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2018 anniversary for Australian Journal of Chemistry Chemical warfare: protection and prevention RACI Centenary Congress wrap-up chemistry chemaust.raci.org.au in Australia October 2017 chemistry A single-cell view of metals

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• 2018 anniversary for Australian Journal of Chemistry• Chemical warfare: protection and prevention• RACI Centenary Congress wrap-up

chemistry

chemaust.raci.org.au

in AustraliaOctober 2017

chemistryA single-cellview of metals

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news & research6 News14 Research17 Aust. J. Chem.42 Cryptic chemistry42 Events

members4 From the President32 From the Centenary

Congress33 New Fellow

views & reviews5 Your say34 Books36 Economics38 Measurement40 Grapevine41 Letter from Melbourne

36October 2017

26chemaust.raci.org.au

18Inside running: a cell-by-cell view of metalsSingle-cell inductively coupled plasma mass spectroscopy offersa potentially significant breakthrough in detailed biologicalstudies.

cover story

22 AJC: celebrating 70 years of chemical science publishingNext year, the Australian Journal of Chemistry will celebrate 70 years ofpublishing research papers from all fields of chemical science, with a focus onmultidisciplinary chemistry and emerging areas of research.

26 Protection and prevention in chemical warfareProtection, antidotes, treatments and of course prevention are the subject ofongoing research in the face of chemical weapons attacks.

30 International diplomacy requires chemistryProfile: Dr Brendon Hammer

Chemistry in Australia4 | October 2017

from the raci

The RACI celebrated its 100th birthday at the CentenaryCongress in Melbourne, 23–28 July 2017. The conference was anoutstanding success, and right from the outset I would like tothank the CEO of the RACI, Roger Stapleford for hisinexhaustible contributions. Roger oversaw much of thelogistics of this congress, and, as one could imagine, theorganisational aspects were enormous. There were many othercontributors to this congress, the Chair Professor Mark Buntine,the Chairs of the respective conferences and divisions thatcontributed to the congress, the RACI office staff, the staff ofthe PCO, ICMS Australasia, the staff at the MelbourneConvention Centre and of course the delegates who contributedto all aspects of making sure the conference was intellectuallystimulating, and socially excellent. No doubt I have leftsomeone out of these acknowledgements, and I apologise, butthe size of the Congress meant this will always happen. Theamount of networking taking place was overwhelming, withformal and informal meetings being held simultaneouslythroughout the Convention Centre and, needless to say, barsand restaurants nearby.

This was easily the biggest chemistry conference organisedin Australia, being well in excess of double anything previously.The numbers elaborate on the size of the Congress (see box).

As part of the 100th celebration, a coffee table bookcovering highlights of the first 100 years of the RACI waslaunched. This book, RACI – a century of bonds, was compiledby Helmut Hügel, but had considerable contributions from manyothers throughout the RACI. The book is an excellent overviewof the first 100 years of the RACI and has snippets of research,education, timelines etc. If you would like to acquire a book,please contact the RACI (see p. 35).

I have attended many more focused conferences in Australia,but this broad congress brought many people together who Ihave not run into for years, old friends from PhD days, workcolleagues from years ago, and many ex-students whom Ihaven’t seen for some time. Conferences are for learning newchemistry and forming networks, but also for the socialstimulation of catching up with old friends, and on this basis, itwas an incredible success. I only wish I would be around in2117 for RACI Congress 200.

EDITOR Sally WoollettPh (03) 5623 3971 [email protected]

PRODUCTION EDITORCatherine Greenwood [email protected]

ADVERTISING SALES Mary Pappa Ph/fax (03) 9328 2033/[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 Peter Junk FRACI CChem

MANAGEMENT COMMITTEESam Adeloju (Chair) [email protected], Amanda Ellis, Michael Gardiner, Helmut Hügel, Colin Scholes, Madeleine Schultz, 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.

© 2017 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

chemaust.raci.org.au

Peter Junk FRACI CChem ([email protected]) is RACIPresident.

From the President

This was easily the biggestchemistry conferenceorganised in Australia, beingwell in excess of doubleanything previously.

Counting up the CongressNumber of delegates 3317: including 126

exhibitors, 3 media, 36staff, 6 sponsors, 26visitors, 31 volunteers

Number of Branch/Division meetings 10 Divisional + 2symposia

Number of affiliated conferences 8 internationalconferences

Number of affiliated seminars 4: ACES, SCI, RSC Panel,A2CS

Other meetings Decadal planRACI diversity and equityWomen in chemistryRSC commonwealthround table

Receptions Royal Society ofChemistryChemical EngineeringSCI

Number of Nobel Laureates 4Number of plenaries for our Congress 11 for the main congressTotal number of plenaries and keynotes 189Total number of invited speakers 211Total talks 1398Total posters 1401Total rooms 32Total number of sponsors 16Total number of booths 74Number of lunches served 11000Number of official dinners organised 6 large

3 small

your say

Chemistry in Australia 5|October 2017

Soil lead contamination of SydneybackyardsWe thank Dr Moritz for bringing to the readers’ attention(August issue, p. 5) our recent article ‘VegeSafe: a communityscience program measuring soil-metal contamination,evaluating risk and providing advice for safe gardening’(http://bit.ly/2v45gba and summarised in the June issue,p. 34).

Our Macquarie University community science program,VegeSafe, is the only pro bono service in Australia that providesgardeners with free soil metal testing. This service informsgardeners of potential metal contamination in their backyardsoils. Our program also offers practical advice on simple andeffective remedies to minimise exposure to toxic metals in theirsoils where present above levels of concern. Since 2013, wehave provided over 8000 free soil screening tests to over2000 Australian households and community garden groups.

In the August issue, Dr Moritz explained briefly how theAustralian health investigation levels (HILs) set by the NationalEnvironment Protection Measure 1999 (NEPM) are used forcontaminated site investigations in Australia. Dr Moritz arguesthat we may have misused the HILs in our research of soil leadcontamination in Sydney backyards. Our June summary restatedthe factual results of our study: ‘40% of 203 Sydney homes wesampled contain lead in garden soil above the Australian healthguideline of 300 mg/kg’. We used the Australian HIL-A for leadin soil (300 mg/kg) and coupled this to known naturalbackground lead concentrations (20–30 mg/kg) to providerelevant context for the results of our study. Neither of ourarticles states that the HIL values are clean-up values, responselevels or desirable soil quality criteria. They are ‘investigation’levels as the NEPM states. However, we provide advice tohomeowners on the basis of the precautionary approach and theknown toxicity of lead, especially to young children.

One in seven Sydney homes (in our study) have soil leadconcentrations greater than 1000 mg/kg, while one in sixhomes have individual sample concentrations in excess of 250%of the HIL (750 mg/kg). Yet, regardless of the extent of leadcontamination in these home environments, it is unlikely anyfurther investigation or remediation of these properties willoccur as the NSW EPA exempts ‘widespread diffuse urbanpollution’ from its Duty to Report on the basis that thecontamination ‘is not attributed to a specific industrial,commercial or agricultural activity’ (Section 2.6 of theGuidelines on the Duty to Report Contamination under theContaminated Land Management Act 1997). This regulatoryapproach means that any effective action needs to executed byindividual homeowners on the basis of relevant information –such as that provided by VegeSafe.

As environmental scientists, our end goal is to enableAustralian gardeners to utilise their garden spaces in a safe,and sustainable, manner. Hence, our motto ‘Carry on gardening’.

Marek Rouillon and Mark P. Taylor

More reflections on Sydney TechnicalCollegeI gained my Chemistry Diploma in December 1950 after fiveyears of part-time study. The lessons and experience I gained atSydney Technical College were invaluable to me for theremainder of my working life. Working as a bucket-and-stickchemist for most of my career, I treasured the input of lecturerssuch as Dwyer and Nyholm in inorganic chemistry and the highstandards set by the remainder of the teaching staff.

One of my outstanding memories is of working late oneevening in the industrial chemistry laboratory, preparing aquantity of nitrobenzene. The batch size was about 10 litres andthe equipment was a 15-litre earthenware open crock with asmall stainless steel electric mixer. I experienced only a slightexotherm but persisted in adding the acid mix. After closingtime, Val Rawson appeared and asked me what I was doing. Hefound that the braised agitator blade had become detached.Rawson calmly told me to turn on all the laboratory water tapsand we tipped the mix down the drain! No need to repeat thisexperiment my boy, just write it up!

Ken Jones FRACI CChem

Got some

thing

to say?

As your RACI member magazine,Chemistry in Australia is theperfect place to voice your ideasand opinions, and to discusschemistry issues and recentlypublished articles.

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

from the Centenary Congress

A chem lab in your phoneUsing your mobile as a diagnostictoolThe mobile phone in your pocket could be used for medicaldiagnostics and environmental testing if Associate ProfessorConor Hogan and his team from La Trobe University have theirway.

This could be potentially life-changing for people indeveloping countries and remote areas with limited resources,by making such chemical measurements more accessible andextremely inexpensive.

‘There are two ways you can bring the cost of medicaldiagnostics down,’ says Conor.

First, you can use less expensive materials and fabricationmethods to make the sensors, so Conor’s team have developed amicrofluidic sensor printed on paper rather than using moretraditional materials such as silicon or glass. The secondapproach is to do away with the need for a scientific instrumentto make the measurements, instead using your phone.

The combination of these two approaches can bring the costof chemical analysis to negligible levels. ‘Scientists around theworld are investigating ways in which to use mobile phones asa way of bringing health care to developing countries andremote communities’, Conor says.

‘With mobile phone penetration now over 80% in thedeveloping world and close to 100% worldwide, the idea issensible.’

They’ve demonstrated the possibility of diagnosing diseaseor detecting harmful chemicals in drinking water using only adisposable paper-based sensor and a mobile phone.

One approach uses a highly sensitive scientific techniqueknown as electro-chemiluminescence or ECL where electricitytriggers a light-producing chemical reaction.

Science in Public

October 2017

Robert Grubbs’ discoveries have enabled industry to produceplastics and drugs more efficiently and with less hazardous waste.

Robert was awarded the Nobel Prize in 2005 for his work onthe chemical reaction metathesis – where carbon atom groupschange places.

While the reaction was first described in 1971, Robertdeveloped a catalyst that improved this reaction, and wasstable in air, making this process more available to industry.

It’s now used daily in the production of pharmaceuticals andadvanced plastic materials.

Now he’s developed a method to drastically reduce the sulfurcontent in diesel fuel more simply and cheaply.

Reducing the sulfur content in diesel will significantly reduceacid rain – which occurs when the diesel is burned and thesulfur is converted to sulfur dioxide, which reacts with water toform acid rain.

Professor Robert Grubbs is based at the California Instituteof Technology.

Science in Public

Nobel Laureate tackles acid rain by getting the sulfurout of diesel

Nino Barbieri/CC-BY-SA-3.0

iStockphoto/rasslava

Petrol cars produce more carbonaceousparticulate matter (PM) emissions thandiesel cars equipped with diesel particlefilters (DPFs; pictured) and catalysts,according to initial laboratory testspublished in a study in Scientific Reports(http://dx.doi.org/10.1038/s41598-017-03714-9). The authors note thatemissions from vehicles are sensitive tothe sampling location, fleet age andambient temperature, and they suggestthat further studies that calculate anaggregate of emissions are required.

Carbonaceous PM consists of blackcarbon, primary organic aerosols(including solid particles fromcombustion) and secondary organicaerosols (produced via the atmosphericageing of organic compounds releasedduring combustion), and is a toxiccomponent of vehicle exhausts. However,the relative contributions of diesel carsequipped with DPFs and petrol cars tothese emissions have not been quantified.

In laboratory investigations, AndréPrévôt and colleagues quantifiedcarbonaceous PM from 11 petrol and sixdiesel cars equipped with DPFs at 22°C

and –7°C. The authors found that petrolcars emitted on average ten times morecarbonaceous aerosol at 22°C and62 times more at –7°C than the dieselcars. They also found that the diesel carstested produced no detectable secondaryorganic aerosols.

The authors note thatcompared to the cars tested, PMemissions are much higher from dieselcars that do not have a DPF, which willproduce the largest fraction of PMemissions for some time.

Springer Nature

The world’s largest lithium ion battery will be installed in SouthAustralia under a historic agreement between French renewableenergy company Neoen, US sustainable energy company Teslaand the South Australian Government.

The energy storage systems from Tesla will be paired withNeoen’s Hornsdale Wind Farm and installed before summer.

Confirming the commitment from Tesla CEO Elon Musk todeliver the battery within 100 days or it will be free, it has beenagreed between Tesla and the South Australian Government thatthe starting date for the 100 days will be once the gridinterconnection agreement has been signed.

After leading the nation in renewable energy, the100 MW/129 MWh battery places South Australia at the forefrontof global energy storage technology.

The battery will operate at all times, providing stabilityservices for renewable energy, and will be available to provideemergency back-up power if a shortfall in energy is predicted.

The deal will also bring other investments by both Neoenand Tesla into South Australia’s economy, with details to beannounced in the future.

Jay Weatherill

news

Chemistry in Australia 7|October 2017

Tesla to pair world’s largest lithium ion battery with Neoen wind farm in SA

ScottDavis/CC-BY-SA-3.0

Certain emissions may be higher from petrol cars than some diesel cars

Dana60Cummins

news

While using X-rays to study the earlystages of a chemical process that canreformulate carbon dioxide into moreuseful compounds, including liquid fuels,researchers were surprised when theexperiment taught them something newabout what drives this reaction.

An X-ray technique at the USDepartment of Energy’s LawrenceBerkeley National Laboratory (BerkeleyLab), coupled with theoretical work by ateam at the California Institute ofTechnology, Pasadena (Caltech), revealedhow oxygen atoms embedded very nearthe surface of a copper sample had amore dramatic effect on the early stagesof the reaction with carbon dioxide thanearlier theories could account for.

This information could prove useful indesigning new types of materials tofurther enhance reactions and make themmore efficient in converting carbondioxide into other products.

The research team developedcomputer models and revised existingtheories to explain what they werewitnessing in experiments. Their resultswere published online in the Proceedingsof the National Academy of Sciences(12 June).

Copper is a common catalyst and,although it is not efficient, it aids in the

production of ethanol when exposed tocarbon dioxide and water.

‘We found more than we thought wewere going to find from this fundamentalinvestigation’, said Ethan Crumlin, ascientist at Berkeley Lab’s AdvancedLight Source (ALS) who co-led the studywith Joint Center for ArtificialPhotosynthesis (JCAP) researchers JunkoYano, at Berkeley Lab, and WilliamGoddard III, at Caltech.

The X-ray work brought new clarity indetermining the right amount ofsubsurface oxygen – and its role ininteractions with carbon dioxide gas andwater – to improve the reaction.

‘Understanding this suboxide layer,and the suboxide in contact with water,is integral in how water interacts withcarbon dioxide in this type of reaction’,Crumlin said.

Goddard and his colleagues at Caltechworked closely with Berkeley Labresearchers to develop and refine aquantum mechanics theory that fit the X-ray observations and explained theelectronic structure of the molecules inthe reaction.

‘This was a good looping, iterativeprocess’, Crumlin said. ‘Just being curiousand not settling for a simple answer paidoff. It all started coming together as a

cohesive story.’At Berkeley Lab’s ALS, researchers

used APXPS (ambient pressure X-rayphotoelectron spectroscopy as theyexposed a thin foil sheet of a speciallytreated copper – known as Cu(111) – tocarbon dioxide gas and added water atroom temperature. In proceedingexperiments, they heated the sampleslightly in oxygen to vary theconcentration of embedded oxygen in thefoil, and used X-rays to probe the earlystages of how carbon dioxide and watersynergistically react with differentamounts of subsurface oxide at thesurface of the copper.

The X-ray studies, planned andperformed by Marco Favaro, the leadauthor of the study, revealed how carbondioxide molecules collide with the surfaceof the copper, then hover above it in aweakly bound state. Interactions withwater molecules serve to bend the carbondioxide molecules in a way that allowsthem to strip hydrogen atoms away fromthe water molecules. This processeventually forms ethanol.

‘The modest amount of subsurfaceoxygen helps to generate a mixture ofmetallic and charged copper that canfacilitate the interaction with carbondioxide and promote further reactionswhen in the presence of water’, Crumlinsaid.

Copper has some shortcomings as acatalyst, Yano noted, and it is currentlydifficult to control the final product agiven catalyst will generate.

‘If we know what the surface is doing,and what the model is for this chemicalinteraction, then there is a way to mimicthis and improve it’, Yano said. Theongoing work may also help to predictthe final output of a given catalyst in areaction. ‘We know that copper works –what about different copper surfaces,copper alloys, or different types of metalsand alloys?’

DOE Science

Chemistry in Australia8 | October 2017

Surprise just beneath the surface in carbon dioxideexperiment

(Left) In this atomic-scale illustration, trace amounts of oxygen (red) just beneath a copper(blue) surface, play a key role in driving a catalytic reaction in which carbon dioxide (blackand red molecules) and water (red and white molecules) interact in the beginning stages offorming ethanol. Carbon dioxide molecules hover at the copper surface and then bend toaccept hydrogen atoms from the water molecules. X-ray experiments at Berkeley Lab’sAdvanced Light Source helped researchers to understand the role of subsurface oxygen inthis process. (Right) This false-colour scanning electron microscopy image showsmicroscopic details on the surface of a copper foil that was used as a catalyst in a chemicalreaction studied at Berkeley Lab’s Advanced Light Source. The scale bar represents50 micrometres. Berkeley Lab

A researcher at Queen’s University Belfasthas discovered a way to convert dirtyaluminium foil into a biofuel catalyst,which could help to solve global wasteand energy problems.

In the UK, around 20 000 tonnes ofaluminium foil packaging is wasted eachyear – enough to stretch to the moon andback. Most of this is landfilled orincinerated as it’s usually contaminatedby grease and oils, which can damagerecycling equipment.

However, Ahmed Osman (pictured) anEarly Career Researcher from Queen’sUniversity’s School of Chemistry andChemical Engineering, has worked withengineers at the university to create aninnovative crystallisation method, whichobtains 100% pure single crystals ofaluminium salts from the contaminatedfoil. This is the starting material for thepreparation of alumina catalyst.

Usually, to produce this type ofalumina it would have to come frombauxite ore, which is mined in countriessuch as West Africa, the West Indies andAustralia, causing huge environmentaldamage.

Osman has created a solution that ismuch more environmentally friendly,effective and cheaper than thecommercial catalyst that is currentlyavailable on the market for the productionof dimethyl ether – a biofuel that is

regarded as the mostpromising of the21st century. Osmansays making thecatalyst fromaluminium foil costsabout £120/kg($200/kg) while thecommercial aluminacatalyst comes in ataround £305/kg($500/kg).

Its uniquethermal, chemicaland mechanicalstability means itcan also be used asan absorbent, in

electronic device fabrication, as a cuttingtool material or as an alternative forsurgical material for implants.

The research has been published inNature Scientific Reports(http://dx.doi.org/10.1038/s41598-017-03839-x).

Osman commented: ‘I have alwaysbeen inspired by chemistry and I believethat catalysis especially can make theworld a better place. One day I took awalk through our laboratories at Queen’sand found lots of aluminium foil waste soI did a little digging and after speakingto my colleagues, I ran my experimentand was astonished by the ultrapuresingle crystals – I didn’t expect it to be100% pure.

‘This breakthrough is significant asnot only is the alumina more pure than itscommercial counterpart, it could alsoreduce the amount of aluminium foilgoing to landfill while also sidesteppingthe environmental damage associatedwith mining bauxite.’

Osman is hoping to continue hisresearch into how these catalysts can befurther improved and explore theopportunities for commercialisation ofbiofuel production or use the modifiedalumina catalyst in the catalyticconverters in natural gas vehicles.

Queen’s University Belfast

October 2017

Turning dirty foil into biofuel catalyst

news

Scientists at the Australian NuclearScience and Technology Organisation’s(ANSTO) Centre for Accelerator Scienceand Australian Synchrotron were part of ateam who have found new proof of theearliest occupation in Australia – some65 000 years – in Kakadu National Park(pictured).

The team, which includedarchaeologists and dating specialists,located the evidence at Madjedbebe, asite found on the traditional lands of theMirarr people, surrounded by the WorldHeritage-listed Kakadu National Park.

The research, published in July inNature (http://doi.org/10.1038/nature22968), was led by AssociateProfessor Chris Clarkson from theUniversity of Queensland.

ANSTO’s Dr Quan Hua oversaw theradiocarbon dating of charcoal sampleson ANSTO’s STAR accelerator. At ANSTO’sAustralian Synchrotron in Melbourne, Dr Helen Brand, used powder X-raydiffraction to identify the mineralspresent in pigment samples of artefacts.

These methods, alongside extensiveoptically stimulated luminescence datingconducted at the University ofWollongong, show the site has a deeplyburied, dense occupation layer dating to65 000 years ago.

Hua said that the charcoal samples

that were analysed were collected duringexcavations in 2012 and 2015. Most ofthe charcoal samples are isolatedfragments but several samples werecollected from in situ hearths.

‘With the STAR accelerator, we wereable to measure carbon-14 or radiocarbonby accelerator mass spectrometry, to helpdetermine the age of the samples’, Huaexplained.

Brand’s expertise enabled the analysisof powder pigments from ochre found atthe site, using the AustralianSynchrotron, a source of light a milliontimes brighter than the sun.

‘Using the powder diffractionbeamline, we investigated thecharacteristics of the ochre, which wasfound quite extensively through the site’,Brand said.

‘The brilliance of the synchrotronallows us to see tiny amounts of minorminerals, giving the site a unique X-rayfingerprint.

‘It is wonderful to see, aftercontributing one piece of the scientificpuzzle, that the impact of the broaderresearch is so far-reaching.’

The excavations, scientific analysis ofartefacts and sediments, and dating haveextended the known duration of humanoccupation of Australia by 18 000 years.

www.ansto.gov.au

Chemistry in Australia10 | October 2017

ANSTO expertise helps proveearliest Aboriginal occupation

Placardingrequirements forhazardous chemicals inbulk containersWhen hazardous chemicals require a bulkstorage placard, they do not need alabel.

Dr Paul Taylor, Director of Chemicalsat Safe Work Australia, said that this willreduce costs to businesses becausewarning information does not need to beduplicated for chemicals stored in bulk.

Correctly labellinghazardouschemicals storedin bulk is animportant aspectto managing theirrisks.

‘Correctly labelling hazardouschemicals stored in bulk is an importantaspect to managing their risks.

‘Businesses that use hazardouschemicals must check that they arecorrectly labelled in accordance with theWHS Regulations, and if they’re unsurethey should speak to their WHSRegulator’, Taylor said.

Safe Work Australia Members agreedto amend the model WHS Regulations inMarch 2017. These amendments arecurrently being progressed to allow themto be implemented in each jurisdiction.

Safe Work Australia

Thom

as Schoch/CC-BY-SA

In January 1991, the Icelandic volcanoHekla erupted in a dramatic geologicalevent that would last for two months.

Half a year after the eruption,geologist Sveinn Peter Jakobsson set outto study some of the cracks in the lava.Inside the cracks, temperatures reached170°C and toxic gases were oozing outfrom the volcano.

Jakobsson collected some of theyellowish encrustations inside the cracksand took them to the laboratory at theUniversity of Copenhagen, where theywere studied carefully.

Now, a quarter of a century later,these investigations have led scientiststo conclude that the volcanic materialcontained previously unknown minerals.The new mineral is described inMineralogical Magazine (http://doi.org/10.1180/minmag.2017.081.022).

‘We chose to name the mineraltopsøeite, after the Topsøe family. Whenyou have a Danish family that has givenso many important people to science,then I think there’s a reason to name amineral after them’, said Tonci Balic-Zunic, associate professor in mineralogyand crystallography at the Department ofGeoscience and Natural Resources,University of Copenhagen, Denmark.

Topsøeite is one of seven newminerals discovered in Iceland since2009. Balic-Zunic led the investigationsinto the new minerals from Hekla andEldfell volcanoes.

‘It’s a relatively unexplored area. Thereare some special geological processes inthe volcanoes, and that means that thereare some unique minerals here that youdon’t see anywhere else’, said Balic-Zunic.

‘Imagine that you are a biologist whohas discovered a place with new speciesof animals or plants. That would grab thepublic’s attention. Unfortunately, geologyis not so popular. So when we say we’ve

discovered a place with seven totally newminerals, it’s only academics that areexcited’, he said.

Topsøeite is formed by the elementsiron and fluorine, along with watermolecules.

Scientists have seen this chemicalstructure before, but this is the firstidentification of it in mineral form, saidHans Dieter Zimmermann, a mineralogistat Aarhus University, Denmark.

For a substance to be recognised as amineral, it cannot just be created in alaboratory.

‘Before Tonci’s study we didn’t knowthat it could also occur in nature as amineral’, said Zimmermann.

There are approximately 5200 known

minerals on Earth. Any new discovery hasto go through the InternationalMineralogical Association (IMA) before itis officially recognised as a mineral.

Balic-Zunic and Zimmermann estimatethat about 100 new minerals areregistered every year.

‘There’s been an increase in thenumber of new minerals in recent years.Half of the minerals we know today werediscovered since 1980. That’s because wehave new methods that make it easier todescribe minerals and identify theirchemical composition’, said Balic-Zunic.

Recently, an American study showedthat human activities have led to adramatic change in the Earth’s minerals.

By Lise Brix, Science Nordic

Chemistry in Australia 11|October 2017

New mineral discovered in Hekla volcano in Iceland

Geologists have discovered a new mineral, topsøeite, in Iceland. It is named after the familybehind the Danish chemical company Haldor Topsøe. Anna Garavelli, University of Bari

news

Chemistry in Australia12 | October 2017

Australia can improve coordination ofnational climate science programs todeliver better climate information tofarmers and infrastructure planners, and toguide national efforts to mitigate thefuture impacts of climate change,according to a review by leading scientists.

The Australian Academy of Sciencereport recommends that governmentconsider mechanisms to ensure bettercoordination of climate research acrossAustralia’s universities and climateagencies. It also recommends increasingclimate science capability in a number ofcritical areas, amounting to around80 new research positions over the nextfour years.

The review surveyed all of Australia’sclimate research agencies and centres,including the Bureau of Meteorology, theCSIRO, the Australian Antarctic Divisionand universities, to identify how manyAustralian researchers are working acrossthe various disciplines and subdisciplinesof climate science, and how well thesedifferent areas are performing.

It reports that while Australia isstrong in areas such as thermodynamicsand extreme weather events, there aresome significant weaknesses in areassuch as climate model development. Thisincludes the Australian CommunityClimate and Earth System Simulator(ACCESS), micrometeorology (the branchof meteorology that deals with weatherconditions on a small scale), boundarylayer dynamics (the dynamics of thelowest part of the Earth’s atmosphere)and the modelling of two-way human–climate interactions.

Academy Fellow Professor TrevorMcDougall, who led the review, saidunder-resourcing in specific areasdetracts from Australia’s ability to delivernecessary climate and weather

information to domestic end users andnational and international organisations.

‘Australia’s climate research sector is afraction of the size of those in America orEurope, but we cover most of the SouthernHemisphere in terms of climate modellingand understanding’, McDougall said.

‘Many of our universities areconsidered to be world-class in thiseffort, but as a country we are fallingbehind in areas such as climatemodelling.’

The report found that there are around420 dedicated climate scientists acrossall of Australia’s universities and researchagencies, with their research providingconstant improvements in weatherprediction and climate models inAustralia and throughout the world.

The area most in need of attention isclimate modelling, where critical under-resourcing means that Australia’s climatemodels are failing to keep pace withworld’s best practice. To address thisissue, the review estimated that around30 new climate modellers and scientistswould be needed over the next fouryears.

‘These capability requirements arebrought into sharper focus when youconsider that our country is potentiallymore exposed to the impacts of climatechange than most developed nations’,McDougall said.

‘Our location means that key factorsthat influence the climate in our regionare not well represented in climatemodels developed by other countries. Itis in our national interest to ensure ournational climate science capability, builtup over the past 50 years, is maintained.This will also mean Australia maintainsits custodianship of many aspects ofclimate science research in the SouthernHemisphere.’

Other key recommendations from thereport include ensuring the work of theAntarctic Climate and EcosystemsCooperative Research Centre is fundedbeyond 2019 and that a broader reviewof climate-related research capabilities isundertaken by the AustralianGovernment.

For a copy of the report visit theAustralian Academy of Science website(science.org.au).

Australian Academy of Science

Review of Australia’s climate sciencecapability reveals a mixed picture

... the reviewestimated thataround 30 newclimate modellersand scientistswould be neededover the next fouryears.

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Chemistry in Australia14 | October 2017

In a recent special issue of AngewandteChemie International Edition dedicated to150 years of the GDCh (the GermanChemical Society) and 100 years of theRACI, researchers from James CookUniversity and Monash University havecontributed a paper on the use of ahighly reactive divalent lanthanoidspecies to reduce and trap a rare[W2(CO)10]

2– anion (Deacon G.B, Guo Z.,

Junk P.C., Wang J. Angew. Chem. Int. Ed.2017, 56, 8486–9). The powerfulreductant bis(pentamethylcyclopenta -dienyl)-samarium(II) (SmCp*2) has ahistory of trapping unusual fragments,from earlier breakthroughs with N2

2–, Bi2

2–, Sb32– and [OC3O2]

2– to the recentspectacular enclosure of [P8]

2– , trappingof iron carbonyl sulfide clusters and thecomplex reduction of arsenic sulfide

species. Likewise, the analogous but lesspowerfully reducing YbCp*

2 has displayedsimilar behaviour, for example trappingtriiron, hexairon, monocobalt andtricobalt carbonyl clusters. In the latestwork, Professors Glen Deacon and PeterJunk report the reduction of tungstenhexacarbonyl by the divalentsamarium(II) complex [SmII

2(N4Et8)(thf)4]((N4Et8)

4– = meso-octaethyl -calix[4]pyrrolide) in toluene at ambienttemperature to yield the remarkableheteronuclear mixed-valentsamarium(II/III)/tungsten complex[{(thf)2SmII(N4Et8)SmIII(thf)}2{(µ-OC)2W2(CO)8}], which features thetrapping of a rare and previously notstructurally authenticated [W2(CO)10]

2–

anion, which has an unsupported W–Wbond. Work is ongoing with thisfascinating divalent [SmII

2(N4Et8)(thf)4]system with various carbonyls,unsaturated organic molecules and otherreactive species.

Antimalaria agents as herbicidesHerbicides were used over 20 years ago to prove that a newlydiscovered plastid in malarial parasites was an essential butnon-photosynthetic chloroplast. Used in drug research since,

this plant/malaria connection was only recently proposed bythe Mylne and Stubbs labs at the University of Western

Australia (UWA) as a way to identify novel herbicides(Sci. Rep. 2017, 7, 45 871). Screening the Malaria Box,a publicly available library of antimalarial leads, theUWA researchers have now found MMV006188 to bean effective herbicide in soil against a model plantand some common weeds. By using physiologicalprofiling, the molecule’s mode of action was alsoestablished (Corral M.G., Leroux J., Tresch S.,Newton T., Stubbs K.A., Mylne J.S. Angew. Chem. Int.Ed. 2017, 56, 9881–5). This test case draws attention

to the wealth of antimalarial compounds that could bedrawn upon to address the alarming rise of herbicide

resistance by bringing a new mode of action to market –something that has not happened in almost 30 years.

Trap got your tungsten

Chemistry in Australia 15|October 2017

Phosphorene for light-driven hydrogen fuel productionThe production of hydrogen fuel using solarenergy is considered a promising strategyto solve global energy and environmentalissues. Recently, Professor Shi-Zhang Qiaoand co-workers at the University ofAdelaide have for the first time usedphosphorene, a two-dimensional allotropeof phosphorus, as a highly active metal-free co-catalyst for metal sulfidephotocatalysts to produce hydrogen(Ran J., Zhu B., Qiao S.-Z. Angew. Chem.Int. Ed. 2017, 56, 10373–7). The teamfound that phosphorene-coupled CdSexhibits a high apparent quantum yield of34.7% at 420 nm. Density functionaltheory calculations and advancedcharacterisation by techniques such assynchrotron-based X-ray absorption near-edge spectroscopy suggest that thisoutstanding activity arises from the strongelectronic coupling between phosphoreneand CdS, as well as the favourable band structure, high chargemobility and plentiful active sites of phosphorene. This worknot only opens up new possibilities in the emerging field of

metal-free co-catalysts, but also provides insight into interfaceengineering of heterostructures for applications in fields besidesphotocatalysis, such as electronics and optoelectronics.

In the transition towards a more carbon-neutral society, thedevelopment of aesthetically acceptable building materials ableto passively collect solar energy is highly desirable. Onestrategy to achieve this goal is to harvest light from transparentsurfaces such as windows by incorporating efficientluminophores with absorption bands in the UV or IR region ofthe solar spectrum. Such light-harvesting devices are known asluminescent solar concentrators. Device operation is based onthe absorption of light by the luminophore, whose emitted lightis trapped in the wave-guiding matrix and concentrated at the

edges of the device. The concentrated light can then beefficiently converted into electric current by high-performancesolar cells. In a recent breakthrough as part of an ongoingexperimental and theoretical collaboration, researchers at theUniversity of Melbourne have identified unusually fluorescentpyridinium enolates as ideal light-harvesting chromophores foruse in fully transparent luminescent solar concentrators (Xu J.,Zhang B., Jansen M., Goerigk L., Wong W.W.H., Ritchie C. Angew.Chem. Int. Ed. 2017, https://doi.org/10.1002/anie.201704832).

Transparent light harvesters

The glycopeptide antibiotics (GPAs), which include vancomycinand teicoplanin, are heptapeptide natural products used as last-resort antibiotics to treat serious bacterial infections. Thechemical complexity of GPAs – which contain 3–4 cross-linksbetween aromatic residues – makes their chemical synthesisunfeasible at scale. Thus, all GPAs in clinical use are derivedfrom bacterial fermentation. GPA biosynthesis combines peptidesynthesis (catalysed by non-ribosomal peptide synthetases) andoxidative cross-linking (catalysed by cytochrome P450s) along

with modifications such as halogenation, but the timing andmechanism of halogenation was previously unclear. Recently,Associate Professor Max Cryle and co-workers at MonashUniversity, together with colleagues in Germany, havedemonstrated that GPA halogenation occurs during synthesis ofthe peptide and that halogenase enzymes use amino acidresidues bound to key carrier protein domains of the non-ribosomal peptide synthetase as substrates (Kittilä T.,Kittel C., Tailhades J., Butz D., Schoppet M., Büttner A.,Goode R.J.A., Schittenhelm R.B., van Pee K-H., Süssmuth R.D.,Wohlleben W., Cryle M.J., Stegmann E. Chem. Sci. 2017,http://doi.org/10.1039/C7SC00460E). Given that halogenationimproves activity and allows synthetic diversification of GPAs,this new understanding will allow the re-engineering of GPAbiosynthesis to generate new versions of these importantantibiotics.

Chemistry in Australia16 | October 2017

research

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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)

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CERTIFIED REFERENCE MATERIALS

Understanding halogenation during glycopeptide antibiotic biosynthesis

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

Chemistry in Australia 17|October 2017

The September’s issue of the AustralianJournal of Chemistry contains a number ofpapers that seek to acknowledge thecontribution of Professor Alan Bond ininorganic and electroanalytical chemistryin Australia. We are indebted to LisaMartin and Anthony O’Mullane for guest-editing this issue. They have both workedclosely with Alan over a number of yearsand these collaborations will undoubtedlycontinue into the future, as Alan’spassion for science seems undiminished.

The foreword to the issue certainlycharts Alan’s course through academiafrom a PhD with Tom O’Donnell (anothergiant of Australian chemistry (seeBond A.M., Martin R.L., ‘Vale TomO’Donnell: Australia’s leading fluorinechemist’, Chem. Aust. 2010, vol. 77(6),p. 13), during which he survived anexploration of the chemistry of HF. Hesubsequently became the FoundationChair of Chemistry at Deakin University,1978, creating a new department thatcontinues to thrive today.

A key feature of Alan’s interests wasthe application of electroanalyticalapproaches for applied research that ledto valued interactions with companiesand colleagues from other disciplines,which continues to this day. Alan movedon from Deakin to La Trobe andsubsequently to Monash University in1995, where he is currently Emeritus. Inpursuing his passion for chemistry, Alanhas been recognised through a number ofawards. A small selection includes: Fellowof the Australian Academy of Science(1991); Royal Society of ChemistryLecturer in Australia 1990; 150thAnniversary Robert Boyle Fellowshipawarded by the Royal Society ofChemistry 1991; Stokes Medal 1992

(award given by the ElectrochemistryDivision of the RACI); Liversidge Award1992 awarded by the Australian and NewZealand Association for the Advancementof Science; Royal Society of ChemistryAward for Electrochemistry 1997; RACIH.G. Smith Medal 1998; Burrows Medal2000 awarded by the RACI InorganicDivision; and Craig Medal from theAustralia Academy of Science 2004.

The special issue contains articlesfrom former students, collaborators andfriends from around the world. A reviewof the controlled grafting ofaryldiazonium salts to form monolayers isa highlight. Metaltetracyanoquinodimethane (TCNQ)complexes feature in two papers. In thefirst, the Cd complex reported by RolandDeMarco and co-workers (including Alan)undergoes an oxidation to form abridging 3D terephthalate ligand. Theother TCNQ paper published by guesteditor Lisa Martin, and Alan, reports tworelated complexes,[Pt(NH3)4](TCNQ)2∙(DMF)2 and[Pt(NH3)4](TCNQ)2, and the discovery thatthe latter is not a catalyst for the redoxreaction of ferricyanide and thiosulfate.

A collaboration between Edith Chow(CSIRO) and Justin Gooding (Universityof New South Wales) has resulted in thepreparation of a potentiometric sensorfor pH monitoring. They demonstrate thata Prussian blue/polyaniline-based read-out system changes colour depending onthe voltage output of the sensor, whichcan be correlated to the pH of thesample solution.

Thomas Maschmeyer and Tony Mastersexamine the electrodeposition of Zn,using an aqueous electrolyte containing1-ethylpyridinium bromide, and

unexpectedly observe the passivation ofthe redox couple after a singledeposition/stripping cycle, the anomalyattributed to the reduction of 1-ethylpyridinium cations to pyridylradicals and their subsequent reactions.

John Bullock (Vermont) shows thatthe oxidation of W(CO)4(a-diimine) givesthe dication [W(CO)4(a-diimine)]2+. Theelectrogenerated radical cations areunstable towards disproportionation andloss of carbonyl ligands in weaklycoordinating media and undergo a varietyof ligand substitution and coupleddisproportionation reactions.

In more fundamental electrochemicalstudies, Alexander Harris and AntonioPaolini examine the oft-used bionicelectrode material iridium oxide,correlating the impedance of anodicallyformed iridium oxide films (AIROF) witheffective electrode area. They concludethat the high charge density and lowimpedance of AIROF may provideimproved neural stimulation andrecording properties compared totypically used platinum electrodes.

Alexandr Simonov (and Alan!)demonstrate that there are issuesassociated with electrochemicaldetermination of mass–transportparameters.

It is clear that Alan retains anunbridled enthusiasm for science andchemistry, which is demonstrated bysome lines borrowed from the foreword:

… the ‘sparkle that appears in his eyes’ whenhe has data or challenging results that defythe obvious interpretation … these are thehallmarks of Alan Bond.

Happy birthday Alan!

George Koutsantonis FRACI CChem and John D. Wade FRACI CChem Co-Editors-in-Chief,Australian Journal of Chemistry

Alan Bond’s 70th birthday Research Front

aust. j. chem.

A key feature of Alan’s interests was the application ofelectroanalytical approaches for applied research that ledto valued interactions with companies and colleagues fromother disciplines, which continues to this day.

‘We’re very interestedin understandingmetals in cells’,says Dr Elizabeth

New, Westpac Research Fellow at theUniversity of Sydney. Metals in cells arepotentially critical to cancertreatments, biological systems affectedby environmental pollution, and thepotentially deleterious effects ofsociety’s increasing exposure tonanoparticles.

ICP-MS (inductively coupledplasma mass spectroscopy) is wellestablished as the go-to method formetals analysis. It has enabledresearchers to identify correlationsbetween metal levels and diseases,metabolic disorders, environmentalexposures and nutrition.

However, the technique has had itslimitations, most particularly in thelevel of detail it can provide. Traditional

ICP-MS methods digest the biologicalmatrix, effectively capturing anaverage concentration across thesample. Until now, the technique hasbeen unable to provide informationabout the concentration distributionacross a biological cell population.

The Australian Institute forNanoscale Science and Technology(AINST) at the University of Sydney iseagerly anticipating the delivery of thesouthern hemisphere’s first single-cellICP mass spectrometer fromPerkinElmer. ‘We already use ICP-MSvery heavily, because it is very helpfulin telling us about the uptake andaccumulation of metals in cells,’ saysNew, ‘but this technology is reallyexciting because it will let us look at anindividual cell and its metal content.That means that we can now look atdifferent types of cells in a cellpopulation and see exactly which has

Chemistry in Australia18 | October 2017

Single-cellinductively coupledplasma massspectroscopy offersa potentiallysignificantbreakthrough indetailed biologicalstudies.

BY DAVE SAMMUT

Inside running

A cell-by-cell view of metals

iStockphoto/ClaudioVentrella

been specifically affected, by adisease or by a certain metaltreatment.’

Cisplatin (cis-diamminedichloro -platinum(II)) is a commonly usedchemotherapy drug used to treatmultiple types of cancer. It is used todestroy rapidly growing cells bybinding to the DNA and interruptingcell replication, so that the cell mustrepair the DNA damage or die.However, experience has shown thatwhile many patients initially respond tothis platinum-based treatment, thedrug is less effective if there is arelapse and further therapy required.

One of three proposed mechanismsfor this reduction in efficiency is thatthe cancerous cells evolve to havealtered cellular accumulation (reduceduptake of the drug and/or increasedexport), but to date there has beenlittle or no data about the distributionof the drug in the complex array ofcells in a tumour. The existing ICP-MStechniques can only measure theaverage concentration across the

whole cell population. Single-cell ICP-MS promises to measure the metalconcentrations of individual cells downto the attogram (10–18 gram) level, toyield critical data about the metaldistribution in the cell population,yielding up to 100 000 data points persecond.

Using the first of the newinstruments in the US, a team at theNational Institutes of Health (NIH) hasbeen looking at individual cellpopulations and their responses toplatinum. By comparison, New and herteam are eager to look atheterogeneous populations, with aview to how different cell typesrespond to platinum drugs. ‘One of thereal challenges in studying cancer isthat the tumour contains so manydifferent types of cells. If we can beginto identify certain cells in a tumour thathave a particular metal fingerprint or aparticular way of handling metals, thenthat will really help us think about howto treat tumours.’

‘We’re interested in understandingthe relationship between copper andplatinum drugs – how cisplatin andother drugs affect copper in the cells’,says New. ‘And we’re also interested inunderstanding oxidative stress in cells.’

‘Oxidative stress is thought to beinvolved in pretty much every diseaseassociated with ageing, but nobodyknows whether it is the cause ofdisease or whether it is just an effect,whether we can measure oxidativestress and predict the outcome of thedisease or response to treatment. If we

can understand the interactionsbetween the disease and the metalpools, or observe certain cell typeswith higher metal level and higheroxidative stress, then that would be areally exciting discovery.’

‘It really was serendipity. I hadn’tparticularly looked for this, but nowevery time I think about something Ithink that this would be a great newuse for the new equipment. It fitsperfectly with what we’re interested in.When I heard about it, it was exactlywhat we needed for our research.’

Sharing New’s sense of anticipationis colleague Dr Wojtek Chrzanowski,senior lecturer and researcher at theFaculty of Pharmacy and the AustralianInstitute for Nanoscale Science andTechnology. One key focus forChrzanowski’s team is nanotoxicity,based on the growing body ofevidence that suggests thatnanoparticles may have a causal rolein various forms of disease, includingcancer.

Nanoparticles occur in manyproducts, including food, make-up,sunscreen, cosmetics, toiletries, babyformula and chewing gum. ‘The mainconcern for us’, says Chrzanowski, ‘isthe nanoparticles in food. One of theproblems is that we are continuouslyexposed to these nanoparticles, butwe don’t know what exactly happens inthe body and whether they have atoxic effect or not, and how they affectgut microbiota. There is already a lot ofevidence that nanoparticles causeproblems in our bodies, exacerbate

October 2017

‘The NexION SC-ICP mass spectrometerallows for the quantification of metal at thelevel of a single ovarian cancer cell’[pictured], Chady Stephan, Senior Leader ofApplications at PerkinElmer and a co-researcher on the [NIH–PerkinElmer]ovarian cancer cell study, says. ‘Thetechnique is based on the ability tomeasure discrete signals generated from acell when it enters the plasma, and allowsfor the quantification of cisplatin withinindividual cells’, Dr Lauren Amable, NIHNational Institute on Minority Health &Health Disparities, explains. (Text and image: PerkinElmer)

When I heardabout it, it wasexactly what weneeded for ourresearch.

symptoms of many diseases (e.g.colitis) and may even impact on thefunction of common drugs.’

‘There are a lot of factors – stress,contamination etc. – but we stronglybelieve that nanoparticles are one ofthe factors contributing to the increasein immune disease, asthma, autism,fertility problems or cancer, as well asan impact on the gut microbiota, thusthe overall host community.’

Chrzanowski’s expectation is that asnanoparticles are incorporated intocells, they consume critical energy asthe cell seeks to consume or reject the

particle, which interferes with thenormal functioning of the cell. He thensees single-cell ICP-MS as a criticaltechnique to allow his team toprecisely screen for how manynanoparticles are taken up byindividual cells, and how the cellschange their normal metalconcentrations in reaction tonanoparticle exposure. This aligns withand complements New’s researchquestions.

Chrzanowski and his team are alsolooking at possibilities for thebeneficial use of nanoparticles in

targeted drug delivery. Malignant cellsmay take up nanoparticles and drugslike cisplatin differently, and the teamwould like to understand how thishappens, why it happens, and howheterogeneous the responses reallyare. ‘This instrument will allow us to putthe nanoparticles onto the malignantand non-malignant cells and screen forhow much of the nanoparticles wereuptaken by which of the cellpopulation. Based on this method, weshould be able to design new drugdelivery carriers.’

Another key functionality of interest

Chemistry in Australia20 | October 2017

One of the key challenges for single-cell ICP-MS is getting thecells into the plasma. Typical spray chambers (pictured) aredesigned to reject larger water droplets (>4 micrometres), butmost biological cells are substantially larger than this.

As such, traditional ICP-MS techniques have involveddigestion of the biological samples prior to analysis.PerkinElmer has developed its new AsperonTM spray chamber toincorporate new flow patterns that transport the larger single-celled organisms to the plasma, as well as limiting lysis(rupture) of the cells from impacts with the chamber walls.

However, prior to aspiration, the cells need to be washedand separated from the matrix, which may also contain theanalyte. For example, a blood sample being tested for platinumdistribution from cisplatin may contain the drug in both theserum and the cells. So the sample is first put through multiplewash and spin (gravity separation) cycles.

PerkinElmer’s latest offering builds on the success of theNexION 350 ICP-MS instrument, introduced a couple of yearsago. At just 10-microsecond dwell time, the company confirmsthat its high-speed detector gives it at least an order ofmagnitude speed advantage over its nearest rival. And thisspeed has been leveraged to create the capability to analysebiological samples at the single cell level of detail.

Let’s take two groups of algal organisms as example.Chroomonas species have a typical size range of

5–7 micrometres. With a cell culture at about 250 000 cells/mLand a sample flow rate of about 15 mL/min, this gives a flow ofapproximately 63 cells/s, requiring a maximum read time of16 microseconds for individual analysis, comfortably greaterthan the 10 microseconds claimed by PerkinElmer.

Gonyostomum semen is a much larger organism. A typicalsize of 50–70 micrometres, with a population of about4500 cells/mL, translates to approximately 11 cells/s and amaximum read time of 89 microseconds. However, because of itslarger cell size, this organism is more vulnerable to the higherpressures exerted at higher sample and gas flow rates, andPerkinElmer recommends a cell viability test prior to analysis.

According to Scott Fraser, National Product Specialist forPerkinElmer, ‘I see a day coming where every medical institute(at least) will have one of these instruments, and this willbecome a routine part of personal, patient specific medicalregimes – minimising the side effects of chemotherapeutictreatment and also maximising the efficacy of drugs withinwhat we now understand to be heterogeneous populations ofcancers.’

‘There is also going to be a great development ofunderstanding of the movement of metals through thebiosphere’, says Fraser, ‘We’ll better assess, per cell, how wastematerials from various processes transfer in the food chain.That will become much more important as time goes on.’

The single-cell ICP-MS instrument

to Chrzanowski is the ability of thetechnique to distinguish the sizes ofthe nanoparticles. He expects thatnanoparticles will aggregate, eitherwithin the cells or within thebloodstream. Being able to measurethe size of particles in individual cellsshould then allow Chrzanowski tobetter understand the differingmechanisms and capabilities thatrelate to the cell’s uptake of individualnanoparticles versus largeraggregates.

‘The new single-cell ICP massspectrometer will be a fantasticaddition to our existing equipment,which can do both physical (size)characterisation and chemicalcharacterisation. We have state-of-the-art facilities here at the University ofSydney that are still not availableanywhere else in Australia. We will linkit together to create a nano toolboxwhich can probe nanotoxicity andresponse from different angles to givethe full picture.’

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

Chemistry in Australia 21|October 2017

Follow that cell: an NIH challengeIn June, the US National Institutes of Health named two biological engineeringresearchers as winners in phase 2 of its Follow that Cell Challenge. The winnerswill share $400 000 in prizes awarded for development of new tools and methodsfor predicting the behaviour and function of a single cell in complex tissue overtime – and how that reflects the health of the tissue. They were chosen fromamong several phase 1 finalists.

Dr Nader Pourmand, University of California Santa Cruz, is the first place winnerwith a prize of $300 000. A team led by Dr Paul Blainey, of the Broad Institute,Cambridge, Massachusetts, will share the second place prize of $100 000.

Pourmand developed an advanced ‘nanopipette’ technology with such a fine tipthat it makes it possible to non-invasively sample tiny amounts of intracellularmaterial to measure biochemical changes, multiple times in the same cell –without disturbing its function. Coupled with parallel development of‘nanogenomics’ technology, this will enable scientists to track molecular changesin cells that develop in response to treatments, such as the development of drugresistance in cancer.

‘This is the only technology I know of that enables us to repeatedly interrogatea single cell without killing it’, said Pourmand.

Blainey’s team designed a new molecular technology to streamline cellularanalysis and allow for wide adoption by labs. Instead of requiring complexphysical sampling of cellular components, it takes advantage of cell secretionpathways to access molecules of interest inside the cell – at multiple time points.Blainey’s findings demonstrated the ability of a cell to ‘self-report’ geneexpression.

Launched in August of 2014, Follow that Cell seeks to incentivise innovationby awarding prizes on the basis of completed work, in contrast to NIH’straditional, prospective grant and contract mechanisms, which provide funding inadvance.

The challenge is aimed at finding new ways to learn how cells transition from ahealthy to a diseased state, become responsive to treatment, and offeropportunities for early detection and precision medicine.

In March 2015, NIH announced selection of 16 finalists from phase 1 of thecompetition, which sought proposed theoretical solutions rather than hands-onexperimentation. All of the phase 1 finalists were eligible to participate in phase 2, during which they were encouraged to execute their ideas in proof-of-concept studies.

‘The prize winners have brought some creative ideas to the study of singlecells’, said NIBIB director Roderic Pettigrew, ‘We challenged competitors todevelop new ways to monitor biochemical changes in individual living cells andthey have demonstrated an impressive capacity for problem solving andinnovation.’

Read the winners’ own brief descriptions of their prize-winning solutions atbit.ly/2sSuvOf.

National Institutes of Health

Chrzanowski’sexpectation is thatas nanoparticlesare incorporatedinto cells, theyconsume criticalenergy as the cellseeks to consumeor reject theparticle, whichinterferes with thenormal functioningof the cell.

In 2018, the Australian Journal ofChemistry (AJC) will achieve themilestone of reaching 70. Toappreciate where AJC now stands,

it is important to understand its roots. In the aftermath of World War II,

there was something of a coming ofage in Australia. We had come close tobeing invaded by Japanese forcesduring the War, and what had beenconsidered ‘the home country’, GreatBritain, had not been able to come toour aid. There was a sense that we hadto stand on our own. In the sciencecommunity, this manifested itself withthe establishment of the AustralianAcademy of Science and the Scienceand Industry Research Act 1949, the Actunder which CSIRO still operates.Scientists of the day were sending theresults of their research to British andAmerican journals, but this was afrustratingly slow process, conductedby sea mail. There was a clear needfor an Australian publishing capability,

but no publisher in the country couldcope with the specialist (mathematical,chemical) typesetting needed forphysics and chemistry publishing, sothe newly formed Academy partneredwith CSIRO to establish the AustralianJournals of Scientific Research.

From this partnership, the firstvolume of the Australian Journal ofScientific Research was published in1948. It consisted of four issues,totalling fewer than 500 pages,publishing papers on both chemistryand physics. Very quickly, the volumeof papers received was so great thatthere was a surplus in content; as aresult, this journal split into two distinctpublications in 1953 – AustralianJournal of Chemistry (volume 6) andAustralian Journal of Physics(volume 6), each consisting of fourissues a year. Continued rapid growthin submissions for AJC meant that in1962 there was enough content to fillsix, rather plump, issues of the journal,

Chemistry in Australia22 | October 2017

Celebrating 70 years of chemical science publishing

BY JENNIFER M. FOSTER

Next year, theAustralian Journal ofChemistry willcelebrate 70yearsof publishingresearch papersfrom all fields ofchemical science,with a focus onmultidisciplinarychemistry andemerging areas ofresearch.

and only two years later, in 1964, therewas enough content to maintainpublication of 12 monthly issues.

At this time, given the constraints ofgeographical reach, the overwhelmingmajority of papers published in AJCwere from Australian authors.Disappointingly, many historicalrecords pertaining to AJC have longdisappeared; the earliest data I couldfind were in the minutes of an EditorialAdvisory Committee meeting, dated26 October 1979. That report showedthe relative geographical breakdownof authorship: around 85% ofpublished output was from Australia(mostly Australian universities and afew from other Australian institutionsand around 8% from CSIRO). Theremaining 15% was from authorsbased overseas. That 15% of overseascontent was impressive compared to

the other journals published by CSIROPublishing at the time, which averagedaround 10% or less. This led to theconclusion that ‘the journals[particularly AJC] were by no means tobe considered “CSIRO housepublications”.’

The geographical distribution ofpublished papers changed rapidlywhen we embraced the internet as achannel to deliver publications,probably the biggest change inpublishing since Gutenberg inventedthe movable-type printing pressaround 1440, a phenomenon thatintroduced the era of masscommunication, thereby permanentlyaltering the structure of society. AJCwas the first Australian journal to bepublished online, and we did thatearly – in 1996 – before Elsevier,before Springer, and before Wiley. The

web changed the landscape ofpublishing rapidly – distance was nolonger a deterrent to publishing ininternational journals, and quickly ourauthor composition changed from anAustralian majority to one with a trulyinternational flavour. Of course, it alsomeant that Australian authors had moretimely and straightforward options topublish in international journals.

When I starting working on thejournal under the stewardship of theinfamous John Zdysiewicz (or John Z,as he was affectionately known amonghis peers), in 1995, as an AssistantEditor, and also as an RACI member, Iwas interested to find that the onlyrelationship AJC had with the RACI,was a 10% discount offered to personalsubscribers. (At that time, personalsubscriptions were plentiful, as thejournal was print-only and hence not

Chemistry in Australia 23|October 2017

L–R: George Koutsantonis,John Wade and and JennyFoster at the RACI CentenaryCongress in July.

so readily available.) Lookingback at that period, I think John Zwas instrumental in the connectionbetween Australian chemists andAJC. He never lost an opportunity toengage with established authorsand referees or to drum up newones, he gave and sponsoredlectures, he visited departments, heattended conferences, and awardedstudent prizes. John was a very visibleparticipant in the corporate life ofAustralian chemistry (Aust. J. Chem.2010, vol. 63, pp. 1139–40).

Over time, RACI members wereoffered greater discounts on personalsubscriptions in an attempt to furtherconnect the journal to its rightfulaudience, and in September 2003 anannouncement formalising a newagreement between the RACI and AJCwas circulated (Chem. Aust. 2003, 9),in which, among other things, heavilydiscounted (almost 50%) personalsubscriptions were offered. At thattime, personal subscriptions wererapidly declining, with contentavailable to most readers throughinstitutional online subscriptions. Inthat announcement, a clear vision forAJC was articulated, and that was ‘toshowcase the best chemical sciencefrom Australasia to the rest of theworld, along with publishing importantinternational contributions’. Further,‘this arrangement provides anothervery good reason to remain (orbecome) a member of the RoyalAustralian Chemical Institute. Wehope that this agreement willenhance the feeling among you, themembers of the RACI, that theAustralian Journal of Chemistry isyour journal’.

Five years later, in 2009, AJCmoved from a publishing modelwith an in-house Managing Editor(Dr Alison Green, who took overthe reins when John Z retired inlate 2000) to an external EditorialBoard under the advocacy ofProfessor Curt Wentrup. Curt’sviews were also consistent withthe 2003 vision, which focused

on improving the status of AJC athome, and making Australianresearchers see the journal as theirjournal, by forging closer links with theRACI, while maintaining itsinternational impact. Curt wasinstrumental in further developing ourrelationship with the RACI back in2012, when we met with CEO RogerStapleford to discuss moving forwardin cementing a formal relationship.From that meeting, foundations for amutually beneficial partnership wereidentified. These include reciprocalarrangements for advertising andhome page links, a link from the RACIwebsite to a free monthly ‘teaser’paper from AJC, space in Chemistry inAustralia each month for an articlerelating to AJC, sharing costs of boothsand/or receptions at agreedconferences and publishing papersfrom RACI prize-winners in AJC.

Chemistry in Australia24 October 2017

Landmarkpapers in AJCvirtual issueAs part of their celebrations, theAustralian Journal of Chemistry will besharing a virtual issue containing freelyavailable landmark papers previouslypublished in AJC, such as those by thelate Sir John Cornforth (‘The troublewith synthesis (Aust. J. Chem. 1993,vol. 46(2), pp. 157–70) and ‘Scientistsas citizens’ (Aust. J. Chem. 1993,vol. 46(3), pp. 265–75)), as a way ofhighlighting the sustained excellenceover the years in publishing papers ofgreat international significance.

… the ongoingtradition of invitingthe recipients ofresearch-relatedRACI medals andawards to publishan account … oftheir work in anannual special issueof AJC …champions ourvision ofshowcasingexceptionalAustralian sciencecarried out byexceptionalAustralian chemists.

|

It has been terrific to see theseideas come to fruition under Curt’sleadership. Sharing the costs of booths(e.g. at the FACS AAC 2013 Meeting,Singapore) and receptions(Pacifichem, Hawaii, 2015) allows us tomake the most of our carefullymonitored funds in promoting journalcontent and the RACI to ourinternational friends. The mostspectacular outcome of this, in myview, is the ongoing tradition of invitingthe recipients of research-related RACImedals and awards to publish anaccount (highlight), review, or paper oftheir work in an annual special issue ofAJC. It champions our vision ofshowcasing exceptional Australianscience carried out by exceptionalAustralian chemists.

Following Curt’s groundwork infostering these strong but informal tieswith the RACI, our two current co-Editors-in-Chief, Professors GeorgeKoutsantonis and John D. Wade, are

committed to finding further ways tostrengthen ties with the RACI, andencourage and engage Australianchemists to publish their work in AJC,with the advocacy of a strong andrefreshed Editorial Board. Tocomplement their efforts, our recentacceptance into COPE (Committee onPublication Ethics) shows we arecommitted to best-practice ethicalstandards, an increasingly importantaspect of online publication.

The vision for AJC articulated backin 2003 continues to be accurate – Istill see AJC as an Australian journal forAustralian chemists. However, I do notthink the majority of RACI membersfeel a sense of belonging to AJC, and Ifeel the gap is widening, no doubt atleast in part due to its perceived lowimpact and the implications of this lowimpact with respect to promotions andgrant applications. Although we areperceived as being low impact, wepublish papers that are highly cited.

Graeme Moad, Ezio Rizzardo and SanThang’s landmark review (Aust. J.Chem. 2005, vol. 58(6), pp. 379–410,https://doi.org/10.1071/CH05072), onRAFT polymerisation chemistry, plusthree updates, published in AJCbetween 2005 and 2012, havegenerated over 3000 citations to date.Four of our top 10 highly cited paperspublished in 2013 and 2014 wereauthored by Australian research teams,and have generated an average of24 citations each.

What can we do to ensureAustralians see AJC as an attractivechoice for publishing their work? Let’sopen the dialogue. I know that many ofyou care deeply about this. George,John and I welcome your thoughts andsuggestions.

Cheers and happy birthday to us! Ihope both AJC and RACI have happyand strong futures to look forward to.

Jennifer M. Foster FRACI CChem is publisher of theAustralian Journal of Chemistry.

Chemistry in Australia 25|October 2017

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World War I imprinted inpeople’s minds thevision of soldiersdonning gas masks

during chemical weapon attacks.These respirators were designed toremove the toxic agent from the airand allow the soldiers to continue tobreath and hence fight. The first use ofthese was during the second battle ofYpres, in a response to a chlorine gasattack. The initial chlorine attack killedthousands, but Reserve Canadiantroops were able to counter the attackby soaking cloth in their own urine andplacing the cloth across their faces.The soldiers realised that the urine’surea would react with the chlorine gas,neutralising the danger, anddemonstrated fast thinking acid–basechemistry.

The use of cloth respirators againstchemical agents goes back to the timeof Leonardo da Vinci. In the15th century, he devised a seafaringchemical weapon based on powdered

arsenic with sulfur in shells; he alsodevised protection for the sailors byhaving them wrap wet cloth aroundtheir faces. Today, wet cloth is used byprotestors and rioters globally inrespond to tear gas release due topolice and military crowd controlefforts.

Most respirators are based on anagent such as activated charcoal thatremoves the toxic gas throughadsorption from the air and henceenables military personnel to breathesafely. These work well for a period oftime, but the active agent will becomesaturated, and in the case of bloodagents such as cyanides they offer onlylimited protection. For militarypersonnel under continual attack, self-contained breathing respirators arerequired, and hence their ability to actis limited to the amount of oxygen theycan carry.

Blistering and nerve agents, such asmustard gas and sarin, are alsoabsorbed through the skin, meaning

additional protective clothing isrequired. This takes the form of fullhazmat suits, which must be gastight,and are generally based on heavyduty PVC, Teflon and/or high-densitypolyethylene. Such bulky suits makemilitary action difficult and are mainlyfound in decontamination efforts. Inresponse to these limitations ofpersonnel protective equipment, asignificant amount of research isdirected at developing antidotes andcounter agents to neutralise chemicalweapons.

The first antidote to a chemicalweapon was developed in World War Iin response to lewisite (2-chloroethenyl -arsonous dichloride), a blisteringagent that also led to arsenicpoisoning. Lewisite easily penetratedclothing and caused immediatestinging, pain and itching to the skin,with chemical burns and largeblistering occurring over a 24-hourperiod. Victims also suffered fromhypotension because of arsenic

Chemistry in Australia26 | October 2017

Protection, antidotes, treatments and ofcourse prevention are the subject ofongoing research in the face of chemicalweapons attacks.

BY COLIN A. SCHOLES

Protection andprevention in

chemical warfare

entering the blood. The antidotedeveloped was dimercaprol, alsoknown as British anti-lewisite, which isa chelating agent of arsenic and bindswith the metal in the blood. Thisprevents arsenic from deactivatingmetabolic enzymes and hence stopsarsenic poisoning. Dimercaprol hasgone on to be a treatment for bloodpoisoning by a range of heavy metals,but it does not prevent the chemicalburns and blistering of the skin due tolewisite exposure.

G-series nerve agents, such assarin, can be easy neutralised byhydrolysis with a base. This is thereason why G-series agents do notpersist in the environment. However,once these agents are in the body, theyare fast acting on nerve cells andhence any antidote must be appliedrapidly to mitigate the agents’ effect,ideally by military personnel and firstresponders during an attack. Atropineis one such treatment to overcomenerve agent exposure, though it is not

an antidote and is only effective forsmall to medium levels of exposure.Atropine in conjunction withpralidoxime, binds to the counter sitesof the acetylcholine enzyme in nervecell receptors. This causes the enzymeto displace the nerve agent from theactive site, returning the enzyme to fullfunctionality. The nerve agent is thenhydrolysed by the body throughmetabolic pathways. However, it iscritically important that atropine bepresent in the body throughout this

period of time; otherwise, it ismerely delaying the effects ofthe nerve agent. Tocomplicate matters,

both atropine and pralidoxime aredeadly in a high enough concentrationand hence they must be administeredat a safe dose.

Atropine and pralidoxime are readilyavailable in medical facilities because oftheir need in a range of standardsurgeries and procedures. In the case ofa chemical weapons attack,supplies of these compoundscan rapidly run out, aswas the case in Syriaduring the recentincidents.

Lewisite and its antidote,dimercaprol.

Atropine and pralidoxime are used in combination to treat exposure to G-series nerve agents.

The bulk of current hazmat suits makesthem impractical during military action.iStockphoto/Arne_Uebel

Military personnel who are likely tobe exposed to nerve agents carryautoinjectors of these two compounds,which allow rapid injection into the thighmuscles in the instance of an attack.

There is active research intodeveloping treatments that are fastacting and destroy nerve agents in theblood faster than the metabolic rate.These treatments are based on thechemical similarities betweenorganophosphate nerve agents andsome agricultural pesticides. Continualpesticide spraying of agriculturalregions has resulted in enzymesevolving in soil bacteria that can break

down pesticides. These enzymes havealso shown selectivity for thehydrolysis of nerve agents. Hence,there is potential to develop andenhance these enzymes for treatingnerve agents in vivo, because theseenzymes will break down the nerveagents at a fast rate. This will alsoovercome the danger of atropinepoisoning. German and Israeliscientists using this approach havedeveloped a therapeutic enzymeagainst the nerve agent vX. It has beensuccessfully tested in guinea pigs;however, human trials of this treatmentare still years away.

Da Vinci’s chemical bullets were aprecedent for the 1675 StrasbourgAgreement, thought to be the firstinternational accord to prevent the useof such weapons. Prevention is betterthan cure, and the Convention on theProhibition of the Development,Production, Stockpiling and use ofChemical Weapons and on theirDestruction is the modern-dayinternational treaty aimed at theireradication, administered by theOrganisation for the Prohibition ofChemical Weapons (OPCW). Theconvention has a broad scope andconsiders any chemical used in warfareas a chemical weapon, and hence doesnot need to be continually updated withthe development of new chemicalagents or the adaptation of existingchemicals for warfare. The conventionwas only drafted in 1992 and came intoeffect in 1997, which is very recentgiven the long history of chemicalwarfare, and relied upon the reductionin global tensions at the end of the ColdWar. The convention has been signedand/or ratified by almost all countries,with the exception of Egypt, SouthSudan and North Korea. This marks theconvention as one of the mostsuccessful international treaties.

The convention prohibits theproduction and use of chemical agentsfor warfare, the destruction of allexisting chemical weapons and theirproduction facilities, assistance betweencountries and the OPCW when

incidences of chemical weapons areused, including inspection, as well asglobal cooperation on the peaceful useof chemical agents. This last condition isrequired because many chemicalagents that have been weaponised arealso used in numerous industrialapplications, such as synthesisprecursors. Hence, these chemicals arecontrolled substances whoseproduction, use and transportation areheavily monitored to ensure they areused for benign purposes.

The convention aims to destroy theworld’s stockpiles of chemicalweapons. As of 2015, a total of72 524 tonnes of chemical agents hadbeen declared to the OPCW, alongwith 97 production facilities. Themajority of these have been in the USand Russia, and their stockpiles andmunitions are currently beingdestroyed, although both countriesmissed their deadline of April 2012.Other countries to have declaredchemical weapons facilities have beenthe UK, Syria, Serbia, Libya, Japan, Iraq,Iran, India, France, China and Bosniaand Herzegovina, plus one non-disclosed country. As of October 2016,

Chemistry in Australia28 | October 2017

Mr Ahmet Üzümcü, Director-General of theOrganisation for the Prohibition of ChemicalWeapons and recipient of the 2013 NobelPeace Prize, speaking at the RACI CentenaryCongress in July about eliminating chemicalweapons.

Atropine is on the World Health OrganizationModel List of Essential Medicines. Skirtick/CCBY-SA 4.0

The nerve agent VX.

93% of the world’sreported chemicalstockpile has beendestroyed, an outstandingachievement of the OPCW.

In some instances, cooperationbetween countries has been required.Japan is responsible for significantstockpiles of chemical agents acrossChina, left over from World War II. Theamount of chemical munitions leftbehind by Japan during its retreat hasbeen estimated from 700 000 to2 million units. One such depot is theNanjing stockpile, which was onlyunearthed in February 2000. Syria’schemical weapon stockpile is currentlybeing processed and destroyedoffshore on a US merchant navy shipspecially configured to handle thedangerous agents. Similarly, the OPCWis monitoring the destruction of the lastof the aforementioned countries’stockpiles of chemical agents.

The convention conveners’ hopewas that chemical agents would neveragain be used in warfare, and that theconvention would generate a stronginternational effort to eradicate them.The dramatic reduction in the globalstockpile of chemical weapons overthe preceding decade, as well as theglobal outrage and response to recentincidents, is making this a reality.

Colin Scholes FRACI CChem is a lecturer in theDepartment of Chemical Engineering at the Universityof Melbourne. A partner article about chemicalwarfare was published in the September issue ofChemistry in Australia (p. 20).

Chemistry in Australia 29|October 2017

New fabric coating could thwart chemicalweapons, save livesChemical weapons are nightmarish. In a millisecond, they can kill hundreds, if notthousands. But, in a study published in Chemistry of Materials(http://dx.doi.org/10.1021/acs.chemmater.7b00949), scientists report that theyhave developed a way to adhere a lightweight coating onto fabrics that is capable ofneutralising a subclass of these toxins – those that are delivered through the skin.The life-saving technique could eventually be used to protect soldiers andemergency responders.

Since their first use in World War I, dozens of chemical weapons with devastatingpotential have been developed. For example, just a pinprick-sized droplet of thenerve gas sarin on the skin is lethal. Recently, scientists have begun exploring theuse of zirconium-based metal–organic framework (MOF) powders to degrade anddestroy these harmful compounds. MOFs are miniscule, porous structures that havelarge surface areas that allow them to absorb vast amounts of gases and othersubstances. The zirconium within them helps neutralise toxic materials. But makingMOFs can be tedious, requiring high temperatures and long reaction times. Plus,most MOF powders are unstable and incorporating them onto clothing has provenchallenging. Dennis Lee, Gregory N. Parsons and colleagues wanted to see if theycould ‘grow’ MOFs onto fabric at room temperature, potentially creating alightweight shield that could be used on uniforms and protective clothing.

Building on previous work, the researchers exposed polypropylene, a non-wovenfabric commonly used in reusable shopping bags and some clothing, to a mixtureconsisting of a zirconium-based MOF, a solvent and two binding agents. To ensurethat the coating spread evenly across the cloth, they treated the fabrics with thinlayers of aluminium, titanium or zinc oxide. They tested this combination withdimethyl 4-nitrophenyl phosphate (DMNP), a relatively harmless molecule that hassimilar reactivity as sarin, soman and other nerve agents. They found that the MOF-treated cloths deactivated the DMNP in less than five minutes, suggesting thisprocess is a viable means to create improved protective clothing.

American Chemical Society

Type 45 destroyer HMSDiamond escorting themerchant ship Ark Futuraduring Operation Recsyr(Removal of ChemicalWeapons from Syria) inFebruary 2014. Theoperation, commencing withOPCW inspection, began inlate 2013. HMS Diamond hascompleted her role escortingships carrying Syria’schemical weapons stock fordisposal. HMS Diamondjoined the Danish-led,Norwegian and British TaskGroup to provide maritimeforce protection to merchantvessels transporting chemicalagents from Syria.Photo: MM140092/MOD/OGL

It’s fair to assume that the mostlikely outcome of a degree inchemistry is a life in thelaboratory. While the lab can lead

to a lifetime of discovery, chemistrycan also open up doors to all sorts ofcareers. Even international diplomacy.

Don’t believe it? Just ask Dr BrendonHammer, a Research School ofChemistry (RSC) alumnus andAustralia’s current Ambassador toAustria, Bosnia-Herzegovina, Hungary,Kosovo, Slovakia and Slovenia.

Dr Hammer completed severalcourses at the Chemistry Departmentat the ANU, which at the time was partof the School of General Studies. As anundergraduate he finished courses inchemistry, physics, biochemistry,maths and philosophy, beforespecialising in inorganic chemistry forhis honours. From here Dr Hammercontinued his studies at the ANU,completing a PhD under thesupervision of Dr Howard Bradbury, inwhich he worked on the isolation andcharacterisation of plant proteinaseinhibitors.

It looked as though Dr Hammer wasbuilding for a long and fruitful career

in the chemistry lab. However, after tenyears of research, Dr Hammer took ajob at the Office of NationalAssessments (ONA), changing his lifeforever. This wasn’t a plan, Dr Hammerexplains, but one that opened up aworld of opportunities.

‘I was happy doing research inchemistry, and was gearing up to get afurther postdoctoral position, this timein the US’, Dr Hammer explains. ‘I’lladmit that I was thinking, though, that ifI went to the USA I would probably tryto stay there where bigger budgetsand excitement levels seemed likely.As such a big step approached, Iguess my overall attitude towards whatI might do next became more labile.’

‘And as it happened, right then,while I was in that zone, I met a personquite by accident at a dinner where, asa result of a bit of a debate rangingfrom economics to how chemotherapyworks – and then some furtherconversations – I got encouraged to trywork at ONA.’

While this was a significant careerchange, in moving to the publicservice Dr Hammer was able todirectly apply his research skills to

very important public policy issues.‘There was a specific link between

my work in chemistry, and sciencemore broadly, and my initial work atONA’, Dr Hammer explains. ‘At thattime, in 1989, the AustralianGovernment – led in this area byForeign Minister Gareth Evans – wasdriving an international effort to banchemical weapons and roll back anyfurther proliferation of chemical,biological and nuclear weapons. Myjob at ONA was in support of thateffort.’

‘My subsequent two jobs with theDepartment of Foreign Affairs and

Chemistry in Australia30 | October 2017

International diplomacyrequires chemistryProfile: Dr Brendon Hammer

BY SIMON COPLAND

There was aspecific linkbetween my workin chemistry, andscience morebroadly, and myinitial work at ONA.

Trade – one in Canberra, and oneposted as a diplomat to Washington –were also focused in this area. Havinga science background was extremelyhelpful – and recognised as such bygovernment and others – to myunderstanding and development ofideas and policies in relation to tryingto stop the spread of these weapons ofmass destruction.’

From these early jobs, Dr Hammerbuilt a career in internationaldiplomacy. This has included postingsin Washington DC and Tokyo, chairinginternational meetings of experts inParis under the umbrella of theAustralia Group, and working on theproduction of the 2000 Defence WhitePaper. Dr Hammer has now beenposted, not just as Australia’sambassador to Austria, Bosnia-Herzegovina, Hungary, Kosovo,Slovakia and Slovenia, but also as aPermanent Representative to the UNagencies in Vienna, to the International

Atomic Energy Agency and to theOrganisation for Security andCooperation in Europe.

Dr Hammer says that in many waysthis has been a pursuit inunderstanding one of the mostcomplex systems around.

‘The international system may bethe most complex semi-orderedsystem human beings have to dealwith. So there is a lot of intellectualsatisfaction in trying to fathom what’sgoing on there, discuss that with otherson the same team, and try to find waysto take advantage of it.’

Amongst all of this, however, Dr Hammer has not forgotten his rootsat the ANU, stating his studies wereintegral to his success.

‘I found that the cast of mind Ibelieve attracts people to chemistryand what I learned in chemistry –particularly in research – helped agreat deal and still does in all of thejobs I’ve had’, Dr Hammer says. ‘In

particular some of the generalattributes and elements relating tochemistry that I have found mosthelpful have been the ability todevelop highly analytical and scepticalapproaches to problem solving, andthe ability to turn abstract ideas intohands-on practical steps.’

While Dr Hammer has had a careerof amazing successes, he still has asoft spot for his time at RSC.

‘Doing a PhD in chemistry at theANU has also been a highlight. I hadsome fabulous times in the lab, both onthe scientific front and socially.

‘There really was a great sense ofcamaraderie among the researchstudents both in the group I was in andmore widely. Having visited RSC acouple of times recently – includingHambly’s bar – I can see that traditionis alive and well!’

First published at chemistry.anu.edu.au. Reproducedwith permission.

Chemistry in Australia 31|October 2017

Dr Brendon Hammer (right) talking with a scientist in Seibersdorf, Austria, who is working ontracing the provenance of foods using naturally occurring isotopic ratios.

from the Centenary Congress

Chemistry in Australia32 | October 2017

Why would a patent attorney organise the Chem-E-CarCompetition, held annually in conjunction with the ChemecaConference and this year as part of the Centenary Congress?Patent attorneys are good at drafting patent specifications toprotect chemists’ inventions but don’t often have ready accessto chemists’ chemicals. As I found out, however, the RACI has anumber of very helpful members who went out of their way toassist by supplying chemicals, glassware and other essentialsfor the entrants. Thank you very much to those people; youknow who you are.

The objective of the Chem-E-Car Competition is to designand construct a car that uses chemical reactions to power it andto control the distance it travels carrying a specified load. Thegoal of the competition is to have your car stop closest to aspecified finish line while carrying a specified load. Thecompetition is all about demonstrating the ability to control achemical reaction.

The two teams who entered the competition were from theUniversity of Queensland and the University of Auckland. Sadly,a team from Malaysia had to withdraw at the last minute. It wastherefore a two-horse race (we were in Melbourne, after all),with comparisons to the Bledisloe Cup being made(appropriately, as it turned out, with the Kiwis convincinglywinning the competition).

The University of Auckland car looked great – it had beenlaser cut with a kiwi badge at the front, and was driven by abank of chromic cells containing acidified potassium dichromatewith zinc and carbon electrodes. Each cell produced about1.5 volts and 0.3 amps, which was plenty enough to drive theircar, albeit faster in reverse. The University of Queensland carwas originally to be driven by a zinc–air battery, but this waschanged in the lead-up to the competition to an aluminium–airbattery.

Chem-E-Car Competition: controlling chemical reactions

The goal of the competition isto have your car stop closestto a specified finish line whilecarrying a specified load. Thecompetition is all aboutdemonstrating the ability tocontrol a chemical reaction.

The University of Auckland’s winning team.

New FellowDerek Zamaere, an industrial chemist, is an overseas memberof RACI based in Malawi, a Central African country. Growing upon a sugar plantation sparked his curiosity in chemicalprocesses at an early age. He went on to study chemistry at theUniversity of Malawi, graduating with an honours degree. He iscurrently finalising his Applied Chemistry MSc thesis for whichhe investigated plant-based antifoaming agents.

Zamaere’s interests lie in the areas of process developmentand optimisation, low-cost production as well as the productionof industrial chemicals from plants. Between 1996 and 2002,while heading the R&D function for Unilever Malawi, Zamaere’scontribution led to some significant savings for the Malawianoperations. He also collaborated in some regional projects thatcovered East, Central and Southern Africa. He later joined awater treatment company where he sold water and wastewaterrelated solutions to a broad range of industries in Malawi andparts of Mozambique. Currently, Zamaere is the OperationsManager of a bioethanol production unit.

Zamaere is passionate about developing the professionalismof chemists and chemical engineers in Malawi. He is activelyinvolved in mentoring young scientists and promoting chemicalsafety and security. He is currently president and one of thefounding members of the Association of Professional Chemistsand Chemical Engineers in Malawi and one of the foundingmembers of the Laboratory Association of Malawi, where he hasserved as a board member. More recently, he has become amember of the National Authority for the implementation of theChemical Weapons Convention in Malawi.

Aside from his career, Zamaere enjoys the outdoors,especially in the company of his wife, Maria, and threedaughters. He is also deeply involved in community outreachprograms.

raci news

Chemistry in Australia 33|

Both teams used an iodine clock reaction as the stoppingmechanism, where a reaction between sodium thiosulfate,starch, potassium iodide, hydrogen peroxide and sulfuric acidstarts clear but turns dark blue depending on the quantity ofhydrogen peroxide. The change of colour triggers a light-dependent resistor to break the electrical circuit driving the car.

The specified distance (14 metres) and load (400 millilitresof water) were decided on the day and the teams were informedan hour before the competition was due to start. The Universityof Auckland team were first up, and did a great job – their carstopped at just over 16 metres on the first run and about18 metres on their second. Sadly, the University of Queenslandteam’s battery was having problems on the day and they didn’tmanage to get the car off the starting line. The University ofAuckland team were therefore declared the winners andcollected the trophy!

The University of Queensland team didn’t go home emptyhanded, as they won the Chem-E-Car Poster Competition,decided by popular vote by the spectators.

Andrew Jones MRACI CChem

The winning Chem-E-Car.

books

Chemistry in Australia34 | October 2017

4th rock from thesun: the story ofMarsJenner N., Bloomsbury Sigma,2017, ISBN 9781472922496,272 pp. $27

What fun Nicky Jenner musthave had researching 4th rockfrom the sun: the story of Mars!What fun you will have reading‘the complete book of Mars’.Jenner is eminently qualifiedfor the job. Her writing ispublished in a variety ofinternational popular sciencemagazines, including NewScientist, Nature, BBC Sky atNight, Astronomy Now, The

Times Eureka and Physics World. She is also a copywriter for theEuropean Space Agency and the European Southern Observatoryand no doubt spends a lot of time looking at Mars.

To bring us the story of Mars, Jenner explored colourpsychology, mythology, cultural studies, astrology, geology,biology, human physiology, history, geopolitics and at least adozen other topics. Without this apparent hodgepodge oftopics, it would be difficult to address the central question 4th rock poses: Why do we want to visit Mars so badly?

We have always been fascinated by the heavens, but onlyrecently have we seriously considered exploring the stars; onlyrecently has it been possible. Jules Verne wrote From the Earthto the moon in 1865, but serious efforts to travel beyondEarth’s atmosphere only began in the early 1900s. Since then, alot has happened rather quickly. Rocket technology emergedfrom World War II, Sputnik 1 was launched in 1957, NeilArmstrong walked on the moon in 1969 and today we haveprivate companies like Space X and Virgin Galactic competingwith NASA to colonise Mars.

Whether or not we get there and if we do manage to surviveon the red planet is less important than we try. Jenner says itbest:

Space agencies across the world are far from a drain on the economies oftheir home countries, instead, acting as drivers for scientific andtechnological research, and inspiring the next generation of innovators.Funding a space agency necessarily funds scientists of all disciplines –engineers, chemists, physicists, doctors, geologists, computer scientists,biologists – all of whom don’t work in space but here on Earth,contributing to societies and economies across the world.

Books like 4th rock are important because they help fire ourcollective imagination and people might start thinkingcolonising Mars might be a better way to spend money thanbuilding a wall to keep out illegal immigrants.

The 4th rock is well organised. If Mars in myth and legend isnot your cup of tea (‘The wolf and the woodpecker’) you can

skip to the intricacies of retrograde motion (‘Motions of Mars’)or planetary geology (‘The draw of Cydonia’). Chapters 9–12 getto grips with what it will take (really) to travel to and perhapscolonise Mars. It is not going to be easy but it is possible andJenner offers convincing reasons why it will be worth the effort.

Jenner’s writing style is engaging and her explanations ofscientific topics are easy to follow for readers with little or nospecialist background. The 4th rock is the perfect book for alittle light reading and would make an ideal gift for anyonewith an interest in the heavens around us.

Terry Erle Clayton

Hawley’s condensedchemical dictionary,16th editionLarrañaga M.D., Lewis R.A. Sr, Lewis R.J.John Wiley and Sons, 2016, hardback,ISBN 9781118135150, 1544 pp.,$214.95 (Amazon.com US$103.97.Online access options available athttp://au.wiley.com/WileyCDA/WileyTitle/productCd-1118135156.html)

It is hard to know where to start towrite a review of a dictionary. Does ithave words in it? Check. Do thosedefinitions look broadly correct?Check. Where to go from here?

At a basic (chemistry pun fullyintended) level, one could considerthat two major criteria for judging the worth of a dictionarywould be comprehensiveness of the field it purports to coverand the accuracy of the information it presents. On both fronts,the 16th edition of Hawley’s condensed chemical dictionarycomes up trumps. The book runs to over 1500 pages and theblurb on the website tells me it contains 1471 new definitions,plus 5236 revised or updated definitions, a new ChemicalAbstract (CAS) number index and numerous other helpfuladditions. As it turns out, for a pleasant change, said websiteblurb is entirely correct.

Aside from the formal definitions, there is also a usefulintroduction giving some of the history of the publication(which, I was interested to learn, has been in print in variousforms since 1919). There is also a list of abbreviations and fiveappendices: (i) on the origin of some chemical terms, (ii)highlights in the history of chemistry (both i and ii are full ofinteresting facts), (iii) a list of manufacturers of trademarkedproducts, (iv) a CAS number index (iii and iv are useful), and(v) a short list of three tables (periodic, elemental and unitconversions).

Unlike a normal dictionary in which definitions are generallyshort, the condensed chemical dictionary is more of acompendium of technical data and descriptive information. Itcovers a vast array of topics, including information on not onlychemistry but also biology, biochemistry, physics and more.

Chemistry in Australia 35|October 2017

While some definitions can be straight to the point, there isvery good cross-referencing throughout and most entriesinclude helpful details, such as information on the substancesused in the manufacture of a particular product. This can beuseful to help you, for example, identify possible interferencesin the measurement of a physical or chemical property of asubstance. A minor negative is that it is not cheap (the RRP ismore than $200), but you certainly get value for money.

Many, if not all, entries are designed for those with minimaltime to devote to a subject. However, it is possible to learnquite a lot from even a short browse in this book. I learnt, forexample, that a dram is actually a formal unit in pharmacology,a rupture disc is a thin piece of metal between flanges thatbreaks at a certain pressure and that Zepel is a fluorocarbontextile finish used as a durable oil and water repellent. Therecertainly is a lot of information here. This could of coursepotentially lead to the age-old problem of going to look up oneterm but getting distracted by other interesting definitions (a

perennial problem when browsing online dictionaries such asWikipedia). This reviewer does not see this as such a bad thing,unless of course one is short on time and/or procrastinatingfrom tasks (such as writing a book review).

I often hear it argued that textbooks are on the way out andthat everything will be digital in future. This reviewer certainlyhopes this is not the case. In this age of tablets andsmartphones, there is something satisfying about a good, heavyreference book (although, if you insist, there is a digital versionavailable). Having seen the general panic that consumes thebest of us when the wi-fi goes down, having a hard copy ofrelevant information to hand is useful (and with the book’sbright orange cover you almost certainly won’t lose it).Whatever form you have, Hawley’s condensed chemical dictionaryis a very helpful addition to the shelf, virtual or otherwise, ofanyone associated with chemistry or chemicals.

Oliver Jones FRACI CChem

Secure a piece of chemical historyRemember the RACI now and in years to

come with this limited edition publication

celebrating the Institute’s centenary year.

To order your copy of this hardback book,email [email protected].$50 plus $10 postage (in Australia)

160 pages of perspectives, profiles,

facts and photos tell the story of RACI

from 1917 to today.

economics

Chemistry in Australia36 | October 2017

In past issues, I have reviewed several approaches to usingdifferent non-fossil fuels for the propulsion of motor vehicles.In recent weeks, there have been several major announcementsof proposed electrification of passenger cars, which may havelong-term consequences and implications for the Australianvehicle fleet.

In Europe, there is increased level of concern about the use ofdiesel passenger cars, especially in congested cities. This has notbeen helped by the behaviour of Volkswagen and their apparentdeceptive conduct. VW claimed they could both deliver high-performance passenger diesel engines and keep the level ofpollution, particularly nitrogen oxides (NOx), to very low levelswithout resorting to the injection of urea (blue additive used byother companies). This claim now appears fraudulent with VWequipping their sophisticated computer-controlled engines withsoftware that could detect when the vehicle was undergoingregulatory performance testing and when it was being used by aVW customer. This was discovered inadvertently by a US researchteam testing emissions in real on-road conditions.

There have been several consequences of this, possibly themain one being that the claims of all the major vehiclecompanies on emissions are no longer believed. Early results ofincreased research on real road emissions, including inAustralia, are showing a significant disparity between real-lifeemissions and manufacturers’ claims for petrol engine vehiclesas well as diesel-fuelled vehicles.

Internationally, the inability of petrol and diesel vehiclemanufacturers to eliminate pollutants has led the French andBritish governments to propose the banning of all petrol anddiesel engine vehicles and replacing them with all-electricvehicles by 2040. However, proposals to electrify the passengervehicle fleet have serious hurdles to overcome, which are nowstarting to be realised.

The penny is starting to drop with governments thatsuccessful electrification will require an enormous increase incharging points, possibly one in every parking bay. Furthermore,electrification will cost the government’s treasuries by the lossof fuel excise duty. The solution to this would be to change thetaxing point by means of a usage charge, possibly usingsatellite geo-positioning to determine the distance travelled byeach road user and to develop a road user charge accordingly.

Moving a nation’s vehicle fleet to electricity will require avery large increase in power generation. At this stage, in Europethis will almost certainly be by nuclear power, which willrequire further significant investment. For the UK, thistransition is estimated to require an additional 10 000 windturbines or 10 nuclear power stations.

In line with this ambition, several vehicle manufacturershave announced further investments in electric vehicles. Forinstance, Volvo has said that it will soon stop production ofdiesel- and petrol-only vehicles. This has been widelyinterpreted as an announcement to build electric-only vehicles,

but it is more likely to mean that fossil-fuel/hybrid vehicleswould replace the present diesel and petrol vehicles.

One of the major issues with electrification is that, withpresent knowledge, the logistics and distribution fleet (trucksetc.) are not amenable to electrification and some other sourceof motive power will have to be found. For zero emissions, thebest option would be hydrogen propulsion, on which I havepreviously commented (March, p. 36). Although there is muchenthusiasm for this solution, generation of hydrogen at areasonable cost is currently beyond reach.

One issue currently missing from the discussion is what todo about jet fuel. Again there has been a lot of media interestin an electric aeroplane but unfortunately although jet enginesin the form of gas turbines are used to generate electricity, theprocess is irreversible and electricity cannot be used to drive ajet engine. Rather, electric-driven aeroplanes would be stuckwith propellers as the means of propulsion. This may be fine fora relatively short European journey but it means the end ofintercontinental jet travel without an alternative approach. Atthis stage, the solution seems to be to use renewable fuels fromagricultural sources with the risk of ongoing degradation oftropical rainforests to produce the fuel required.

The Australian demand for transport is different from that ofthe European major centres such as Paris and London. InAustralia, the use of very small cars, such as the Smart Car, israre. Passenger vehicles are larger and many are expected tohave a significant towing capacity. For instance, in Europe,owning a boat is for the rich whereas in Australia boatownership is more egalitarian, with many boats parked indomestic driveways to avoid high mooring costs. Not only this,but many owners expect to be able to tow caravans and smalltrailers, again not as common in Europe. At this stage ofdevelopment, electric vehicles do not offer any significanttowing capacity. It is a moot point if hybrid/electric vehiclescould offer towing capacity to any significant degree.

The new world of electric cars

Another field of research ... isadvanced materialcomposites, which arerequired to further lower theweight of vehicles, therebyimproving their range. Thisdemand should spur researchinto carbon-fibre-reinforcedplastic construction materialsand light metal alloys.

Chemistry in Australia 37|October 2017

Another difference is that many vehicles in Australia travellong distances every day. This is true for country dwellers, butmany trade vehicles also travel the breadth of the urbanconurbations several times a day, covering distances of morethan 200 kilometres daily. This is also true of Europe and I amnot sure if the proponents of electric-only vehicles have fullytaken this into account.

Fortunately for the chemist, this unbounded enthusiasm forelectric vehicles will bring significant amounts of cash forresearch to make utopia achievable. Electric vehicles themselvesrequire significant improvements to battery technology toimprove charge-carrying capacity. This will probably require amove away from Li/Ni-Co systems and into Li metal technologyand this move will require a significant level of chemicalresearch and innovation in the chemistry fundamentals

underpinning battery design. Another field of research into improving electric vehicles is

advanced material composites, which are required to furtherlower the weight of vehicles, thereby improving their range.This demand should spur research into carbon-fibre-reinforcedplastic construction materials and light metal alloys. The majorweight problem is due to the mass of copper carried in motorwindings and it would be nice if an alternative based on carboncould be found – windings made of graphene fibres perhaps?

The non-fossil fuel production of hydrogen is another area ofresearch. The present technology is poor and there are manyopportunities for improvements from the chemistry standpoint.

New chemistry input will also be required for the upgradingof lithium (and graphite) ores to reduce costs. Recently, RioTinto have announced the timeframe for the development oftheir massive Serbian Jadarite (a lithium borate) prospect,which may be cheaper to develop than the spodomene reservescurrently used and under development in Australia. If Australiais to play a significant role in this vehicle electrification, thenthis field is the obvious one in which to make a significantinvestment to lower lithium production costs.

However, whatever the outcome it seems that electrificationwill cost a lot of money and it is not clear if the nationalgovernments promoting it can afford it.

BMW i8 plug-in hybrid concept car cutaway showing the carbon fibre structure and the electric motor. Mariordo (Mario Roberto Duran Ortiz)/CC BY-SA 3.0

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

measurement

Chemistry in Australia38 | October 2017

As the seasoned mom of three grown children, I’m happy to saythat they all made it through babyhood without any majorhealth issues. While I worked as an analytical chemist at the USNational Institute of Standards and Technology (NIST) duringtheir baby years, I wasn’t working on reference materials formeasuring nutrients in the foods that they ate or, even worseto think about, toxic elements in them.

I mention this because recently I was asked about an articlethat reported traces of lead had been found in baby food. Whilefeeding my babies I just assumed, and expected, the baby foodthey were eating was safe for them. After all, I thought, theyare just babies, and we live in the land of milk and honey. Don’twe? Of course we do, and of course their baby food was safe forthem, wasn’t it? And what about that milk and honey? Werethose safe too?

Standard reference foodFor the past 10 years, I have been producing and analysingStandard Reference Materials (SRMs) for foods. Food SRMs aretypical foods you might buy at the grocery store: chocolate,spinach, peanut butter and, yes, baby food. What makes theseSRMs different from ‘normal’ food is the fact that they havebeen carefully tested to measure the exact amounts of minerals,vitamins, fats, proteins and other nutrients in them. Whenmanufacturers analyse our SRMs and get the right answer, i.e.the same answer we got, chances are good that they got theright answer when they were testing their own products andcan be confident about the values they publish on theirnutrition labels.

Now, you may have noticed that lead, arsenic, cadmium andmercury are not listed on the food nutrition labels. So how dowe know if there are toxic elements in the foods we eat?

Besides putting nutrition facts on the labels of the foods theysell, food manufacturers must also follow safety guidelines. Inthe US, the Food and Drug Administration (FDA) sets theguidelines, or limits, for the levels of toxic elements permittedin foods. Even though they don’t list toxic elements on theirlabels, manufacturers still need to make sure their products aresafe, and so they use NIST SRMs to do this as well.

You’re probably thinking, wait a minute, it’s okay to havetoxic elements in our food? Well, it’s complicated. We certainlydon’t want these toxic elements in our food, and foodmanufacturers and regulators do everything they can tominimise them, but the truth is that if you want to eat, youwill likely be eating some (probably tiny) amount of toxicelements with that food.

One reason for this is that plants absorb elements, bothgood and bad, from the soil they are grown in. The toxicelements may be naturally occurring in the soil or may havecome from human activity, such as mining or waste disposal.Regardless of their source, when we eat those plants, or whenwe eat the animals that ate the plants, we eat the toxicelements as well. When plants are grown in heavilycontaminated soils, or foods are contaminated duringpreparation or packaging, the toxic elements become a realproblem. Companies do everything they can to keep theirproducts safe – if foods with unsafe levels of toxic elementsend up being sold to the public, companies recall them.Additionally, the FDA has the authority to keep contaminatedfoods from entering the US.

Toxic traces in baby foodNIST SRM 2383 Baby Food Composite is a weird combination offoods and not actually a real baby food. This SRM wasspecifically designed to contain certain amounts of vitaminsand elements so that it could be used for nutrition labelling.We did try to measure some toxic elements, though. When thismaterial was first developed, we measured both arsenic andmercury. We found that mercury was undetectable and thearsenic concentration was only 3 nanograms per gram, or3 parts per billion (ppb). That means if you ate half a jar of theSRM, about 35 grams, you’d be eating 0.000 001 05 grams ofarsenic – a speck about 600 times smaller than a single grain ofsugar.

The NIST baby food SRM had never been tested for lead andcadmium, so I wanted to know if those elements were in theretoo. A quick test found about 12 ppb of lead and less than19 ppb of cadmium, lower than what I can reliably measure.Right now, I’m unable to tell how much lower.

Should we believe these very, very small numbers? Imentioned that mercury could not be detected at all and thatthere was less than 19 ppb cadmium. We cannot say exactly

... food manufacturers andregulators do everything theycan to minimise them, but thetruth is that if you want toeat, you will likely be eatingsome (probably tiny) amountof toxic elements with thatfood.

(Baby) food for thought: the limits of detecting toxicelements

Chemistry in Australia 39|October 2017

how much cadmium is in the baby food since it is below whatwe call the limit of quantification – the level at which we’reconfident that our measurements are accurate. Generally, wecan measure things reliably at levels that are three or fourtimes higher than the minimum we can detect. For lead, thelevel where we know the measurements are accurate is evenlower than cadmium, about 2 ppb. Twenty-five years ago, whenmy kids were babies, the state-of-the-art equipment that weused was about a hundred times less sensitive than what wehave today.

Measured to the limitThe fact that we couldn’t detect lead in baby food 25 years agodoesn’t mean that it wasn’t there. It may have always beenthere, but our instruments couldn’t see it. Now that our testsand equipment have improved, we know it’s there, and we canuse that knowledge to try to improve the safety and quality ofour food supply. When we cannot see an element at all in afood, we say it is below the detection limit. Mercury is belowthe detection limit in the NIST SRM 2383 Baby Food Composite,but we can never say it is not in there – there may just be toolittle to see. With new technology, elements can be detected atlower and lower levels, but we need to be careful that whatwe’re measuring is really in the food we’re testing and not froma source of contamination in the laboratory.

So, knowing what I know now, would I still have fed babyfood to my kids? In short, yes. I work closely with foodmanufacturers and scientists. I know that the manufacturers ofbaby food, and all food, have expert chemists who work hard tomake sure those foods are as safe as they possibly can be formy kids – and for you.

And they use NIST’s food SRMs to help them do this!

A 30-year veteran of the US federal government, Laura Wood is one of theProgram Coordinators for the food and the dietary supplements SRM programs andfor the Dietary Supplement Laboratory Quality Assurance Program (DSQAP) atNIST. In her spare time, Laura enjoys being with her husband and their threechildren, as well as her dogs, cat and bearded dragons. She also volunteers withher church and with the Delaplaine Arts Center in Frederick, Maryland. Firstpublished at http://nist-takingmeasure.blogs.govdelivery.com.

Whether into my children or test tubes, I’ve had a lot of practice spooning baby food. F. Webber/NIST

Mercury is below thedetection limit in the NISTSRM 2383 Baby FoodComposite, but we can neversay it is not in there – theremay just be too little to see.

grapevine

Chemistry in Australia40 | October 2017

Durif – an alternativecultivar?During my time as a distance education student inoenology at Charles Sturt University, I was requiredto undertake vintage work in the subject known as‘Winery Experience’. I was fortunate to meet severalwinemakers from north-east Victoria and this led meto seek a practical placement at Fairfield inRutherglen with Stephen Morris as my ‘guide’.Fairfield was very much an old-style winery withopen fermenters and old oak barrels and casks fordeveloping the red and fortified wines. Many of thevines were dry-grown, i.e. without irrigation, as iscommon practice in many parts of Europe.

It was here at Fairfield that I was introduced tothe grape Durif. I was somewhat sceptical of theclaimed qualities of Durif, especially as my previous knowledgewas more about red cultivars that are grown in the coolerclimate regions. But I soon came to see the benefits of usingDurif in a red wine blend and also as a component of a fortifiedred wine. The greater surprise was seeing how it worked as asingle-component Durif-only red wine.

Durif is the result of a crossing between Peloursin and Syrah(Shiraz). Most reports suggest that it is named after Dr FrançoisDurif, a plant breeder from the south-east of France, althoughthe timing of this breeding activity ranges from the 1860s tothe 1880s, depending on the report of the cultivar’s origin. Thechoice of cultivars for the breeding is intriguing: Syrah is wellknown, while Peloursin is somewhat obscure. One has towonder why the breeding trials were ever established. Durif hasnever been highly regarded in France. Perhaps the tolerance ofDurif to powdery mildew was seen as a potential advantage, yetthe quality of the wine from these grapes was never successfuland plantings in France have almost disappeared.

In California, the cultivar is known as Petite Sirah. Aresearch investigation into the identity and parentage of thiscultivar using DNA marker analysis was carried out at Universityof California, Davis in 1999 (see Meredith et al. Am. J. Enol.Vitic., vol. 50, pp. 236–42). This work confirmed thatDurif/Petite Sirah is in fact a cross, with Peloursin being thematernal parent and Syrah (Shiraz) the pollen (or male) parent.Intriguingly, some supposedly Durif vines were shown to beactually Peloursin. In times past, as still today, it was notuncommon for errors in labelling and/or transport records tooccur: the fairly recent Savignin/Albariño issue is a goodexample (bit.ly/2vcBkfy).

Australian wine industry statistics for 2015 list the areaplanted to Durif as 625 hectares, while that for Shiraz was39 893 hectares. Plantings of Tempranillo, the rising red cultivarat the moment, amounted to 736 hectares. While Rutherglen likesto claim that the region produces special characters in Durif, it isplanted elsewhere, including some cool climate regions (seebit.ly/2vnJCl7 for a listing of wineries and regions).

Rutherglen winemakers (bit.ly/2uf0pSw) argue that theirclimate and generally dry vintage conditions assist in the slowdevelopment of Durif on the vine. Durif is one of the lateripening varieties and warm autumn weather is important inthis development. Andrew Smith of Warrabilla Wines, whodescribes himself as a ‘Durif tragic’ or latter-day convert, goesone step further by saying that Durif is ‘a pig to growviticulturally’ (bit.ly/2f3H8kQ). By this, Andrew is referring tothe thin skins, which can split, leading to infection, as well asdifficulties in getting the crop load right to achievephysiological ripeness (see June issue, p. 40). Some of theseissues are different from my experience working with non-irrigated vines on the soils on the east side of Rutherglen;Warrabilla is on the west side and closer to the Murray Riverand consequently prone to fog later in the harvest season.

When the ripening process all comes together, the wines aresimply amazing. There is an intensity of red colour that isdifficult to achieve in other red varieties: descriptors include‘black purple’, ‘blood plum with ruby halo’, ‘dark morellocherries’ and ‘satsuma plums’. Aroma terms include‘blackberries’, ‘violets’ and ‘aniseed’. The palate can show spiceand pepper with fine tannins and a lingering finish. The hugemouthfeel is dominated by fruit and tannin characters and oakshould be minimal. In some cases, all these characters can onlybe obtained when harvested at 15.5–16% potential alcohol.

Rather than recommend wines to try, and clearly showing mybias for Rutherglen, I simply invite you to explore what theregion has to offer. The wines do not come out every year – theconditions need to be right for a stand-alone (unblended) wine.Ageing in bottle is also highly beneficial to the development ofDurif. A further perspective on Durif by Peter Dry can be foundin the Wine and Viticulture Journal (2017, vol. 32(2), p. 5) inthe ‘Alternative Varieties’ section.

Durif vines in Rutherglen. Courtesy Warrabilla Wines

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.

We have been reading a lot about the years of the Great War,but the centenary of an important scientific meeting passedwithout much comment. I am referring to the meeting of theBritish Association for the Advancement of Science (BAAS),which held its meeting (the 184th) in Australia in 1914.European (mainly British) participants stopped off for scientificmeetings in Perth, Adelaide and Brisbane, but the main actionwas in Melbourne and Sydney where the main sessions tookplace between 13 and 26 August.

Some participants had accepted an invitation to travel on toNew Zealand for further meetings with Canadian and Americanscientists who had been invited to join them there. The officialBAAS report said that while the Australian meeting was inprogress, the New Zealand arrangements had to be cancelled‘owing to the effects of the European War’. The biographer of IraRemsen (see below) wrote that the BAAS meeting wascancelled, but it was only the New Zealand add-on that did notgo ahead.

The New Zealanders had invited leading scholars fromAmerica and Canada to take part in the post-BAAS meetings,and in this they were more successful. Participants wererecruited by the President of the Massachusetts Institute ofTechnology, R.C. Maclaurin (not the Maclaurin of the famousmathematical series), who had been professor of mathematicsat the University of New Zealand (Victoria University College,Wellington) from 1899 to 1907. The group consisted ofDr L.H. Bailey, formerly Director of the School of Agriculture atCornell, but latterly Chairman of the Roosevelt Country LifeCommission; Dr Charles Davenport, Director of the Institute forExperimental Evolution at Cold Spring Harbor, New York;E.G. Conklin, Professor of Biology at Princeton; Dr W.M. Wheeler,Professor of Economic Entomology at Harvard University; Dr Paul H. Hanus, Professor of Education at Harvard; andProfessor Ira Remsen (1846–1927) of the Johns HopkinsUniversity in Baltimore. Remsen had been professor ofchemistry from the university’s foundation in 1876, and then itspresident 1901–12.

The Americans set sail from San Francisco in July aboard thesteamer Tahiti, bound for Sydney. At the Captain’s request, eachof them gave a talk about his work, Remsen’s being particularlywell received. A 24-hour stop at Tahiti enabled them to samplethe local culture, and the ship also stopped at Raratonga topick up copra and oranges for New Zealand. During this leg, theCaptain asked Remsen to translate a German message thatturned out to be about the declaration of war. Subsequently,the ship was ordered, by wireless, to proceed to Wellington andto travel without lights because there were German raiders inthe vicinity. Arriving at Wellington on 31 July, the ship wascommandeered as a troop ship, and sailed for Britain two weekslater with 800 troops and 2000 horses.

A series of lectures was organised at the University Collegein Wellington. Wheeler lectured on ‘Ants and other social

insects’, and Hanus on ‘The search for standards in education’.Remsen spoke about ‘science and industry’, emphasising thevalue of pure research but noting how difficult it was at first‘for his students, who did not know how to make soap, to getplaces’ in industry. Now, they were eagerly seized upon, he said.The reporter who covered the talk for the Wellington EveningPost noted that Remsen had ‘taught the art and mystery of achemist’ and that ‘the audience found him a delightfullyhumorous man, seriously insistent upon his subject, but readyto make fun of himself’. Davenport did not linger in NewZealand, where he had been expected to speak on eugenics, butinstead took ship for Sydney and then addressed the Melbournemeeting on ‘Heredity of some emotional traits’, drawing on theresults of research into the families of ‘165 wayward girls instate institutions’.

Although the American visitors wished to depart NewZealand soon after the Wellington lectures, there were no shipsavailable and so the NZ government arranged tours for them.Remsen and Bailey went to Rotorua where they ‘saw theWaimangu geyser’ but perhaps they saw another one, sinceLonely Planet says the Waimangu went extinct in 1904. Theythen travelled by ‘luxurious steamboat’ down the WhanganuiRiver for over 100 miles, and thence to Auckland by road wherethey boarded the Makura for the trip across the Pacific toVancouver, once again travelling without lights. The shipstopped briefly at Fiji then encountered a big storm on the wayto Samoa, but eventually docked at Victoria, BC, where therewas some delay before they could proceed home. His biographerobserved that Remsen, who had had to step down as Presidentat Johns Hopkins on account of poor health, felt that the seavoyage was beneficial.

Chemistry in Australia 41|October 2017

letter from melbourne

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.

Remsen spoke about scienceand industry, emphasisingthe value of pure researchbut noting how difficult it wasat first for his students, whodid not know how to makesoap, to get places inindustry. Now, they wereeagerly seized upon, he said.

Remsen visits New Zealand

cryptic chemistry

Chemistry in Australia42 | October 2017

Across1 Hence core meltdown was displayed by

6 Across. (9)6 Fires aluminium inclusion over

beam. (5)9 Bond lithium with nitrogen then add

potassium and mature. (7)10 Loss of iodine during baseline crash is

helpful. (7)11 Start on group. (5)12 Indicated G&T. Guessed otherwise. (9)13 Tossed dented pan; relying on

another. (9)16 Osmium held by the ones that are

indicated. (5)17 X = 247616. (5)18 Grows due to lack of iron? (9)20 Hit a polymer without using iridium? It

can go either way. (9)23 Prepares to lose iodine on the other

side. (5)25 First time radical iodine container is

unimportant. (7)26 Look at the cost, Spooner: it’s clear-

cut. (7)27 Edible paper? (5)28 Vault with sulfur multidentate

ligands. (9)

Down1 Pass back diol which is dispersed and

stable. (7)2 Applause for handwriting? (5)3 Art stance could bring us back to

where we started. (9)4 Wants poverty? (5)5 Strangely greet nice and forceful. (9)6 Holiday permission. (5)7 Mixtures of answers. (9)8 Uranium in live part left. (7)14 New hopes pin on hydrogen and

PH3. (9)15 Decalin is a start to locating

information challenging your classiclaboratory in chemistry. (9)

16 Does care for matter net trouble? (9)17 Confused tea with oxygen. Jerk! (7)19 Plans schemes. (7)21 Oxygen and hot fruit. (5)22 Bare drain. (5)24 Chloride? Negative! (5)

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

2nd International Conference on Pharmaceutical Chemistry2–4 October 2017, Barcelona, Spainhttp://pharmaceuticalchemistry.conferenceseries.com

ChemComm Symposia on Energy Science and Materials –Beijing9 October 2017, Beijing, Chinawww.rsc.org/events/detail/26254/chemcomm-symposia-on-energy-science-and-materials-beijing

6th Modern Solid Phase Peptide Synthesis and itsApplications Symposium12–14 October 2017, Fraser Island, Qldwww.solidphase.org

International Conference and Exhibition on PharmaceuticalNanotechnology 27–29 October 2017, Rome, Italyhttp://nanotechnology.pharmaceuticalconferences.com

2nd International Conference on Applied Chemistry30 October – 1 November 2017, Chicago, Illinois, USAhttp://appliedchemistry.conferenceseries.com

Emerging Polymer Technologies Summit 22–24 November 2017, RMIT University, Melbourne, Vic.http://epts17.org/index.html

QACS 2017 – Qld Annual Chemistry Symposium27 November 2017, Queensland University of Technology,Brisbane, Qld

WattsFest201727–29 November 2017, Hydro Majestic Hotel, BlueMountains, NSWEmail [email protected] or [email protected] formore information.

Join the conference crowdTo promote your forthcoming conference or event here, email details to the Editor at [email protected].

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