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• A passion for chemistry and crystals• What makes a great chemistry teacher?• National Science Week: STEM for schools

in Australiachemistry

August 2016

chemistry

When cobalt and competition don’t mix

chemaust.raci.org.au

The Organising Committee would like to invite you to the 2017 RACI Centenary Congress.

The RACI is the oldest scientific or technical professional society in Australia. The Centenary Congress is anopportunity to celebrate the contributions that chemistry hasmade to Australia’s (and the world’s) social, economic andintellectual advancement over the past century.

ACCC66th Asian Conference onCoordination Chemistry

17 ACC17th Asian Chemical

Congress and 19th General Assembly of

FACS

AIMECS 201711th AFMC InternationalMedicinal Chemistry

Carbon 2017World Conference on

Carbon

Tetrahedron18th Asian Edition

Tetrahedron Symposium

GSC88th International

Conference on Green andSustainable Chemistry

Chemeca 2017Australian and NewZealand Federation ofChemical Engineers Annual Conference

www.racicongress.com #RACI100

For all enquiries, please email

[email protected]

Registration opens

July 2016Call for abstracts closes

November 2016

August 2016iStockphoto/webphotographeer


cover story

news & research6 News11 On the market13 Research16 Aust. J. Chem42 Cryptic chemistry42 Events

members4 From the RACI28 New Fellows29 RACI news

views & reviews5 Your say30 Books32 Technology & innovation36 Economics38 Education39 Grapevine40 Postdoc diary41 Letter from Melbourne

20 Expressing a passion for chemistry and crystalsFour PhD students at the University of Warwick are exploring the creativeside of crystal research.

24 What makes a great chemistry teacher?Pedagogical content knowledge from teachers and academics has beencaptured and coded to create a new resource for chemistry education.

Cobalt bluesAlongside inspiring stories in elite sport are those centred on the use ofbanned substances such as cobalt.

20

17

24

On behalf of the Organising Committee, it is with greatpleasure that I invite you to the 2017 RACI Centenary Congress.That’s right; the RACI will soon be 100 years old! We’re theoldest scientific or technical professional society in Australia.The Centenary Congress is an opportunity to celebrate thecontributions that chemistry has made to Australia’s (and theworld’s) social, economic and intellectual advancement over thepast century as well as to look forward to the challenges andopportunities in the century ahead.

The Centenary Congress will bring together several thousanddelegates from across the breadth of the chemical sciences andtechnologies. The Congress will encompass the RACI’s CentenaryConference, based on the traditional national scientificgathering of chemists from across the breadth of our discipline,both technical and geographic. However, the Congress will beso much more as it is being held in collaboration with severalpartner conferences, including the 17th Asian ChemicalCongress (17ACC), which is the biennial gathering of theFederation of Asian Chemical Societies, Carbon 2017 (The WorldCarbon Conference), Chemeca (Australian and New ZealandFederation of Chemical Engineers Conference), AIMECS17 (TheAsian Federation of Medicinal Chemists’ Conference), ACCC6 (TheAsian Conference on Coordination Chemistry), GSC8 (8thInternational Conference on Green and Sustainable Chemistry),Elsevier’s Tetrahedron – an Asian seminar, and the Asian Hub fore-Drug Discovery (AHeDD) conference.

Centenary Congress delegates will be freely able tocontribute to and enjoy the scientific and technical programs ofall of these partner meetings at no extra cost. The Congress willcelebrate Australian chemistry’s place in the Asia Pacific regionand the world. It will incorporate the energetic and enthusiasticcontributions of many student and early-career scientists andengineers from academia and industry as well as industrialleaders, world-renowned researchers and leaders in chemistryeducation. Congress Plenary speakers include several Nobellaureates, and several other outstanding chemists who may wellbe future laureates.

The Congress is being held in Melbourne at the MelbourneConvention and Exhibition Centre, which is located in the heartof the city, with easy access to a wide range of accommodation

within walking distance or via an excellent public transportnetwork. Melbourne hosts a vibrant social life with excellentrestaurants, bars and performing arts venues. Moreover, forthose addicted to sport, Melbourne is Australia’s ‘sportingcapital’ with options to watch top-tier professional sportingevents including Australian Football and Rugby League matchesonly a short stroll from the Congress venue. Melbourne is aninternational city, easily accessible from any part of the world.It’s a fantastic base to explore south-east Australia and enjoysome of the best food, wine and unique flora and fauna thatAustralia has to offer.

A key element of the centenary Congress will be thecomprehensive exhibition program showcasing the latestinnovations in chemistry, and we encourage interestedorganisations to make contact.

I am very pleased to welcome you to attend the RACICentenary Congress in Melbourne in July 2017. I’m sure you’llenjoy an intellectually stimulating and socially enjoyable event.Details can be found at www.racicongress.com. Please check thewebsite regularly for up-to-date information.

EDITOR Sally WoollettPh (03) 5623 [email protected]

PRODUCTION EDITORCatherine Greenwood [email protected]

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

PRODUCTIONControl Publications Pty Ltd [email protected]

BOOK REVIEWSDamien [email protected]

RESEARCH HIGHLIGHTSDavid [email protected]

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

PRESIDENT Paul Bernhardt FRACI CChem

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

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

© 2016 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproduced whollyor in part without written permission. Further details on thewebsite (chemaust.raci.org.au). ISSN 0314-4240 e-ISSN 1839-2539


Chemistry in Australia4 | August 2016

from the raci

Centenary Congress: conferences and celebration in 2017

Mark Buntine FRACI CChem, Centenary Congress Chair

#RACI100 www.racicongress.com

http://chemaust.raci.org.au

Randwick recollectionsI was interested to read in the June issue (p. 5) Robert Ryan’srecollections and musings, and took particular note of hisstatement that trams to the University of New South Walesstopped in 1961.

In the early 1960s, the University of NSW acquired the siteof the tramway workshops in adjacent Randwick, which becamethe Randwick subcampus of the university.

During my time at the University of NSW (1987–95), I wasfrequently at the Randwick subcampus where, among otherbuildings, there was (is?) a fuel technology laboratory. It wasdesigned by Dr Ken Basden MRACI CChem, whose obituary Iwrote for the July 2011 issue of Chemistry of Australia. Ken’sfirst tertiary qualification was an ASTC (Associate of the SydneyTechnical College), which provides a further link with the themeof Robert Ryan’s article.

I did a little research on the history of the area once, andsaw photographic evidence that trams would be out in force ona day when there was a major event at Randwick racecourse!

Clifford Jones FRACI CChem

www.chemaust.raci.org.au

your say

Chemistry in Australia 5|August 2016

‘Your say’ guidelinesWe will consider letters of up to 400 words in response tomaterial published in Chemistry in Australia or about novelor topical issues relevant to chemistry. Letters acceptedfor publication will be edited (no proof supplied) forclarity, space or legal reasons and published in print andonline. Full name and RACI membership type will bepublished. Please supply a daytime contact telephonenumber (not for publication).

Publication does not constitute an endorsement of anyopinions expressed by contributors. All letters becomecopyright of the Royal Australian Chemical Institute andmust not be reproduced without written permission.

Send letters to [email protected].

ApologyRACI does not endorse the comment related to DollyParton in the book review of Rare: the high stakes race tosatisfy our need for the scarcest metals on Earth, publishedin the June issue of Chemistry in Australia (p. 34). Thecomment has been removed from the online issue. Weapologise for any offence caused.

Our 2016 media kit is now available atchemaust.raci.org.au.

For further information,contact Marc Wilson at Gypsy Media Services:[email protected],0419 107 143

news


Funding for commercial waste-to-biofuel plantsTechnology of Australian renewable energy start-up Licella, co-founded by ProfessorThomas Maschmeyer FRACI CChem and developed in partnership with the University ofSydney, is the subject of a new contract with global investors that allows the re-imagining of the huge pulp and paper industry as biorefineries – turning waste intorenewable or recycled fuel blend-stocks. The Catalytic Hydrothermal Reactor (Cat-HTR™)technology converts low-cost, non-edible, waste biomass into a stable biocrude oil.

Canadian pulp and paper producer CanFor has announced it will invest fundssufficient for a full-scale commercial operation that will transform the resource-intensive pulp and paper industry by turning biomass waste into a petroleumsubstitute, biocrude. Also known as bio-oil, it will be ready to go into existingpetrochemical refinery streams to generate renewable fuels and/or chemicals.

University of Sydney

Laboratory safety taskforce calls for renewedresearch safety commitmentUniversity-wide efforts to renew and strengthen a culture of research safety arenecessary to avoid tragic accidents, according to a guide released by the Association ofPublic and Land-grant Universities’ (APLU) Task Force on Laboratory Safety. In thedocument and on a companion website (bit.ly/1WRJnWV), the taskforce provides USuniversity presidents and chancellors with 20 recommendations to strengthen theculture of safety.

The task force was created by APLU in coordination with the American ChemicalSociety (ACS), the Association of American Universities and the Council on GovernmentRelations. It was composed of senior research officers, environmental and health safetyexperts, and representatives from industry and national labs.

American Chemical Society

Cancer technology couldhelp cure crop diseaseproblemsResearchers at the Centre for Crop andDisease Management (CCDM), co-supported byCurtin University and the Grains Research andDevelopment Corporation (GRDC), are usingdigital polymerase chain reaction (dPCR)cancer detection technology to discoverfungicide resistance mutations in cropdisease.

dPCR works by allowing researchers tocollect multiple samples from one crop, poolthem, and extract fungal DNA to look forresistance mutations. dPCR is also capable ofquantifying the amount of DNA that containsthe resistance mutations.Curtin University

iStockphoto/DrPAS

Given the recentnumber of seriousacademic labaccidents, APLU’sreport shouldserve as a criticalclarion call toimprove lab safetyThomas Connelly, ACS Executive Director and CEO

... it is now clearerthan ever beforethat fungicideresistance iswidespread … requiringintegrated diseasemanagementoptions …Dr Fran Lopez-Ruiz, leader of Fungicide Resistance

Group, Centre for Crop and Disease Management

Using the wholetree and not just aminor part willmove the industrytowardsbiorefining.Dr Len Humphreys, Licello CEO


Using the oldest fossil micrometeorites(space dust) ever found, MonashUniversity-led research has made asurprising discovery about the chemistry ofEarth’s atmosphere 2.7 billion years ago.

This is one of 60 micrometeorites extractedfrom 2.7-billion-year-old limestone, from thePilbara region in Western Australia. Thesemicrometeorites consist of iron oxideminerals that formed when dust particles ofmeteoritic iron metal were oxidised as theyentered Earth’s atmosphere, indicating thatthe ancient upper atmosphere wassurprisingly oxygen-rich. Andrew Tomkins

The findings of a new study publishedin Nature (doi: 10.1038/nature17678) –led by Dr Andrew Tomkins and a teamfrom the School of Earth, Atmosphere andEnvironment at Monash, along withscientists from the AustralianSynchrotron and Imperial College, London– challenge the accepted view thatEarth’s ancient atmosphere was oxygen-poor. The findings indicate instead thatthe ancient Earth’s upper atmospherecontained about the same amount ofoxygen as today, and that a methanehaze layer separated this oxygen-richupper layer from the oxygen-starvedlower atmosphere.

Tomkins explained how the teamextracted micrometeorites from samplesof ancient limestone collected in thePilbara region in Western Australia andexamined them at the Monash Centre forElectron Microscopy (MCEM) and theAustralian Synchrotron.

‘Using cutting-edge microscopes, wefound that most of the micrometeoriteshad once been particles of metallic iron –common in meteorites – that had been

turned into iron oxide minerals in theupper atmosphere, indicating higherconcentrations of oxygen than expected,’Tomkins said.

‘This was an exciting result because itis the first time anyone has found a wayto sample the chemistry of the ancientEarth’s upper atmosphere,’ Tomkins said.

Imperial College researcher Dr MatthewGenge – an expert in modern cosmic dust– performed calculations that showedoxygen concentrations in the upperatmosphere would need to be close tomodern-day levels to explain theobservations.

‘This was a surprise because it hasbeen firmly established that the Earth’slower atmosphere was very poor inoxygen 2.7 billion years ago; how theupper atmosphere could contain so muchoxygen before the appearance ofphotosynthetic organisms was a realpuzzle,’ Genge said.

Tomkins explained that the new resultssuggest Earth at this time may have had alayered atmosphere with little verticalmixing, and higher levels of oxygen in theupper atmosphere produced by thebreakdown of CO2 by ultraviolet light.

‘A possible explanation for this layeredatmosphere might have involved amethane haze layer at middle levels ofthe atmosphere. The methane in such alayer would absorb UV light, releasingheat and creating a warm zone in theatmosphere that would inhibit verticalmixing,’ Tomkins said.

Tomkins outlined the next steps in theresearch.

‘The next stage of our research will beto extract micrometeorites from a seriesof rocks covering over a billion years ofEarth’s history in order to learn moreabout changes in atmospheric chemistryand structure across geological time. Wewill focus particularly on the greatoxidation event, which happened2.4 billion years ago when there was asudden jump in oxygen concentration inthe lower atmosphere.’Monash University

New IChemE president

Professor Jonathan Seville, ExecutiveDean of the Faculty of Engineering andPhysical Sciences at the University ofSurrey, UK, is the new President of theInstitution of Chemical Engineers(IChemE).

Seville studied chemical engineeringat Cambridge, and joined the researchdivision of Courtaulds Ltd beforereturning to academia to complete a PhDat Surrey under the supervision ofProfessor Roland Clift. He then embarkedon a successful academic career, whichtook him to the University ofBirmingham, UK, as the head of chemicalengineering where he established theUK’s first research centre in formulationengineering. He then moved to theUniversity of Warwick, UK, where heserved three years as dean ofengineering, before returning to Surrey in2011.

Throughout his career, Seville haschampioned the application of chemicalengineering to the design andmanufacture of products for thepharmaceutical, home care and fast-moving consumer goods industries. He isalso active in energy-related projects,including biomass conversion and solarpower, and is co-founder of thesuccessful spin-out company RecyclingTechnologies.

John McGagh, Chief Digital Officer atrenewable energy supplier, Snowy Hydro,was confirmed as IChemE’s DeputyPresident. He will succeed to thepresidency at the end of Seville’s 12-month term, in May 2017. Allyson Black,Corporate Development Manager at CaltexAustralia, will replace McGagh asAustralian Board representative.Institution of Chemical Engineers

Cosmic dust reveals Earth’s ancientatmosphere

news

US federal government researchers have successfully pilot testeda new method to more quickly and cheaply collect data that canhelp define the potential cancer and other human health risksfor more than 80 000 chemicals now in commerce and theenvironment. The research lays the groundwork for far-reachingadvances in managing chemical risks.

The new approach will help government regulatory agencies,such as the US Environmental Protection Agency, decide whichamong the thousands of chemicals should receive greaterscrutiny first. Priorities would be set on the basis of chemicals’potential hazardous effects on humans and on their potential toget into human lungs and other organs. Using rapidly evolvingcomputer-based methods to integrate data and informationfrom many sources, the researchers say, will make it possible tostart defining levels at which chemicals might cause harm andthen select those chemicals in the environment that should bemore fully assessed. That ability has long been recognised as acritical unmet need.

‘In my opinion, this work is starting to lay the foundationthat will allow risk assessors and risk managers around theworld to couple high-throughput screening tests and adverseoutcome pathways for risk assessment,’ said Dr Lyle D. Burgoonof the US Army Engineer Research and Development Center.Quantitative high-throughput screening (qHTS) uses roboticsand other technological devices. These technologies allowresearchers to quickly conduct millions of chemical tests.Adverse outcome pathways, or AOPs, trace changes in biologicalsystems that lead to harmful effects.

To assess the usefulness of the qHTS-AOP approach, Burgoonworked with colleagues from the Oak Ridge Institute for Scienceand Education. Their research used the cancer-causing chemicalbenzo[k]fluoranthene to pilot test the promising chemical riskassessment method and was published in the online version ofRisk Analysis (doi: 10.1111/risa.12613). The research focusedon benzo[k]fluoranthene’s putative ability to cause steatosis, acell disease in which excess fatty molecules build up in cells. Italso focused on the chemical’s potential to damage DNA as aresult of oxidation, which can cause electron losses associatedwith some diseases and cancers.

Burgoon says the qHTS-AOP approach is especially critical forthe chemicals currently in the environment for which data arelacking. ‘High-throughput screening provides an avenue to getmore data on these chemicals in a shorter amount of time, atan overall lower cost. As scientists generate more data fromthese high-throughput tests, our approach will allow these datato be integrated together, to create a better sense of what asafe exposure may be.’

Ideally, risk assessors would use qHTS data in combinationwith reverse dosimetry data and models. Such data are based onlevels of chemicals found in biological samples (from humanhair, blood etc.). The samples are used to define chemical levelsin the environment that caused the exposures, but data derivedfrom reverse dosimetry are currently insufficient. Until the gapin reverse dosimetry data can be filled, the qHTS method willallow chemicals to be ranked for regulatory attention. Prioritieswill depend on which chemicals the qHTS tests find arepotentially more harmful relative to other chemicals. Thosefindings will be paired with real-world data on how much of thechemical is found in air, water or other places.

‘Overall, we feel confident that as more qHTS data becomeavailable we will be able to translate these into risk assessmentresearch needs and risk screening assessments,’ the authorswrote. ‘We are equally confident that transparency can beenhanced over time, as we continue to migrate towards morecomputationally efficient, semi-automated methods.’

Society for Risk Analysis


Successful pilot method for chemical risk data

Benzo[k]fluoranthene

PTYLTDRowe Scientific

www.rowe.com.au

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

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CERTIFIED REFERENCE MATERIALS

An unprecedented molecular view of thecritical early events in gene expression, aprocess essential for all life, has beenprovided by researchers at Georgia StateUniversity, the University of California atBerkeley and Northwestern University.

Cryo-electron microscopy (cryo-EM), atechnique that studies samples at cryogenictemperatures, combined with state-of-the-art computational modelling, allowedresearchers to visualise large transcriptionpre-initiation complexes (PIC) at near-atomic resolution. The PIC is a proteinassembly that positions the enzyme RNApolymerase so it can start transcription.

The new structures shed light on thesequential conformational changes in the PICthroughout the transcription initiationprocess, including recognising the promoter region of DNAwhere transcription of a gene starts, opening this promoterregion and initiating transcription. The study was published inNature (doi: 10.1038/nature17970).

Genes are made up of DNA, which serves as a repository ofall our genetic information. To use the information encoded in agene, RNA polymerase must make a copy in the form ofmessenger RNA. The copying process – transcription – is one ofthe central activities necessary for life.

At the beginning of this tightly controlled process, RNApolymerase and general transcription factor proteins assembleat a specific site along the DNA to form a PIC. The PIC assemblyis required for opening the double-stranded DNA helix of thepromoter, positioning the DNA in the active site of RNApolymerase and starting the transcription process. Themessenger RNA transcripts are then used to produce proteins,the building blocks of human bodies.

‘This paper provides detailed structural information on thecomplexes that participate in the early stages of thetranscription process,’ said Ivaylo Ivanov, associate professor ofchemistry at Georgia State University. ‘We explore the steps thatRNA polymerase and general transcription factors take in orderto open the transcription bubble and begin the process oftranscription. This is a very important system that wasn’taccessible by either crystallography or any other structuralmethod before. This is the very first near-atomic cryo-EMreconstruction of the human PIC assembly.’

Chemical cross-linking and crystallography had providedglimpses of partial RNA polymerase complexes from eukaryoticorganisms such as yeast, but these techniques could not solvethe structure of the entire PIC complex. The events andprocesses leading to DNA unwinding by the PIC and theformation of a transcription bubble, a molecular structure that

occurs during transcription when a portion of the DNA doublestrand is unwound, were insufficiently understood.

To build detailed atomic models of the PIC complex, Ivanovand his team applied integrative molecular modellingtechniques. The calculations relied on modern supercomputingtechnology available though the National Science FoundationExtreme Science and Engineering Discovery Environmentprogram and the National Energy Research Scientific ComputingCenter. The researchers showed that judicious combination ofcomplementary techniques – molecular dynamics flexible fittingand refinement of atomic coordinates with the Phenixcrystallography software package – led to models comparable inquality to crystal structures in the same resolution range.

The researchers captured the human PIC in three differentfunctional states: a closed state engaged with the DNA doublehelix of the promoter region; an open state engaged with thetranscription bubble; and an initial transcribing complex poisedto carry out the chemistry of messenger RNA synthesis. Theywere also able to visualise numerous previously undeterminedcomponents of the human PIC assembly. The findings revealedthe complete subunit organisation of a transcription factorcalled TFIIH, which has a critical role in opening the promoterregion. TFIIH proved one of the most difficult pieces of the PICassembly to resolve.

Comparisons between the closed, open and initialtranscribing states of the PIC provide new mechanistic insightsinto the processes of DNA engagement, promoter melting andtranscription bubble stabilisation.

Georgia State University


New, detailed images of DNA transcription

Architecture of the human transcription pre-initiation complex (PIC).A critical step in transcription is the process of promoter opening,resulting in a nascent transcription bubble. This is accomplished byRNA polymerase (Pol II) in association with general transcriptionfactors that assemble to form the PIC. The structure of the core PICis fitted into the cryo-EM density map and shown in two orientations.

news

Dr Mark Keevers with one of the spectrum-splitting, four-junctionmini-modules developed at the University of New South Wales.

A new solar cell configuration developed by engineers at theUniversity of New South Wales has pushed sunlight-to-electricity conversion efficiency to 34.5% – establishing a newworld record for unfocused sunlight and nudging closer to thetheoretical limits for such a device.

The record was set by Dr Mark Keevers and Professor MartinGreen, Senior Research Fellow and Director, respectively, of theUniversity of New South Wales’s Australian Centre for AdvancedPhotovoltaics, using a 28 cm2 four-junction mini-module –embedded in a prism – that extracts the maximum energy fromsunlight. It does this by splitting the incoming rays into fourbands, using a hybrid four-junction receiver to squeeze evenmore electricity from each beam of sunlight.

The new result, confirmed by the US National RenewableEnergy Laboratory, is almost 44% better than the previousrecord – made by Alta Devices of the US, which reached 24%efficiency, but over a larger surface area of 800 cm2.

‘This encouraging result shows that there are still advancesto come in photovoltaics research to make solar cells even moreefficient,’ said Keevers. ‘Extracting more energy from every beamof sunlight is critical to reducing the cost of electricitygenerated by solar cells as it lowers the investment needed, anddelivering payback faster.’

The result was obtained by the same team that set a worldrecord in 2014, achieving an electricity conversion rate of over40% by using mirrors to concentrate the light – a techniqueknown as CPV (concentrator photovoltaics) – and then similarlysplitting out various wavelengths. The new result, however, was

achieved with normal sunlight with no concentrators.‘What’s remarkable is that this level of efficiency

had not been expected for many years,’ said Green, apioneer who has led the field for much of his 40 yearsat the University of New South Wales. ‘A recent studyby Germany’s Agora Energiewende think tank set anaggressive target of 35% efficiency by 2050 for amodule that uses unconcentrated sunlight, such as thestandard ones on family homes.’

Australia’s research in photovoltaics has alreadygenerated flow-on benefits of more than $8 billion tothe country, Green said. Gains in efficiency alone, madepossible by PERC cells, are forecast to save $750 millionin domestic electricity generation in the next decade.PERC cells were invented at the University of NewSouth Wales and are now becoming the commercialstandard globally.

The record-setting mini-module combines a silicon cell onone face of a glass prism, with a triple-junction solar cell onthe other.

The triple-junction cell targets discrete bands of theincoming sunlight, using a combination of three layers: indium–gallium–phosphide, indium–gallium–arsenide, and germanium.As sunlight passes through each layer, energy is extracted byeach junction at its most efficient wavelength, while theunused part of the light passes through to the next layer, andso on.

A diagram of the spectrum-splitting, four-junction mini-module.


Milestone in solar cell efficiencyBy Wilson da Silva

Some of the infrared band of incoming sunlight, unused bythe triple-junction cell, is filtered out and bounced onto thesilicon cell, thereby extracting just about all of the energy fromeach beam of sunlight hitting the mini-module.

The 34.5% result with the 28 cm2 mini-module is already aworld record, but scaling it up to a larger 800 cm2 – therebyleaping beyond Alta Devices’ 24% – is well within reach.‘There’ll be some marginal loss from interconnection in thescale-up, but we are so far ahead that it’s entirely feasible,’Keevers said. The theoretical limit for such a four-junctiondevice is thought to be 53%, which puts this result two-thirdsof the way there.

Multi-junction solar cells of this type are unlikely to findtheir way onto the rooftops of homes and offices soon, as theyrequire more effort to manufacture and therefore cost more thanstandard crystalline silicon cells with a single junction. But theteam is working on new techniques to reduce the manufacturingcomplexity, and create cheaper multi-junction cells.

However, the spectrum-splitting approach is perfect for solartowers, like those being developed by Australia’s RayGenResources, which use mirrors to concentrate sunlight, which isthen converted directly into electricity.

The research is supported by a $1.4 million grant from theAustralian Renewable Energy Agency (ARENA). The University ofNew South Wales team is working with another ARENA-supported company, RayGen, to explore how the advancedreceiver could be rolled out at concentrated solar PV powerplants. Other research partners are Trina Solar, a PV modulemanufacturer and the US National Renewable Energy Laboratory.

University of New South Wales/CC BY-NC 3.0

on the market


Thermal analysis webinars

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Webinars will address thermal analysis themesfrom various standpoints, including:• specific techniques, such as differential scanning

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Each webinar will also offer a Q&A session whereattendees can have their most pressing thermalanalysis application questions answered by METTLERTOLEDO experts without leaving the comfort of theiroffice chairs.

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research

August 2016

Fixing nitrogen with lightAmmonia has played a pivotal role in the expansion of society over the pastcentury, as the basis for chemical fertilisers that have improved crop yields andfed a growing world population. However, the industrial production of ammonia(roughly 200 million tonnes/year) is an energy-intensive process that consumesapproximately 3% of world energy supplies. Finding new and sustainablemethods to generate ammonia without carbon-based energy is therefore astrategic goal to combat global warming. Besides its use in fertilisers, ammoniaalso has a bright future as a fuel. Fuel cells that provide power to vehicles anddevices can be designed to use ammonia, making it a carbon-free fuel source.In recent work published by Professor Douglas MacFarlane and co-workers atMonash University, a new method to reduce nitrogen to ammonia using lighthas been discovered (Ali M., Zhou F., Chen K., Kotzur C., Xiao C., Bourgeois L.,Zhang X., MacFarlane D.R. Nat. Commun. 2016, 7, 11 335). The method relies ona nanostructured silicon wafer with gold nanoparticles deposited on its surfaceto absorb light and use the absorbed energy to reduce molecular nitrogen toammonia in an aqueous electrolyte. Electrons generated in the nanostructuredsilicon semiconductor under illumination are sufficiently energetic toaccomplish the six-electron reduction reaction. The ammonia yields arecurrently not sufficient for large-scale application, but there is much scope toimprove this process in the future.

research


In recent years, advances in chemical protein synthesis haveenabled racemic protein crystallography, a method by whichboth L- and D-amino-acid-containing proteins are mixedtogether to promote crystal growth and to remove a majorbottleneck in structure determination. The research groups ofDistinguished Professor Margaret Brimble and Dr ChristopherSquire at the University of Auckland have solved the structureof the snakin-1 protein through a novel combination ofracemic protein crystallography and radiation damage-inducedphasing (Yeung H., Squire C.J., Yosaatmadja Y., Panjikar S.,López G., Molina A., Baker E.N., Harris P.W.R., Brimble M.A.Angew. Chem. Int. Ed. 2016, doi: 10.1002/anie.201602719).

The incorporation of an unnatural 4-iodophenylalanine residueinside a quasi-racemic crystal of the protein and thesubsequent breakage of the exogenous C–I bond by X-irradiation were critical factors in the successful structuredetermination. The structure of this protein is the first fromthe GASA/snakin superfamily, whose members are involved indevelopment, hormonal cross-talk and antimicrobial defence inmany plant species. The structure provides a starting point forrational antimicrobial peptide design, and also suggests thegeneral applicability of the 4-iodophenylalanine residue in radiation-mediated phasing ofcrystals prepared from chemically synthesised proteins.

Anions play essential roles in biology, medicine, catalysis and theenvironment. So the ability to selectively detect anions hasnumerous real-world applications. Most of these applications requireanion recognition to occur in water. However, selective anionreceptors that operate in water are exceptionally rare, particularlywhen the target anion is inorganic sulfate, which is heavily hydratedin aqueous solution. Nature has overcome this challenge byemploying an idealised arrangement of hydrogen-bondinginteractions in the sulfate-binding protein. This has served as theinspiration for a series of macrocyclic sulfate receptors synthesised inthe Jolliffe research group at the University of Sydney (Qin L.,Hartley A., Turner P., Elme R.B.P., Jolliffe K.A., Chem. Sci. 2016,doi: 10.1039/C6SC01011C.) These macrocyclic structures are simpleto prepare and their structures can be readily tuned to providesolubility in different solvents, including aqueous mixtures. Theywere found to be extremely potent and selective ligands for inorganicsulfate, with one of the receptors better able to discriminatebetween sulfate and chromate than the sulfate-binding protein.

Selectively sensing sulfate

Structure determination using radiation-damaged quasi-racemic crystals


Silicene is a two-dimensionalnanomaterial that is the silicon analogueof graphene. It holds great potential fornext-generation electronics, batteriesand gas sensors (see September 2014issue, pp. 24−7). But the full applicationof silicene is hindered by its instabilityunder ambient conditions and highreactivity with oxygen (Spencer M.J.S.,Morishita T. Sci. Rep. 2015, 5, 17570). DrMichelle Spencer (RMIT University) andDr Tetsuya Morishita (National Instituteof Advanced Industrial Science andTechnology, Japan) have recently editedthe first book on silicene (Silicene:structure, properties and applications,Springer, 2016). The groups of DrSpencer, Dr Morishita and Dr HideyukiNakano (Toyota Central R&D Labs, Japan)have also recently discovered a newallotrope of silicon containing four-, five-and six-membered sp3-hybridised siliconrings (Yaokawa R., Ohsuna T.,Morishita T., Hayasaka Y., Spencer M.J.S.,

Nakano H. Nat. Commun. 2016, 7,10 657). In total, three types of bilayersilicenes were obtained after treatingcalcium-intercalated monolayer silicene(CaSi2) with a BF4

–-based ionic liquid. Thebilayer silicenes were sandwiched

between planar crystals of CaF2 and/orCaSi2, making them highly resistant tooxidation and thus providing scope fornew applications of bilayer silicene thatrequire greater stability underatmospheric conditions.

Stabilising silicenes

Light switch for polymerisationproductsThe concept of orthogonality in macromolecular synthesis – theability to create a series of polymers with varied architecture orsequence from a single reaction mixture through independentchemical reactivity – has wide-reaching applications. The teamof Dr James Blinco at the Queensland University of Technologyand Professor Christopher Barner-Kowollik at the QueenslandUniversity of Technology and the Karlsruhe Institute ofTechnology in Germany have done just this and it is as easy asswitching a light on and off (Hiltebrandt K., Eiles K.,D’hooge D.R., Blinco J.P., Barner-Kowollik C. J. Am. Chem. Soc.2016, 138, 7048–54). The researchers introduced a reactionmanifold for a polymer with an o-methylbenazaldehyde endgroup. When mixed in a solution containing a primary amineand a maleimide, different ligation products were achieveddepending on the presence or absence of a light stimulus. Whenirradiated, the end group underwent photo-enolisation,activating it for Diels–Alder cycloaddition. If left in the dark,the imine reaction preferentially occurred. Through controlled

irradiation, the composition of the final product formed couldbe adjusted from 100% imine (0% photo product) to less than5% imine (95% photo product). The team also demonstratedthat the methodology is not only amenable for polymer end-group modification but also for the linking of two polymerchains to form block copolymers.

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

aust j chem

Communications: do weneed them?It is fair to say that the process of publishing a manuscript haschanged remarkably over the course of our academic careers.While, unlike our older colleagues, we were spared the tediumof typewritten manuscripts with carbon paper providing thecopies, we still had to endure the tyranny of distance, servedby the postal service. We must remember that the wholeprocess of academic publishing was considerably slower, thecopies of the manuscript had to be posted to the editor andfrom there to the referees. All deliberations were by post and itcould take up to six months to publish a paper. In fact, in ourown journal, which went fully electronic in 1997 and was thefirst of the CSIRO journals to do so, the average time fromsubmission to online publication was six months. Gradually,authors started to provide their manuscripts on electronicmedia, which shortened typesetting times as prior to that thetext was re-keyed in by our in-house typesetters.

It was in this environment that the Communication wascreated to serve the community. Communications were used toprovide our peers with the quickest possible dissemination ofimportant results. Our own journal suggests that aCommunication should be for ‘short reports of urgent researchfindings, and should not exceed 2000 words and three graphics.’However, some Communications could still take up to a yearfrom submission to publication. Once we went to conferencesto hear the most important new results, but now they are reallyopportunities to network because no one likes to report theirunpublished results given the possibilities afforded by theaccelerated publishing process.

The current publishing paradigm sees us with drasticallyshorter submission to publication times with articles appearingonline sometimes within a month of submission depending onthe rate-determining step of the reviewing process. So thequestion is, do we need the Communication as an article typein any journal? Perhaps not! People will point to impact factoras a reason to publish in these journals but these are ofteninflated by the incorporation of review articles, perhaps thevery opposite of ‘short reports of urgent research findings’.

Our view is that the chemical community would be betterserved by the publication of full papers in which all the detailsand full scope of the work are provided. There is still a place fora shorter full paper telling a complete story but in our mindsthere is no need for ‘urgent’ publication because if you wantyou can tweet it! It just won’t be peer reviewed.

What do our readers think?

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


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Alongside inspiringstories in elite sportare those centred onthe use of bannedsubstances such ascobalt.

Public scandals of doping insport have becomelegendary. A tiny minority ofcompetitors seek unfair

advantage through the misuse oftherapeutic and other drugs, and thiscreates problems for all. The fall ofWestern greats such as Ben Johnsonand Lance Armstrong and the 2015suspension of the entire Russianathletics federation from internationalcompetition show that this is a globalsporting issue.

The problem is much wider thanjust the issue of cheating. Many of thedrugs and techniques used in dopinghave serious and long-term health

consequences. Danish cyclist KnudJensen died suddenly duringcompetition in the 1960 Olympics, withone autopsy finding amphetaminesand the drug pyridin-3-ylmethanol (avasodilator) in his system. The causesof Jensen’s death are debated eventoday, but this tragic event promptedthe International Olympic Committeeto establish its first medical committee,the start of ongoing efforts to protectthe health of athletes and the fairnessof competition.

A fundamental aspect ofperformance in elite sport – human oranimal – is the oxygenation of themuscles. So there are many routes by


CobaltbluesBY DAVE SAMMUT

iStockphoto/olgalT

which athletes and their trainers seekto enhance the capacity of the body tocarry oxygen.

Arguably at its most benign,anaerobic training at high altitudecreates hypoxic conditions in thesystem, which stimulates a naturalincrease in production ofhaemoglobin, which in turn enhances

performance on return to the oxygenpartial pressures at sea level. Withinthe body, sea level oxygen partialpressures are medically termed‘normoxia’ (see box).

The same principle applies to thetechnique of drawing the athlete’sblood over time and then re-injecting itjust before race day. However, whethernatural or forced, higher red-blood celllevels pose a risk to the system byincreasing the viscosity of the blood,placing a greater strain on the heart topump the blood around the body.

The recent AFL supplementsscandal embodies a key problem withdoping. The athletes were found tohave been doped, allegedly withouttheir knowledge or consent, with theprohibited substance thymosin beta-4.These players have incurredsubstantive sporting sanctions, andnow face unknown long-term healtheffects.

Take this one more step to the issueof doping in horse racing, where theanimals can in no way give consent totheir treatment, therapeutic orotherwise. According to Racing NSW:‘United States racing officials becameconcerned with the use of cobalt inJanuary 2013 when officials detectedits presence in a large number ofsamples that were taken at TheMeadowlands in New Jersey’.

Why cobalt? Since the 1980s, a keychallenge for antidoping authoritieshas been the detection and control ofthe use of erythropoietin (EPO). EPO isthe hormone responsible forcontrolling the generation of red bloodcells (‘erythropoiesis’) in bone marrow.So the use of EPO represents anothermethod of boosting haemoglobinlevels in the blood. However, as theanalytical techniques to detect EPO inboth blood and urine, particularlyrecombinant human EPO (rhEPO) andits analogues, have improved, andbecause EPO is expensive,unscrupulous athletes and trainers areincreasingly seeking alternatives.Cobalt(II) is known to activate EPOproduction in the body (see box).

Cobalt is found in trace levels in awide range of foodstuffs, includingnuts, green leafy vegetables, fish andcereals. In both humans and animals, itis active in various coenzymes such ascobalamins, the best known of which isvitamin B12. It is therefore a criticalmicronutrient. However, there are nopublished reports of cobalt dietarydeficiency in humans, nor in horses.Indeed, there are reports of healthyhorses grazing in cobalt-deficientgrasses that are unable to supportsheep or cattle.

The US National Research Councilrecommends a minimum daily cobaltintake of 0.5 milligrams of cobalt perday for a 500-kilogram horse. Thisshould be readily achievable fromdietary sources for a healthy adulthorse, but supplementation might belegitimately used for the treatment ofdiseases that interfere with the take-upof vitamins and minerals.

In a 1958 human study(doi: 10.3181/00379727-99-24395), theadministration of 120–150 mg/day ofcobalt chloride induced additionalhaemoglobin production up to 20%above pre-treatment levels in sixsubjects within 7–22 days, returning tonormal levels within 9–15 days aftercessation of cobalt administration.

From the 1940s to the 1970s, cobaltwas used therapeutically to treatvarious types of anaemia in humans(septic infection, myeloid hypoplasia,sickle-cell disease), as well asrheumatoid arthritis and chronickidney disease. However, thesetreatments were associated withsignificant harmful side-effects: organdamage, gastrointestinal illness,neurological dysfunction, impairedthyroid activity and myocardialfunction, reversible hearing loss andlong-term loss of visual acuity. Giventhese serious side-effects, cobalttreatments for anaemia wereabandoned in the 1970s in favour ofandrogens, until rhEPO becameavailable in the 1980s.

Although cobalt is known to havetherapeutic benefits in humans, there


How cobalt(II) activatesEPO production The erythropoietin (EPO) gene andother oxygen-regulated genes arecontrolled by the transcription factorhypoxia inducible factor 1a (HIF-1α).This is a specific protein required forthe initiation of the synthesis of RNA,using a DNA template catalysed by anRNA polymerase enzyme.

Under normoxic conditions, HIF-1αis rapidly degraded by a proteasome,an intracellular enzyme that degradesmisfolded or damaged proteins andmodulates the quantity of regulatoryproteins (like HIF-1α) in the cell. Co2+

induces a form of hypoxia, and therebymarkedly inhibits the degradation ofHIF-1α. The HIF-1α then binds to HIF-1β, crosses the nuclear membrane andpowerfully activates erythropoietingene transcription.

The glycoprotein erythropoietin includesfour alpha helices stabilised by disulfidelinks. Wikimedia/CC-BY-SA-3.0

is little or no evidence that cobaltsupplements enhance racingperformance for healthy horses. Thefirst direct study of single-doseintravenous cobalt administration in18 horses (Knych et al., 2014,doi: 10.1002/dta.1737) did not find anychange in blood EPO concentrations,red blood cell parameters or heart ratewithin the period studied. Instead, itsuse in horses appears to be based onanecdotal evidence and extrapolationfrom its former use in humantherapeutics.

Various sources of cobalt arereadily accessible and cheap. It is alsofound in various veterinarytherapeutics, and commerciallyavailable supplements.

The unregulated abuse of cobalt inhorse racing has yielded some majorconsequences. Given in excessivedoses, it has caused side effects suchas ‘shaking, trembling and sweatingup’. According to news reports, therehas been a number of unexplaineddeaths of US racehorses, later foundwith high levels of cobalt in theirsystem.

In a scathing article in theSeptember 2015 Veterinary Journal(doi: 10.1016/j.tvjl.2015.04.005),authors Mobasheri and Proudmanstated ‘… the lay public does not haveaccess to detailed information aboutthe potential risks and many trainersdo not have the scientific knowledge toassess the risk : benefit ratio for theuse of cobalt salts.’

Harness Racing NSW took the leadin regulating cobalt in Australian horseracing. In December 2013, it introduceda threshold limit of 200µg/L of cobalt inrace-day urine samples. Dr TerenceWan, considered a world leading racinganalyst, advised the authority that ‘no

untreated horse should have a levelgreater than 60µg/L but, to be safe, alevel of 100µg/L would clearlyrepresent a treated horse on raceday’.Racing Victoria and South Australiafollowed suit in 2014. A nationalthreshold of 200µg/L was subsequentlyimplemented by Racing Australia in2015.

Emeritus Professor Brynn HibbertFRACI CChem, newly inductedPresident of the Royal Society of NewSouth Wales, conducted statisticalanalyses for the racing industry,concluding that: ‘it was reasonable toinfer that those [horses] below 50µg/Lhad not been treated’. Hibbert advisedthat if 50µg/L can be taken as anupper level of a ‘normal’ population,then an action level (level at whichregulatory action would be taken) of100µg/L gives odds of 1 : 116 000against such a concentration in anormal population.

Speaking to the author, Hibbertemphasised that up to 50µg/L was therange used to establish the typicalpopulation, but that higher levels don’tautomatically imply doping. However,above 200µg/L ‘the chances areessentially zero that a typical horsewould have these levels’.

Using the threshold of 200µg/L, theVictorian Civil and AdministrativeTribunal handed leading horse trainersMark Kavanagh and Danny O’Brienmulti-year suspensions in January 2016after they were convicted foradministering cobalt to horses in theircharge. Two other trainers, Lee andShannon Hope, were found guilty ofadministering cobalt to their horsesthe previous November. Some cobaltvalues in these prosecution were inconsiderable excess of the 200µg/Llimit.

NSW Racing currently uses theNational Measurement Institute for itscobalt analysis, pending theprocurement, development andvalidation process of its own ICP-MSanalysis technique. This is the ‘goldstandard’ method, and works well forthese types of samples. Hibbertadvises that a limit of detection of1µg/L is practical, with a median levelfor a typical population of severalthousand horses of approximately3µg/L cobalt.

The good news is that, based onfurther studies, Hibbert reports thatcobalt levels in horse racing are fallingappreciably. The trainers are takingnote, and the goal of protecting thewelfare of the horses in the industry isbeing achieved in this respect.

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


The unregulatedabuse of cobalt inhorse racing hasyielded some majorconsequences.Given in excessivedoses, it hascaused side effectssuch as ‘shaking,trembling andsweating up’.

Emma Ravenhill, Faduma Maddar,Harriet Pearce and Maria Adobes-Vidal have a passion for chemistryand crystals. They want to share andcelebrate the contributions womenmake to chemistry in today’s world.They are part of the ElectrochemistryGroup at Warwick University, which iscomposed of 45% women. The Headof the Department of Chemistry,Professor Alison Rodger, is also awoman.

Emma, Faduma, Harriet and Mariaare PhD students in theElectrochemistry and Interfaces


Expressing apassion forchemistryand crystals

An optical microscope image of a partiallydissolved crystal of an API becomes a verycurious character in Mary Courtney’s pieceentitled ‘The idea was crystallising himself’.

Four PhD students atthe University ofWarwick areexploring thecreative side ofcrystal research.

BY UNIVERSITYOF WARWICK

The Crystal Crew (Left to right: Harriet,Faduma, Maria and Emma), University ofWarwick Chemistry Department.

Group at Warwick University. They usestate-of-the-art microscopes andinstruments in new ways to reveal theproperties of crystalline materialswith applications from enginedeposits to kidney stones. Their workhelps to improve the composition ofdrugs, improve fungicides, enhancedrug development and benefitindustry.

Faduma, Harriet and Maria all studythe growth and dissolution kinetics andmechanism of organic crystals. Theymonitor in situ topography changes ofsingle crystals at the micro and nano

scale by using Raman spectroscopy, X-ray diffraction, vertical scanninginterferometry, optical microscopy,scanning ion-conductance microscopyand atomic force microscopy toprovide a holistic view of theprocesses involved. The data informmathematical modelling to obtainquantitative information of the drivingforce and the rate-limiting step of thegrowth/dissolution processes.

Known on campus as the CrystalCrew, the chemists produce imagesthat not only assist their research intocrystals but also reveal a strange and

beautiful micro-world. Because theirwork provides lots of interesting newimages, the Crystal Crew is involved ina Chem-Art project led by ProfessorPatrick R. Unwin and Mary Courtney,an artist in residence at the Universityof Warwick’s Chemistry Departmentsupported by the Leverhulme Trust.The project, ‘Drawing on thenanoscale’, uses high-resolution probemicroscopes to allow the chemists toexpress a different side to theircreativity. These images serve asinspiration for some of Mary’screations.



Maria Adobes VidalI am particularly interested in active pharmaceuticalingredients (the active component in drugs) and pathologicalcrystals (for example kidney stones) due to their importancefor human health. Understanding the process of dissolution orgrowth of these crystals makes it possible to improve thecomposition of drugs for a better performance or develop newstrategies or treatments to cure certain illnesses.

Maria concentrates on organic crystals with a greatimpact on human health, such as active pharmaceuticalingredients or pathological crystals, for example kidneystones. L-Cystine crystals are the cause of kidney stonesassociated with the genetic disorder cystinuria and theavailable treatments for this condition are not totallyeffective in the removal (dissolution) or prevention(growth) of new stones. As a consequence, there isconsiderable interest in understanding thegrowth/dissolution kinetics of these crystals in order toimprove the treatment of cystinuria. Maria has workedwith Professor Michael D. Ward at New York Universityimaging the dissolution of L-cystine crystals by in situatomic force microscopy. They were able to recordmovies of the surface process that occurred by theformation of hexagonal spirals formed from screwdislocations.

Harriet PearceThe use of fungicides is vital for farmers to avoid croplosses. I want to understand the dissolution and growthprocesses of the fungicide crystals to make them moreefficient to use.

Harriet focuses on agricultural fungicideformulations in aqueous media with surfactants.The active ingredient (AI) is an organic crystallinemolecule with poor aqueous solubility and thesurfactant aids its uptake into the plant from theleaves. Fungicides are normally delivered by aspray-dry process where the formulation exhibitsa variety of liquid-crystalline phases as water(anti-solvent) evaporates from the surface of theleaf. Evaporation of water increases the organiccontent of a droplet on the leaf and thus thesolubility of the AI. The crystalline AI can thendissolve, becoming available for uptake.Furthermore, if it rains, the spray deposit will pickup water, causing the AI to become insoluble andcrystallise on the leaf surface. Hence, dissolutionand crystallisation cycling of organic crystals isimportant in determining the efficacy of AIs with aview to improving the delivery process.

A bicalutamide crystal.

Optical image of a partially dissolved crystal of an activepharmaceutical ingredient.


Not all is science for Emma,Faduma, Harriet and Maria. Emmaplays the guitar, paints in her sparetime and bakes fantastic cakes. Harriethas been part of the Croydon YouthTheatre Organisation and loves goingto the theatre. She also plays canoepolo and enjoys climbing and going

hiking with her dog. Faduma is anamazing photographer, enjoyssketching and loves running. Mariawas a ballet dancer before becominga chemist and now she enjoys theadrenaline rush of skiing, kayaking andclimbing. They also do other activitieslike fundraising for charity. Faduma

and Maria are taking part in anupcoming UWCB (Ultra White CollarBoxing) event organised together withCancer Research UK, and will have aproper boxing match (but not againsteach other).

First published by University of Warwick and adaptedwith permission.

Faduma MaddarI am looking into new approaches, combining optical imaging,microscopy and spectroscopy techniques to provide further indepth understanding and in turn assist in enhancement of drugdevelopment and formulation.

Faduma works in collaboration with pharmaceuticalcompany AstraZeneca, developing new approaches tounderstand the dissolution of active pharmaceuticalingredients. In pharmaceutical science, dissolution testing isa key step to determine the rate at which an activepharmaceutical ingredient is released and is madeavailable for absorption in the gastro-intestinal tract. Despitethis importance, the general processes governingdissolution and crystallisation of crystals are poorlyunderstood. As a case study, Faduma has focused onbicalutamide, the active pharmaceutical ingredient in

AstraZeneca’sproduct CASODEX.Bicalutamidebelongs to class II of thebiopharmaceuticsclassification system(low solubility, highpermeability). The lowsolubility/dissolutionrate of bicalutamide is a key factor limiting its oralbioavailability and clinical application. In fact, nearly 40% ofnewly developed compounds face the same problem andso in-depth understanding of dissolution of suchcompounds is fundamental as it is the rate-limiting step forin vivo absorption.

Emma RavenhillAll gasoline and diesel car engines contain a rangeof essential additive chemistries. These are required,for example, to inhibit corrosion, enhancelubrication, and keep the engine clean. My projectinvolves using microscopy and analytical techniquesto study the crystal growth processes behind thisdeposit formation, allowing us to tailor futureadditives to prevent these unfavourable reactionsfrom taking place.

Emma’s project is focused on the study ofengine additives. Although each additive playsa key role in protecting the engine,unfavourable side reactions take placebetween them, resulting in the formation ofcrystalline deposits. She uses in situ opticalmicroscopy and analytical techniques such asRaman spectroscopy and X-ray diffraction tostudy the crystal growth processes, crystalmorphology and polymorphism behind thisdeposit formation, obtaining information totailor future additive chemistries that willprevent these unfavourable reactions andimprove engine performance. Calcium sulfate crystal interferometry.

Optical image of a bicalutamide singlecrystal.

Classroom teaching practiceis a personal skill thatdevelops with experienceand through reflection.

Teacher behaviour involvesresponding to a specific group ofstudents in a particular class and so isimpossible to completely plan inadvance. However, steps towards thedevelopment of more effectiveteaching methods are possible evenwith limited time and resources.

Associate Professor Gwen Lawriefrom the University of Queensland andI, together with research assistantsBronwin Dargaville and Chantal Bailey,have spent the past two years

investigating teaching strategies withinthe framework of pedagogical contentknowledge (PCK) as described in theSeptember 2014 issue. PCK can beloosely defined as ways of teachingspecific content, including the choiceof representations, examples andanalogies along with an understandingof typical student difficulties. Whilethere is a vast body of research intoPCK at the secondary level and it isexplicitly taught and practised, PCKhas been investigated less at thetertiary level.

The motivation for this project camefrom the recognition that in general,novice teachers in universities rarely


Pedagogical contentknowledge fromteachers andacademics has beencaptured and codedto create a newresource forchemistryeducation.

BY MADELEINE SCHULTZ

What makes agreat chemistryteacher? Findings of the ChemPCK project

It is surprising that science academics who place high levels of importance uponevidence‐based practice for research do not consider the same evidence‐base as beingimportant in their teaching.

da Silva K.B. (2008). Raising the profile of teaching and learning: scientists leading scientists. ALTC. p. 25

receive professional development indiscipline-specific teaching practices.Instead they rely on a mixture of theirown learning experiences, advice ormentoring provided by theircolleagues and learning from theirown mistakes as they gain experience.This process is in stark contrast to theculture in secondary school teachertraining in which awareness of howstudents learn is linked to adisciplinary context to help teachersdevelop their PCK, and PCK is oftentaught explicitly.

A decade prior to this project,internationally renowned chemicaleducator Professor Bob Bucat from theUniversity of Western Australia wrote inChemistry Education Research andPractice, 2004, vol. 5(3), pp. 215–28):

The chemical education enterprise iscrying out for ‘applied research’ thatprobes and documents the topic-specificPCK of respected teachers.

Currently in the teaching profession theaccumulated PCK of each of itsparticipants grows with experience,peaks at retirement, and then disappears- often with hardly a contribution to thecollective wisdom of the profession. (p. 225)

To try to capture some of thewisdom to which Bucat refers, thisproject has collected topic-specificPCK from more than 50 chemistryacademics from around Australiawithin workshops. In addition, weconducted interviews with tenrecognised exceptional tertiaryteachers about their personal teachingstrategies. The interviewees werechosen on the basis of institutional ornational awards for teachingexcellence and were a mix of teachingand research-intensive academicsrepresenting different subdisciplines ofchemistry. The resulting data fromworkshops and interviews were coded

and a website was built(chemnet.edu.au/chem-pck), whichdistils the specific teaching strategiesthat are used for particular topics inchemistry. The site can be searched bychemistry topic or type of teachingstrategy. Teaching strategies havebeen collated for a range of topics andsubtopics (see table).

The website has been live sinceApril this year and has attractednational and international attention.Feedback from users has been verypositive, showing that it is a usefulresource, particularly for those new toteaching a particular topic. Furtherteaching strategies will be added andreaders are invited to contribute theirown favourite strategies to the website.

We collected many insightful quotesfrom the expert teachers. Combiningthese with the current educationalliterature led to the development of aseries of seven steps (see box) to


iStockphoto/ViktorCap

enhance teaching that are applicablein any discipline. The website and thesteps are recommended to anyacademics in the early stages of theirteaching careers.

We found that the most favouredteaching strategies evolve withincreasing numbers of years of teachingexperience. In the first two years ofteaching, most academics’ teachingstrategies rely on demonstration andexplanation. Participants with three toseven years of teaching experiencewere more likely to use examples andreal-world applications as their mostfavoured teaching strategies. After eightyears of teaching, the most commonstrategies involve student participation,and this persists through to the mostexperienced and expert academics.Thus, these strategies are likely to bemost effective and novice teacherscould attempt to move towards expertbehaviour.

Tertiary chemistry teacherstypically have a focused researchbackground within a specificchemistry subdiscipline other thanchemical education. This backgroundinfluences their epistemologicalperspectives and can inform theirunderstanding and explanations ofbasic chemical concepts. This projectaimed to capture the PCK of chemistryteachers with a variety of backgroundsto compare their teaching strategiesfor the same topics and to seekcommon threads that tie togetherchemistry PCK.

Some quotes illustrate the depth ofinterviewees’ affiliation to theirsubdiscipline. For example, an organicchemist, describing the use of curlyarrows to understand reactionmechanisms, said

... it takes organic chemistry from a rotelearning discipline ... to an understandingand an intuitive discipline ... for students

that can make that transition and can fullyunderstand that concept, then they have amuch deeper and more profoundunderstanding of and relationship withthe whole discipline ...

A bioinorganic chemist had adifferent perspective on what is mostimportant:

It is imperative for all futureunderstanding of chemistry that theyunderstand that molecules are 3D things,they have a spatial requirement and a 3Dshape that may change when themolecule reacts with something.

Perhaps the strongest statementabout what is fundamental tounderstanding chemistry came froman inorganic chemist:

... that’s the underpinning of all chemistry.If you don’t understand how atoms bondtogether, you can’t do chemistry, or youcan’t understand chemistry ... chemistryis all about electrons and electronconfiguration, and you can forgeteverything else, it’s just what’s yourelectron configuration? How does thatatom attain more stable electronconfiguration? And that’s chemistry.

The expert teachers gave examplesof advice they wished they hadreceived when starting out. Forexample, in terms of preparation: ‘it’svery important to be able to knowwhat’s coming, know what’s gonebehind and know what you’re doing atthe moment fits both ways’. Duringclass time, perceptive comments were‘focus on what they’re doing ratherthan what you’re doing’ and ‘teachingthrough intuition is not good enough,and teaching the way you were taughtis not good enough’. The value ofexperience is shown by the quote: ‘it’staken me a little while to realise is thatthe students weren’t understandingwhat the question was’.

Finally, to help combat what Bucathas called ‘professional amnesia’, ametareview of all outcomes offederally funded chemistry educationprojects in Australia over the past20 years was completed. Theoutcomes from the 22 grants for whichinformation was available form amajor source of PCK and TSPK (topicspecific professional knowledge), and


ChemPCK website topics and subtopicsTopic Subtopics

General chemistry Chemical bonding

Electronic structure/electronegativity/shape

Foundations of chemistry

Nature of matter

Practical chemistry

Stoichiometry/equations/formulae

Organic chemistry Functional groups

Mechanisms

Organic structure and bonding

Stereochemistry

Structure determination/NMR

Inorganic chemistry Acid–base chemistry

Electrochemistry

Aqueous solutions

Physical chemistry Chemical and physical properties

Equilibrium

Intermolecular forces

Kinetics

Phase transitions

Quantum mechanics

Thermodynamics

Analytical chemistry Spectroscopy

Other analytical techniques

the outputs provide additionalresources relevant to this project’scommunity. The review will bepublished in the Australian Journal ofEducation in Chemistry in 2016 andthe collected resources are availableon the website.

If you are interested in more detailon the project or would like tocontribute a teaching strategy to thePCK website please [email protected].

Madeleine Schultz MRACI CChem was a seniorlecturer in chemistry at Queensland University ofTechnology until recently and is currently working atthe European Molecular Biology Laboratory inHeidelberg, Germany, synthesising fluorescent dyesfor live cell microscopy. Support for this project hasbeen provided by the Australian Government Officefor Learning and Teaching (SD14-3737). The viewsexpressed in this project do not necessarily reflectthe views of the Australian Government Office forLearning and Teaching.


1 Know your studentsFind out who they are and be willing to adjust to theirneeds: students in tertiary classes are usually more diversethan you assume. Question the students – a show ofhands gives you quick feedback.

2 PrepareQuarantine 20–30 minutes before you teach to think aboutwhat you are aiming for students to learn in your classthat day and how you will know whether they haveunderstood you. Plan the strategies that you will use toaddress important concepts.

3 Reflect Reflect on what you did after each teaching experienceand make a note of what you could adjust. Did you feelthat you communicated the essential concepts effectively?Did students engage with the material and the teachingstrategies that you used? How many students grasped theconcepts?

4 Observe your peers teaching and invite them toobserve youInvite colleagues to observe you and to give you feedbackon your teaching, and also ask whether you can observetheir teaching.

5 Use ChemPCKThe website chemnet.edu.au/chem-pck contains teachingstrategies and insights from a large number of tertiarychemistry teachers. You can search by topic that you areteaching to find specific strategies that have beensuccessfully used by others.

6 Practise high-impact teaching• Flipping: move the bulk of the new content into

resources that students access before class time, suchas readings, videos or screen casts.

• Peer teaching (with or without flipping): during class,have the students work in small groups to discussstimulus material or problem solve.

7 Assess student learning and provide feedbackAssessment informs teachers of what their students knowand can do, and this information is important whenchoosing teaching strategies.

Steps to transform your teaching


raci news

New FellowsIan Eckhard graduated fromLoughborough University with a BTech(1966) and a PhD (1969). Afterpostdoctoral fellowships in Palo Alto,California (1970), University ofNewcastle, Australia (1972), andUniversity of Warwick, Coventry (1973),he returned to Australia and worked inthe biochemistry department of RoyalPrince Alfred Hospital for 10 years.While there, he set up the firstbenchtop gas chromatograph–massspectrometer imported into Australia,where it was used for drug screening

and quantitative drug analyses. In 1985, Eckhard joined Australian Analytical Laboratories as

chief chemist and operated a variety of analytical equipmentused in environmental, pharmaceutical, food and trade wasteindustries. In 1995, soon after the company was taken over byAmdel, he left to join Australian Environmental Laboratories toadvise management on strategies and equipment requirementsto keep the company at the forefront on environmentalanalysis.

In 1998, Eckhard joined the Australian GovernmentAnalytical Laboratories as Manager and Principal ResidueChemist in Organic Residues with responsibility for managingvarious major environmental projects. There he assisted insetting up the dioxin analysis facility since at that time therewere no facilities for measuring dioxin levels in theenvironment in Australia. For this he was awarded an AustraliaDay Medallion in 2003.

In 2003, together with three other ex-AGAL employees,Eckhard started Advanced Analytical Australia P/L and took therole of technical director. It was intended to set up thebusiness for the analyses of organic and inorganic compoundsthat no other company were prepared to accomplish, ratherthan analyse routine environmental and food contaminants. Thecompany grew successfully over the next 10 years and continuesto occupy a niche market in the analytical industry.

Eckhard has been a NATA assessor for 15 years and a memberof the New South Wales RACI Analytical and EnvironmentalGroup for 20 years.

Eckhard is married with two children and five grandchildren.He retired in February and was presented with his RACIFellowship at his retirement dinner by Professor Roger Reid. Heintends to travel both in Australia and overseas for long periodsover the next few years.

Jonathan Morris is an organic/medicinalchemist based at the University of NewSouth Wales, where he currently is anAssociate Professor and the Deputy Deanof Graduate Research.

He was born in Perth but grew up inthe Pilbara region of Western Australia.He received his BSc(Hons) (first class)from the University of Western Australiain 1990, then moved to the labs of LewMander at the RSC at the AustralianNational University. His PhD researchfocused on the total synthesis of raregibberellins and he completed his PhD in1994. From 1994 to 1996, he carried out postdoctoral researchwith Phil Magnus at the University of Texas at Austin. On theflight back to Australia, he interviewed for a lectureship at theUniversity of Canterbury in New Zealand, which he wassuccessful in securing. He worked at the University ofCanterbury from 1997 to 2004, then moved to the University ofAdelaide. In late 2009, he was recruited to the University ofNSW as an Associate Professor to direct the new Bachelor ofMedicinal Chemistry degree that had just been set up.

Morris has supervised 13 PhD students, three Mastersstudents and numerous Honours students, with many of thesenow working in biomedical research and pharmaceuticalcompanies. He was awarded the 2014 Vice Chancellors Award forTeaching Excellence.

Morris’ research interests are in the broad areas of organicand medicinal chemistry. He is interested in utilising the powerof synthetic organic chemistry to investigate biologicalproblems. Much of his work is centred on the synthesis ofbiologically active natural products, with the goal of restoringaccess to these valuable materials so that further biologicalinvestigations can be initiated. In recent years, his group hasfocused on the development of inhibitors of the kinases thatcontrol alternative splicing as these kinases are implicated inmany diseases. In 2013, his work on SRPK1 inhibitors led to theestablishment of Exonate Ltd, which is a start-up companyfocused on the discovery and development of small moleculedrugs that modulate alternative mRNA splicing to addressdiseases of high unmet medical need.

Morris has been very active in the RACI, especially since hisreturn to Australia. He was Vice-President of the SouthAustralian Branch of the RACI in 2004 and is currently thetreasurer for two different Divisions: Organic Chemistry (since2012) and Medicinal Chemistry and Chemical Biology (since2013).

He is married to Joanna Drimatis, who is a musician. Theyhave two daughters, Zoe (14) and Eva (7).


Over 160 speakers

7 Plenary sessions

Over 100 exhibiting companies

27 Sessions

Over 1000 participantsAbundance of networking opportunities

24 – 27 October 2016, Melbourne Convention Centre, Australia

Host Body Major PartnerHost Organisation

Contact: [email protected] @AusBiotech | #IBS2016 IBS 2016

17th International Biotechnology Symposium and Exhibition

www.ibs2016.org

Mr Paul Perreault – CEO and Managing Director, CSL, USA

Biotechnology and innovation: risk and precaution: social license or not?

Prof Sir Peter Gluckman – Chief Science Advisor to the Prime Minister, O�ce of the Prime Minister, New Zealand

2016 Millis Oration

Prof Ian Gust AO – Professorial Fellow, University of Melbourne

A New Model for Drug Development in Academic Institutions

Prof Dennis Liotta – Executive Director Emory Institute for Drug Development, Emory College, Atlanta USA

Interrogating and Guiding the Microbiome for Macro-organism Health and Productivity

Dr James Tiedje – Director, Centre for Microbial Ecology, Michigan State University, USA

Self-Assembled Supramolecular Nanosystems for Targeting Therapy of Intractable Diseases

Prof Kazunori Kataoka – Professor, Department of Materials Engineering and Bioengineering Graduate Schools of Engineering, University of Tokyo, Japan

Synthetic Designer Vaccines Protect from Bacterial Infections

Prof Dr Peter Seeberger – Director, Max-Planck Institute of Colloids and Interfaces, Germany

Biotech and the future of man

Prof Huanming Yang – President, Beijing Genomics Institute, China

2015 Archibald D. Ollé PrizeThe Archibald D. Ollé Prize is an annual national RACI award fora published treatise, paper or journal article on any topic ofinterest to the Institute. The award is administered by the NewSouth Wales Branch. The 2015 Prize was awarded to ProfessorStephen Pyne FRACI CChem, University of Wollongong, by DrJoseph Bevitt (ANSTO), RACI NSW President, at the NSW BranchPresidents’ Dinner and Awards Night on 7 April 2016. The awardwas for the book chapter ‘The boronic acid Mannich reaction’(S.G. Pyne, M. Tang, Organic reactions, 2014, Wiley, vol. 83,Ch. 2, pp. 211–498).

The boronic acid Mannich reaction (or Petasis reaction) is athree-component coupling reaction involving boronic acids orboronate esters, carbonyl compounds and amines. This reactionis extremely versatile for preparing important chiral startingmaterials for the synthesis of molecules of biological interest,including chiral α-amino acids, 1,2-amino alcohols, 2-aminoalkyl phenols, heterocycles and alkaloids. This chapteraddresses the mechanism, stereochemistry and scope andlimitations of each of the three components of this reaction.Some typical experimental conditions are provided along with acomprehensive tabular survey.

RACI Board electionsNominations are open for the following positions on theRACI Board.• President elect• Treasurer• Ordinary board memberForms are available at www.raci.org.au/theraci/corporate-governance/board-elections-2016Nominations close 20 August and elections will be

held the first week in October.

Successful womenceramic and glassscientists and engineers:100 inspirational profilesMadsen L.D., Wiley, 2016, hardback,ISBN 9781118733608, 640 pp., $92.95

Successful women ceramic and glassscientists and engineers presents theprofiles of 100 female professionals, some

of whom were pioneers in the ceramics industry. These profilesfeature current and retired university researchers, professorsand industry contributors to the glass and ceramics community.The author, Dr Lynnette Madsen, is herself an industryprofessional working as a consultant and for the US NationalScience Foundation. She describes her intentions of compilingthe book as multifaceted – ‘for the reader to find someone inthis book who reflects who they are and where they want to go’– and to recognise the contribution of women to the industryas a whole. The book is also designed as a resource for futurecollaboration and networking by listing personal contact detailsfor each profile.

The individual profile format (while relatively simple)provides the best of both worlds with a detailed professionalbiography and a selection of personal remarks. Eachprofessional biography provides details such as education andcareer history, awards received and details of publications. Manyof the profiled women were awarded multiple degrees in theirfield, and held positions in some of the most recognisedscientific organisations in the world (including NASA, MIT,Cambridge University and UNESCO). Nonetheless, the book’shighlights are the personal reflections of the women featured.Their responses to ‘Challenges’, ‘On being a woman in this field’,‘Words of wisdom’ and ‘Proudest career moment’ are eachincredibly honest, unique and inspirational. Thus from LisaKlein: ‘What has helped me over the years is the idea that weare all in it together. And if we stick together, everyone willmove forward ...’

One of the drawbacks of the book is its limited indexing, andwhile there is a ‘quick guide’, it does not provide a clear way tonavigate the entire group of profiles. Most of the womenfeatured are from Europe and the US, although there are anumber of Australian-born women featured including SylviaMarian Johnson (NASA), Rachel Caruso (University ofMelbourne) and Cathy Patricia Foley (CSIRO, NSW). A number ofother women feature who participate in Australian research andindustry, but they are from home countries other than Australia.

There are a number of applications for the enormous amountof information contained in this book – among them takinginspiration from the personal remarks. The women featured inthe book provide an opportunity to see a modelled career path,to select contributors to professional events and to makepersonal contact if preferred. Successful women ceramic and

glass scientists and engineers provides an opportunity torecognise the contributions of female scientists and engineers.It also provides an avenue to ensure that the contributions ofwomen continue to be recognised in scientific research and inthe ceramics and glass industry.

Samantha Profke MRACI

A tale of seven elementsScerri E., OUP, 2013, hardback,ISBN 9780195391312, 270 pp., $20.95

Chemistry is about understanding ourphysical world, how and why things are asthey are and why they behave as they do.However, it is also very much a science ofprediction, of anticipation of what is likely,or unlikely, to occur in any set of defined,sometimes imagined, circumstances.Assuredly, one of the most significantmilestones in the long history of chemistrywas the invention of that great unifyingand classifying tool, now something of a scientific icon, theperiodic table.

The periodic table emerged as a somewhat rough draft,which has undergone a lot of amendment and adapting on theway to becoming the form now familiar to us. For sure, there isplenty of argy-bargy and numerous tales of jealousy,nationalism, racism, bitter disputes, obfuscation, chicanery anddownright dishonesty to be found in the story of the modernperiodic table’s emergence. In my view, we try too hard to hidethe essential humanity of our great chemistry forbears behindthe gloss of their glorious achievement. They were real people,with all the same strengths, weaknesses and foibles as the restof us. Surely, this has to be inspirational! For my money, ‘wartsand all’ is best.

Eric Scerri, probably the best historical analyst of theperiodic table, wrote The periodic table: its story and itssignificance (OUP, 2007). Everybody ought to read it. Plenty of‘warts and all’ and jolly interesting too. A tale of seven elementsis, if you like, a worthy appendix to his earlier work, insofar asit is a detailed exploration of the discovery of the last sevenelements, which existed as gaps in the 92-element periodictable about the beginning of the 20th century. These sevenelements, in order of their discovery, were 91-protactinium, 72-hafnium, 75-rhenium, 43-technetium, 87-francium, 85-astatineand 61-promethium. The time span covered is 1917 (91Pa) to1947 (61Pm), part way through World War I until after World WarII. Unless you have a photographic memory, at this stage youmight find it helpful to grab a copy of the periodic table andsee just where these elements fit in.

Bear in mind that Mendeleev published his version of theperiodic table in 1869, although his underlying premise was notquite right (by a long shot). However, it was a pretty

books


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groundbreaking effort, and, equally, the credit might well havegone to a German (Meyer). There are tinges of nationalism herein ascribing credit. All of this was accompanied by a hugeexplosion of knowledge about atomic and subatomic structuresfrom about 1900. You can see how geopolitics and science getentangled. Scerri devotes several chapters to elaborating onthese themes, in addition to his seven elements.

The chemical research leading to the discovery of the seven‘unknowns’ makes great reading and highlights some of theserendipity of chemistry. Things don’t always go to plan andthere are many instances of lucky discoveries on record. I guessthe real skill is to recognise your discovery, before you say ‘Oh!@@##!!!’ There are also wrong turns and missed opportunitiesin every chemist’s career. This happened along the way todiscovery of these seven elements: sometimes people got lucky;sometimes they just got it wrong; sometimes the cards justdidn’t fall right. Science at its best is altruistic and everythingnoble and exalted, but it is not always like that. There arebitter disputes, disputed and spurious claims, and plenty ofrancour, hatred, detestation and nationalism littering theglorious history of chemistry. If you don’t believe me, then readthis book to find some excellent examples.

I really enjoyed reading this book. It is a well written,interesting, informative and thoroughly fascinating account ofhow our central guiding tenet, the periodic table, came to its

full fruition. It taught me a lot in a painless way. You can readit on the bus; you can read it on the train; or, like me, you canread it in bed at night. The chapters are short and more-or-lessself-contained. Read it! You’ll love it.

R. John Casey FRACI CChem

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

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

The chemical researchleading to the discovery ofthe seven ‘unknowns’ makesgreat reading and highlightssome of the serendipity ofchemistry.

Drones, droids and robots

technology & innovation

The Australian Government’s ‘National Innovation and ScienceAgenda’ is hosting the schools theme of ‘Drones, Droids andRobots’ as part of National Science Week this month. The aim ofthis theme is to ‘embrace [in schools] … real-world applicationof autonomous technologies in areas including agriculture,mining, manufacturing, medicine and space and deep oceanexploration’.

A robot is pretty much any device that automaticallyperforms physical tasks, sometime repetitively. The borderbetween machines and robots can be quite fuzzy, but we cansay this: all robots are machines but not all machines arerobots. Generally speaking, robots include very high levels ofcomputer control and many sensors, and, in some form oranother, they often replicate one or more human functions.

Consider a welding robot in an automotive manufacturingfacility. It looks very much like a large and quite intimidatinghuman arm, performing similar functions to a human arm butwith much greater speed, higher accuracy and precision, loweroverall costs and virtually no occupational health and safetyrisks.

Droids are a subset of robots – those that are mobile andthat often have a humanoid form. Until recently, droids onlyexisted in science fiction books and movies, but they have nowbecome a reality as technology has allowed the production ofautonomous droids for all sorts of functions. These includesoccer-playing droids created for the Robocup competition andhousehold ‘butler’ droids that have popped up on crowd-sourcing funding sites.

At a tradeshow in China, I noticed a little droid runningaround one of the neighbouring booths. It combined thefunctions of vacuuming and drink delivery. The novelty value ofsuch an oddity probably outweighed the risks of people trippingover it.

The autonomy of real-life droids sometimes requires a formof ‘artificial intelligence’ to provide functionality. Today thisartificial intelligence is usually developed within extremelylimited physical environments (such as a soccer pitch) and isreally just binary software code that is able to make ‘decisions’in most possible scenarios within such a closed physicalenvironment.

Certainly no machine, droid or otherwise, has completelypassed the Turing test in an open environment. The Turing testrequires that a machine can fool a human into ‘perceiving’ thatthe machine is a human. Indeed, in order to pass this test in anopen environment a machine would probably require, inaddition to artificial intelligence, both artificial sentience andartificial consciousness; we are a long way off developing such amachine.

A drone is very different from a robot or droid. It is a vesselguided by humans using remote control. The ready availabilityof cheap technologies for wireless communications and high-density electric battery storage, usually containing lithium, has

allowed for the introduction of low-cost flying drones(unmanned aerial vehicles or UAVs), which have captured theimagination of many large businesses, hobbyists and smallbusiness entrepreneurs. In addition to UAVs, there are manyground vehicles and water-borne vehicles that are also drones.

Lithium polymer batteries use lithium ion chemistries buthave polymer separators that effectively reduce energycapacities compared to lithium ion batteries but permit higherdischarge rates. Lithium polymer batteries can have a flat packconfiguration as compared to the cylindrical shape of lithiumion batteries. This ease of packaging combined with higherdischarge rates has resulted in a situation where most UAVs arepowered by lithium polymer batteries.

The future for robots is a given. They have been with us fordecades and will continue to get more sophisticated, especiallyin the manufacturing sector where ever-increasing productivityrequires the removal of labour from factories. A similar trend isalso occurring in the agricultural and mining sectors, wherelabour is seen as an inhibitor to cost reductions andproductivity gains. This trend is underpinned by the fact thatrobot technology is steadily becoming cheaper and moresophisticated.

Of more interest in the near term is how the specificcategories of drones and droids will evolve. Drones and droids,in their modern context, have only just emerged from high-techlaboratories as cost-effective technologies that are available forreal-world applications. Previously, costs were so high that


iStockphoto/Marco Maccolini

these technologies were limited to very high-value nicheapplications.

In terms of commercial deployment, drones have gonethrough a massive non-linear uptake in consumption primarilydriven by UAV applications. Droids, although threatening such aleap, have yet to take off in quite the same way.

For UAVs there are five interesting trends.• The maximum flight time and distance of UAVs is slowly

increasing as battery technologies improve.• The payload of UAVs is slowly increasing with improved

motors, better batteries and higher strength but still lightchassis.

• Authorities are limiting the application of UAVs, for safetyand privacy reasons, while at the same time exploringpolicies that will allow widespread commercial applicationsof UAVs.

• The cost of UAVs (per kilometre of flight or per kilogram ofpayload per kilometre of flight) is rapidly decreasing.

• Technology groups are developing autonomous flightsystems, i.e. fly-by-GPS systems. Strictly speaking, when aUAV flies according to GPS settings, it is no longer a dronebut more of a flying robot. All of these trends are pointing towards multiple commercial

applications of UAVs. In some cases, UAVs are replacing whatwas formerly ground-based commerce, such as high-value cargotransport. In other cases, such as cinematography, drones areallowing video filming of what was previously not possible to

capture. Indeed, every time I talk to an entrepreneur workingwith UAVs, I discover a new and unexpected use of thetechnology.

Dow Chemical has recently used UAVs to inspect its chemicalplants for issues such as cracks in pipes and tanks. Before itcould do so, however, Dow had to apply to the US FederalAviation Administration for approval to fly the UAVs over Dow’sown property.

This is an area where government regulations can accelerateor hinder technology deployment. For large-scale commercialdeployment of UAVs, it is critical that standards for flight pathsystems and guidance systems are developed. What is mostneeded is international standards in the area so that the sametechnology can be deployed globally and thus benefit from thegreatest economies of scale. In English, this means that costswill come down quicker.

Standing in the way of such efforts is the fact that it maytake years for different nations to collaborate on what iscurrently seen by many as just a nuisance to aviation. In themeantime, many technology groups are busily filing patents inthe area, and these will further confound future efforts tostandardise technologies in the UAV market.


In some cases, UAVs(unmanned aerial vehicles)are replacing what wasformerly ground-basedcommerce, such as high-value cargo transport. Inother cases, such ascinematography, drones areallowing video filming of whatwas previously not possibleto capture.

Ian A. Maxwell ([email protected]) is a serial (andsometimes parallel) entrepreneur, venture capitalist and AdjunctProfessor in Electrical and Computer Engineering at RMITUniversity and Visiting Professor in the Faculty of Engineering andInformation Technology, UTS, who started out his career as aphysical polymer chemist.

Your RACI Member Benefit Program

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Chemistry in Australia 35August 2016

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Patent strategy essentialsDr John Landells, Partner and Registered Patent Attorney, FB Rice

e chemical sciences provide a competitive andcommercially innovative technology area where, inmany cases, patenting is critically important forcommercialisation. e chemical sciences, inparticular the chemical life sciences, is an area thatoen presents significant barriers tocommercialisation, for example where there are highcosts in developing an invention into a marketable

product, or where chemical products can be easily and cost-effectivelycopied by competitors. Maintaining an invention as a confidentialtrade secret is a sensible option in some situations, such as for someindustrial chemical processes. However, relying on confidentiality alsocarries risk, particularly with many organisations having a largenumber of transiting employees working in collaborating teams.Patenting can provide protection for an invention for up to 21years inmost countries, with confidentiality being maintained for the first18months.

Without patent protection for a chemical invention, it may be verydifficult to attract investment necessary for commercial development.Seeking patent protection is oen essential to establishing andbuilding value in an organisation’s research and development efforts.

A successful approach around patent protection involves morethan simply the preparation, filing and grant of patent applications.Some patent strategy essentials are as follows.• PATENT LANDSCAPE AND PRIOR ART REVIEW –

maintain a regular understanding of the patent landscape and priorart in your technology area, particularly by identifying the closestdocuments from the point of view of identifying opportunities forpatenting new inventions, and in understanding the extent of yourfreedom to commercialise your invention without infringing otherpatents.

• INVENTORSHIP/OWNERSHIP – carefully document allcontributions from each individual involved in development of the

invention and ensure ownership has been assigned in a writtenagreement by each of the individuals, preferably before theycontribute.

• CONFIDENTIALITY – control disclosures to ensureconfidentiality is maintained at least until a first (provisional)patent application is filed, and preferably until all applications (e.g.an international application) have been filed.

• WHEN TO FILE – filing your patent application early reducesthe risk that another party researching in the same area will publishor file its own patent application before you do. However, thisneeds to be weighed against how far developed your own inventionis (see below).

• WHAT TO FILE ON – the breadth of protection that a patentwill provide depends on factors including the nature of the priorart and the data/research results provided to support the patent. Inmany cases, a patent application that contains more supportingdata will allow for broader protection to be obtained. Broad patentfilings based on little supporting data may have the undesired resultof allowing only narrow protection to be obtained while at thesame time creating prior art that is detrimental to possible futurepatent applications in the same research area. e right decision onhow broadly to file will depend on the circumstances, but it shouldform part of your discussions with your patent attorney.

• PATENT PORTFOLIO REVIEW – carry out a regular review ofyour patent portfolio in view of changing commercialcircumstances, including considering whether existing patents stillcover the proposed commercial product and if so whether there arenew opportunities for patent filings, balancing commercialimportance against projected patent costs, particularly prior totime points where significant patent costs are incurred such as atnational phase entry (30 months aer first filing) and validation ofa European patent.

For more information, email [email protected].

www.�rice.com.auThe IP Navigators

economics

The production of steel from coal and iron ore by the blast-furnace route accounts for the major portion of the world’s steelproduction of 1650 Mt/year. This route has good economies ofscale and is now practised in facilities producing volumes ofabout 1 million tonnes of iron per year or more. Steel productionis seen by many countries as a strategic necessity and for manycountries (such as New Zealand) production of steel on thisscale is not warranted. This develops the opportunity forsmaller scale technologies, many of which are grouped asdirectly reduced iron (DRI).

DRI technology has been commercialised for over 100 years.In essence, there are two approaches, one uses coal and theother uses natural gas. Of the approximately 75 Mt/year of DRIproduced, about 80% is produced from gas. The coal-based DRItechnologies are generally all different, being developed toprocess particular ores and coals. In recent times new facilitieshave been built that use coal as coke oven gas or coalgasification to provide the reducing gas.

For gas-based technologies, a shaft-based system developedand promoted by the Midrex Corporation (www.midrex.com) hasachieved a high level of take-up. In this process, iron ore lumps(>6.3 millimetres) are loaded into the top of the shaft-furnaceand are reduced by an upward flowing stream of reducing gas, amixture of hydrogen and carbon monoxide.

The reducing gas is produced in a steam reforming unit fromthe natural gas. Relative to other steam reformers that producesynthesis gas for ammonia or methanol production, reducinggas reformers operate at high temperatures and low pressures,which maximises hydrogen and carbon monoxideconcentrations.

As the iron ore is reduced, water and carbon dioxide areproduced, which could reverse the reaction if the concentration

becomes too high. To prevent this, excess reducing gas is fed tothe furnace and recycled after water and carbon dioxide havebeen removed. Reduced iron is separated from the ash. Asproduced, DRI is pyrophoric and is passivated by a briquettingprocess prior to shipment.

Because of the demand for lump ore for this technology (andits benefits to blast furnace operations), there is a significantprice premium for lump ore over fines, typically 20%. Fines canbe used but require pelletising at additional cost prior to use.Because of this price differential, there have been attempts touse iron ore fines in the direct reduction process.

In the 1970s, Esso succeeded in the fine iron ore reduction(FIOR) process on a semicommercial plant in Texas. Thetechnology required the fines to be fluidised in an ascendingstream of reducing gas. Four sequential reactors were requiredwith fresh ore charge to the first reactor and passingprogressively to other reactors, which completed the reductionprocess. However, attempts to transfer the technology at fullscale to ore reduction in the Orinoco region of Venezuela failedbecause the ore used, on partial reduction, became sticky andaggregated and clogged the reactors.

The technology was improved by Voestalpine (an Austriansteel conglomerate), who managed to get the technology towork and marketed this as the FINMET process.

In the late 1980s, BHP decided to use the FINMET processrather than the more proven Midrex process for a very large-scale DRI operation at Boodarie in Western Australia. This wasknown as the BHP HBI (hot briquetted iron) plant. It ranintermittently for several years but seems to have suffered fromthe same problems as the original Esso FIOR plant: sticky, partlyreduced ore, which adversely impacted on production rates. Afatal accident at the site persuaded the company not topersevere with the process and the facility was closed in 2005.

Prior to steel making, the DRI is melted in an electric arcfurnace, which separates impurities from the iron as a slag.Unlike the blast furnace, an electric arc furnace has limitedability to handle slag and this limits the level of impurities inthe feed. The main feed competitor to DRI for electric arc


Directly reduced iron technology: steel-making using gas

0.00

100

200300

400

500

1.00 2.00 3.004.00 5.00 6.00 7.00 8.00 9.00 10.00

Gas price (US$/GJ)

DRI (US

$/t) HBI WA

DRI Texas

Rio Tinto HIsmelt facility. This high-intensity smelting facility wasdeconstructed in 2013. Liberty Industrial Comparison of DRI production costs in Western Australia and Texas.

furnace operations is scrap steel for which there is a large andextensive international market – especially good-quality scrapcontaining few tramp metals produced by the scrapping ofships, particularly the oil tanker fleet, which has a highturnover rate.

Despite BHP’s experience, the large reserves of natural gasand iron ore in Western Australia will always attract DRI typeoperations. The graph illustrates some of the key economicissues for the cost of DRI production. The graph plots theproduction costs for an HBI operation in Western Australia anda conventional DRI facility in Texas against the prevailing gasprice. The salient data are given in the table for the twofacilities of similar scale. The HBI data have been escalatedfrom published BHP SEC filings (capital cost $A2.6 billion in1999) and the Texas DRI from Midrex/Voestalpine publicationsfor an export DRI operation based near Corpus Christie. This has

just been completed. For comparison the cost of good qualityscrap (US market, May 2016) is $250/t.

The main difference clearly evident is that despite low gasprices (<US$5/GJ) and lower iron ore cost (run of the minecost), the very high capital cost for operations in Australiamakes DRI production in Australia non-viable. This is in contrastto the US Gulf area where both low capital costs and low gascosts (typically $3/GJ) can deliver DRI well below the cost ofscrap. This makes export of DRI from the US to Europe viable.

DRI operations are of interest because of their relativelylower emissions of carbon dioxide. Other methods that havebeen tried include the CSIRO/Rio Tinto HIsmelt process, whichreduced ore with powdered coal in a molten metal bath. Thisproject has now been abandoned in Australia and thetechnology transferred to India for further development.

A fully ‘renewable’ route would be to use wood charcoal forthe reduction. This has been practised in the past (prior to thecoal age) and is still found in some countries, such as India.The problem is that blast furnaces are restricted in size andrequire enormous quantities of biomass (wood) for theoperation.


Data for DRI operations

DRI Texas HBI WA

Capacity (kt/year) 2000 2000

Capital (late 2015) (US$ million) 770 2875

Iron ore (type) Lump Fines

Iron ore pricing basis* FOB fines + 20% Run on mine cost

Iron ore price (US$/t) 66 35

Gas usage (PJ/year) 19.7 19.7

FOB, free on board. (FOB fines = US$55/t)

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

BHP’s hot-briquetted iron facility. The facility was demolished in 2011. Liberty Industrial

education

National Science Week is an annual celebration of science andtechnology at all levels and in all areas of education, butespecially through non-formal and informal education asoutreach events by the CSIRO, the RACI, museums, Scouts,Guides and other community groups. This year, National ScienceWeek will be held during 13–21 August. Its popularity hasincreased over the years – it has increased from seven days tonine, including two weekends, with some events being held inthe weeks before and after the formal National Science Week.

One highlight of National Science Week 2016 will be a livestage show, A Journey into Deep Space, by English physicist andBBC presenter Professor Brian Cox. There will be approximately1000 other events, all aiming to encourage an interest inscientific pursuits among the general public, and to encourageyounger people to be fascinated by the world we live in. A fewother examples will illustrate the scope of the events.

The ScienceWorks Museum in Melbourne is presentingSTEMania. This is a series of theatrical sketches to createhilarious and fact-filled scenes that are based on STEM (science,technology, engineering and maths) themes. The scientificmethod will be applied to a cricket game, showing how scienceis all about asking and answering questions. An engineer, tryingto design a new car, will solve complex problems throughartistry, testing and the implementation of trial and error. Therewill also be sketches about technology and maths.

The Chemistry of Scouting is a collaboration between ScoutsACT and the Australian National University’s Research School ofChemistry. Each participant will attend a talk by a scientist,have two hands-on laboratory sessions, watch a fire safetydemonstration, make ice cream using liquid nitrogen and takepart in water-testing, as well as seeing various hands-ondisplays.

Last year, more than 700 workplaces around the countryregistered to celebrate National Science Week by organising aBrain Break Morning Tea. There are no hard-and-fast rules forthe Brain Break: there can be science-related quizzes, groupactivities or a few quick science demonstrations. Other ideasinclude science-themed foods such as molecular models madefrom lollies and toothpicks, cakes decorated with dinosaurs andbiscuits in the shape of lab equipment.

The 2009 report Learning Science in Informal Environments:People, Places, and Pursuits by the National Research Council(USA), found that, by some estimates, individuals spend aslittle as 9% of their lives in schools, and that many oftenoverlook or underestimate the potential for science learning innon-school settings, where people actually spend most of theirtime:

Contrary to the pervasive idea that schools are responsible for addressingthe scientific knowledge needs of society, the reality is that schools cannotact alone, and society must better understand and draw on the full range ofscience learning experiences to improve science education broadly.

I have previously discussed the differences between formal,non-formal and informal education (see October 2014 issue,p. 33; December 2014 issue, p. 38). Learning science in non-formal and informal environments both complements andsupplements formal science education, and education generally.In recent years, the Journal of Chemical Education has beenpublishing about one article per month on science outreach,science camps and public engagement.

One important aspect of National Science Week is that ittakes STEM education out of the school classroom, where STEMexperiences often seem divorced from the daily lives of youngpeople. National Science Week and other out-of-school STEMactivities can help young learners enhance and support theirlearning in other contexts.

See the National Science Week website(www.scienceweek.net.au) to find an event near you. Betterstill, why not run your own Brain Break Morning Tea or otherevent?


National Science Week: taking STEM education out ofthe classroom

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

Scouts Science Night, National Science Week 2015.

Chardonnay is an amazing grape cultivar that seems to thrive inmost wine-growing regions throughout the world. In Australia,the success of Chardonnay was the driving force for our exportmarkets to the UK and Europe. Our ability in Australia to blendacross regions and to use oak and especially oak chips whenthey were not approved for use in Europe gave rise to winesthat were seen by consumers as consistent in style and full offlavour. Jacob’s Creek Chardonnay is a classic example.

One consequence of the Chardonnay success (‘Chardonnaymania’ it was sometimes called) was that many consumers haddifficulty in differentiating between a wine made from theChardonnay grape and wine in general. In a winery where Iworked on occasions, a group of customers came to the cellardoor, asking to try the white Chardonnay. When advised thatthis wine was not made at the winery, they then asked to trythe red Chardonnay. In a survey of UK consumers, Chardonnaywas listed as a wine region in Australia, along with the BarossaValley and Hunter Valley.

The success of Chardonnay led to a surge in plantings inAustralia and other new world wine countries, especially NewZealand and the US (California). In Australia, there are morethan 25 000 hectares planted to Chardonnay or 17% of totalplantings; in California, plantings are more than 38 000 hectaresor 20% of total vines; whereas Argentina has under7000 hectares (3%). Plantings in France are more than47 000 hectares, which is only 6% of total grapevine plantings.

It is perhaps in the Burgundian region of France that theexpression of the Chardonnay character reaches its peak. Thisregion is often regarded as the homeland of Chardonnay. There iseven the village of Chardonnay and the local tourism industry caneffectively piggy-back on the name. However, it is the regionaround Montrachet in Burgundy that produces some of thespectacular and certainly the most expensive wines from thiscultivar. For example, in a list of the five most expensive whitewines, four of the five came from Burgundy (see bit.ly/1TDxaig).

The craze in purchasing high-priced Montrachet led ForbesMagazine in 1996 to run a divorce settlement carton (seeimage) with the caption ‘She gets to keep the chalet and theRolls, I want the Montrachet’. Montrachet even rates a mentionin the movie Hopscotch, in which Glenda Jackson responds to

Walter Matthau’s suggestion of gin and ginger ale for her bysaying ‘Mine was never gin and ginger ale. Montrachet ’69, rightnext to the beer’.

The other region of France where Chardonnay comes to thefore is Chablis. This cool climate region produces wines ofmarked acidity that allows good fruit expression and a steely orgunflint character on the palate. The use of new oak tends tobe minimal, which allows better expression of fruit characters.

Chardonnay is grown in most regions in Australia. During mytime at Charles Sturt University, I had the opportunity toexplore Chardonnay wines made from grapes grown on irrigatedvines in warm to hot conditions. While acid adjustment wasalways necessary, careful vineyard management and winemakingproduced wines of character at a price that suited manyconsumers. The cooler climate regions such as Margaret River,Adelaide Hills, Tasmania and the Yarra Valley produceChardonnay wines of distinctive character. Acid adjustment isstill required because we do not seem to be able to reach theacidity levels that are common in Chablis, for example.

The success of Chardonnay, especially the big, fruity, over-oaked styles, led some wine consumers to seek ABC wines(Anything but Chardonnay; bit.ly/1WQ1hsn). But these ABCdays would seem to be well and truly over, as discussed byMichael Austin recently in the Chicago Tribune(http://trib.in/1sdUIn4). Perhaps part of the reason for theswing back to Chardonnay is better knowledge of the impact ofgrape-growing and winemaking on the characters of the wine.This is where chemistry comes to the forefront! JoannaGambetta and co-authors from the University of Adelaide havereviewed the science behind the aroma composition asinfluenced by production techniques (J. Agric. Food Chem. 2014,vol. 62, pp. 6512−34). I shall look at these findings in my nextcolumn.

grapevine


Chardonnay or anything but

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.

winefolly.com/update/24-funny-wine-quotes/CC BY-NC-SA 3.0

It is perhaps in theBurgundian region of Francethat the expression of theChardonnay characterreaches its peak. This regionis often regarded as thehomeland of Chardonnay.

postdoc diary

I have come to realise that I am good at something that maynot at first appear to be a particularly desirable talent: I’m agood quitter. It’s a weird thing to be proud of, I know,especially in a society that seems to emphasise ‘sticking with it’and ‘being in it for the long haul’. But I’ve actually foundquitting isn’t necessarily a bad thing and sticking with it isn’tnecessarily a good one.

How often have you found yourself with a job, responsibility,relationship or living situation that isn’t working out for you?And how often have you stuck it out out of a sense ofobligation, duty or fear of being in aworse situation than if you quit? I’m sureeach of us could think of at least onejob, apartment lease or relationship thathas gone on too long. Wouldn’t we havebeen better off if we just quit?

So if quitting is often a necessity oflife, doesn’t it make sense to be good atit? The thing is, most people have solittle experience with quitting that theyhave little opportunity to perfect this (inmy opinion) essential skill.

I am not advocating wantonabandonment of all responsibility. No,there are some things that are worthresisting the urge to head out the doorwhen the going gets tough. But somejust aren’t.

Let me give you an example. I recentlyquit a job. This was particularly difficultto do because it was my first job in a newcountry and marked the culmination of along and painful job search (six months). But it was clear tome, from the first day, that I was going to be unhappy in thejob. The work culture wasn’t one that resonated with my valuesand I found the tasks to be far less demanding than I wasanticipating. So on day 5, I walked up to my boss and let herknow that I was quitting.

This was pretty brave, given that I was staring down thebarrel of further unemployment with no end in sight, but Idecided that the opportunity cost of sticking it out was toohigh. Every minute I spent at this job was one I didn’t spendlooking for another. And so I quit and I was unemployed again.And two weeks later I was interviewing for a job withtremendous potential and one I was really excited about. It wasa great interview and I made it to the final round of selectionand only missed out because there was an excellent internalcandidate.

So did I do the right thing by quitting? Especially given thatI sit here typing this as an unemployed scientist? Absolutely! Ihad a shot at a perfect job, which I would not have got if I was

in the other job. I had a great interview experience andimpressed a potential employer who I am still in contact with.None of this would have happened if I hadn’t quit and releasedthe bird in my hand to chase the nicer one in the bush.

Since I consider myself so good at quitting, here are threesmall bits of advice to all the bashful quitters.• Be honest. I told my employer exactly why the job wasn’t

working out. I explained that I didn’t want to be anythingless than an excellent employee and I would prefer they hada candidate in the role who truly appreciated it.

• Be professional. I let my boss know that I would stickaround as long as possible to ease the transition for the newperson. She actually asked me to stay a couple of weekslonger, which I thought was worth it to not sour arelationship. I’ve heard of people giving two weeks noticeand then taking two weeks of personal leave – not really allthat classy.

• Be diligent. I worked just as hard on my last day as on myfirst. I was fast friends with all my co-workers and they weresad to see me leave even though we’d only known eachother for a short time. This is really important to me sincethe last thing I want is to give people a bad impression as Iwalk out the door.So there you have it. My three little steps to being a better

quitter. I encourage you to try it with something small first andsee if you like it. If you don’t, well … you can always quitquitting.

The author is trying to break into the corporate world in Portland, Oregon. It is along-term goal and he isn’t about to quit. Yet.


The gentle art of quitting

iStockphoto/Ximagination

R.N. (Ram Narayan) Chakravarti (1916–2007) was an Indianchemist who spent two years in the late 1940s working on thestructure of the alkaloid strychnine at Oxford with Sir RobertRobinson. Chakravarti returned to India and worked at theCalcutta School of Tropical Medicine before becoming Directorof the Indian Institute of Experimental Medicine. Robinsonvisited him when he was at the Indian Science Congress in 1950but they failed to meet up when Robinson spent a few days inDelhi in 1960 on his way to the IUPAC Natural ProductsCongress in Australia. However, both were great letter writersand they exchanged more than 200 letters over three decades.

In 1986, on the centenary of Robinson’s birth, Chakravartipublished a long article about his work at Oxford, concentratingon unpublished results and the discussions he had withRobinson. In those days before the widespread adoption ofspectroscopic methods, structure determination of naturalproducts proceeded by stepwise degradation. A key step, in thiscase, was the conversion of strychnine into neostrychine. Therewere several known methods for effecting this change but nonegave a good yield, the best, 15%, being achieved by boiling asolution of strychnine with selenium. In Chakravarti’s hands theyield was improved to 50% but the smell of hydrogen selenidemilitated against widespread adoption of the method. Driven todiscover a new procedure, Chakravarti found that a quantitativeyield could be obtained by boiling a solution of strychnine inxylene with finely divided Raney nickel. Others in the lab wereunable to reproduce his success.

Neostrychine is an isomer of strychnine, and is formed bythe shift of a double bond in the bridged ring structure,something that would have been hard to characterise by themethods then available to organic chemists. Chakravartidescribed the change as ‘hydrogenation cum dehydrogenation’and I suppose that’s a good summary of the change that hastaken place, essentially a 1,3-shift of a hydrogen atom.Elemental selenium had long been used, just as elemental sulfurwas, to effect dehydrogenations and it was probably used withstrychnine in an attempt to reveal (as an aromatic ring system)the carbon skeleton of the alkaloid. It’s hard to see howselenium could have produced the observed isomerisation, butsince the yield was so low, and other products were notidentified, I should put the reaction in the anything-can-happen basket. On the other hand, Raney nickel is ahydrogenation catalyst and since the finely divided metal is ahydrogen-carrier, it’s a bit easier to see how it might producethe change.

The failures in the hands of other competent chemists weredue, according to Chakravarti, to their not exactly following themethod he had devised and communicated to them. First, theRaney nickel had to be freshly prepared and well washed withalcohol, and the last traces of alcohol and water had to be

removed byazeotropicdistillation of asmall portion ofthe xylene.Second, the Raneynickel had to bekept in suspensionand this wasachieved byallowing thesolution to ‘bump’as the mixture at the bottom of the flask became superheatedduring the boiling process. Bumping was normally avoided, butit was a good way to stir up the heavy metal powder. The flask,condenser, sand-bath and support stand needed to be robustand well supported to avoid accidents.

Three of the failures were explained in detail.K.H. Pausacker, an Australian postgraduate student, ‘had a fire,due to which a fume-chamber was burnt, because he did not fixthe sand-bath with the tripod stand he used. He went out withhis wife for dinner and on coming back at night he saw the fire’.Professor D.S. Tarbell, a visitor from the University of Rochester,New York, ‘for avoiding the bumping … heated the flaskimmersed in an electrically heated oil-bath. There was, nodoubt, very smooth boiling and no bumping, but the catalystremained practically as a hard cement-like sediment at thebottom of the flask’. Conversion was poor and although therewere no by-products, the difficulty of separating strychnine andneostrychine was a complicating factor. Third, South AfricanA.M. Stephen failed because his Raney nickel catalyst was nogood. Following a published method that began with 300 gramsof the Raney Ni–Al alloy, Stephen reduced everything by afactor of 30 and set off with 10 grams. While proportionatereduction was appropriate for quantities such as solvent volumeand amount of alkali, he was wrong to reduce the reaction timeby a factor of 30 and to use three washings with distilled waterinstead of the recommended 30. ‘I saw the white particles ofscum actually floating on the catalyst prepared by him’, wroteChakrvarti, and ‘his catalyst was not only coated withaluminium hydroxide but there was also presence of thehindering agent, sodium hydroxide, as a consequence of grosslyincomplete washing’.

Needless to say, Robinson was delighted by all this butChakravarti didn’t make many friends.


Chakravarti and the strychnine story

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.

Strychnine

cryptic chemistry

Across1 Changes answers. (9)6 Burn boron and not lift a finger. (5)9 Test court case. (5)10 Vein sites become painful. (9)11 1 Down is one place where one feels

comfortable. (7)12 Dry house wrecked when final bottle

lost but holds water. (7)13 Hikes in wrinkles. (9)16 Program is Par Matches. (5)18 Digger sounds small. (5)20 Chemistry phenomena adversely

centred on naming errors. (9)22 Relation 3719A32. (7)23 Does NaI need to change

nucleobase? (7)25 Can Chairs work out C7H5NO3S? (9)26 Figured on making further

comment. (5)27 Controlled with lines. (5)28 Expel cobalt and mendelevium making

bound ligand and metal. (9)

Down1 In honour of the Russian empire hum

tune 77 badly. (9) 2 Bearing –N3 and making a comeback

in the work of Reed Izatt. (5)3 Lone ute crashed compound. (7)4 Beginning attack. (5)5 Combination shy, sets in chaos. (9)6 Accumulation of publicity. (5-2)7 R2NO

– ion a mixed bag. (9) 8 Neon in 4 Down and argon in 16

Across. (5)14 A form contributing to the structure of

six elements. (9)15 In proportion to my crimes

undermining loss of oxygen. (9)17 Interrupted hanging. (9)19 About painful hit. (7)21 Lover 13 unlucky in general. (7)22 Shining light on Spooner’s

seaman. (5)23 Year in which roman numerals were

first used. (5)24 Order ratio. (5)

events

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

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

Southern Highlands Conference on Heterocyclic Chemistry28–30 August 2016, Peppers Manor House, Moss Vale,NSWwww.chemistry.unsw.edu.au/SHC16

6th International Meeting on Antimicrobial Peptides1–3 September 2016Leipzig, Germanyhttp://peptideconferences.org/imap-2016

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

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

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

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

RACI events are shown in blue.


Researchers have suspected for several years that the flaring ofwaste natural gas from industrial oil and gas fields in theNorthern Hemisphere could be a significant source of nitrogendioxide and black carbon pollution in the Arctic. Research froma NASA-sponsored study lends new weight to that hypothesis.

Nitrogen dioxide is a well-known air pollutant that is centralto the production of ground-level smog and ozone. It is closelyassociated with black carbon (also known as soot), which is anagent of global warming, particularly in the Arctic. In additionto absorbing sunlight while aloft, black carbon darkens snowwhen it settles on the surface. Both processes lead to heatingof the air and the land surface, accelerating the melting ofsnow and ice.

The amount of black carbon that reaches the Arctic is poorlyestimated, but scientists know that any soot could have asignificant impact. ‘The Arctic starts from a very clean state, asthere are no significant local sources of dust or smokepollution,’ said Nickolay Krotkov, an atmospheric scientist atNASA’s Goddard Space Flight Center and a member of a teamexamining the origins of Arctic black carbon. ‘In this kind ofpristine environment, even small anthropogenic sources make abig difference.’

Previous research has suggested that gas flares from oil andnatural gas extraction near the Arctic could be a key source ofblack carbon. But since international inventories of industrialemissions have gaps in observations and in reporting, theyoften over- or under-estimate the amount of pollutants.

Gas flares are an often-overlooked subset in that alreadymessy data set. Regional estimates from Russia, for example,suggest that gas flaring may account for 30% of all blackcarbon emissions. But with few monitoring stations near flaringsites, the scientific community has had great difficulty gettingaccurate estimates of emissions.

Can Li and other researchers at NASA Goddard were recentlyasked by atmospheric modellers to see if they could provideflaring estimates based on satellite data. Black carbon levels inthe atmosphere cannot be directly measured by satellites, butthey can be derived indirectly. Black carbon is associated withnitrogen dioxide and with the total concentration of aerosolparticles in the atmosphere. Nitrogen dioxide and black carbonparticles are often produced at the same time when fossil fuelsare burned.

The modellers were simulating the trajectories of pollutionthrough the atmosphere based on existing, flawed emissioninventories. And their results generally underestimated theamount of black carbon reaching the Arctic compared to whatscientists in the field were measuring directly.

The first step for Li, Krotkov and colleagues was to find gasflares. They compiled ‘night lights’ data from the VisibleInfrared Imaging Radiometer Suite on the Suomi NPP satellite(see back cover). They examined four known fossil fuel

extraction sites: Bakken, North Dakota; Athabasca Oil Sands inAlberta, Canada; the North Sea near Great Britain and Norway;and western Siberia, Russia. The researchers pinpointed gasflares by excluding electric light from nearby towns and roads.

For each study site, Li and Krotkov analysed nitrogen dioxidedata from the Ozone Monitoring Instrument aboard the Auraspacecraft. Fellow NASA researchers Andrew Sayer and ChristinaHsu retrieved aerosol concentration data from the ModerateResolution Imaging Spectroradiometer aboard NASA’s Aquasatellite.

‘We found a pretty good match-up between the gas flaresignals from the night lights and the nitrogen dioxide retrievalsfor two regions – Bakken and the Canadian oil sands,’ said Li.Every year from 2005 to 2015, the levels of atmospheric NO2

rose about 1.5% per year at Bakken and about 2% per year atAthabasca. This means the concentration of black carbonproduced by those flares was also likely on the rise.

The team saw a smaller rise in nitrogen dioxide in westernSiberia, and no discernable flaring signal from well-establishedoil rigs in the North Sea. According to Li, the North Sea signalwas likely obscured by the abundance of nitrogen dioxidepollution in Europe.

Aerosol data were less conclusive. Aerosols tend to linger inthe atmosphere longer than nitrogen dioxide, making it moredifficult to establish whether there was an increase due to oilfield activities, as opposed to general background levels, Sayersaid.

The new observational results fit well with modelling done byJoshua Fu, an atmospheric modeller at the University ofTennessee at Knoxville and a collaborator on the paper. WhenFu and colleagues added the gas flare locations and estimatedemissions into a model of chemical transport in the atmosphere,they were able to reproduce the amount of black carbonobserved in the Arctic by ground stations and aircraft.

Visible Infrared Imaging Radiometer Suite day-night band (back cover) courtesy ofthe Suomi National Polar-orbiting Partnership (NPP) Earth Observation Group.Suomi NPP is the result of a partnership between NASA, the National Oceanic andAtmospheric Administration, and the Department of Defense. Text by Ellen Gray,NASA Earth Science News Team, with Mike Carlowicz.

on the back cover


Connection between gas flaring and Arctic pollution

‘We found a pretty goodmatch-up between the gasflare signals from the nightlights and the nitrogendioxide retrievals for tworegions – Bakken and theCanadian oil sands’

Bakken Formation

Athabasca Oil Sands

‘Night lights’ data of fossil fuel extraction sites Athabasca Oil Sands (Canada) and Bakken Formation (US)from the Visible Infrared Imaging Radiometer Suite on the Suomi National Polar-orbiting Partnership (NPP)satellite (see page 43). Suomi NPP Earth Observation Group

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