with the lipids in myoral cavity means that my assessment will be different’. Or youcan simply say, as I do, ‘I am right and the rest of you arewrong’! That usually starts a good argument, especially after aday of tasting.

grapevine


Prediction of astringency

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.

Recently, the national mediahas reported incidents ofplagiarism and cheating byyear 12 and university students.Plagiarism is not just practised bystudents; nor is it new. There havebeen reports of scientists, politicians andothers engaging in plagiarism and other forms ofcheating. There is even a RetractionWatch website.

The internet,electronic resources,books and otherresources provide aninformation-richenvironment, in which it isextremely easy to copyinformation. Sometimes suchcopying constitutes misconduct but atother times copying is not misconduct. For example, discussionabout occupational health and safety probably requires theinclusion of the exact wording of the relevant legislation.Whether copying is or is not misconduct can be confusing.

According to a widely used classification suggested byOxford Brookes University, there are six ways to use sources. 1 Copying a paragraph verbatim from a source without any

acknowledgment2 Copying a paragraph and making small changes, e.g.

replacing a few verbs, replacing an adjective with asynonym; acknowledging in the bibliography

3 Cutting and pasting a paragraph by using sentences from theoriginal but omitting one or two and putting one or two in adifferent order, no quotation marks; acknowledging in thetext and bibliography

4 Composing a paragraph by taking short phrases from anumber of sources and putting them together using words ofyour own to make a coherent whole with in-textacknowledgments and a bibliographical acknowledgment

5 Paraphrasing a paragraph by rewriting with substantialchanges in language and organisation; the new version alsohaving changes in the amount of detail used and theexamples cited; citing source in bibliography

6 Quoting a paragraph by placing it in block format with thesource cited in text and in bibliography

At senior secondary and tertiary levels, point 1 is plagiarism;point 6 is not. What is considered plagiarism depends on theculture of the community. For example, it is the culturalpractice in some disciplines to quote verbatim, sometimeswithout citing the source if the source is extremely well known.What is considered well known depends on the particularcommunity.

Teachers and educators are often reluctant to discussplagiarism. They are afraid that discussion in a public forummay help the small number of dishonest or lazy students to

plagiarise (cheat) and to avoiddetection procedures. This

silence also causesproblems. A fewyears ago, a northAmerican study of

two universitystudent cohorts found that

the students in this samplegenerally considered themselves honest

and that most of them stated that cheating wasnever acceptable, or acceptable only in rare

circumstances. However, a number of them did report that theyhad engaged in practices that many academic staff consideredas cheating, suggesting that these practices were partially dueto ignorance of what was considered acceptable academicpractice. The silence also means that teachers and educatorsoften have inconsistent notions and expectations of acceptableacademic practice, by drawing the line between acceptablepractice and plagiarism at different points in the classificationof the use of sources.

A further problem is that plagiarism can affect staff morale.In common law, Blackstone’s formulation says that it is betterthat ten guilty persons escape than one innocent suffers. Sinceacademic misconduct depends on whether it was an honestmistake or whether there was an intention to cheat, oftenschool and university authorities only issue a warning withoutfurther penalty or consequence, in applying this legal principle.Teachers and educators can then feel that the institution doesnot care about plagiarism, which serves to discourage themfrom tackling plagiarism.

A previous column (February 2014 issue, p. 38) discussedthe importance of including ethics as an essential part ofchemistry education. What is needed to reduce plagiarism andother forms of cheating is better education and clarification ofwhat is considered acceptable and unacceptable practice,reducing the opportunities and motivations for cheating, andobviously acting to detect and penalise all forms of cheating.But we can all start by discussing the issue and modelling whatis ethical professional practice.

education

Chemistry in Australia| September 201540

Plagiarism is a dirty word

Kieran F. Lim ( ) FRACI CChem([email protected]) is an associate professor in the Schoolof Life and Environmental Sciences at Deakin University. Thecontent of this column has been influenced by, and partly based on,the work of other authors. Full citations are available on request.

iStockphoto/Sielan

The exploitation of Australian natural products has a longhistory, in which the Xanthorroea or blackboy turns up fromtime to time. The earliest reference I found was in theMemorials and Proceedings of the Chemical Society (of London)in 1845 (vol. 3, pp. 10–13). It was a paper entitled‘Observations on the Resin of the Xanthorœa hastilis, or YellowGum-resin of New Holland’ by John Stenhouse, Esq., PhD.

Stenhouse was born in Glasgow in 1809 and after a longcareer ‘down south’ he died in London in 1880 and his body wasreturned to his native town for burial. Since the PhD did notappear in Scotland or England until much later than 1845, hemust have earned this degree on the continent, probably in thetime he spent with Justus Liebig, 1837–9, in Giessen. Returningto England, he took up an appointment as professor in St Bartholomew’s Hospital and remained there until 1857,during which time he was elected a Fellow of the Royal Societyin 1848. A stroke in 1857 terminated his hospital career butafter recuperating at a Mediterranean resort, he set up shop asa consultant chemist with rooms in London. Laboratory workwas out of the question but his assistants performed well and in1865 he was appointed as assayer to the Royal Mint, a titularappointment that did not require actually doing the assaying.His chemical work, which included other natural products,dyeing, waterproofing, textile chemistry, glues, tanning and theuse of wood carbon in deodorising and in respirators earnedhim the gold medal of the Royal Society in 1871.

In his 1845 paper, Stenhouse described it as ‘this remarkableresin, which is known in commerce as the yellow gum or acaroidresin of Botany Bay’ that ‘exudes from the Xanthorœa hastilis, atree which grows abundantly in New Holland, especially in theneighbourhood of Sidney (sic)’. He went on to observe that the‘resin was first described in Governor Phillip’s Voyage to NewSouth Wales in 1788’ and that Phillip believed that it was‘employed by the natives and first settlers as a medicine incases of diarrhœa’.

By repeated crystallisation from aqueous alcohol, Stenhouseisolated a small amount of an acid that carbon and hydrogenanalyses suggested was a mixture of cinnamic and benzoicacids. The presence of cinnamic acid was consistent with theproduction of ‘oil of bitter almonds’ when it was treated withmanganese dioxide and sulfuric acid. The benzaldehyde waspresumably identified by smell, since Stenhouse gives nodetails.

When the resin is treated with moderately strong nitric acid,Stenhouse wrote, ‘a violent action ensues with the evolution ofnitrous fumes’, and evaporation of the solution produced ‘amass of fine yellow crystals, consisting chiefly of carbazoticacid, but mixed with some oxalic acid and a little nitrobenzoic

acids’. No evidence is produced about the identities of the by-products, but carbazotic (= picric) acid was identified bycombustion analysis of the acid and its silver salt. We canspeculate that the complex structure of the resin was brokendown by oxidation by nitric acid, and then nitro groups wereadded to the carbon skeleton, replacing hydrogen or carboxylsubstituents.

The yield of picric acid was high and it was easily purifiedfrom the reaction mixture, causing Stenhouse to opine that‘this resin seems likely to prove the best source of thatsubstance’. He did not discover the explosive potential of picricacid, which had to await the researches of Sprengel in 1863,and he would not have imagined its use in warfare under thename ‘Lyddite’. In 1849, Stenhouse did discover a nitrate esterthat was extremely shock sensitive. It was formed from‘erythromannite’ that he had extracted from a lichen, byreacting it with a mixture of sulfuric and fuming nitric acids,and was apparently a pentanitrate. He was working by analogywith the work of French chemists who had, two yearspreviously, converted mannite (mannitol) into its pentanitrate.The French chemists described their compound as ‘a curiousdetonating compound’ that ‘possesses the remarkable propertyof detonating so violently when struck with a hammer’ andothers observed that it might be used as a substitute forfulminate in percussion caps.

Stenhouse reported the results of his combustion analyses indetail, and they match pretty well for the C4H10O4 formula oferythritol but with the hydrogen result a little high. However,such was the state of chemical knowledge at the time that hetook the atomic masses of carbon and oxygen as 6 and 8,respectively, so he calculated that erythritol was a C11

compound and in like vein he accepted that mannitol, which wenow know is a hexitol, was a C12.

Later in the century the Xanthorroea resin found use invarnishes, and quantities of it were exported from Australia,ostensibly for that purpose. By the early 20th century, however,suspicious minds noted that the major destination for theexports was Germany, and memories of the production of picricacid were stirred. The eventual result, as war neared, was anembargo on such exports. Phenol from coal tar and later frombenzene, courtesy of the burgeoning chemical industry, becamethe major source of picric acid for explosives.

letter from melbourne


Ever heard of carbazotic acid?

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.


cryptic chemistry

Across9 Opening for if I centrifuge in it. (7)10 Make it item A. Copy? (7)11 Two letters sounded out collapse. (5)12 Supplies apparatus. (9)13 Thought about it and gave it back. (9)15 1024 holding somewhat to yellowcake

inversion. (5)16 Dog split present. (7)18 So cap uranium and sulfur at the

temperature at which melting begins. (7)20 Extract electron tube. (5)22 Relocates decals. (9)25 Airing may damage abstract. (9)26 Capacity to make it. (5)28 One sound compound! (7)29 Use of solvent to extract line-out

restart?! (7)

Down1 Hydrogen with aged supporter. (6)2 30 = last in 6. (4)3 First lemon extract with lysine used to

make a reactive intermediate whichcontains a neutral divalent silicon atom. (8)

4 Choose, sulfur. Choose! (6)5 We object after three pound the

temperature at which melting iscomplete. (8)

6 Does sulfur indicate plainly? (6)7 C20H19N3· HCl made. Get any

reaction? (7,3)8 True! Sulfur, aluminium and nitrogen

combine to form unaligned states. (8)14 Prepared four malted concoctions. (10)16 Revolutionary claim about one of our

substances. (8)17 Used 16 Down analytical method bird

assessed. (8)19 Shiny excitement with sour mixture. (8)21 Stand two effects of drug use. (6)23 Yes! Ran around the compounds. (6)24 Enigma: 16151537 unknown. (6)27 A 10 is a point about which it all

revolves. (4)

events

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

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

11th Australasian Conference on VibrationalSpectroscopy and 5th Asian Spectroscopy Conference 29 September – 2 October 2015, Sydney, NSWhttps://acovsandasc.wordpress.com

Medicinal Chemistry and Chemical Biology VicSymposium 30 September 2015, Parkville, Vic.http://wired.ivvy.com/event/BOD501

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

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

HAZOP Study for Team Leaders and Team Members20–22 October 2015, Perth, WAwww.icheme.org/hazopperth#.Va22kEW8Kfc

7th International Conference on Recent Progress inGraphene and Two-dimensional Materials ResearchConference 25–29 October 2015, Lorne, Vic.http://rpgr.physics.monash.edu.au

Australia and New Zealand Magnetic ResonanceSociety Conference29 November – 3 December 2015, Bay of Islands, NZhttp://anzmag2015.co.nz

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

RACI events are shown in blue.

Coming up• Salmon and their strontium

signatures

• Regulating e-cigarettes

• Public perceptions of chemistry

• Stay tuned for November's publicedition!

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The RACI’s ‘Chemistry is Everywhere –Bubble Mania’ Schools Program has beenbringing the fun and excitement ofscience to schools across Victoria.

The new program has been designedto highlight the role that chemists playin the development of everyday products.Students look at the maths, physics andchemistry of bubbles before taking onthe role of formulation chemists trying todevelop the formula for the ultimatebubble. Along the way, they learn aboutthe chemistry of water, detergents andthe various industrial applications ofbubbles.

There is some serious science inbubbles. Students look at how somethingas seemingly simple as a bubble isactually very complex and how bubbleshave fascinated scientists andmathematicians from Newton to Einsteinand Joseph Plateau.

Learning science and chemistry isseen by many as difficult or boring, butthis program strives to break down thosebarriers and highlight the wonderfulworld of science through fun hands-onactivities. After all, everybody lovesbubbles.

According to Esha at St Patrick’sPrimary School in Stawell: ‘It was themost exciting science lesson I have everhad and I can relate it to what may beahead when I partake in science atsecondary school.’

Ashley H at Irymple Secondary Collegesaid he ‘can’t believe how much there isto know about bubbles. Such a simpleactivity contains so much complexity.’

The program is suitable for upperprimary years 5 and 6 to secondary year 10 with the chemistry adjusted ateach level to match the students’ sciencelevel. It is a hands-on program with thestudents actively involved in preparingand testing their formulas. It is seriousscience and a lot of fun. The program canbe used to introduce a range of science-related topics and investigations and ismapped to the AusVELs sciencestandards.

The program is self-contained and

does not require anything from theschools other than space and students.Each session can cater for up to36 students and runs for 100 minutes.Each student receives theory andworkbooks. The RACI is committed tomaking the program accessible to schoolsacross the state.

For further information, details orcosts or to organise a program for yourschool, contact the RACI Victorian BranchCoordinator on (03) 9328 2033 or at [email protected].

Matthew Corkhill

events


Bringing bubble mania to Victorian schools

Liam of Alexandra Secondary College with his bubble and St Patrick’s Primary School,Stawell, students Kobe and Ajay working on their bubble geometry.

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chemistryPlan draft document highlighting Australia’s current position ... ph 0419 107 143 [email protected] PRODUCTION Co ntrol Publications Pty Ltd Ph/fax (03) 9500 0015/0255