Indigenous people and chemistry - Chemistry in Australia ... · The editorial, production and advertising team of Chemistry in Australia is a small and efﬁcient group that is great

• Launching the Decadal Plan for Chemistry• New creations in the periodic table• Carbon sinks beneath the desert

in Australiachemistry

May 2016

chemistry

Indigenous peopleand chemistry:addressing theparticipation gap

chemaust.raci.org.au

The RACI National Awardsrecognise and promote thecontributions and achievementsof our members.

The awards cover a broadrange of areas and are aimed atthe full membershipdemographics.

They are open to all membersof the RACI. Some can beapplied for by the candidate;others have to be nominated bythird parties.

National AwardsAcademia: Applied Research Award Cornforth Award CS Piper Award HG Smith Memorial Award Rennie Memorial AwardDistinction: Citation Distinguished Contribution to Economic Advancement (Weickhardt) Award Distinguished Fellowship Award Leighton Memorial AwardEducation: Fensham Award for Outstanding Contribution to Chemical Education RACI Chemistry Educator of the Year AwardYoung Chemists:Masson Memorial Award

MRACI Post Graduate Student Travel BursaryAn amount of $2000 to assist Post Graduate Student members of the RACI to travel professionally from their home institution, to collaborate with a research group, at another Australian university or overseas, or to make use of specialised research facilities (e.g. an advanced light source), or to deliver a paper at a meeting overseas.

Full details of the awards and the requirement criteria can be found on the RACI website at:

www.raci.org.au/events-awards/national-awards-2016

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cover story

news & research7 News15 On the market16 Research19 Aust. J. Chem42 Cryptic chemistry42 Events

members4 From the President28 From the RACI30 New Fellow

views & reviews4 Editorial5 Your say31 Books34 Economics36 Plants and soils39 Grapevine40 Environment41 Letter from Melbourne

24 Completium! Race to the end of period 7Four more superheavy elements have made it to the periodic table, but whatevidence did their creators need to get them there?

28 Chemistry: the next 10 yearsThe 2016–2025 Decadal Plan for Chemistry supports growth in chemicalmanufacturing and research, explains the working group chair.

Increasing Indigenous presence in chemistry A lack of Indigenous people in chemical science is not unique to Australia.We can learn much from progress made in the US.

24

Angkerle (Standley Chasm), part of the Iwupataka Land Trust in the Northern Territory. At the 2011 nationalcensus, Aboriginal and Torres Strait Islander Australians constituted 30% of the population of the NorthernTerritory, the highest proportion of any state or territory. Two-thirds of Aboriginal and Torres Strait IslanderAustralians were living in regional or remote areas of Australia. (Source: Australian Bureau of Statistics).

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20162016

Since the publication of the March edition, a few readers havecontacted me to find out more about the table of esters andtheir smells on the back cover. This table, and a similar one onthe back cover of this month’s issue, are the brainchild ofJames Kennedy, a VCE chemistry teacher at Haileybury inMelbourne. James very kindly gave me permission to use someof the excellent graphics on his website(jameskennedymonash.wordpress.com).

The magazine would be a bunch of blank pages without thegratis contributions of feature writers and columnists, andothers like James. Each month, I search for good stories aboutchemistry and of interest to chemists. I have some more ideasfor infographics, so keep a lookout. Better still, please send meyour infographic suggestions.

After I come up with some story possibilties, I must findwriters and tailor articles to the Chemistry in Australia audience.It’s so stimulating to be able to collaborate with many peoplein this process, and to be able to offer the end results toreaders each month.

The editorial, production and advertising team of Chemistryin Australia is a small and efficient group that is great at long-distance professional relationships. Their home offices rangefrom Melbourne to Gippsland to Tasmania, with a printer inSingapore. Thanks to ICT, the magazine can be produced verywell with this arrangement, but occasional face-to-facemeetings are nice to have nonetheless.

After a short stint as a research chemist, I started with themagazine nearly 20 years ago and have been involved in-houseor freelance for most of the time since then. CatherineGreenwood has been involved with Chemistry in Australia, offand on, for 20 years. Her current role is production editor – shesubedits and works out the layout of each issue – how features,news, reviews and columns will all fit in with any advertisingmaterial that needs to be included.

Catherine and I choose suitable images and she designs thefeature articles. Catherine and I edit the text and then send it,along with sample layouts, to Guy Nolch, who has beentypesetting the magazine for more than a decade. Guy combinesthe text, images and advertisements to transform our combinedediting and design efforts into the vibrant pages you turn ineach edition of the printed magazine. After several rounds ofproof checking, including authors’ corrections, the magazine’sfinal layout is uploaded to the printer.

Marc Wilson of Gypsy Media services is the appointed mediarepresentative for all RACI media, including Chemistry inAustralia, the RACI website and all RACI e-newsletters. His roleis to prospect, attract and convert third-party companies toadvertise their products and services to the members in thevarious RACI media.

Marc has been representing the RACI now for five years, andhe is a part of the team that has guided Chemistry in Australiainto the high-quality publication that it is today.

The dedicated website, launched in 2014(chemaust.raci.org.au), provides access to the content of theprint magazine, plus a news feed, indexes and a magazinearchive, and more.

Gratis contributions are not limited to writing. Twocommittees assist the running of the magazine: a managementgroup, which discusses finances, advertising and generaleditorial matters; and a subcommittee, which meets to talk inmore detail about the content that is published. The magazineis supported in many ways by these generous volunteers.

EDITOR Sally WoollettPh (03) 5623 [email protected]

PRODUCTION EDITORCatherine Greenwood [email protected]

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

PRODUCTIONControl Publications Pty Ltd [email protected]

BOOK REVIEWSDamien [email protected]

RESEARCH HIGHLIGHTSDavid [email protected]

GENERAL ENQUIRIESRobyn TaylorPh/fax (03) 9328 2033/[email protected]

PRESIDENT Paul Bernhardt FRACI CChem

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

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.

© 2016 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 | May 2016

editorial

Sally Woollett ([email protected])Thanks to Guy, Catherine and Marc for providing someinformation for this editorial.

Cover-to-cover chemistry

http://chemaust.raci.org.au

CSIRO’s futureRecently there have been several articles in the press about thecuts to staff and changes in climate positions in the CSIRO.

Even the previous Chief Scientist has expressed concern onABC Radio about what is planned for the CSIRO. About2900 researchers from nearly 60 nations have expressed concernabout plans to halve the number of researchers working onclimate monitoring and modelling.

In the September 2015 issue of Chemistry in Australia, LarryMarshall was described as a serial entrepreneur, venturecapitalist and private investor. He has gone to the US to try andsecure deals for the CSIRO to be engaged in big projects(Sydney Morning Herald 13–14 February 2016).

A proposed cut of 100 full-time positions out of about140 staff alarmed the global research community.

There are ethical, scientific and economic reasons for havinga strong climate change unit at CSIRO. Ethically, climate changeand the world’s ability to survive must be a major concern forCSIRO and Australia given our place in the Pacific. Scientifically,the impact and flow-on from these cuts could be large. AlreadyCSIRO has developed exceptional data, monitoring techniquesand sustainability projects in urban and rural societies short ofwater or food resulting from climate change.

A change in direction for the CSIRO will come at a loss forthe basic issue for this world, which is the nature, causes andremedies for climate change. Spin-off from climate changeresearch has already created industry for the future.

Christopher Michael Owens FRACI CChem

High-tech nonsenseWhat a refreshing change from the stuff in the hack media toread the article by Ian Maxwell (March issue, p. 36). In additionto the frequent press nonsense about ‘high-tech, innovationetc., etc.’ we also are frequently assailed by motherhoodstatements from politicians and press hacks about the hugeshortage of STEM-qualified young scientists and engineers andthe consequences for the future of Australia.

Given that the Australian workplace is a ‘free market’, in sofar as supply and demand regulate salaries and workingconditions, one would expect sky-high salaries for people insuch ‘high demand and importance’. This appears not to be so(with the possible exception of financial mathematicsspecialists) and it does make me wonder as to the motivation ofthe spruikers of this material.

B.F. Gray FRACI CChem

Thoughts from the February issueThe February 2016 edition of Chemistry in Australia againprovided many points for further thought and discussion.

Firstly, congratulations to Clarrie Ng of ABG and RichardThwaites of A&W, who I remember from my years spent at BBA– the biggest flavour house in Australia in the 1970s, when ABG

was a customer and A&W a sister company. Clarrie and Richardare the only two RACI 2015 National Award winners who spenttheir professional careers in industry; the other 10 recipientsare all from academia or teaching.

From some demographic data prepared by RACI (May 2015),58% of RACI members were classified as ‘Commercial’ and yetanecdotally industry is under-represented in the annual awards,while many of the major articles in Chemistry in Australia have apractical approach.

The main time we appreciate the chemistry input fromindustry-based members is in the Obituary column. In myopinion, industry members should have their stories told beforethe final word is written of their lives.

Secondly, the article by Kieran Lim, ‘Improving laboratorylearning’ (p. 36), makes some great points, particularly aboutthe ‘decline in STEM’ enrolments, which is reflected in numbersand quality of graduates available for industry.

However, the two photos accompanying the article showstudents conducting laboratory experiments without safetyglasses, even if in the breaking strain experiment it appearsunlikely that safety glasses are required. The metal corrosionexperiment offers no excuse, although one student is wearingglasses (optical or safety?) and both are wearing gloves andproper aprons as an option to laboratory coats.

This same error occurred several years ago in an earliereducation article, which showed a group of overseas women in atitration situation wearing reasonable safety equipment butagain no safety glasses.

Thirdly, on a lighter note, on receipt of the February edition,my immediate and habitual attention to Ian Rae’s Letter fromMelbourne was diverted by the back page, which is usuallyreserved for advertisements. This particular back page may bealso an ad but I could not immediately or on further inspectiondetect the ‘message’. This particular page was innovative in thevisual and practical manner of showing the chemistry of estersthat are part of the organoleptic spectrum of foods andparticularly flavours. There are many lists, tables and descriptivepages providing the same information but none as dramatic oreducational yet simple and illustrative as this back page.

Tony Zipper FRACI CChem

your say

Chemistry in Australia 5|May 2016

your say

Two letters critical of my article on countering science denialunfortunately display a lack of awareness of the scholarlyresearch into science denial.

First, Chris Fellows objects to the term ‘denial’ in reference tothe rejection of climate science. However, a large body ofpsychological research examines what drives rejection of scientificevidence and how scientists might respond. This is necessary tounderstand why people might reject humans’ role in causingglobal warming when many independent lines of empiricalevidence find human fingerprints in climate change. Thesefingerprints include satellite measurements of outgoing heat, thechanging structure of the atmosphere and the shrinking annualcycle with winters warming faster than summers. Thesefingerprints also rule out other natural causes – and yet climatescience deniers persist in attributing climate change to naturalcauses. The consilience of evidence has resulted in a consensusamong climate scientists, with 97% of publishing climatescientists agreeing that humans are causing global warming.

Psychological research finds that the strongest predictor ofclimate science denial is political ideology. Politicalconservatives are more likely to reject humans’ role in climatechange because of the policy implications: regulation ofpolluting industries. Psychological experiments have also foundthat presenting scientific evidence has little effect on those

who reject climate science, and can be counter-productive. Theimplications of this research are that climate science denial isexpected to persist despite the strengthening evidence (and,indeed, this has been observed). Consequently, scientists needto develop evidence-based responses to misinformation.

Second, Ray Hodges argues that ‘percentages do notconvince’, referring to my mention of the 97% consensus andrefutation of the 31 000 dissenting scientists argument.Psychological research says otherwise. Public perception of thescientific consensus is a ‘gateway belief’, meaning people useexpert opinion as a mental shortcut, or heuristic, to guide theirviews on complicated scientific matters. Communicating the97% consensus has been observed to significantly increaseacceptance of climate change, particularly amongconservatives. Conversely, the 31 000 dissenting scientistsargument is one of the most potent climate myths in loweringacceptance of climate change. My own research, usingrandomised psychological experiments, found that explainingthe ‘fake expert’ fallacy in the 31 000 dissenters argumentcompletely removes the influence of this particular myth. Myresults have been replicated by researchers at Yale University,who also found that explaining the techniques of science denialis a potent strategy in neutralising misinformation.John Cook


I am unhappy with the philosophy that Iperceive to underlie John Cook’s essay oncountering ‘science denial’ (March issue,p. 28). Science is a process, not aninerrant collection of facts. ‘Sciencedenial’ does not consist of advancing ahypothesis contrary to a consensusposition, but of – for example – refusingto consider alternative hypotheses whenthe predictions of a hypothesis are notconfirmed by observation; rulingalternative explanations for observationsout of bounds for discussion on groundsother than scientific ones; and applyingpejorative labels to people who disagreewith you rather than addressing theirsubstantive criticisms.

As a science communicator, I thinkthe greatest disservice to science I cando is push a simplified emotive version ofsome ex cathedra truth. My duty is toimpart a true sense of the complexity ofthe universe, how science allows us tobegin to understand that complexity, andthe contingent nature of theunderstanding we achieve.

Chris Fellows FRACI CChem

Congratulations for the March issue,which included several informativecontributions appropriate for teachingchemistry (e.g. your editorial plus articlesfrom Jeff Hughes, John Cook, DuncanSeddon, Ian Maxwell and Ian Rae).

A difficulty for teaching often comesup when science involves society. When Iwas teaching, one topic involvedmisrepresentation within a subject‘Science and Society’. This was intendedto alert students to some of the tricksused in politics, prospectuses,shareholder reports, and even equipmentbrochures to sugar-coat objectives. Wecovered things such as ‘gee whiz’ graphs,distorted bar graphs, cherry-picking, buzzwords and inappropriate use ofpercentages to exaggerate facts. Not onlydid this approach allow students to seethrough the fog of misinformation, but apossible side effect was teaching themhow to create ‘spin’ if they were everasked to do so in a workplace.

In the important contribution ‘Bustingmyths’, the author advocates giving factsfirst, then uses an analogy of acourtroom plus refers to a challenge

given to Rutherford to keep explanationssimple. These are important for allowingan untrained jury to reach a verdict.When applying the proposed method inthe author’s example of climate changemyths, key facts supplied involvepercentages of opinions. Withoutdebating the complexities of climatescience, this practical example appearsself-defeating. To say 99.9% of thepetition of 31 000 dissenting scientistswere not peer-reviewed ‘climate’scientists contradicts the article’s intent.Simple facts do convince other scientists.Phrases used in the past such as ‘thescience is settled’ or advocating a ‘noregrets’ policy and percentages do notconvince. Most of the 31 000 so-called‘deniers’ would not argue with facts suchas [CO2] has doubled to 0.04% sinceindustrialisation or that we are in acurrent warm period, but differ on thecause. Reversing [CO2] is costly toachieve; better options would be toreverse other humankind degradations toour planet.

Ray Hodges FRACI CChem

Denying science

Researchers at the US Department of Energy’s Lawrence BerkeleyNational Laboratory (Berkeley Lab) have developed a newimaging technique, tested on samples of nanoscale gold andcarbon, that greatly improves images of light elements usingfewer electrons.

MIDI-STEM (matched illumination and detectorinterferometry scanning transmission electron microscopy(STEM)), combines STEM with an optical device called a phaseplate that modifies the alternating peak-to-trough, wave-likeproperties (the phase) of the electron beam. This phase platemodifies the electron beam in a way that allows subtle changesin a material to be measured, even revealing materials thatwould be invisible in traditional STEM imaging.

The highly focused beam of electrons used in traditionalSTEM can easily destroy delicate samples, so a low-electrondose is needed to image biological or other organic compounds,such as chemical mixes that include lithium. Cryo-EM, anelectron-based technique used to determine the detailedstructure of delicate, frozen biological samples, is generally notuseful for studying samples with a mixture of heavy and lightelements.

‘The MIDI-STEM method provides hope for seeing structureswith a mixture of heavy and light elements, even when they arebunched closely together,’ said Colin Ophus, a project scientistat Berkeley Lab’s Molecular Foundry and lead author of a study,published in Nature Communications(doi: 10.1038/ncomms10719), that details this method.

If you take a heavy-element nanoparticle and add moleculesto give it a specific function, conventional techniques don’tprovide an easy, clear way to see the areas where thenanoparticle and added molecules meet.

‘How are they aligned? How are they oriented?’ Ophus asked.‘There are so many questions about these systems, and becausethere wasn’t a way to see them, we couldn’t directly answer them.’

While traditional STEM is effective for ‘hard’ samples thatcan stand up to intense electron beams, and cryo-EM can imagebiological samples, ‘We can do both at once’ with the MIDI-STEM technique, said co-author Peter Ercius, a Berkeley Labstaff scientist at the Molecular Foundry.

The MIDI-STEM technique could prove particularly useful fordirectly viewing nanoscale objects with a mixture of heavy andlight materials, such as some battery and energy-harvestingmaterials, that are otherwise difficult to view together atatomic resolution. It also might be useful in revealing newdetails about important two-dimensional proteins, called S-layerproteins, that could serve as foundations for engineerednanostructures but are challenging to study in atomic detailusing other techniques.

‘If you can lower the electron dose, you can tilt beam-sensitive samples into many orientations and reconstruct the

sample in 3D, like a medical CT scan. There are also data issuesthat need to be addressed,’ Ercius said, as faster detectors willgenerate huge amounts of data. Another goal is to make thetechnique more ‘plug-and-play’, so it is broadly accessible toother scientists.

Lawrence Berkeley National Laboratory

news


High-resolution views of lightweightatoms

In MIDI-STEM (right), developed at Berkeley Lab, an electron beamtravels through a ringed ‘phase plate’, producing a high-resolutionimage (bottom right) that provides details about a samplecontaining a heavy element (gold) and light element (carbon).Details about the carbon are missing in an image (bottom left) ofthe sample using a conventional electron imaging technique (ADF-STEM). Colin Ophus/Berkeley; Nature Communications: 10.1038/ncomms10719

news

8 | May 2016Chemistry in Australia

Twelve teachers from schools around New Zealand areheading back into the classroom as confident leaders ofscience within their school community. In December, theycompleted phase one of the Science Teaching LeadershipProgramme, where they worked alongside scientists to gain adeeper understanding of New Zealand’s overarching sciencecurriculum strand, called the Nature of Science, as well asundertaking leadership training.

Now these teachers are returning to school to commencephase two of the program that involves working with students,staff and their local community to enhance the quality ofscience teaching and learning.

An integral part of being selected on to the ScienceTeaching Leadership Programme is that schools or sciencedepartments and their nominated teacher commit to sciencebeing a major professional learning focus where the quality ofscience teaching and learning is significantly enhanced.

Minister of Science and Innovation, Hon Steven Joycelaunched the program early last year, which supports thegovernment’s strategic direction for science in society, asoutlined in the document A Nation of Curious Minds – HeWhenua Hihiri i te Mahara. The program is administered by theRoyal Society of New Zealand.

Royal Society of New Zealand

BASF now has 145 ingredients for personal and home-careproducts certified to the international halal standard HAS23000. Along the entire value chain, strict guidelines for rawmaterial purchasing, manufacturing, filling, warehousing andtransport are followed to ensure product purity in compliancewith Islamic law.

BASF’s portfolio of halal ingredients ranges from sugar-basedsurfactants, pearlisers, emollients and protein derivatives forpersonal care applications – such as facial cleansers or baby

Prediction of iceXVIIA group of chemists, led by Xiao ChengZeng from the University of Nebraska-Lincoln and Jijun Zhao from the DalianUniversity of Technology, have predicteda new molecular form of ice: ice XVII.

If the proposed ice XVII can besynthesised, it would become the 18thknown crystalline form of water, accordingto Zeng, Zhao and their colleagues. Itwould be about 25% less dense than arecord-low form, ice XVI, synthesised byWerner Kuhs from the University ofGöttingen and co-authors in 2014.

‘We performed a lot of calculationswhether this is not just a low-density ice,but perhaps the lowest-density ice todate. A lot of people are interested inpredicting a new ice structure beyond thestate of the art,’ said Zeng, senior authorof a paper in Science Advances (doi:10.1126/sciadv.1501010).

Zeng, Zhao and their colleagues useda computational algorithm and molecularsimulation to determine the ranges ofextreme pressure and temperature underwhich water would freeze into thepredicted configuration. Thatconfiguration takes the form of aclathrate – a series of water moleculesthat form an interlocking cage-likestructure.

It was long believed that these cagescould maintain their structural integrityonly when housing ‘guest molecules’ suchas methane, which fills an abundance ofnatural clathrates found on the oceanfloor and in permafrost. Like Kuhs’ teambefore them, however, the chemists havecalculated that their clathrate wouldretain its stability even after its guestmolecules have been evicted.

Synthesising the clathrate will takesome effort. Based on the team’s

calculations, the new ice will form onlywhen water molecules are placed insidean enclosed space that is subjected toultra-high, outwardly expanding pressure.

According to the Science Advancesarticle, ice XVII is the most stable icepolymorph in the pressure region below−5834 bar at 0 K (–273°C) and below−3411 bar at 300 K (29°C).

Sci-news.com

Proposed molecular configuration of ice XVII. Yingying Huang/Chongqin Zhu


bubble baths – to detergent and cleaning agents, and rawmaterials for the pharmaceutical industry. These ingredientshave been approved by Halal Control, Russelsheim, or the HalalFood Council of Europe, Brussels, which are both recognised bythe Indonesian Council of Ulama (Majelis Ulama Indonesia) – amajor umbrella association of Islamic quality managementorganisations.

BASF

Safe Work Australia has completed an update of theHazardous Substances Information System (HSIS) databaseand the GHS Hazardous Chemical Information List (HCIL) toincorporate assessments made by the National IndustrialChemicals Notification and Assessment Scheme (NICNAS).These changes represent human health assessments made aspart of tranches 1–7 of the Inventory Multi-tiered Assessmentand Prioritisation (IMAP) framework.

This update includes approximately 300 new entries andapproximately 130 amendments to existing entries for bothdatasets. A full list of the changes to HSIS and HCIL can bedownloaded at safeworkaustralia.gov.au.

Safe Work Australia

In search ofEarth’s oldest iceThe search for the world’s oldest ice core– likely to be a million years or older –was among the key topics for a majormeeting of climate scientists in Hobart inMarch.

The International Partnerships in IceCore Sciences (IPICS) Second OpenScience Conference brought more than200 scientists and drilling experts from22 countries to Tasmania for a week ofscientific presentations and planningdiscussions. The conference was co-hosted by the Australian AntarcticDivision and the Antarctic Climate andEcosystems Cooperative Research Centre.

Conference Chair, Tas van Ommen,said: ‘Ice cores are immensely importantto climate science but the logistical andtechnical challenges of drilling ice coresare enormous, and require extraordinarylevels of cooperation between nations.’

Van Ommen said one of the majorpriorities for the conference was progresstoward finding and drilling the world’soldest ice.

‘The oldest ice core retrieved fromAntarctica to date is about 800 000 yearsold, which falls just short of a major shiftin global ice age cycles that occurred

about a million years ago. We think thatmillion year-old ice exists deep withinthe Antarctic icecap, and if we canrecover it, then we can start to piecetogether exactly what caused thisfundamental change in climate cycles.’

Van Ommen said there wasconsiderable optimism about thepotential for new and emergingtechnologies to improve the efficiency ofice core drilling projects: ‘Antarctic ice

cores can be well over three kilometresdeep and hundreds of kilometres awayfrom any permanent base, which tends tomake ice core drilling costly and timeconsuming,’ he said. ‘There is quite a bitof excitement at the conference aboutthe potential for new rapid access drillingtechnology, which can penetrate severalkilometres of ice in just days or weeks.’

University of Tasmania

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

Suppliers of:

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CERTIFIED REFERENCE MATERIALS

CSIRO

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Methamphetamine residue found in thewastewater of a Queensland city hasincreased by a factor of almost five since2009. University of Queensland scientistsfrom The National Research Centre forEnvironmental Toxicology (Entox) workedwith Wayne Hall of the Centre for YouthSubstance Abuse Research to obtain theresults.

‘More than 1000 samples were takenfrom a coastal metropolitan city and amajor inland regional city between 2009and 2015,’ Hall said. ‘Methamphetamineconsumption increased 4.8 times in themetropolitan area over the time frame,and 3.4 times in the regional area. Thiscoincides with a recent study thatshowed an upsurge of more than170 000 regular meth users acrossAustralia between 2009 and 2015, to atotal of 270 000 users nationwide.’

Jochen Mueller of Entox andcolleagues Phong Thai, Foon Yin Lai and

Jake O’Brien collaborated to build onprevious insightful studies featuringwaste testing. Armed with knowledgeabout the ways that specific drugs areexcreted, they used census populationsfor both the metropolitan and regionalcatchments to ascertain their results.

In 2009, the mean for the coastalmetropolitan area was234 mg/day/1000 people, whichincreased to 1126 mg/day/1000 people in2015. The study began a year later in theinland regional city, marked by a mean of115 mg/day/1000 people in 2010, whichincreased to 398 mg/day/1000 people in2015.

Hall said the wastewater analysisalone did not determine whetherconsumption had increased because therewere more users or because existing userswere consuming more. ‘However, whenyou view this together with other timelyresearch, it is consistent with there being

exponential growth in the number ofusers,’ Hall said.

A report on national estimates, led byLouisa Degenhardt from the NationalDrug and Alcohol Research Centre at theUniversity of New South Wales, wasreleased in March. Hall was a contributorto the report, which gave the totalnumber of regular users in Australia as270 000 – greater than the 2014 totalpopulation figures for Hobart (219 243)or Townsville (178 649).

Both the wastewater study(doi: 10.5694/mja15.01054) and thestudy on Australian usage estimates(doi: 10.5694/mja15.00671) have beenpublished in the Medical Journal ofAustralia.

University of Queensland

Methamphetamine residue increase in wastewaterFir0

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Copper at the right time more beneficial for wine

Charles Sturt University (CSU) research is giving winemakers new insight intohow timing the use of copper can work more effectively to remove anunpleasant smell that’s sometimes created during fermentation.

CSU senior lecturer in wine chemistry Andrew Clark said, ‘During thefermentation process, sometimes a tiny amount of hydrogen sulfide can beproduced. The unpleasant smell can be removed by winemakers adding verysmall amounts of copper to bind with the hydrogen sulfide and remove thesmell. The new compound, copper sulfide, is then removed from the wine.’

The research at the National Wine and Grape Industry Centre at CSU inWagga, funded by Wine Australia, found:• copper added early in the production process, when protein from the grapes

is still present, is more easily removed• copper added late in the production process doesn’t bind as effectively and

it is harder to remove• if significant copper sulfide is left in the wine, the copper and hydrogen

sulfide are not inert and copper can still be active in catalysing lessdesirable reactions

• adding copper just before bottling ‘just in case’ is counter-productive.Clark said the research is providing winemakers with valuable information

about the most effective time to add copper if it is needed.The researchers, Clark, PhD student Paris Grant-Preece from CSU, Natalie

Cleghorn, a former CSU student who works for Yalumba, and Geoff ScollaryFRACI CChem from the University of Melbourne have been recognised for theirwork (see February issue, p. 30). Their research paper, ‘Copper(II) addition towhite wines containing hydrogen sulfide: residual copper concentration andactivity’ (doi: 10.1111/ajgw.12114), was named the Australian Society forViticulture and Oenology’s Oenology Research Paper of the Year for 2015.Further research about metals in wine is being conducted at CSU, incollaboration with the Australian Wine Research Institute.

Charles Sturt University

Andrew Clark in the laboratories at Charles Sturt University. Charles Sturt University

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University of Chicago scientists have discoveredevidence in a meteorite that the rare elementcurium was present during the formation of thesolar system. This finding ends a 35-year-old debateon the possible presence of curium in the earlysolar system, and plays a crucial role in reassessingmodels of stellar evolution and synthesis ofelements in stars. Details of the discovery appear inScience Advances (doi: 10.1126/sciadv.1501400).

‘Curium is an elusive element. It is one of theheaviest-known elements, yet it does not occurnaturally because all of its isotopes are radioactiveand decay rapidly on a geological time scale,’ saidthe study’s lead author, François Tissot, from theMassachusetts Institute of Technology.

And yet Tissot and his co-authors NicolasDauphas and Lawrence Grossman have foundevidence of curium in an unusual ceramic inclusionthey called ‘Curious Marie’, taken from acarbonaceous meteorite. Curium becameincorporated into the inclusion when it condensed from thegaseous cloud that formed the sun early in the history of thesolar system.

On Earth today, curium exists only when manufactured inlaboratories or as a by-product of nuclear explosions. However,curium could have been present early in the history of the solarsystem, as a product of massive star explosions that happenedbefore the solar system was born.

The longest-lived isotope of curium (247Cm) decays over timeinto an isotope of uranium (235U). Therefore, a mineral or a rockformed early in the solar system, when 247Cm existed, wouldhave incorporated more 247Cm than a similar mineral or rockthat formed later, after 247Cm had decayed. If scientists were toanalyse these two hypothetical minerals today, they would findthat the older mineral contains more 235U than the youngermineral.

Early studies in the 1980s found large excesses of 235U in anymeteoritic inclusions they analysed, and concluded that curiumwas very abundant when the solar system formed. More refinedexperiments showed that these early results were spurious, andthat if curium was present in the early solar system, itsabundance was so low that state-of-the-art instrumentationwould be unable to detect it.

Scientists had to wait until a new, higher-performance massspectrometer was developed to successfully identify, in 2010,tiny excesses of 235U that could be the smoking gun for thepresence of 247Cm in the early solar system.

Models predict that curium, if present, was in low abundancein the early solar system. Therefore, the excess 235U produced bythe decay of 247Cm cannot be seen in minerals or inclusions thatcontain large or even average amounts of natural uranium. Oneof the challenges was thus to find a mineral or inclusion likely

to have incorporated a lot of curium but containing littleuranium.

With the help of study co-author Lawrence Grossman, theteam was able to identify and target a specific kind ofmeteoritic inclusion rich in calcium and aluminium. These CAIs(calcium, aluminium-rich inclusions) are known to have a lowabundance of uranium and likely to have high curiumabundance. One of these inclusions – Curious Marie – containedan extremely low amount of uranium.

‘It is in this very sample that we were able to resolve anunprecedented excess of 235U,’ Tissot said. ‘All natural sampleshave a similar isotopic composition of uranium, but theuranium in Curious Marie has 6% more 235U, a finding that canonly be explained by live 247Cm in the early solar system.’

Thanks to this sample, the research team was able tocalculate the amount of curium present in the early solarsystem and to compare it to the amount of other heavyradioactive elements such as iodine-129 and plutonium-244.They found that all these isotopes could have been producedtogether by a single process in stars.

‘This is particularly important because it indicates that assuccessive generations of stars die and eject the elements theyproduced into the galaxy, the heaviest elements are producedtogether, while previous work had suggested that this was notthe case,’ Dauphas explained.

University of Chicago

Evidence for curium at solar system formation

The Allende carbonaceous meteorite is peppered with inclusionsthat have a ceramic-like chemistry (red for calcium, blue foraluminium, green for magnesium in the false colour image shown;field of view is 0.5 mm). When they formed, these inclusionsincorporated the short-lived nuclide curium-247 (with a half-life of15 million years), traces of which have been detected as asignificant excess in uranium-235, its decay product. François L.H. Tissot


Gene regulation boostsammonia productionNitrogen fixation in cyanobacteriametabolic processes may provide animportant means for producing ammonia, acrucial ingredient in the chemical industry.Regulating the cellular processes involvedto optimise microbial ammonia productionhas been a challenge. Researchers at TokyoInstitute of Technology have successfullydemonstrated a gene regulation strategyfor enhancing ammonia production in thecyanobacterium Anabaena strain PCC 7120(A. 7120).

The researchers first investigated thegene expression system in Anabaenausing tetR (tetracycline resistanceregulatory gene) promoter, which isregulated by anhydrotetracycline.Anydrotetracycline is an antibiotic knownto have a strong affinity to the Tetrepressor protein, TetR. When a nitrogen-dependent tetR promoter was used, theyobserved a nitrogen-dependence in theamount of anhydrotetracycline needed toexpress the desired gene.

For the production of ammonia, theresearchers repressed expression of glnAwith an antisense small RNA. The geneglnA encodes an essential enzyme,

glutamine synthase, for nitrogenassimilation in cyanobacteria. Theantisense RNA – which represses it – wasexpressed under the control of thepromoter previously used in this study,and tetR was expressed under the controlof the nitrogen-dependent promoter.They successfully observed increasedexcretion of ammonia when theexpression of antisense RNA was induced.

They conclude: ‘These resultsdemonstrated that the antisenserepressors, used as the regulators ofendogenous gene expression, maybecome useful tools for the production ofdesired substances in A. 7120.’

The study was published in Plant andCell Physiology (doi: 10.1093/pcp/pcv202outer).

Tokyo Institute of Technology

Plant biologists at the University ofWestern Australia (UWA) have discoveredthat the commonly used antibioticciprofloxacin, which kills bacteria, alsokills plants by blocking the DNA copyingmachinery of the plants.

The research, published in the Journalof Biological Chemistry(doi: 10.1074/jbc.M115.689554), was acollaboration between UWA researchersand Tony Maxwell from the John InnesCentre in the UK. The work at UWA wascarried out by graduate research assistantJulie Leroux and Joshua Mylne, a FutureFellow in UWA’s School of Chemistry &Biochemistry and affiliated to the ARCCentre of Excellence in Plant EnergyBiology.

Mylne said theresearchers found aplant that could growon ciprofloxacin andby working out whichgene mutationenabled this, couldprove how theantibiotic killed plants. ‘The machinerythat ciprofloxacin affects is not currentlytargeted by known herbicides, making thisan untried mode of action to focus on.’

This work built on prior knowledgefrom Maxwell’s lab that the enzyme DNAgyrase (part of the DNA copyingmachinery) is made in plants and isessential in plant growth anddevelopment.

By generating mutations in the modelplant Arabidopsis thaliana and findingone plant that is resistant to theantibiotic ciprofloxacin and analysing itsgenome, the team confirmed that DNAgyrase in plants can be targetedeffectively by this antibiotic.

University of Western Australia

Common antibiotic inspires hunt fornew herbicide

The metabolic engineering system for ammonia excretion developed in the study. Duringnitrogen starvation, some cyanobacteria form specialised nitrogen-fixing cells calledheterocysts.

Ciprofloxacin-resistant (columns 1, 6), wild-type (column 5) andresensitised (other columns) Arabidopsis thaliana on a gradedrange of ciprofloxacin concentrations. J. Leroux

news


Concerns have been raised over the long-term use of nutritionalsupplements containing chromium, after an Australian researchteam found the supplement is partially converted into acarcinogenic form when it enters human cells.

Chromium is a trace mineral found primarily in two forms: arange of chromium(III) forms are sold as nutritionalsupplements, while hexavalent chromium(VI) is its ‘carcinogeniccousin’, gaining notoriety from the book and 2000 movie ErinBrockovich, which linked a cluster of illnesses to its presence indrinking water. Controversy remains over whether the dietaryform of chromium is essential, with an increasing body ofevidence indicating it is not safe.

In the study, researchers from the Universities of Sydney andNew South Wales treated cells with chromium(III) beforecreating a map of every chemical element contained inside thecell, using an intense synchrotron X-ray beam at the AdvancedPhoton Source (APS) in Chicago. The team accessed the APSthrough the Federal Government’s Australian SynchrotronResearch Program, which provided researchers with synchrotronaccess prior to the Australian Synchrotron opening in 2007.

Research lead Dr Lindsay Wu, from the University of NSW’sSchool of Medical Sciences, said the high-energy synchrotronbeam allowed the team to identify and classify chromium spots

throughout the cell.‘The powerful X-ray enabled us to determine whether the

spots were chromium(III) or a combination of chromium(III),chromium(V) and chromium(VI).

‘The health hazards associated with exposure to chromiumare dependent on its oxidation state – we were able to showoxidation of chromium inside the cell does occur, meaning itloses electrons and transforms into carcinogenic forms, whichno one had been able to do in a biological sample before.’

Supplements containing chromium are consumed for thepurported treatment of metabolic disorders, such as insulinresistance and type 2 diabetes, but chromium’s mechanism of

action in the body is not well understood.These supplements are also commonly used for

weight loss and body building with some containingup to 500 micrograms per tablet, above the200 micrograms estimated as a safe and adequatedaily dietary intake for adults by the US NationalAcademy of Sciences. Australia’s current NationalHealth and Medical Research Council NutrientReference Values, which are currently under review,recommend 25–35 micrograms of chromium daily asan adequate intake for adults.

Professor Peter Lay from the University of Sydney’sSchool of Chemistry said with the latency period forchromium(VI)-related cancers often greater than20 years, the finding raises concerns over the possiblecancer-causing qualities of chromium compounds andthe risks of taking chromium nutritional supplementslong term or in high doses.

‘With questionable evidence over the effectivenessof chromium as a dietary supplement, these findingsshould make people think twice about takingsupplements containing large doses of chromium.

‘However, additional epidemiological research isneeded to ascertain whether chromium supplementssignificantly alter cancer risk, since long-termlaboratory experiments have not been conducted

under the conditions of high oxidative stress (which promoteschromium(III) oxidation) associated with diabetes.’

The researchers said the findings are very unlikely to applyto trace amounts of chromium(III) found in food.

Experiments were also conducted at the former AustralianNational Beamline Facility at the Photon Factory in Japan,operated by the Australian Synchrotron, which helped clarifythe nature of the chromium(V) and chromium(VI) speciesformed in the cells, both of which can cause cancer.

The research, published in Angewandte Chemie(doi: 10.1002/anie.201509065), was also supported by theAustralian Research Council.

Australian Synchrotron. Original story published by UNSW Media.

Concerns over long-term use of chromium diet pills

The coordination compound tris(picolinate)chromium(III) ismarketed and sold as a nutritional supplement. Hydrogen atomsare omitted in the model shown. Wiki

on the market

May 2016 Chemistry in Australia 15|

Measure surface-moleculeinteractions and detect structuralchangesThe launch of Q-Sense Initiator enables surface scientiststo gain access to the well-established Q-Sense technologyat an entry level. Q-Sense Initiator maintains the core Q-Sense functions and quality while focusing on newcustomer segments who have a need for an introductory Q-Sense system capable of fundamental analysis. The newQ-Sense Dfind software dramatically simplifies datahandling and reporting through an intuitive interface andpowerful tools for complex analysis.

Traditional Quartz Crystal Microbalance (QCM) has beenused for more than 50 years to analyse mass changes onrigid surfaces. However, this technique starts to breakdown when the added mass is not rigidly coupled to thesensor surface.

Quartz Crystal Microbalance with Dissipation monitoring(QCM-D, patented by Q-Sense) enables real-timemeasurements of both mass/thickness (frequency) andstructural properties (dissipation) of molecular layers. Bymeasuring the dissipation parameter (D) the QCM-D allowsfor the accurate analysis of soft films that do not obey thelinear relation between change in frequency and change inmass. In this way, the dissipation parameter provides novelinsights regarding structural (viscoelastic) properties ofadsorbed layers. Combined with the new Q-Sense Dfind, thenext generation analysis software, the user can accessinformation such as mass, thickness, viscoelasticproperties, adsorption rates etc .andquantify, compile and compare data, fromstart to end.

Defining qualities:• Analyse surface-molecule interactions

at the nanoscale• Real-time, label-free technology• Mass, thickness and structural properties• Simultaneously combine with, for example, ellipsometry,

electrochemistry or microscopy• Wide range of sensor surfaces

For further information, contact ATA Scientific Pty Ltd,ph. (02) 9541 3500, email [email protected] visit www.atascientific.com.au

Streaming answers: SurPASS™3Anton Paar launches SurPASS™3 – another milestone in surfacecharge analysis.

SurPASS™3 determines the zeta potential at the surface of amacroscopic solid in contact with an aqueous solution. Thecompact instrument design with plug-in sample holders giveseasy access to material surface charge to everyone – fromscientists in academia to technicians in industrial labs.

The laboratory space occupied by SurPASS™3 is significantlyreduced compared to previous models of streaming potentialanalysers. The compact instrument design does not contain anymoving parts, unnecessary tubing or cables, which may besubject to measuring artifacts. SurPASS™3 keeps the promise ofa real plug-and-measure instrument: simply plug in themeasuring cell and hit the START button.

The enhanced SurPASS™3 principle gives access to zetapotential data in less than three minutes. The high timeresolution for data acquisition and the extremely sensitivemeasurement of streaming potential improve the reliability andreproducibility of zeta potential even in the range below 3 mV.

The operating software of SurPASS™3 offers the selection ofsingle zeta potential data, the analysis of the surfaceisoelectric point, or a full pH scan. The operation modes arecomplemented by the investigation of solute effects on thesolid surface to characterise adsorption and desorptionprocesses.

Independent of sample geometry, size and origin,SurPASS™3 determines reliable and reproducible zeta potentialvalues. Elaborate measuring cells for individual samplematerials give you the utmost flexibility for your quality controland investigations. Mounting sample holders was never thateasy. The measuring cell in use is automatically detected by theSurPASS™3 software.

The lean structure of the SurPASS™3 operating softwarehelps you to focus on the important task: the analysis of thesurface zeta potential of your sample. The software still remainsintuitive even if you do not care much about the physicalbackground of the surface zeta potential. Together with theenhanced measuring principle of SurPASS™3, the softwarefacilitates the fastest route to the zeta potential ofmacroscopic solids.

The full range of Anton Paar instruments and solutions isavailable at MEP Instruments – a Metrohm and Anton PaarCompany. For further information, contact MEP Instruments,ph. (02) 8899 5200, email [email protected] or visitwww.mep.net.au.

research


Chemical-free catalystsIt is often thought that the ability to control reaction rateswith an applied electrical potential gradient is unique to redoxsystems. However, researchers from the Australian NationalUniversity, the University of Wollongong and the University ofBarcelona have recently demonstrated that a simple Diels–Alderreaction can be catalysed with an oriented electric field(Aragonès A.C., Haworth N.L., Darwish N., Ciampi S.,Bloomfield N.J., Wallace G.G., Diez-Perez I., Coote M.L. Nature2016, 531, 88–91). In principle, such electrostatic catalysisshould be possible because most transition structures can bestabilised via minor charge-separated resonance states that canbe further stabilised by an appropriately aligned electric field.However, in practice, orienting molecules in an applied fieldposes a significant challenge. To overcome this problem, theresearchers designed a surface model system to probeunfavourable Diels–Alder chemical reactions and coupled this tothe break-junction technique in scanning tunnellingmicroscopy. They showed that the reaction rate increased withfield strength when the field was negatively biased andremained constant for positive bias, in agreement withquantum-chemical calculations on the same system. The workopens up a new way of studying chemical reactivity and heraldsa new ‘chemical-free’ approach to chemical catalysis.

Living organisms are intricate machinesthat can perform specific chemicalreactions in succession in a highlyregulated manner in a complex molecularenvironment. For example, protein

synthesis can be activated or deactivatedin response to external stimuli in order tocontrol and regulate a specific function.The ability to mimic the precise control ofbiology over molecular structure would

have far-reaching consequences forpolymer synthesis. The research team ofAssociate Professor Cyrille Boyer at theUniversity of New South Wales has takensignificant steps towards this goal. Theyhave taken advantage of selectivephotoactivation of thiocarbonylthiocompounds to implement single-unitmonomer insertion reactions and selectivecontrolled radical polymerisation viavisible light-mediated photo-inducedelectron transfer-reversible addition–fragmentation chain transfer (PET-RAFT)(Xu J., Shanmugam S., Fu C., Aguey-Zinsou K.-F., Boyer C. J. Am. Chem. Soc.2016, 138, 3094–106). Precise single-unitmonomer insertion into dithiobenzoatewas achieved with high yield (>97%) usingan organic photoredox catalyst,pheophorbide a (PheoA), under red lightirradiation. Furthermore, the exceptionalselectivity of PheoA towardsdithiobenzoate was used in combinationwith another catalyst, zinctetraphenylporphine (ZnTPP), to prepare acomplex macromolecular architecture.

Mimicking nature with light-controlled polymerisation


Two-dimensional (2D) crystals such astransition metal oxides anddichalcogenides are leading successors tographene with diverse properties andapplications. As with graphene, theproperties of 2D nanocrystals aresensitive to structural features, includingthickness, lateral size, crystal planes anddefects. Lateral size is particularlyimportant and is correlated withadvanced properties. For example, small2D manganese oxide (MnO2) crystals withmore exposed edge sites are better forelectrocatalysis than large ones. Ingeneral, small 2D nanocrystals are usefulfor applications such as catalysis,biosensing and drug delivery, while largenanocrystals (>500 nm) can stack to formthree-dimensional networks for energystorage. Thus, lateral size control of 2Dcrystals is critical for specificapplications. Professor Shi Zhang Qiaoand coworkers at the University ofAdelaide have reported a universaltechnique for sorting subnanometre-thick

2D crystals according to their lateraldimensions (Chen S., Duan J., Vasileff A.,Qiao S.Z., Angew. Chem. Int. Ed. 2016,55, 3804−8). The technique is based ontuning the zeta potential of aqueousdispersions of 2D crystals, which induces

selective sedimentation of large crystalsand leaves smaller crystals in suspension.Small MnO2 nanocrystals that wereselected in this way demonstratedoutstanding performance aselectrocatalysts for urea oxidation.

Size fractionation of 2D nanomaterials

Revolution in microgram-scaleabsolute structure determination

The determination of the absolute structure of naturalproducts presents a major challenge, particularly foroily compounds that preclude analysis via X-raycrystallography. The research teams of Dr Sylvia Urbanat RMIT University and Professor Makoto Fujita at theUniversity of Tokyo have unveiled the absolutestructure of elatenyne, an oily dibrominated marinenatural product first isolated 30 years ago (Urban S.,Brkljača R., Hoshino M., Lee S., Fujita M. Angew. Chem.Int. Ed. 2016, 55, 2678−82). This was achieved on themicrogram scale using the crystalline sponge method,in which a porous coordination network (a crystallinesponge) capable of absorbing organic guests is used toorder the absorbed guests and thereby render themcrystallographically observable. The study represents the firstapplication of the crystalline sponge method to determine theabsolute configuration of a natural product and provides a newavenue for both natural product and synthetic chemists toobtain complete crystal structures for compounds that wouldotherwise not be amenable to X-ray crystallographic analysis.The ability to establish the absolute configuration of highly

complex bioactive natural products by this method will begroundbreaking, particularly for drug discovery.

research


New medicines and food security measures are critical forcoping with an ever-increasing world population confrontedwith problems such as drug and insect resistance. AssociateProfessor Craig Williams at the University of Queensland and DrJohn Tsanaktsidis and Dr Paul Savage of CSIRO Manufacturinghave taken an innovative step towards tackling this problem. Ina recent study involving an extensive collaborative team, theyshowed that the hydrocarbon cubane, which consists of eightcarbon atoms bonded in the shape of a cube, behaves as asurrogate for benzene, a commonly occurring structural motif inmany pharmaceuticals and agrochemicals (Chalmers B.A.,Xing H., Houston S., Clark C., Ghassabian S., Kuo A., Cao B.,Reitsma A., Murray C.P., Stok J.E., Boyle G.M., Pierce C.J.,Littler S.W., Winkler D.A., Bernhardt P.V., Pasay C., De Voss J.J.,McCarthy J., Parsons P.G., Walter G.H., Smith M.T., Cooper H.M.,Nilsson S.K., Tsanaktsidis J., Savage G.P., Williams C.M. Angew.Chem. Int. Ed. 2016, 55, 3580−5). Organic chemists at theUniversity of Queensland synthesised analogues of a variety ofdifferent drugs, replacing the benzene ring motif with cubane.Extensive biological assessment showed that some analogueshad similar bioactivity to their benzene counterpart, whileothers were superior. The precedent set by this study has thepotential to reduce the time and cost of drug discovery and torejuvenate pharmaceuticals and agrochemicals currently on themarket.

The conjugation of multiple components into a single antigenicconstruct is a promising strategy for vaccine development. Ateam from the University of Queensland School of Chemistry andMolecular Biosciences, School of Pharmacy, and DiamantinaInstitute, has established a synthetic pathway to conjugatepeptide antigens and adjuvant moieties into a single fully-defined multicomponent system (Hussein W.M., Liu T.-Y.,Maruthayanar P., Mukaida S., Moyle P.M., Wells J.W., Toth I.,Skwarczynski M. Chem. Sci. 2016, 7, 2308−21). The syntheticstrategy combined a Michael addition mercapto-acrylateconjugation and a copper-catalysed alkyne-azide 1,3-dipolarcycloaddition (CuAAC) reaction to produce constructs bearing

N-termini conjugated peptide antigens and newly designed self-adjuvanting lipids. The efficiency of this novel technology washighlighted through the production of a library of therapeuticvaccine candidates against human papillomavirus type-16 (HPV-16) infection, which causes most cervical cancers. Thesevaccine candidates targeted the HPV-16 E6 and E7 proteins.However, because of their oncogenic properties, only smallfragments of these proteins were selected as antigens. The leadvaccine candidate produced using this double conjugationstrategy self-assembled into microparticles, induced cellularimmunity, and was able to eradicate a model tumour in 46% ofimmunised mice.

Double conjugation strategy for self-adjuvanting peptide vaccines

Synthetic hydrocarbon breathes new life into drug discovery

aust j chem


Tribute to Brice Bosnich The May issue of the Australian Journal ofChemistry contains a significant number ofpapers that pay tribute to the memory ofa great Australian chemist, Brice Bosnich(or Bos, as he was known to all andsundry). This issue of the journal is guestedited by Bos’s last PhD student, JamesCrowley, who is now at Otago University,and also contains a paper by, from what Iunderstand, his first PhD student, MichaelFryzuk, University of British Columbia, andmany other coworkers.

By no means do I want to supplant the excellent Foreword to the issuewritten by James, but I thought I’d reflect on what I knew of Bos. I’d like tosay that I knew him well, but that’s not quite the truth. The profound effect hehad upon his co-workers and their delight in passing on their stories about hisidiosyncratic ways is really why I feel as if I knew him. Thus, the many stories Iknow about Bos came from my colleague and friend Jack Harrowfield, who wasone of a number of Australians who joined Bos in Canada as postdoctoralfellows.

Others with similar tales of Bos’s delight in upsetting the equilibrium of hisco-workers were S. Bruce Wild and Greg Jackson, and if you ever catch up withBruce you should ask him about the tale of the Meker burner. The followingquote from the online guestbook of The Canberra Times might also help set thescene.

I am one of few women who trained with Brice Bosnich as a PhD chemist. Many consider it abadge of courage. But I also consider myself lucky. Elegant, thoughtful project design,concentration, focus, attention to detail, and respect for the materials, methods and toolsof the trade were high standards set and demanded by Professor Bosnich. They were rarethen. They are almost unheard of now. We snapped to attention when we heard Bos coming,his distinctive gait down the hallway from his office to the lab in Searle. Nicknames, Aussie-isms, debatable politics, bonsai trees and white lab benches so clean that we used them forafternoon tea are other memories that I won’t soon forget. There is no question, oureducation was unique.

Cassandra Fraser, University of Virginia

While Bos’s unique personality was well known, his chemistry was worldclass, and perhaps better known, as evinced by the many awards to Bos. Hiswork in developing rational approaches to the design of chiral diphosphineligands, the best known perhaps being chiraphos, is a case in point. While we,of course, take time for contemplation of a life lived, it should be said thatthese issues of the journal are also a celebration of an individual’s chemistryand more importantly the impact of that individual on others.

I’ll leave you with the dedication from Jack Harrowfield’s contribution to theissue: ‘Vale Bos, we miss his cheerful and memorable hypercynical and irreverentaphorisms, e.g. “In the land of the one-eyed, the two-faced man is king”.’

George Koutsantonis FRSC, FRACI CChem ([email protected])

Affordable additives forageless gas-separationmembranesThe key to commercialising polymermembranes that do not age is to use ahighly dispersible and scalable additive.Following up from their previous work onselectively ageing polymer membranescontaining porous aromatic frameworksproduced via onerous chemical reactionconditions, CSIRO researchers led by Dr CherHon (Sam) Lau, Dr Matthew Hill and Dr ColinWood have made significant steps towardscommercialisable ageless polymer membranesfor carbon capture from flue gases andnatural gas (Lau C.H., Mulet X., Konstas K.,Doherty C.M., Sani M.-A., Separovic F.,Hill M.R., Wood C.D. Angew. Chem. Int. Ed.2016, 55, 1998−2001). By using affordabledichloroxylene-based hypercrosslinkedpolymers as additives, they effectively haltedageing in polyacetylenes without sacrificinggas permeability. Membrane fabrication timewas also drastically reduced compared withthat for porous aromatic frameworks. Thesuperior processability of thesehypercrosslinked polymers is due to theirinherent particle size. The study advancesmembrane use for alternative energyproduction. The CSIRO team is expandingthis study to solvent separations andpharmaceutical purification.

Compiled by David Huang MRACI CChem([email protected]). This section showcasesthe very best research carried out primarily in Australia.RACI members whose recent work has been published inhigh impact journals (e.g. Nature, J. Am. Chem. Soc.,Angew. Chem. Int. Ed.) are encouraged to contributegeneral summaries, of no more than 200 words, and animage to David.


A lack of Indigenouspeople in chemicalscience is notunique to Australia.We can learn muchfrom progress madein the US.

Chemistry is connected withthe wider communitythrough ways other thanthe products of chemical

industry or the promise of chemicalresearch. Careers in science are wellrecognised for being personallyrewarding as well as having positiveimpacts on society. Unfortunately,Indigenous Australians are under-represented in the chemistrycommunity in Australia. This significantissue is an example of a lack of culturaldiversity within Australian science.

Generational discrimination anddisenfranchisement are the most

obvious causes of low representationof Indigenous Australians in thesciences (Indigenous engagement withscience: towards deeperunderstandings, 2013,www.innovation.gov.au).Compounding this are strongperceptions that I have observed in thebroader Indigenous community thatthe sciences are ‘whitefeller business’and science education alienatesIndigenous students from theirtraditional culture, as well as astereotype in the education systemthat Indigenous students performpoorly in maths and science.

Increasing Indigenous

presence inchemistry

BY COLIN A. SCHOLES

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Science in Australia has benefitedfrom and should continue to seekIndigenous engagement andknowledge. Ngarrindjeri man DavidUnaipon (1872–1967), for example,made significant contributions toAustralian science and engineering,including in mechanical engineeringand ballistics. Indigenous knowledgeis very relevant to medicinal and foodchemistry. It includes a deepknowledge of the ecology of theAustralian natural environment;similarly, there is a detailed body ofwork associated with animal trackingand footprints, comparable tofingerprinting in forensic science, anda unique understanding of localmeteorology. However, this knowledgeis often passed down in an oraltradition and so until relatively recentlyhas been overlooked by ‘mainstream’science.

Recently, I was fortunate toundertake a study tour of USinstitutions that have a range ofprograms focused on engaging NativeAmericans in the sciences. The tourwas supported by the AustralianGovernment through an EndeavourFellowship. Native Americans havebeen subject to many of the sameexclusion pressures as IndigenousAustralians, but progress in the US isbetter, partly because the NativeAmericans are very well organised atpromoting wider career choices totheir youth and importantly at thesame time keeping links with theirheritage. They have achieved thisthrough strong networks betweenNative American scientists, promotingand demanding Native Americaninclusion into scientific professions, aswell as developing strong mentoringschemes.

Lack of networks and mentoringschemes is a core barrier to culturaldiversity in science in Australia. Thereare very few Indigenous chemists,which makes it extremely difficult toprovide Indigenous students with rolemodels to emulate and be inspired by.Most Indigenous school students

cannot identify with any type ofscience career. This is exacerbated bya critical lack of support for scientificcareers within Indigenous families andcommunities. For many secondaryschool students, the primarymotivation in terms of subject choice,career direction and support is fromparents and other family members. Inthe broader community, childrengenerally follow their parents intosimilar professions, or are motivatedby their parents to pursue alternativeprofessions that offer better financialprospects. This motivation within theIndigenous community appears to bestrongly directed to the medical, legaland business professions. This can bepartially understood becauseIndigenous involvement in the medicaland legal professions has beenpromoted for a number of years.

I and others have been developingprograms in Australia to overcomethese barriers to the sciences forIndigenous people at both secondaryand tertiary levels. They are beingdeveloped by universities, researchorganisations and NGOs, such asScientifiques Sans Frontières Australia.All of the programs aim to increase

Indigenous students’ knowledge aboutchemistry and science in general, inan effort to retain their interest inscience throughout their secondaryeducation. These programs are gettingscientists into schools and augmentingIndigenous students’ scienceeducation through access to additionalresources. Mentoring networks arebeing established to encourage andsupport Indigenous students to remainwithin sciences, and provide guidancefor their career development.

Another barrier for Indigenousstudents is their predominantresidency in regional or remote areas.Geographical isolation preventsaccess to role models, educators,resources and exposure to scientific


Lack of networksand mentoringschemes is a corebarrier to culturaldiversity in sciencein Australia.

Some aspects of the deep knowledge of Indigenous Australian culture are comparable tothose of the Indigenous peoples of North America, and many have much relevance toscience. This illustration is based on part of a model developed by the Lower KuskokwimSchool District, Alaska.

infrastructure, taken for granted by those living in capitalcities. The CSIRO’s Aboriginal Summer School forExcellence in Technology and Sciences (ASSETS) iscurrently addressing geographical challenges by takinghigh-achieving Indigenous secondary students and gettingthem involved in hands-on programs involving academicsand educators from institutions such as James CookUniversity and the University of Adelaide. The purpose is toovercome geographical distance in terms of resources,access to science mentors and exposure to the universityexperience. Similarly, the Murrup Barak Institute forIndigenous Development at the University of Melbourneruns an annual experience camp that brings Indigenousstudents outside of Victoria in their final years of secondaryschool to the University of Melbourne for five days. Thepurpose is to introduce students to university and city life, aswell as build networks among themselves and witheducators that will overcome issues of isolation when theystart their tertiary education.

A lot more work is needed in this area, and one of thebest examples to emulate are those run by sporting codes.The Korin Gamadji Institute, coordinated in part by theRichmond Football club and AFL, is an excellent example oftying together education, Indigenous culture and sportingachievement to assist Indigenous students to achieve in allaspects of life. Incorporating a strong science componentinto this model is easily achievable, and transferring thismodel from a sporting to science foundation is possible.

For primary school students, the Australian Academy ofSciences undertook a pilot study in 2007 (Small study – bigsuccess story: primary connection incorporating Indigenousperspectives pilot study report, 2008) exposing students toscience through a coordinated interactive program in ruralWestern Australia. The study found no difference betweenIndigenous and non-Indigenous students’ interest inparticipating in the program and no difference inunderstanding the science being presented. Essentially, themost important aspect was providing an interesting andactive forum for students to engage with science, which issadly lacking in rural environments. It is hoped that aspectsof this study will be trialled in other rural locations and on alarger scale in the near future.

For all of the excitement these programs are causing, weneed to be honest about the task in front of us. ImprovingIndigenous Australians’ presence in Australian scientificcommunity will be a multi-decade effort. The initial work hasalready been undertaken, and we now know what worksand where we can make improvements. Importantly,continuing commitment will be needed from a range ofgovernments, schools, universities, scientific institutions andthe active engagement of individual scientists, focused onmaking a difference.

Colin A. Scholes FRACI CChem is a lecturer in the Department of Chemical andBiomolecular Engineering at the University of Melbourne.


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In 2013, a group of like-minded Australians got together todiscuss why there were so few Indigenous Australians in thefield of engineering.

In 2015, the first National Indigenous Engineering Summitbrought together the engineering industry, professionalbodies, educational providers and policy leaders to exchangeideas and develop strategies to create and support pathwaysinto the engineering profession for Indigenous Australians.

A head count showed there are practising Indigenousengineers in Australia, but in low numbers.

Summit organisers gave an undertaking to identify the keyobstacles to Indigenous Australians joining the profession andto formulate a strategy for achieving demographic parity by2030.

Stakeholders have been aware of the reasons for low levelsof interest in the field, and while this is not confined toIndigenous students, it is reflective of a general societalignorance of what engineers actually do. Arguably thissituation also needs attention.

One way to focus on change was through The Partners forPathways, a nationwide initiative being led by the Universityof Melbourne through a Commonwealth grant of $700 000. Theproject aims to create scholarships and devise strategies topromote pathways into engineering and remove barriers toentry for Indigenous and other students who do not have theSTEM prerequisites.

Most of the major Australian university engineering schoolswere represented at the summit.

The stakeholders examined the blockages preventingIndigenous students from pursuing studies in engineering,with a view to devising ways of working around these barriers.

One of the key barriers was a lack of take-up of maths andscience subjects among Indigenous school students. There arelow levels of attainment in maths by the end of year 12.Studying engineering at university without good results inadvanced maths at secondary school is not ideal, and isarguably a set-up for failure.

Professor Ian Anderson, Pro-Vice Chancellor (Engagement),says the University of Melbourne has a commitment topopulation parity as a key feature of the 2015 ReconciliationAction Plan (RAP).

‘Building on that commitment and taking greater stepstowards setting hard targets to achieve population parity, theuniversity will look towards the recruitment and retention ofAboriginal and Torres Strait Islander students,’ Anderson said.‘This will certainly assist with young Aboriginal childrenseeing real-life role models of Indigenous engineers and howthat it is possible.’

Understanding the high level of connectedness between

the First Australians and the land itself is perhaps a key tobetter representation in engineering pathways.

The impact of decisions made by engineers in both thedesign and specification processes is profound and oftenirreversible, especially when these decisions becomecontractual requirements.

The collective Indigenous cultural ignorance of non-Indigenous engineers needs consideration. But Indigenousengineers can have a real influence over what is beingplanned and is a worthwhile aspiration.

There are many projects, especially in the resources sectorin remote locations that are of significant cultural importanceto the traditional owners. These projects often hold real, localemployment opportunities for traditional owners but suchroles are usually taken Fly-in Fly-out staff at the highertechnical levels.

Several major resource companies are showing the way inproviding employment opportunities to locals, especially atlower skill and knowledge levels, with some outstandingexamples of Indigenous engineers in key roles.

Until recently, there was little or no consideration of theenvironmental impact of what we were designing andspecifying in terms of engineering the land. Environmentalawareness arose and changed that forever and no engineernow does anything without a comprehensive evaluation ofenvironmental impact and any remediation required.

Perhaps in a decade or two, the community will benefitfrom having a similarly deeper understanding of, andcommitment to, the impact of our actions on our FirstAustralians and our shared land. For that to happen we needto get more Indigenous students into engineering studies.

Adapted with permission from The Voice 2015, vol. 11, no. 7, University ofMelbourne.

Shaping an Indigenous future inengineering

Professor Iven Mareels, Dean of the Melbourne School ofEngineering, signing the declaration of the event: the NationalIndigenous Engineering Summit Communique (bit.ly/1TgLiCx).


Complete-ium!Race to the end of period

7BY DAVE SAMMUT

Four more superheavy elements havemade it to the periodic table, but whatevidence did their creators need to getthem there?

iStockphoto/cybrain

Science is celebrating thecreation of four newelements. On the cusp ofNew Year's Eve 2015,

IUPAC’s Joint Working Partyannounced its decision on thediscovery and priority of elements113, 115, 117 and 118, and globaljoy erupted in fireworks the verynext day.

Chemists are, of course,delighted to hear that period 7 ofthe periodic table is now complete –a delight somewhat tempered bythe knowledge that we’re going tohave to buy a new edition of SIchemical data now, and again whenthe elements are actually named.

My first response was, of course,‘how?’ How were these newelements created? How can we eventell? How do these new elementsbehave?

Creation and competitionMy high school chemistry teacheronce likened subatomic particlephysics to ‘crashing two cars intoeach other at really high speed, thentrying to work out what they’re madeof by looking at what falls off’. Insimple terms, the science of creatingthese synthetic new superheavyelements is pretty similar. We crashtwo atomic cars into each other atsome fraction of the speed of light,and hope that if they stick togetherfor just long enough they’ll fuse intoa new atomic truck … then we lookat the bits that start falling off.

The creation of ununtrium (Uut,atomic number 113) is a perfectcase in point. It was claimed in 2003from the Joint Institute for NuclearResearch (JINR) in Dubna, Russia(via a collaborative project with theLawrence Livermore National

Laboratory (LLNL) in California USA),based on the production ofelement 115 by bombarding anamericium target with high-energycalcium particles, where the newatoms then quickly decayed toelement 113.

The problem was that thiselement 113 atom then fissioneddirectly (rather than decaying toalready known isotopes), and thereforedid not meet the criteria set down byIUPAC that the new atom mustdemonstrate ‘firm connections toknown nuclides’. Falling back on theanalogy, the truck fell apart again intoa couple of wrecked cars beforesomeone could read the license plate.

The JINR/LLNL team then claimsthat over the subsequent years, it hasproduced element 113 ‘about 100’times across five different isotopes,and that this is sufficient evidence fortheir joint discovery with theAmericans. IUPAC disagreed.

A group at the RIKEN facility inJapan claimed the discovery ofelement 113 in 2004 via thebombardment of a bismuth target withzinc. Their atom had the advantage ofdecaying via a series of alphaemissions to an ‘anchor’ element (aknown isotope), which comes closer to

satisfying IUPAC’s criteria for the‘discovery’ of a new element. However,the RIKEN facility produced only twoatoms, then spent another seven yearstrying fruitlessly to repeat their results.They only succeeded in 2012; hencethe fact that the element has only now

been ratified, 13 years since itwas first claimed by either side.

Press comments from thegroups in response to the IUPACannouncement pretty stronglyindicate competitive feelings.The RIKEN team expressedpride in discovering element113; so too the Livermore group,in being credited with thecollaborative discovery of 115,117 and 118 (oh, and alsofinding 113 first). The JINR teamwas more blunt – what I readbetween the lines was ‘not onlydid we find 113 first, but weproduced much more of it, ourslasted longer and we taught theJapanese team leadereverything he knows. So there[tongue poke].’

Detecting the new elements

The next obvious question is how theyeven detect just one atom of a newelement. The high-energy particles arebombarded onto static metal targets.These targets are extremely thin, sothe new particles are basically‘knocked free’ following the collision.Remember, those particles are comingat a decent fraction of the speed oflight. Coming off as charged particles,the target atoms are separated in gas-filled separators based on the averagecharge state and momentum viadipole/quadropole controls andmagnetic fields – the same principlesas mass spectroscopy.

Two main types of silicon radiationdetectors are used in superheavyelement research: those working onthe principle of charge separation(resistive strip passivated implantedplanar silicon (PIPS) detectors) andpositional detectors termed double-side silicon strip detectors (DSSD).

Advanced calculations are used toseparate/suppress the decay ofbackground products from the raredecays of the anticipated elements.

If that sounds vague, that’s becauseit is. As Arthur C. Clarke noted in histhird law, ‘any sufficiently advancedtechnology is indistinguishable frommagic’. Even having read a couple ofJINR papers on the topic, as far as thisauthor is concerned that’s how the newatoms are detected – magic.

Superheavy elements and the‘island of stability’Elements with more than 82 protonsare unstable. Up to this point in theperiodic table, theoretical physicalchemists have pretty accurate modelsto predict the behaviour of theelements, balancing the strong nuclearforce (holding nuclei together) againstthe repulsive force of the protons(seeking to tear the nuclei apart). Evenneutrons are slightly repulsive towardseach other.

These theories predict ‘magicnumbers’ of protons and neutrons to fill‘shells’ of quantum energy levels withinthe nuclei and confer stability, in muchthe same way that electron shelltheories work. One ‘magic number’combination is 82 protons and126 neutrons, and 207Pb is the heaviestnaturally occurring stable element.

According to these theories, an‘island of stability’ is suggested to existsomewhere up in the region of about114, 120 or 126 protons, and (acrossmultiple models) 184 neutrons. At thiscombination, the atoms should beresistant to alpha decay, and half-liveshave been predicted anywhere fromminutes to millions of years.

The problem is that the modelsdon’t work well for superheavyelements because of relativistic effects,so the estimates are still rubbery.Relativistic effects can be used toexplain anomalous properties of theknown elements, such as why mercuryis a liquid to –39°C. The 6s2 orbital iscontracted and the bonding of the Hg–Hg pair is dominated by van der Waals


iStockphoto/AlexLMX

forces; hence, the weak bonding andlow melting point.

The exact nature of the strong forceis still subject to extensive research, andthe global study of SHEs contributes tothis developing understanding.

The isotopes being produced forthe most recent four elements are stillwell short of the ‘magic number’ intheir neutron count. But variouscommentators have noted that we arenow ‘lapping the shores’ of the islandof stability.

One fact should be emphasized from theoutset: while the various theoreticalpredictions about the superheavy nucleidiffer as to the expected half-lives andregions of stability, all theoreticalpredictions are in agreement: superheavynuclei can exist. Thus, the search forsuperheavy nuclei remains as a unique,rigorous test of the predictive power ofmodern theories of the structure of nuclei.

Seaborg G.T., Loveland W. Contemporary Physics,

1987, vol. 28, p. 33

Properties of the new elementsGiven their extremely short half-lives(just milliseconds for some isotopes),the new elements have been subject torelatively little physicalexperimentation.

Element 113 sits in group 13, undergallium, indium and thallium. It ispredicted to have a much higherdensity than thallium (potentially 16–18 g/cm3, as compared to 11.9 g/cm3),with a counter-trend atomic radiussmaller than thallium. However, the fewexperiments conducted on Uutisotopes conducted by JINR have beeninconclusive, given the tiny number ofelements produced.

A more thoroughly studied elementis flerovium-289 (element 114). It has a‘magic number’ of protons, but too fewneutrons for stability, giving it a half-lifeof 2.6 seconds. This slightly longer half-life has allowed some limitedexperimental chemistry, but this is


The JINR/LLNL collaboration bombarded an americium target with calcium, producing multiple isotopes of element 115 depending on theenergy of the collision. It was claimed that these isotopes showed an alpha decay to element 113, then via four alpha decays to dubnium,which then fissioned. (Main data source: bit.ly/1THCANj)The RIKEN team bombarded a bismuth target with zinc to directly produce element 113 as an extremely rare event. The element 113 atomsunderwent four alpha decays to dubnium-262. In a subsequent experiment, RIKEN confirmed this path by bombarding a curium target withsodium to produce bohrium, which showed an alpha decay to the same dubnium-262 isotope, then to lawrencium-258, which was a knownisotope. (Main data source: bit.ly/1THCANj)

The isotopes beingproduced for themost recent fourelements are stillwell short of the‘magic number’ intheir neutroncount. But variouscommentatorshave noted that weare now ‘lappingthe shores’ of theisland of stability.

287115243Am48Ca

23Na

283113a 279Rga 275Mta 271Bha 267Dba

278113209Bi70Zn 274Rga 270Mta 266Bha 262Dba 258Lr

244Cm

a

288115 284113a 280Rga 276Mta 272Bha 268Dba

Original discoveryConfirmation path

again limited by the rarity of thesynthesis reactions – generally onlyone or two atoms at a time.

A 2008 report from JINR initiallysuggested that flerovium has chemicalproperties closer to noble gases thanto lead (its nearest group 14 element)(bit.ly/1LgULqx). This was anunexpected result, and differed fromthe models, but experiments sufferedfrom the decay of the flerovium todubnium during transport through thegas separator (1–2 seconds). Follow-up tests by the same collaborativeteams in 2010 cast further doubt onthe initial interpretation.

The GSI Helmholtzzentrum fürSchwerionenforschung weighed inwith a 2012 paper stating‘Relativistically stabilized sub-shellclosures give rise to a new category ofelements in the Periodic Table: volatilemetals (bit.ly/1oLgwF1). The prototypefor this property is element 114 which,due to the relativistic stabilization of itselectron configuration, is volatile in itselementary state …’. In simple terms,just as relativistic effects are cited asthe reason that mercury isunexpectedly a liquid at room

temperature (a break from theexpected metallic bond trend), the GSIpaper predicts that the enhancedrelativistic effects for the heavierflerovium might actually make it a gasat the same temperature.

GSI’s paper is one of the moreaccessible works found by the authoron the predicted theoretical physicaland chemical properties of the super-heavy elements. Even so, it was stillheavy going.

Forging aheadEvery scientist working on thisendeavour is to be congratulated forfurther extending the limits of humanknowledge, and for the way that theirwork has captured the public’simagination. Like a modern-dayHaphaestus, science is forgingfantastical new materials for the world,the ultimate act of creation. Who knowswhat more might lie just beyond theedge of our current capabilities?

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

May 2016

What’s in a name?IUPAC’s decision on priority is not without controversy and deep division, just asit was during the 30 years of discovery and naming of elements 104–109, whichwere only resolved in 1997.

The Transfermium Wars, as they came to be known, were a period ofacrimonious debate, where both the priority of discovery and the naming of thosesynthetic elements were hotly contested between laboratories in the US, Russiaand Germany. The debate only ended when IUPAC awarded elements 104(rutherfordium) and 106 (seaborgium) to the US, 105 (dubnium) and 107(bohrium) to Russia, and 108 (hassium) and 109 (meitnerium) to Germany.

Since 1992, IUPAC’s rules have stated that new elements can be named after amythological concept, a mineral, a place or country, or a property or scientist. Thename should sound similar across multiple languages, and it should have anending that reflects and maintains historical and chemical consistency. This wouldbe in general ‘-ium’ for elements belonging to groups 1–16, ‘-ine’ for elements ofgroup 17 and ‘-on’ for elements of group 18 (noting that this aspect is underreview).

The successful laboratories now have the right to propose names. However, fansof author Terry Pratchett (who died in 2015) are actively campaigning forelement 117 to be named octarine after the magical element in Pratchett’s novels(chn.ge/1paf92G).

DLe M1788 AP ads Litesizer500 76x275.indd 1 3/9/16 10:42

On 19 February, the firstAustralian Decadal Planfor Chemistry waslaunched. As Chair of the

National Committee for Chemistry, Ihad the honour of doing this, alongwith Professor Andrew Holmes(President of the Australian Academyof Science) and Professor Aiden Byrne(Chair of the Australian ResearchCouncil). This important event wasattended by more than 80 people fromall areas of chemistry, includingindustry, RACI, CSIRO, secondaryeducation, government and academia.

The preparation of a decadal plan isanother step forward along the path tore-building Australia’s chemicalmanufacturing base and growing thequality and relevance of its strongchemistry research base. The decadalplan is a grass roots document, puttogether by a working group under

the auspices of the NationalCommittee for Chemistry (NCC). Thekey goals of such a bottom-upapproach are to ensure that it is thechemistry community itself thatestablishes the directions of the fieldand identifies the opportunities andchallenges ahead.

The decadal plan is the first overallreview of the chemistry discipline inAustralia since the publication ofChemistry: a vision for Australia by PaulSavage and colleagues in 1993. In2005, a review of chemistry (Future ofchemistry study – the supply anddemand of chemists) was carried outby the RACI, but this focused tightly oneducation and training aspects. Afurther, smaller report, commissionedand managed by CSIRO in 2006(G. Upstill et al., ‘Innovation strategiesfor the Australian chemical industry’,J. Bus. Chem. 2006, vol. 3, p. 9),


The 2016–2025Decadal Plan forChemistry supportsgrowth in chemicalmanufacturing andresearch, explainsthe working groupchair.

BY PAUL MULVANEY

ChemistryThe next 10 years

explored the state of the chemicalindustry.

Chemistry is the largest scientificdiscipline, and is often termed the‘central science’. In 2014, the globalchemicals industry contributed 4.9%of global GDP and the sector hadgross revenues of US$5.2 trillion. Thatcorresponds to US$800 for everyperson on the planet. We anticipatethat, during the 21st century, chemistrywill continue to define the directions oftechnological change. For example,chemical research and developmentwill contribute to energy-efficientLEDs, solar cells, electric vehiclebatteries, water desalinationtechnology, biodiagnostics, advancedmaterials for durable clothing,aerospace, defence, agriculture andhealth and medicine.

Without doubt, chemistry inAustralia is in a comparatively healthystate. Currently around 35 000secondary school students do year 12chemistry, although there has been aconsistent decline in participation overrecent decades. At present, at least 27of Australia’s universities havededicated, RACI-accredited, chemistrydepartments (bit.ly/20WlBGa).Contrary to popular belief, there isclose to gender balance, with just55.7% of all graduates in chemistrybeing male. According to GraduateCareers Australia, mean salaries are$50 000 p.a. with a mean graduationage of 22. Currently, around 50% ofchemists work in industry, 25% work inuniversities or teaching and most ofthe remaining 24% are employed ingovernment laboratories. The peakacademic body for chemistry, theRACI, currently has some5000 members and has a risingmembership, while the Plastics andChemicals Industry Association(PACIA) remains the largest industrygroup. Chemicals and plastics supply109 of Australia’s 111 industries. Morethan 60 000 people are employed inthe chemical industry and it is oursecond largest manufacturing sector.According to PACIA’s 2011 Strategic

Roadmap, the sector contributes$11.6 billion annually to Australia’sGDP.

Because of the enormous impact ofchemistry across so many parts of theeconomy, it is difficult to formulate asimple and linear plan for the future.Instead, the goal of the NCC was tofirst create a decadal plan, which isbasically a bottom-up survey of all thestakeholders in chemistry, and tounderstand the current landscape.There are large-scale global forcesshaping the future of chemistry, suchas climate change, demographic andeconomic market-driven shifts, as wellas technology-driven shifts. These canhave enormous ramifications forinvestment in Australia’s chemistryfuture. For example, the fluctuatingglobal oil and gas prices willdetermine whether long-terminvestment in natural gas production inAustralia is viable. Natural gas is a vitalfeedstock for fertiliser (ammonia)production, which currently consumes3–5% of the world’s energy and isessential for production of grain foralmost 40% of the planetarypopulation.

The Decadal Plan Working Groupbegan collecting information fromacross Australia in September 2014and carried out 26 public meetings atvarious universities in every state, atCSIRO in Victoria, at the AustralianNuclear Science and TechnologyOrganisation in New South Wales andat CONASTA, the annual NationalScience Education Conference of the


Left to right: Paul Mulvaney, Aiden Byrne and Andrew Holmes at the launch of the 2016–2025 Decadal Plan for Chemistry in February in Melbourne. Australian Academy of Science

The implementationof the core goals ofthe decadal planwill require thechemistrycommunity tocoordinate thedevelopment ofpolicies across thechemistry industry,R&D and educationsectors.

Australian Science TeachersAssociation, in Adelaide. Organisationssuch as BioMelbourne Networkhelped to run workshops or otherforums. They also conducted twoindustry-focused meetings and helddiscussions at a Women in Chemistrymeeting in Melbourne, sponsored byPhillips Ormonde Fitzpatrick.Telephone and internet surveys, aswell as web-based data collection,were used to survey the chemistrycommunity until March 2015.

The working group compiled awhite paper that was open to thepublic for feedback via the Academyof Science website duringSeptember–October 2015. Finalediting was carried out in late 2015and the decadal plan was sent to pressin early February.

From the findings of the decadalplan process and the statistics outlinedabove, it is evident that chemistry inAustralia remains a healthy butunderperforming science. On thepositive side, chemistry graduatescontinue to find jobs across a broadspectrum of employment fields andresearch quality is undoubtedly high.Chemistry is an attractive careerchoice, with a wide range of smallercompanies and large multinationalsemploying graduates. Chemistryremains vital to many Australian

industries, including construction,mining and agriculture. Despite this,there are declining numbers ofstudents studying chemistry as aproportion of students enteringtertiary education.

The biggest challenge identified bythe Decadal Plan Working Group ispoor communication across the sector.While scientific publication quality andpatenting rates are comparable toother leading countries, the efficiencyof translation into new jobs, companiesand value-adding products isalarmingly low. For example, while40% of companies in many Europeancountries have direct interactions withuniversities and research institutions,only 4% of Australian companiesreport such links. These numbers,while likely to be somewhat subjective,correlate strongly with recent reportsfrom the Office of the Chief Scientist onthe STEM disciplines and with OECDnumbers on innovation. Australia cando much better in exploiting itsgenuinely strong chemistry know-howand its multidisciplinary research base.A major conclusion is that thechemistry community must worktogether more effectively to create agenuine ‘value-adding chain’. Ahealthy chemistry industry in Australiawill create high-quality chemistry jobs,and this will in turn attract students to

stay in science. Better linkagesbetween universities and industry willensure Australia can generate theproducts needed to maintain highliving standards. Governments need tosupport this value-adding chain bydeveloping long-lasting, bipartisanpolicies that foster risk-taking andgreater investment in manufacturing.We may have heard a lot of this beforebut now it is being said with one voice.

The second, more ambitious, part ofthe program will be designing andcreating an implementation plan,beginning in 2016. Theimplementation of the core goals of thedecadal plan will require thechemistry community to coordinatethe development of policies across thechemistry industry, R&D and educationsectors. A key goal from workingtogether will be to drive the creation ofgovernment policies that increase thevalue of the entire chemistrychain – from primary school programsthat attract children into doing science,through to incentives for companies toinvest in R&D and which can enablestart-up companies to sell into Asia.While it has been a rewardingexperience interacting with so many ofthe chemistry community during thisprocess, the real work is only justbeginning. We know what thechemistry community aspires to, wenow have to work hard to get there.

The 2016–2025 Decadal Plan forChemistry is available atwww.science.org.au/node/2216.

Paul Mulvaney FRACI CChem is Chair of the DecadalPlan Working Group, National Committee for Chemistry.


The biggest challenge identified by theDecadal Plan Working Group is poorcommunication across the sector.

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

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The ten mostbeautifulexperimentsJohnson G., Alfred A. Knoff, 2008,hardback, ISBN 9781400041015,190 pp. approx.

The ten most beautiful experiments,16 years after publication, may beon the precipitous brink of becomingan oldie, but be very assured it is agoodie. It is readily available for amodest price, new or used, hardback,paperback and e-book. On the frontcover of the paperback, celebrated

English mathematician and physicist Sir Roger Penrose is citeddescribing the book as, ‘delightful, succinct and elegant’. Icouldn’t put it better myself. It really is a lovely little book often chapters (can you guess why?) about ten of the great leapsin the history of science that were associated with splendid andelegant thought and experimentation. Each chapter standsalone, so it is ideal to read on the train on the way to work, inbed before you fall asleep, or in the doctor’s surgery instead offuming about the delay, and so forth. And it is really interestingstuff, carefully and competently explained so it is readilyintelligible to scientist and non-scientist alike.

Author George Johnson, a widely respected American sciencewriter, has obviously had to make some hard, and perhapseclectic, choices. Why only ten experiments? Well, I guess it isa nice round number, makes for a reasonably sized book andprovides an obvious enough title! What about the selection?The history of science is resplendent with beautifulexperiments, some of which led to wildly spurious conclusionsand theories. I guess they got left by the wayside and thechoice is from what is left. In an Afterword, Johnsonacknowledges that none of his beautiful experimenters (or, ifyou prefer, doers of beautiful experiments!) were women. Heexcludes Marie Curie, claiming her work was more hard slog thaninspirational, but acknowledges that Rita Levi-Montalcini’sdiscovery of nerve-growth factor or Barbara McClintock’s workon genetic regulation and jumping genes would be worthy of an11th chapter. The closest we really get to the female of thespecies is to Marie Anne Lavoisier, who assisted her husbandAntoine and made elegant drawings of his experimentalapparatus, reproduced in the book. She and Antoine weremarried when she was 13 and he was in his mid-20s (Australianlaw takes a jaundiced view of this sort of thing these days, butit did get her out of marrying a 50-year-old, so she possiblywasn’t too stressed). After Antoine lost his mind (and the restof his head) courtesy of the guillotine, she married renownedscoundrel Count Rumford (Benjamin Thompson), he of thework–heat nexus, but he denied entry to her friends. So shetossed him out, albeit with a couple of hundred thousand francsto encourage him not to return.

The people selected for inclusion in Johnson’s top ten areGalileo (motion on inclined planes), William Harvey (bloodcirculation), Isaac Newton (light and colour), Lavoisier(chemical experiments), Galvani (animal electricity), Faraday(associating electricity and magnetism), Joule (energy),Michelson (speed of light), Pavlov (conditioning) and RobertMillikan (electronic charge). These are all worthy of inclusion,and I’m sure you can think of plenty more worthies. It isparticularly interesting to read about the people as well as thescience and why the insights were important. Johnson hasmelded these elements splendidly. These are some of the giantson whose shoulders we stand. I can’t guarantee you’ll seefurther from reading this book, but you’ll certainly know a lotmore about some of your scientific forebears and the reading isan altogether pleasant experience.

R. John Casey FRACI CChem

Curious tales fromchemistryÖhrström L., OUP, 2015, paperback,ISBN 9780198743927, 257 pp., US$20approx.

Curious tales from chemistry is a veryeasy book to review, because the frontcover highlights Nature magazine’sdescription of ‘charming’, while the backcover provides further glowingtestimonials to its worth. One of these,from Chemistry World, sums it up prettywell: ‘This excellent book will provide anentertaining read to all chemists and is also just the kind oftext to place in the hands of school students.’ I couldn’t havesaid it better myself! It really is a great little book, dartingdown different pathways, full of interesting juxtapositions andconjectures, brim-full of fascinating facts and information,great bedtime reading for nerds (not so big and heavy that itwill break your nose when you fall asleep reading it, and, in anycase, you’ll find it too engaging to nod off!), awash with goodchemistry, and utterly good fun. For instance, did you knowthat all of the world’s lapis lazuli comes from one mine inAfghanistan? Or that Agatha Christie studied pharmacy (andknew a bit about the Marsh test)? Or that Astrid Lindgren (ofPippi Longstocking fame) was at one time secretary to HarrySoderman, a founder of modern forensic science and ofInterpol? Or that Chaim Weizmann, the first president of Israel,used to be a chemistry lecturer at the University of Manchester?

Author Lars Öhrström is a Swedish chemist and chemicalengineer, currently professor of inorganic chemistry at ChalmersUniversity of Technology in Gothenburg. His teaching interestslie in curriculum development and teaching first year chemistry,while his research interests are in metal–organic frameworkswith applications in green and sustainable chemicalengineering.

Students are interested in the people and the context ofchemistry. They are interested to see what Fritz Haber lookedlike (a remarkably mild-looking chap, despite his invention ofchemical warfare), or that Marie Curie was a fairly ordinary-looking, plumpish (dare I say motherly looking?) woman inmiddle age, despite her Nobel Prize. It is always interesting andinstructive to see the characters behind the facts. As a personalaside, many years ago I followed with great interest thepublications of inorganic chemist (Harry) Irving from theUniversity of Leeds. When I subsequently visited thatuniversity, Irving’s photograph was displayed in the Chemistryfoyer. Beneath the picture of this bespectacled figure werelisted his achievements, together with his hobby – tap dancing.That just made him so much more ‘real’ for me than his dour‘professorial’ picture.

Chemistry is about people, what they were (and are) like,what ‘floated their boats’, and the context and motivation fortheir discoveries, as well as being a vehicle providing a way ofmaking sense of our physical world. There is a risk in ignoringthe first aspect and concentrating all our teaching on the lastbit. This may sometimes lead to a sterile student experience, orat the very least to one that could be so much richer. Curioustales from chemistry is a significant contribution to the contextof chemistry and helps allay concerns that it is overlooked.Every chemistry teacher in Australia ought to buy this book,read it and apply its message. The rest of you ought to read ittoo. It’s great fun.


The future of theprofessions: howtechnology willtransform the work ofhuman expertsSusskind R., Susskind D., OUP, 2016,hardback, ISBN 9780198713395,256 pp., $29.95

One thing you can say about thefuture is it is likely to be differentfrom the past. The future of theprofessions: how technology willtransform the work of human experts is

a groundbreaking work, challenging the relevance ofprofessionals in the 21st century, predicting a decline in theprofessions as we currently know them and postulating newparadigms for knowledge interchange and what we now think ofas professional work in the future. Bold stuff, indeed! RichardSusskind, a lawyer, has a prominent career advisinginternational business and governments at the highest level(including as IT advisor to the Lord Chief Justice of Englandand Wales), while his son and co-author Daniel lectures inEconomics at Balliol College, Oxford.

The authors write of ‘the grand bargain’, the arrangementsunder which many professionals currently work and which grantthem a monopoly over the services they render. For example,you cannot simply decide to nail up a shingle proclaimingyourself a doctor, lawyer, pharmacist, accountant and so on.There are laws and gatekeepers to exclude outsiders and to defacto grant a monopoly on provision of services to the elect.The Susskinds’ thesis is that in an information age, we neitherwant nor need doctors, teachers, accountants, architects, theclergy, consultants, lawyers and sundry others performing theirroles in the traditional ways. Interestingly, neither engineersnor scientists get any particular mention. Contemporaryprofessions are painted as antiquated and hidebound, no longeraffordable and, generally speaking, rarely providing any genuinebest practice service to clients.

The Susskinds suggest six new models to produce anddistribute expertise to society. Machines can out-performhuman beings in their capacity to generate and analyse vastamounts of information, even pointing out correlations andobservations beyond your dreams. At a trivial level, you onlyhave to consider the mountain of information that must beavailable from the use of loyalty cards and credit cards. Forexample, the book remarks that the British Taxation Office hasaccess to more documents in its records than the British Library(which has everything ever published in English!). So whoshould own all this information? Who should control it? What isthe role of people in the scheme of things where computers cannot only store knowledge, but, more importantly, generate it?There are serious moral and ethical issues at stake here.

In teaching, for example, the authors see a change from ‘thesage on the stage’ to ‘the guide beside’ occurring in practice,but not being reflected in the architecture and curriculum ofschooling. There is not too much doubt things are changing. InThe tombs of Atuan (Ursula Le Guin), Ged Sparrowhawk (thewizard) describes what a wizard does. There are spells andincantations to learn and various practices to be mastered, butultimately he concludes the paramount skill a wizard needs is’knowing how to know’. But is that all we need? Yes, it istremendously important to know how to find out things. Theinternet is crammed to the gunwales with information. Hardcopies of chemistry (and other) journals seem doomed toimminent demise because neither institutions nor individualscan afford them, so it is becoming doubly important that anyundergraduate course in chemistry ought to incorporatefamiliarity with and exploration of the literature. But you alsoneed some knowledge or you are like the minister and SirHumphrey Appleby (But minister, you have only to ask! But, Idon’t know what to ask!). So, claims of the death of traditionaleducation may be, as Mark Twain remarked, premature. And, ofcourse, the internet is largely unfiltered. And, boy-oh-boy isthere some guff on it!

The authors have not considered the ownership aspects ofprofessional work. If an academic, say, develops an onlinecourse (when Harvard put its first course online, it instantly

books



recorded more enrolees than it had graduated in its entirehistory), ownership will, of course, be claimed by theiremployer, who may well adopt the short-term financialexpedient of sacking the person and using computer-generatedand -marked assessment. Does a professional have anyproprietorial interests in the new scheme proposed?

And what about privacy and confidentiality? With huge, all-encompassing data banks, the possibilities of fraud, hackingand the like become more worrying. Given hackers seem to havebeen able to penetrate the Pentagon, the slackness inherent inprofessionals’ keeping their own decentralised records might notbe all bad.

Overall, this is a very well written and cogently argued book.There is much wisdom in its observations and food for thoughtin its prognoses. In some ways, it paints a picture of a bravenew world, with a certain inevitability to its progression, and inothers of a dawning of an age of mass human empowerment.There are messages for chemists, for the future of chemistry andchemical education, and for the future of professional societies.It is an engaging, thoughtful and fascinating work and avaluable contribution to futurology. All professionals (evenretired ones like me) ought to read it.


How life works: theinside word from abiochemistElliott W., Elliott D., CSIRO Publishing, 2015,paperback, ISBN 9781486300471,176 pp., $29.95

How life works: the inside word from abiochemist is the distillation of a life’swork in biochemistry by William (Bill)Elliott, who spent many yearsresearching and teaching at theUniversity of Adelaide. This short book iswritten for readers without scientific

training, and Elliott’s desire to impart the ‘big picture’ of life ashe knows it is evident. After Bill Elliott died in 2012, his wifeand colleague, Daphne Elliott, prepared the book forpublication. Science writer Sarah Keenihan contributedadditional material.

Starting from the Big Bang and the formation of theUniverse, the book takes you from subatomic particles to cells.

Along the way, Elliott introduces the challenges to theexistence of life posed by the nature of the universe; both itsconstituents (atoms, subatomic particles and elements) and itsphysical laws (such as thermodynamics and quantummechanics). Then, in straightforward prose that’s easy to follow,he describes how life solves these challenges.

Readers may come to this book with background knowledgethat makes some of the content familiar. But the strength ofHow life works is its systematic progression through increasinglevels of complexity. For people without a biochemistrybackground, this introduction to the intricate working of atomsand molecules to create life is fascinating.

The book answers questions such as: How do we harness theenergy in our food so that we can grow? How does growing asophisticated organism not contravene the second law ofthermodynamics (that entropy, or disorder, must alwaysincrease)? How do enzymes speed up a chemical reaction? Whyare vitamins and minerals so important? How can proteinmolecules have so many different structures and roles in thebody?

If William Elliott had a favourite chemical bond, it may wellbe the hydrogen bonds between the base pairs of DNA. Ifadenine didn’t always bond with thymine, and guanine alwayswith cytosine, then the DNA molecule that is the basis of alllife would not replicate consistently, and life would be vastlydifferent or perhaps impossible. We learn how gene sequencesare ‘read’ to create the proteins that build up our bodies,another subject I knew something of, but not the details.

How life works touches on modern areas of research, such asepigenetics, stem cells and genetic engineering, too briefly toreally inform decisions on such issues. But it provides a clearand engaging explanation of the underlying processes of lifethat may encourage some non-scientists to give due credenceto modern life sciences.

Margie Beilharz

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

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

economics


Presently there is renewed interest inbanning or taxing plastic bags used insupermarkets. The aim is to reduceperceived problems with plastic baglitter. Supermarket chains import thesebags by the billion and I am not awareof any production in Australia.

When I first came to Australia in theearly 1980s, supermarkets used paperbags. There was a bagger (usually aspotty youth) employed on eachpayment aisle to assist the customer andspeed up throughput. Plastic bags areconsiderably cheaper than paper bagsand, along with the metal holding rack,allow the cashier to do the bagging,hence eliminating the bagger.

Plastic bags first came to be an itemof use in the 1950s when low-densitypolyethylene (LDPE) became available.Bags made from LDPE are very strongand useful for carrying heavy materialsuch as fertiliser. They are often reusedby builders’ merchants selling sand.

LDPE is the original form ofpolyethylene, accidently discovered inthe 1930s in attempt to convertethylene into lubricating oil at highpressure (2000 atmospheres). In thepresent day technology, ethylene andfree radical initiators polymeriseethylene at 200 atmospheres.

LDPE chains have a high level ofbranching. Many of the branches are C2and C4 units caused by a primary radicalback-biting the growing chain. There arealso longer branches, with pendentC2/C4 groups, and some long-rangecross-linking.

In the early 1950s, organometalliccatalysts for ethylene polymerisation atlow pressure were discovered anddeveloped by Ziegler and by workers atPhillips Petroleum. The product theydeveloped, called high-densitypolyethylene (HDPE), had little if anybranching and the chains could be closelypacked, resulting in higher density. HDPEis cheaper to produce but bags producedfrom it are generally weak and used forsuch things as groceries.

In the 1960s, the idea was developedthat copolymers of ethylene, butene andhexene made by the low-pressure routecould have similar properties to LDPE.Copolymers were produced in whichbutene/hexene was incorporated randomlyinto a growing ethylene chain and thushad randomly distributed pendant C2/C4groups. The density was intermediatebetween LDPE and HDPE and thecopolymer was named linear low-densitypolyethylene (LLDPE). Bags made in thisway were durable (sometimes better thanLDPE) and relatively cheap to produce.

My first industrial R&D job (40 yearsago) was subsequent to a project todevelop a new and cheaper way to makeLLDPE. Organometallic chemistry was allthe rage in the late 1960s and early 1970sand the company was researching novelorganometallic catalysts forpolymerisation. A new system wasinvented that appeared to deliver LLDPEcheaper than the routes in use at thetime. A large research program waslaunched that involved three separatedivisions of the company – central

The plastics project that went to waste

Minihaa (Own work) [CC0], via Wikimedia Commons

Chemistry in Australia 35May 2016

research, the monomer division and thepolymer division.

It was thought that if the catalystcould randomly copolymerise monomers,then copolymerisation of ethylene,propylene and a diene could lead to EPDMelastomer (rubber). This could lead togreater profits for the company through anew rubber division. And so more resourceswere allocated to the project. This was atime of general downturn in the chemicalindustry and researchers not involvedlooked on jealously as more resources werepoured into the effort.

One chemist on the project, realisingthat resources were unlimited, took theopportunity to research the best solventfor cleaning old paintbrushes. He foundthe best to be ethanolamine.

Because of the complexity of theproject and the need for goodcommunications, it was decided to have amonthly conference at a central locationwith easy access for the various researchgroups. A suitable conference facility wasidentified that also just happened to havea fine dining restaurant, wine cellar andovernight accommodation.

At an early coordination meeting, theaudience was enrapt by a physicist whodescribed testing procedures for the filmsbeing produced. This involved dropping adart on the film and measuring, inexacting detail, the shape of thedeformation, which was dulymathematically modelled, proving thehigh quality of the LLDPE produced. Achemist working in an analyticallaboratory related how he had examinedthe products by infrared spectrometry. Hesaid he thought there were someproblems with the LLDPE (long runs ofhomo-polymer in the chains) and theEPDM did not look much like rubber.Denialists of this ilk were not welcomeand he was not invited to furthermeetings. After a lavish dinner of duck àl’orange with fine Burgundy, and as theport was served with Stilton, the benefitsof ethanolamine solvent were discussed.

The project got bigger, with a largetechnical plant producing the LLDPE and abagging line to produce bags. A productdemonstration was organised and thecompany directors were invited to witnessthe beauty of the new bags.

Back then it was common for fertiliserbags to be unloaded from trucks bymanually throwing them off. LDPE wasdurable enough for this treatment. OneFriday, at the demonstration, fertiliserbagged in the new LLDPE was placed onthe back of a truck along with two likelylads to do the unloading.

The assembled crowd with thedirectors in front, all in fine suits,gathered around the truck tailgate andthe first bag was off-loaded. On strikingthe ground, the bag split and sprayedfertiliser over the witnesses. Thedirectors dusted themselves off and tooka step back. Perhaps the first was just aone-off, so a second was off-loaded withthe same result and again with a third.

The directors dusted themselves offagain and left. The silent crowd slowlydispersed. Only the two likely ladsseemed to be amused by the event.

In private enterprise things canhappen quite quickly. By 9 a.m. onMonday the project was canned. All thereports were re-classified as ultra secretonly to be accessed with writtenpermission of a director. Scientists werere-assigned to managers not involvedwith the project, who now with largergroups were promoted. The inventor wassent back to the lab (he later had acareer as an academic), the analyst wassent back and was never promoted. Noone knows what happened to thephysicist. The chemist went on todiscover other uses for ethanolamine.

And so this was my first experience ofthe cycle for major projects:unquestioning enthusiasm,disillusionment, panic and hysteria, thehunt for the guilty, punishment of theinnocent and reward for the uninvolved.It was not the last.

Duncan Seddon FRACI CChem is a consultant to coal, oil, gas and chemicals industriesspecialising in adding value to natural resources.

iStockphoto/Suljo

plants & soils

The world’s deserts may be storing some of the climate-changing carbon dioxide emitted by human activities, a recentstudy suggests. Massive aquifers underneath deserts could holdmore carbon than all the plants on land, according to the newresearch.

Humans add carbon dioxide to the atmosphere through fossilfuel combustion and deforestation. About 40% of this carbonstays in the atmosphere and roughly 30% enters the ocean,according to the University Corporation for AtmosphericResearch. Scientists thought the remaining carbon was taken upby plants on land, but measurements show plants don’t absorball of the leftover carbon. Scientists have been searching for aplace on land where the additional carbon is being stored – theso-called ‘missing carbon sink’.

The study suggests some of this carbon may be disappearingunderneath the world’s deserts – a process exacerbated byirrigation. Scientists examining the flow of water through aChinese desert found that carbon from the atmosphere is beingabsorbed by crops, released into the soil and transportedunderground in groundwater – a process that picked up whenfarming entered the region 2000 years ago.

Underground aquifers store the dissolved carbon deep belowthe desert where it can’t escape back to the atmosphere,according to the new study.

The study estimates that because of agriculture roughly14 times more carbon than previously thought could beentering these underground desert aquifers every year. Theseunderground pools that taken together cover an area the size ofNorth America may account for at least a portion of the ‘missingcarbon sink’ for which scientists have been searching.

‘The carbon is stored in these geological structures coveredby thick layers of sand, and it may never return to theatmosphere,’ said Yan Li, a desert biogeochemist with theChinese Academy of Sciences in Urumqi, Xinjiang, and leadauthor of the study accepted for publication in GeophysicalResearch Letters (doi: 10.1002/2015GL064222), a journal of theAmerican Geophysical Union. ‘It is basically a one-way trip.’

Knowing the locations of carbon sinks could improve modelsused to predict future climate change and enhance calculationsof the Earth’s carbon budget, or the amount of fossil fuelshumans can burn without causing major changes in the Earth’stemperature, according to the study’s authors.

Although there are most likely many missing carbon sinksaround the world, desert aquifers could be important ones, saidMichael Allen, a soil ecologist from the Center for ConservationBiology at the University of California-Riverside who was not anauthor on the new study.

If farmers and water managers understand the role heavilyirrigated inland deserts play in storing the world’s carbon, theymay be able to alter how much carbon enters these undergroundreserves, he said.

‘This means [managers] can take practical steps that couldplay a role in addressing carbon budgets,’ said Allen.

Examining desert waterTo find out where deserts tucked away the extra carbon, Li andhis colleagues analysed water samples from the Tarim Basin, aVenezuela-sized valley in China’s Xinjiang region. Water drainingfrom rivers in the surrounding mountains supports farms thatedge the desert in the centre of the basin.

The researchers measured the amount of carbon in eachwater sample and calculated the age of the carbon to figure out


‘Carbon sink’ detected underneath world’s deserts

Knowing the locations ofcarbon sinks could improvemodels used to predict futureclimate change and enhancecalculations of the Earth’scarbon budget ...

Researchers gathered groundwater flowing under the desert sands.The amount of carbon carried by this underground flow increasedquickly when the Silk Road, which opened the region to farming,began 2000 years ago. Yan Li

how long the water had been in theground.

The study shows the amount ofcarbon dioxide dissolved in thewater doubles as it filters throughirrigated fields. The scientistssuggest carbon dioxide in the air istaken up by the desert crops. Someof this carbon is released into thesoil through the plant’s roots. Atthe same time, microbes also addcarbon dioxide to the soil when they break down sugars in thedirt. In a dry desert, this gas would work its way out of the soilinto the air. But on arid farms, the carbon dioxide emitted bythe roots and microbes is picked up by irrigation water,according to the new study.

In these dry regions, where water is scarce, farmers over-irrigate their land to protect their crops from salts that are leftbehind when water used for farming evaporates. Over-irrigatingwashes these salts, along with carbon dioxide that is dissolvedin the water, deeper into the earth, according to the new study.

Although this process of carbon burial occurs naturally, thescientists estimate that the amount of carbon disappearingunder the Tarim Desert each year is almost 12 times higherbecause of agriculture. They found that the amount of carbonentering the desert aquifer in the Tarim Desert jumped aroundthe time the Silk Road, which opened the region to farming,begin to flourish.

After the carbon-rich water flows down into the aquifer nearthe farms and rivers, it moves sideways towards the middle ofthe desert, a process that takes roughly 10 000 years.

Any carbon dissolved in the water stays underground as itmakes its way through the aquifer to the centre of the desert,

where it remains for thousands of years, according to the newstudy.

Estimating carbon storageBased on the various rates that carbon entered the desertthroughout history, the study’s authors estimate20 billion metric tonnes of carbon is stored underneath theTarim Basin desert, dissolved in an aquifer that containsroughly 10 times the amount of water held in the NorthAmerican Great Lakes.

The study’s authors approximate the world’s desert aquiferscontain roughly 1 trillion metric tonnes of carbon – about aquarter more than the amount stored in living plants on land.

Li said more information about water movement patterns andcarbon measurements from other desert basins is needed toimprove the estimate of carbon stored underneath desertsaround the globe.

Allen said the new study is ‘an early foray’ into this researcharea. ‘It is as much a call for further research as a definitivefinal answer,’ he said.

American Geophysical Union


Scientists followed the journey ofwater through the Tarim Basin fromthe rivers at the edge of the valley tothe desert aquifers under the basin.They found that as water movedthrough irrigated fields, the watergathered dissolved carbon and movedit deep underground. Yan Li

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Acidity management is one of the most important wine qualityissues, especially in terms of wine stability. Some of thesignificant stability issues related to pH include the inhibitionof spoilage organisms at low pH, reflecting how a lower pHfavours ‘molecular sulfur dioxide’, the antimicrobial form.Oxidation rates decrease as pH decreases and there is a higherred colour at low pH, with the wine going to ‘blue’ as the pHincreases.

Winemakers assess acidity in grapes and wine using twoparameters: pH and titratable acidity (TA). The pH is measuredin the usual way while TA is determined by titration withsodium hydroxide to a pH 8.2 endpoint. The volume ofhydroxide is then converted to a mass of tartaric acidequivalents, as tartaric tends to be the dominant acid in wine.In some parts of the wine world, a pH 7 endpoint is chosen andthe results quoted as an equivalent mass of sulfuric acid. Thisreflects the old (now not permitted) practice of adding sulfuricacid to increase the acidity if the natural acidity was regardedas too low. Several countries have regulations that include totalacidity (the same as titratable acidity), volatile acidity (steam-distillable acids such as acetic) and fixed acidity(non-distillable acids).

There is a mixture of organic acids found in wine, someoriginating from the grape and others from the fermentation.The two major acids that originate from the grape are tartaricacid and malic acid. Vitis vinifera would appear to be the onlycultivated European plant that accumulates L(+)-tartaric acid insignificant quantities and it is produced as a secondary productfrom sugar metabolism, actually being formed from ascorbicacid in the grape berry. Of the major organic acids in wine,tartaric acid is the strongest. It is relatively stable towardsdegradation during the berry ripening process. Some losses mayoccur late in ripening as the pH of the berry pulp increases,thus increasing the proportion of the hydrogen tartrate anion.If the concentration of potassium is high, precipitation of KHT(in wine jargon) may occur.

Malic acid is common in many plants (green apples, for one).In grapes, its formation proceeds by well-characterisedpathways including links to the phosphoenolpyruvate, glycolyticand TCA cycles. Malic acid respires after véraison (the transitionfrom berry growth to ripening), but the mechanism is not fullyunderstood. The extent of respiration and malic acid lossdepends on the temperature of the growing region. Thus, inAustralia’s warm climate grape-growing conditions, malic aciddegradation is significant, leading to lower acidity in the grapesat harvest and often higher than optimal pH values. This is theopposite of what happens in the cool-to-cold growing regionswhere the malic acid concentration at harvest may equal orexceed that of tartaric acid.

Succinic acid and citric acid are both formed during yeastfermentation. Citric acid addition to a wine post-fermentationmay be used for young wines to add an ‘acid zest’ taste. The

contribution of succinic acid to a wine’s structure is nowreceiving more attention. Some active dried yeasts can producesuccinic acid at a concentration where it can contribute to thewine’s taste. This is rather unfortunate, as the taste is far frompleasant, being described as ‘sour’, ‘salty’ and ‘bitter’.

Lactic acid is produced from malic acid in wine throughbacterial-mediated decarboxylation, commonly known as malo-lactic fermentation (MLF). Lactic acid is milder than malic acid,so MLF results in a decrease in acidity and a softening of theacid taste. Some acetic acid is formed during fermentation,although the amount is small, unless there are problems withthe fermentation. The major source of acetic acid is aconsequence of the aerobic oxidation of ethanol by Acetobacter.Acetic acid is readily volatile and gives an unpleasant ‘vinegar’aroma to oxidised wine.

With all these different acids in wine, it is often asked ifexternal factors such as climate change may be affecting thevarious amounts formed. A recent 2015 article by Peter Gooden,Eric Wilkes and Dan Johnson of the AWRI entitled ‘Trends in thecomposition of Australian wine 1984–2014’ (Aust. J. Grape WineRes. 2015, vol. 21, pp. 741–53) includes data for TA and pHover this time frame. There is good evidence for a decrease inTA and an increase in pH, especially since 2008 for red wines.While it may be easy to relate this to climate/prolongeddrought issues, the authors note that ‘It is difficult … toattribute any of the compositional trends discussed here toeither any change in climate or compressed vintages.’ Marketingissues may also be contributing to these changes as higher pHwines are perceived as softer in mouthfeel and more consumerfriendly.

The need for adjustment to the natural acidity, that is theacidity that is grape derived, is an issue that has always beensomewhat contentious. While it is common practice in Australiato add some form of acid during the winemaking practice, Ihave worked in one winery where the winemaker absolutelyrefused to allow acid addition. In this case, the argument wasthat acid addition brings the wine out of balance with all theother natural features derived from the grape. Many who followbiodynamic principles do not add acid for the same ‘balance’reason and acid addition is contrary to the so-called naturalwinemaking practice. In my next column, I will outline some ofthe processes used for acid addition.


Grape and wine acidity

Geoffrey R. Scollary FRACI CChem ([email protected]) wasthe foundation professor of oenology at Charles Sturt Universityand foundation director of the National Wine and Grape IndustryCentre. He continues his wine research at the University ofMelbourne and Charles Sturt University.

grapevine

environment

Australia’s appetite for new residential land means that marketgardens and orchards on the urban fringe are being taken overby houses. It is also revealing a legacy of decades ofhorticultural pesticide and fertiliser use.

In my contaminated land work, my first port of call forbackground information on potential contaminants, insecticidesin particular, was Ben Selinger’s classic, Chemistry in themarketplace. My 1975 edition was an aid to understanding old-style horticultural practices. While I had an inkling thatinorganic pesticides were predominant before the introductionof the synthetic organic pesticides, I was surprised to learn thatfluorides (such as sodium fluoride and cryolite, Na3AlF6) wereused. My knowledge had been limited to a few lead- andcopper-based compounds. Some natural Australian soils, such assilurian clays, are naturally high in fluoride, so determiningwhat is background and what is introduced (i.e. contamination)requires a bit of extra effort.

Inorganic compounds don’t degrade, and so persist in soilunless leached away (thus causing a water contaminationproblem). The organochlorine pesticides (OCPs) were introducedto address this, as well as the problem of metal toxicity tohumans and other vertebrates. However, there was probably nota lot of work done on understanding the persistence of thesecompounds before they were introduced, nor on the unintendedconsequences of their use. They were subsequently banned inthe 1980s.

The environmental data we collect now tell us that the OCPsare only marginally less persistent than the inorganics theyreplaced, at least on an intergenerational time scale. Thetoxicology literature also records that the human healthimpacts are not trivial. In the National Environment ProtectionMeasure (NEPM) for contaminated sites, the HealthInvestigation Level (HIL) for lead, on a standard residentialsite, is 300 mg/kg. For chlordane it is 50 mg/kg and for aldrinplus dieldrin it is 6 mg/kg. So, what were once promoted as

safer, alternative insecticides turn out not to be so safe in allcases, after all, and they can still be found in the environment,decades after their last use.

For some of the OCPs, the HIL values are for totalconcentrations of the compound that was applied plusdecomposition products. This is the case for DDT, and itsbreakdown products DDE and DDD, and for aldrin plus dieldrin asmentioned above. This is so because when the parent compoundslowly degrades in the environment, the product(s)are also slowto degrade, and often have appreciable toxicity. Some pesticidesare not the active compound with lethal effect on the targetspecies. Rather, the insect metabolises it to a toxic form in vivo(to dieldrin, in the case of aldrin).

It is also important to understand how OCPs were used inpractice, as well as understanding their chemistry andtoxicology. If insecticides are sprayed throughout an orchard ormarket garden, with a boom or mist sprayer pulled behind atractor, it creates a fairly uniform distribution across the site,meaning a regular sampling pattern is likely to identify anaverage concentration. Hot spots of higher concentrations areusually associated with storage areas, or areas whereconcentrated bulk chemicals were diluted and loaded into thesprayer. However, on one site I know, to prevent termite attackon the roots of trees, aldrin was applied to the soil directly,into the hole into which seedlings were to be planted. Theoutcome was that there were small hot spots in a regularpattern across the site. A conventional grid-based samplingpattern won’t necessarily detect all of the hot spots and, whenthe trees were removed, there was some degree of mixing of thesoil. Some of the hot spots become bigger and some werediluted with uncontaminated soil. The result was a complexpattern of contamination, which taxes the routine samplingprocesses of the environmental assessor.

Earlier on, I mentioned the use of lead as an insecticide,which was often applied as lead arsenate, and discussed its NEPMHIL value. In 2015, the NHMRC revised its guidance on theallowable blood lead level in children, halving it from 10 mg/dL to 5 mg/dL. The NEPM HIL value is based on theallowable blood lead level, so this reduction will eventually resultin a reduction of the NEPM HIL for lead. With the risk assessmentmethodology used to derive the HIL, there is not a linearrelationship between blood lead level and the HIL value, so arevised HIL may be less than half the current value. If the samewere to happen to the HILs for OCPs, a new set of standards willapply to all those orchards and market gardens out there still tobe assessed for urban use. What that might mean for sitesalready converted to urban use is an interesting question.


A persistent pesticide problem

Paul Moritz FRACI CChem ([email protected]) isa Principal Contaminated Land Consultant with Douglas Partners,and an EPA-appointed Environmental Auditor in Victoria and theNorthern Territory. The assistance of Ben Selinger and Ian Rae in thepreparation of this column is acknowledged.

The Ammunition Factory in Gordon Street, Footscray, had a longhistory of service to the Victorian and then the Australianeconomy. Bullet cases were fashioned from brass and stuffed withgunpowder, originally imported but later manufactured at theExplosives Factory a few kilometres away. All part of the Arsenalof the West, that also included the Ordnance Factory where thebig guns were made.

By the 1990s the Ammunition factory had outlived itsusefulness. The business was transferred to a new AustralianDefence Industries (ADI) factory at Benalla in central Victoria,while the Footscray land was sold off for housing. All except onepart of the factory, that is – the magazine that dated back to the1870s. It had not been used in recent decades, but in 1987 it wasclassified by the National Trust and thus afforded a measure ofheritage protection. It had always been known as Jack’s Magazinebut nobody at ADI could remember who Jack was. ‘Jack who?’ wasthe question that management asked as they combed throughcompany records and consulted present and (where possible) pastemployees as they prepared to vacate the site.

They never found the answer, but it turned up a few years laterwhen the magazine was the subject of heritage interest and theNational Trust of Australia (Victoria) organised an open day at thesite for which they prepared some explanatory material. Again thequestion was raised, ‘Jack who?’, but the answer came from avolunteer worker at the Trust, Nancy Jack. It was her uncle, MrJack, who was manager of the magazine and she rememberedthat, as a small girl, she had stayed with the Jack family in themanager’s house, adjacent to the magazine.

Wally (Walter Annandale) Jack (1876–1969) was the keeperfrom World War I days until 1943. He was awarded an MBE in 1960for his social welfare work with young people but other than thatI don’t know much about him. His younger brother, Keith AndrewJack (1885–1966) was an Associate and Original ACI Member(1917) and FRACI (1944), having graduated MSc in physicalchemistry from the University of Melbourne in 1914. He was amember of Shackleton’s disastrous Antarctic expedition in 1914.Jack was in the Ross Sea party stranded in Antarctica for severalyears. From 1916 he worked at the Explosives Factory, dealingwith small ammunition, detonators and fuses. He spent war yearsattached to Australia House, London, as an explosives expert andreturned to be Secretary of Operational Safety in theCommonwealth Department of Supply until he retired in 1950.

When ADI moved out, the plan was for Jack’s Magazine to besold but nobody wanted to purchase two vaulted buildings withone-metre thick walls and tiny ventilation slits (protected bycopper gauze) that was tucked away behind massive earth walls(www.jacksmagazine.org.au). The only interest seems to havecome from metal thieves, who made off with the copper, includingthe lightning protection structures. Victoria’s government hasaccepted that the magazine will remain in public hands and it hasjoined a list of facilities for which an advisory committee is tryingto find uses. I reckon Jack’s Gym and Jack’s Disco (no noise

problems for the neighbours!) would be good. To have your say,visit www.workingheritage.com.au.

Opened in 1878, the magazine was constructed of localbluestone (basalt) for the Victorian Government, on a site abovethe flood plain of the Maribyrnong (then known as the Saltwater)River. Two buildings were protected by high earthen blast wallsand accessed through short tunnels. Imported gunpowder arrivingin Port Phillip was trans-shipped into barges for transport up theshallow river. They entered a canal leading to the magazine, whereloads were winched up, then trundled along a tramway throughthe tunnels to secure storage. In 1888, the Colonial AmmunitionCompany, an offshoot of the New Zealand company led by CaptainJohn Whitney, built a factory next door to the magazine. TheCommonwealth Government leased the factory from 1921 andpurchased it in 1927.

letter from melbourne


Jack’s magazine and his brother

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

Across2 Particular Vice-Chancellor begins to

make polymer. (1.1.1.)5 Hard water drug. (3)8 Third prime boron. (4)9 Decides standards. (5)10 A couple of unknowns about radium

used for medical imaging. (1-3)11 Shapes out solid and liquid,

perhaps. (6)12 Procedure for each guy on his bike. (8)13 Rocks or transuranic element. (4)14 See 27 Across.15 Scrutinise sulfur and tin. (4)16 Light researcher oddly forced lens

back. (7)19 Meant to take away the music?! (7)23 We object to transuranic element

applications. (4)25 The 8th Greek or the 73rd. (5)27 & 14 Across Remain calm, remain

free. (4,5)29 Made and put on. (8)30 The simplest carboxylic acid for Metal-

induced crystallisation. (6)31 Guys with uranium list. (4)32 Fashion icons held with charges. (5)33 Get out! Way out! (4)34 Alternate music to a higher

degree. (1.2.)35 Impugn sailor. (3)

Down1 One or the other organic compound

holds iodine. (6)2 P.S. Sister is out and carries on. (8)3 Moving closer to methylphenol. (6)4 Metal chill over hydrogen

compound. (7)5 Opener is over CH2=C(CH3)CH=CH2. (8)6 Additional charges included in next

rascal’s ruse. (6)7 Little truck with a meeting about VO4

3–,perhaps. (8)

13 & 21 Down Not performing well whennot scheduled to work. (3,3)

17 Again waited, distant. (8)18 The lowest and sharpest melting point

of a solid mixture of Te/Ti/Cu/Ce. (8)20 Obstetrics computer can’t fully

participate. (8)21 See 13 Down.22 Interpretation of Spooner’s expensive

circle. (7)24 Eleventh sulfur disgrace. (6)26 F2 etc. a new influence. (6)28 A group of investigators in charge of

low pH. (6)

events

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

Fire Australia & Hazmat 2016 4 and 5 May 2016, Melbourne Convention and ExhibitionCentre, Melbourne, Vic.www.fpaa.com.au/events/fire-australia.aspx

7th Heron Island Conference on Reactive Intermediatesand Unusual Molecules9–15 July 2016, Heron Island, Qldwww.Heron7.org

27th International Conference on OrganometallicChemistry(incorporating the RACI Inorganic Chemistry DivisionConference)17–22 July 2016, Melbourne Convention and ExhibitionCentre, Melbourne, Vic.http://icomc2016.com

International Conference and Exhibition on Marine Drugsand Natural Products 25 July 2016, Rydges, Melbourne, Vic.http://naturalproducts.pharmaceuticalconferences.com

2nd Energy Future Conference and Exhibition4–6 July, University of NSW, Sydney, NSWhttp://energystoragealliance.com.au/event/energy-future-conference-exhibition

NZIC-1621–24 August 2016, Millennium Hotel, Queenstown, New Zealandwww.nzic16.org

European Symposium of Biochemical EngineeringSciences (ESBES)11–14 September 2016, Dublin, Irelandwww.esbes2016.org

Chemeca 201625–28 September 2016, Adelaide Convention Centre,Adelaide, SAwww.chemeca2016.org

6th International Conference and Exhibition onPharmaceutical Regulatory Affairs and IPR 29 September – 1 October 2016, Orlando, Florida, UShttp://regulatoryaffairs.pharmaceuticalconferences.com

AusBiotech 201624–26 October 2016, Melbourne Convention Centre, Vic.www.ausbiotechnc.org

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Indigenous people and chemistry - Chemistry in Australia ... · The editorial, production and advertising team of Chemistry in Australia is a small and efﬁcient group that is great