November 2017 in Australia 2 19 - Chemistry in Australia ... · Online content aggregators and SEO...

• Compliance problems with European chemical regulations• Google’s Cornforth tribute• Eutectics in your wardrobe

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news & research6 News15 On the market17 Research19 Aust. J. Chem.42 Cryptic chemistry42 Events

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views & reviews4 Editorial5 Your say34 Science ↔ society36 Economics38 Science for fun40 Grapevine41 Letter from Melbourne

36November 2017

24


20IUPAC’s centenary: creating the common languageof chemistryPreparations for the centenary of IUPAC in 2019 are alreadyunder way, reports Mary Garson.

cover story

24 Chemical companies fail to comply with EU regulationsChemical companies are required to document that their chemicals are safebut the majority withhold or submit incomplete information to the Europeanauthorities, allowing dangerous substances to stay on the market.

Chemistry in Australia4 | November 2017

editorial

I suspect (or at least hope) I was among the last few cohorts ofstudents to hole-punch index cards for scientific literaturesearches. Computers and the internet have been a mercifulrelease from those, and annual print indexes of key words are athing of the past. What is the function of key words these days,and how has the internet affected their generation and use?

See and be seenOf course, the first step on the road to being seen is to bepublished. Titles and abstracts have an important role herebecause publishers use them in deciding whether a submittedpaper is worth sending for peer review. Key words can be usedat this stage as an indicator of novelty and relevance. Moregenerally, they can be signposts to peer reviewers and (inbibliometrics) to discipline trends.

A colleague employed by an online content aggregator (abusiness producing databases such as CAS, Web of Science andGoogle Scholar) eloquently explained that the purpose of keywords:

… is primarily to maximise resource discovery. … When you releasecontent into the wild, it is wise to equip it with whatever protectionpossible against being instantly devoured by bigger, stronger playerswith insatiable appetites for attention.

Wanting to be read and cited is nothing new, but we nowhave access to extraordinary volumes of research, and we nolonger need to find what we want by trawling through tables of contents. Readers can discover a paper via a search engine, a specialist indexed database or a link in another paper’sreference list.

Authors want to be seen in different ways, and can choosetheir key words accordingly. If you want to reach out tocolleagues in a very specific field, you might choose differentkey words than if you are looking for a broader audience. Buthow much pulling power do your key words have if thedatabases where your paper appears don’t actually includethem? (More on that later.)

Online content aggregators and SEOThe quest for high visibility has spawned countless contentaggregators and, more recently, the now-burgeoning marketingdiscipline of SEO (‘search engine optimisation’). (If you own awebsite, check your spam folder and you’re bound to find someinformation about it.)

Springer Publishing refers to database indexing and searchengines as a stepping stone to readers, and advises authors tochoose key words with both readers and citations in mind:

Key words are a tool to help indexers and search engines find relevantpapers. If database search engines can find your journal manuscript,readers will be able to find it too. This will increase the number ofpeople reading your manuscript, and likely lead to more citations.

However, the discovery methods I mentioned before lean moreon research paper titles and abstracts than they do on key words.

A colleague with experience in the journal publishingenvironment told me that author-chosen key words are notgenerally requested by online content aggregators. This suggeststhat titles and abstracts work harder online than key wordsbecause they are more accessible. Titles can be found asreferences in other people’s papers, and abstracts are not hiddenbehind database paywalls. So would-be readers are more likely toget to the full text of a research paper based on words in its titleor abstract. They won’t see the key words until they arrive.

If you’ve used Google Analytics, you’ll know that you cantrack data about any number of online activities. (According totheir live internet statistics, Google processes more than3.3 billion searches each day.) Search engines use robots calledcrawlers to collect data, for example on word occurrence.Sophisticated algorithms determine online relevance andpopularity before ranking online content.

So aggregators and SEOs have a lot of power over yourcitations. Consider the Wall Street Journal, which says thepublication’s Google traffic dropped significantly, because oflower search rankings, after it tightened its subscriber paywall(bit.ly/2rGBjfs).

Vocab-controlled key words and indexed key words I said earlier that online content aggregators don’t usuallyinclude author-chosen key words. What they do publish arevocabulary-controlled key words, from extensive and hierarchicalthesauruses. These nested lists of words are available as machine-readable data from, for example, the US Library of Medicine, theprovider that revises and updates Medical Subject Headings(MeSH; bit.ly/1QznhVX). This control achieves consistencybecause it helps readers to find what they’re looking for, even ifthey search using a non-preferred variant of a term. By contrast,author-chosen key words offer flexibility, particularly in instanceswhere terms are very new or specific. The trade-off is relevance ofresults and thus online rankings.

My content aggregator colleague explained that ‘Key wordsenable application of natural-language terms; controlled vocabsare more highly refined and predefined’. However, neither anaggregator nor a search engine index will know that a certainesoteric concept in your paper, which is discussed but notnamed, is important. The only way to draw it out is to give itkey word status. The uniqueness of author-chosen key words isin the name: they are still the most meaningful indicator ofwhat an author most wants to say.

So key words still have unique uses, but knowing which onesappear where will give your choices more mileage.

Choosing your (key)words carefully

Sally Woollett ([email protected]) With thanks to the journaleditors and online content professionals who have discussedthis fascinating topic with me.

your say

Chemistry in Australia 5|November 2017

Historical clarityThe obituary for Dr Peter Wilkinson (September, p. 32) shonelight on earlier truncated communications and why I missedseeing Peter at the spectacular RACI Centenary Congress inMelbourne. The obituary reporting Peter’s time as National RACIPresident, identical to mine (1987–88), activated my pedantgene to revisit the name change for the University of New SouthWales (UNSW). UNSW was incorporated in 1949 and initiallynamed the NSW University of Technology. The timing (1958) ofthe UNSW name change was referenced in an ‘official’ UNSWhistory and repeated in an issue of Chemistry in Australia (June2016, p. 5). In reality, students studying at UNSW in 1960 wereenrolled with the NSW University of Technology.

It is remarkable that Sydney Technical College spawned twouniversities: UNSW (1949) and University of Technology, Sydney(UTS; 1964). It is noteworthy that UNSW set up another twouniversities: Newcastle University (1951) and University ofWollongong (1961).

All of the above institutions evolved from the SydneyMechanics’ School of Arts (SMDA), a precursor for SydneyTechnical College (now TAFE). The SMDA (1833) is still a veryactive institution, and I recently attended a joint lecture sharedbetween SMDA and the Royal Society of NSW (1821). Thecurrent Chairman of the Royal Society of NSW is the well-knownEmeritus Professor Brynn Hibbert FRACI CChem.

So for the record, the name change from ‘NSW University ofTechnology’ to ‘University of New South Wales’ happened aroundthe time the last tram passed by UNSW, 1961 (the nearcompletion of the new light rail construction along AnzacParade, Kensington, is surely another case of ‘back to thefuture’).

Robert F. Ryan FRACI CChem

More science for fun

Ian MacLeod (September, p. 5) was not the only granddad to tryout Jeremy Just’s red cabbage juice pH experiment (June,p. 36) with grandchildren. My eight- and five-year-oldgranddaughters were similarly fascinated by colourful kitchenchemistry’s pH indicator.

Ian Southwell FRACI CChem

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‘Your say’ guidelinesWe will consider letters of up to 400 words in response tomaterial published in Chemistry in Australia or about novel ortopical issues relevant to chemistry. Letters accepted forpublication will be edited (no proof supplied) for clarity, spaceor legal reasons and published in print and online. Full nameand RACI membership type will be published. Please supply adaytime contact telephone number (not for publication).

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news


New way to clean up mercury pollution

The porous polymer cubes (the high surface area version of the polymer) are very effectiveat capturing inorganic mercury in water, organomercury compounds and mercury vapour.Max Worthington

(a) Mercury bead (in green box) contaminating soil and (b) the polymer before (left) andafter (right) capturing the mercury so it can be removed from soil.

Scientists have devised a way to use wastecooking oil and sulfur to extract theneurotoxin mercury from the environment.

For the first time, researchers havedemonstrated that the dynamic new canolaoil polymer can trap the most dangerous andcommon types of mercury pollution –mercury metal, mercury vapour and highlytoxic organo-mercury compounds – whichharm both aquatic and terrestrial systems.

‘Our previous research studied a singletype of inorganic mercury, so this is asignificant advance’, said Dr Justin Chalker,senior lecturer in synthetic chemistry atFlinders University.

‘With the Minamata Convention onMercury coming into force around the worldthis year, this discovery is an importantadvance in protecting the environment andhuman health.

‘We can use this material to protect theenvironment by capturing toxic mercurypollution – a pernicious problem around theworld, causing brain damage and loss of IQpoints in unborn children.

‘At the same time, every atom of themercury-binding material can be derivedfrom industrial by-products, so this is also an exciting advance in recycling and re-purposing waste.’

Chalker and fellow researchers fromaround the world have combined second-hand cooking oil and sulfur – a common,low-cost by-product from petroleumproduction – to produce a new kind ofpolymer to use in remediation of soil, waterand even the air.

After absorbing mercury pollution, thenovel rubber-like polymer changes colour toindicate the job is done. More of theaffordable polymer mixture can then beplaced in the area to continue to process.

The material is being tested in field trialsat mining sites and areas where mercury-based fungicides are used.

Flinders University

There is a reason why whisky is diluted with water before beingbottled. The same reason also makes many whisky enthusiastsadd a few drops of water in their glasses – it makes the whiskytaste better. But why is this so?

Whisky is a chemically complicated beverage. After malting,mashing, fermentation, distillation and maturing, for at leastthree years in oak barrels, the whisky is bottled. However, firstit is usually diluted to around 40% of alcohol by volume by theaddition of water, which changes the taste significantly. Forthat same reason, whisky enthusiasts often add a little water intheir glasses.

But why and how does water enhance the taste of whisky?Up until recently, no one had been able to answer thisquestion, but now Björn Karlsson and Ran Friedman, researchersin chemistry at Linnaeus University, have solved a piece of thepuzzle that will help us better understand the chemical qualitiesof whisky (http://doi.org/10.1038/s41598-017-06423-5).

‘The taste of whisky is primarily linked to so-calledamphipathic molecules, which are made up of hydrophobic andhydrophilic parts. One such molecule is guaiacol, a substancethat develops when the grain is dried over peat smoke whenmaking malt whisky, providing the smoky flavour to the whisky’,Karlsson explained.

Karlsson and Friedman carried out computer simulations ofwater–ethanol mixtures in the presence of guaiacol to study itsinteractions. They found that guaiacol was preferentiallyassociated with ethanol molecules and that in mixtures withconcentrations of ethanol up to 45% guaiacol was more likely tobe present at the liquid–air interface than in the bulk of theliquid.

‘This suggests that, in a glass of whisky, guaiacol willtherefore be found near the surface of the liquid, where itcontributes to both the smell and taste of the spirit.Interestingly, a continued dilution down to 27% resulted in anincrease of guaiacol at the liquid–air interface. An increasedpercentage, over 59%, had the opposite effect, that is to say,the ethanol interacted more strongly with the guaiacol, drivingthe molecule into the solution away from the surface’, Friedmancontinued.

Combined, these findings suggest that the taste and aromaof guaiacol, and similar compounds in whisky, are enhancedwhen the spirit is diluted prior to bottling and this taste maybe more pronounced on further dilution in the glass. So what isthe optimal number of water drops to put in your whisky?

‘How we experience taste and aroma is highly individual.Some people choose to add ice cubes to their whisky, to cool itdown and give it a milder taste. Thus, there is no generalanswer to how much water you should add to your whisky toget the best taste experience’, Karlsson concluded.

Linnaeus University


Why whisky tastes better with water

... in mixtures withconcentrations of ethanol upto 45% guaiacol was morelikely to be present at theliquid–air interface than in thebulk of the liquid.

iStockphoto/Alexey Lysenko

OH

CH3O guaiacol

Australian tiger snakes have ‘hit the jackpot’ because preycannot evolve resistance to their venom.

While that may sound foreboding, University of QueenslandSchool of Biological Sciences expert Associate Professor BryanFry said this discovery had medical benefit for humans.

That’s because tiger snake antivenom has an extraordinarylevel of cross-reactivity against other snake species, and cantherefore neutralise the lethal effects on humans in snakebitecases.

‘The level of conservation in the toxin sequences is not onlyreally unusual, but this is why the corresponding tiger snakeantivenom is so useful in treatments against bites from manyAustralian snakes that affect the blood in the same way’, Frysaid.

‘No other antivenom in the world is so spectacularlyeffective against such a wide range of snakes this way and nowwe know why.’

Fry said the research had overturned a centralparadigm of venom evolution.

‘A long-held belief is that snake venom varieswith diet – that is, as the snakes evolve into newspecies and specialise on new prey, the venomchanges along with it’, he said.

‘Our research has shown that tiger snakes andtheir close relatives have toxins that are almostidentical, despite this group of snakes being almost10 million years old.

‘We worked out the reason was that the toxinstarget a part of the blood-clotting cascade that isalmost identical across all animals.

‘So we have a new addition to the theory ofvenom evolution: that when the target itself isunder extreme negative selection pressure againstchange, then the toxins themselves are undersimilar such pressure.

‘This is a novel twist to the chemical arms racewhich most snake venoms evolve under. But it isone with direct human benefit since this is whytiger snake antivenom is so effective against

treating the effects on the blood by quite a few other Australiansnakes. No other antivenom is so widely useful.’

Fry said normally, snake venom placed pressure on the targetso that animals with some variance were more resistant to thepoison, which in turn put pressure back onto the venom forchange.

‘In this case, if the animals had variation in their blood-clotting proteins, they would die because they would not beable to stop bleeding’, he said.

Fry’s team studied the venom of 16 tiger snake populationsfrom across Australia, including five island populations in theBass Strait, and venoms from 11 other snakes in related genera.

‘This is the most comprehensive examination of this clade ofmedically important snakes ever undertaken, including the firstexamination of the venom of the enigmatic Lake Cronin snakefrom Western Australia’, he said.

‘This study is a great example of the human medical benefitsthat can come from studying evolution.’

The study involving researchers from the University ofQueensland’s Venom Evolution Lab, Swansea University, UK,University of Melbourne, Venom Supplies South Australia,Snakes Harmful & Harmless, Western Australia, and the FaunaVet Wildlife Veterinary Consultancy, Beerwah, is published inComparative Biochemistry and Physiology, Part C (doi:10.1016/j.cbpc.2017.07.005).

University of Queensland

news


Tiger snake toxin overturns venom evolution paradigm

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Girls encouraged to follow careers in STEM

Students building a prosthetic limb. Left to right: Roshan Doherty (St Hilda’s), Kate Kang(Methodist Ladies’ College), Amy Boyd (St Hilda’s) and Jaime Dunn (Methodist Ladies’ College).

More than 100 Year 9 and 10 female students recently learntabout some of the exciting career opportunities available tothem in science, technology, engineering and mathematics(STEM) subjects at an event held at the University of WesternAustralia.

Girls in Engineering Discovery Day is part of the Girls inEngineering program at the University of WA, which issupported by foundational partner Rio Tinto. The event aimedto inspire young women interested in a STEM career by breakinggender stereotypes and encouraging them to pursue a careerthat they are most passionate about.

A report issued by the Office of the Chief Scientist in 2016estimated that only around 16% of Australia’s qualified STEMworkers were female.

The students got involved in activities ranging from workingin robotics and programming miniature robots, to developingprosthetic limbs, using virtual reality systems to createexperiences that help those with physical and mentalimpairments and completing activities to understand howalgorithms, patterns and maths can be used to help solve someof the world’s most complex problems.

A keynote speech by world leader in cancer researchProfessor Christobel Saunders from the University of WA MedicalSchool’s surgery division, who was also a recent recipient of aPremier’s Science Award, was a highlight of the day, withSaunders imparting her knowledge and advice to the students.

Saunders said engineering was a wonderful career for

women, with incredibly broad options and the opportunity tomake a big difference.

‘It’s not just about building roads or machines that go “bang”;engineering is a hugely diverse career that encompasses a lot ofother things within science’, Saunders said.

‘I think inspiring young women is really important and it’salso important to help them realise that there is a spark thereand you really can make a difference in the world through whatyou choose to study.

‘This is an incredibly bright bunch of motivated girls and I’dlove to see them enjoy a rewarding career in STEM.’

St Hilda’s Anglican School for Girls student Amy Boyd, 14, ofBicton said the event was a rewarding experience and opened upmany possibilities of what she might like to study after school.

‘I really enjoyed the work we did using virtual reality, thepossible uses of this technology to improve areas such asmedicine and how it can be used to carry out different surgerieswithout needing to hurt anyone or be invasive’, Miss Boyd said.

‘I’m interested in pursuing a career in chemical andbiomedical engineering, which looks pretty fun and it was greatto see some of the options in practice at the Girls inEngineering Discovery Day.’

Participating schools at the Girls in Engineering DiscoveryDay included St Hilda’s Anglican School for Girls, MethodistLadies’ College, St Mary’s Anglican Girls College, Belmont CityCollege and Governor Stirling Senior High School.

University of Western Australia

news


Ancient pottery testspositive for wine

The storage jar was discovered in a cave in the province ofAgrigento, Sicily. Alun Salt/CC BY-SA 2.0

Chemical analysis conducted on ancient pottery coulddramatically predate the commencement of winemaking in Italy.A large storage jar from the Copper Age (early fourthmillennium BCE) tested positive for wine.

This finding published in Microchemical Journal(http://doi.org/10.1016/j.microc.2017.08.010) is significant asit’s the earliest discovery of wine residue in the entireprehistory of the Italian peninsula. Traditionally, it’s beenbelieved wine growing and wine production developed in Italyin the Middle Bronze Age (1300–1100 BCE) as attested just bythe retrieval of seeds, providing a new perspective on theeconomy of that ancient society.

Lead author Dr Davide Tanasi, University of South Florida inTampa, conducted chemical analysis of residue on unglazedpottery found at the Copper Age site of Monte Kronio inAgrigento, located off the south-west coast of Sicily. He and histeam determined that the residue contained tartaric acid andits sodium salt, which occur naturally in grapes and in thewinemaking process.

It’s very rare to determine the composition of such residuebecause it requires the ancient pottery to be excavated intact.The study’s authors are now trying to determine whether thewine was red or white.

University of South Florida


Charging ahead with zinc–air batteries

A University of Sydney researcher holds up arechargeable zinc–air battery. University of Sydney

University of Sydney researchers have found a solution for oneof the biggest stumbling blocks preventing zinc–air batteriesfrom overtaking conventional lithium–ion batteries as thepower source of choice in electronic devices.

Zinc–air batteries are powered by zinc metal and oxygenfrom the air. The global abundance of zinc metal makes thesebatteries much cheaper to produce than lithium–ion batteries,and they can also store more energy (theoretically five timesmore than that of lithium–ion batteries), are much safer, andare more environmentally friendly.

While zinc–air batteries are currently used as an energysource in hearing aids and some film cameras and railway signaldevices, their widespread use has been hindered by difficultieswith recharging them. This is due to the lack of electrocatalyststhat successfully reduce and generate oxygen during thedischarging and charging of a battery.

Published in Advanced Materials(http://doi.org/10.1002/adma.201701410), a paper authoredby chemical engineering researchers from the University ofSydney and Nanyang Technological University, Singapore,outlines a new three-stage method to overcome this problem.

According to lead author Professor Yuan Chen, from theUniversity of Sydney’s Faculty of Engineering and Information

Technologies, the new method can be used to createbifunctional oxygen electrocatalysts for building rechargeablezinc–air batteries from scratch.

‘Up until now, rechargeable zinc–air batteries have beenmade with expensive precious metal catalysts, such as platinumand iridium oxide. In contrast, our method produces a family ofnew high-performance and low-cost catalysts’, he said.

These new catalysts are produced through the simultaneouscontrol of the composition, size and crystallinity of metaloxides of earth-abundant elements such as iron, cobalt andnickel. They can then be applied to build rechargeable zinc–airbatteries.

Paper co-author Dr Li Wei, also from the Faculty ofEngineering and Information Technologies, said trials of zinc–air batteries developed with the new catalysts haddemonstrated excellent rechargeability – including less than a10% battery efficacy drop over 60 discharging/charging cyclesof 120 hours.

‘We are solving fundamental technological challenges torealise more sustainable metal–air batteries for our society’,Chen added.

University of Sydney

news


Out, damned purple spot!What’s under that purple spot? Italian researchers working inthe Secret Vatican Archive had been struggling to read a five-metre long parchment written in 1244 because it’s covered inpurple spots. Sparing ancient documents from the ravages oftime is a difficult process, and while they are now kept inrooms with carefully controlled environmental conditions, manyhave already been attacked by water, air and even microbial lifefor centuries. The researchers knew that the spots were left bymicrobes that also caused the top layer of the document tosplinter off. Using genetic techniques, the researchers wereable to identify exactly what kind of bacteria were leaving thestains, and hope that this will allow them to restore otherdocuments damaged in this manner.

The microorganisms responsible for purple spots on a 13th-century scroll have been identified in a study in ScientificReports (https://doi.org/10.1038/s41598-017-05398-7).Ancient parchments are commonly attacked by microbes,resulting in purple spots and the detachment of the superficiallayer of the document, which affects the readability. Theauthors hope that their findings may help in the restorationand conservation of ancient parchments.

The five-metre long parchment, A.A. Arm. I-XVIII 3328,written in 1244 for a canonisation inquiry, tells the story of a

young soldier called Laurentius Loricatus who killed a man byaccident. To make amends for his crime, he retired to a cavenear Subiaco, Italy, for the next 34 years. However, thedocument is covered in purple spots, with damage to thecollagen structure significantly affecting its readability. Thedamage is most likely to have occurred prior to the scroll beingmoved to the Vatican Secret Archive at the end of the18th century, where it is now kept under controlledenvironmental conditions.

By performing a genetic analysis of the microbialcommunities colonising the scroll, Luciana Migliore andcolleagues found that Gammaproteobacteria were present in thepurple spots but absent in the undamaged areas of theparchment. The authors suggest that deterioration of theparchment occurred during a process of microbial succession, inwhich Halobacteria – responsible for the rhodopsins thatproduce the purple spots – were replaced byGammaproteobacteria, only leaving the purple stains behind.The authors suggest that further studies could help identify theexact sequence of microbes that produced the rhodopsinsresponsible for the spots and may reveal new approaches to aidin the restoration of documents damaged in this manner.

Springer Nature

G. Vendittozzi


Researchers from Edith Cowan University have developed a wayto modify the atomic structure of iron to create a metal thatcan strip impurities from water in just a few minutes.

The breakthrough, recently published in Advanced FunctionalMaterials (http://doi.org/10.1002/adfm.201702258), offersnew applications in the mining, textile and other industrieswhere large amounts of wastewater are produced.

Associate Professor Laichang Zhangfrom ECU’s School of Engineering was ableto change the atomic structure of iron toform what is known as metallic glass.

Metallic glass gets its name not fromthe fact that it is transparent and can beused in windows, but because its atomicstructure resembles that of glass.

Whereas the atomic structure oftraditional metals is very ordered, withthe atoms forming a grid-like structure,metallic glass atoms have a much moredisorganised composition.

‘It is this disordered atomic structurethat gives metallic glass its veryinteresting and useful characteristics’,Zhang said.

A thin strip of the iron-based metallicglass developed by Zhang can removeimpurities such as dyes or heavy metalsfrom even highly polluted water in justminutes.

‘It works by binding the atoms of thedye or heavy metals to the ribbon, leavingbehind useable water’, Zhang said.

‘This offers a number of benefitscompared to the current method of usingiron powder to treat wastewater. Firstly,using iron powder leaves you with a largeamount of iron sludge that must bestored. Secondly, it is expensive toproduce and can only be used once.

‘In contrast, the iron-based metallicglass we have developed can be reused upto 20 times, produces no waste ironsludge and can be produced as cheaply afew dollars per kilogram.’

Zhang said the technology could havesignificant applications in the textile andmining industries.

‘Mining and textile productionproduces huge amounts of water that iscontaminated with heavy metals and dyesrespectively’, he said.

‘We have already had significant interest from companies inboth China and Australia who are keen to work with us todevelop this technology, including Ausino Drilling Services,whose clients include Rio Tinto and the Aluminium Corporationof China.’

Edith Cowan University

Small technology to clean huge volume of wastewater

Professor Laichang Zhang (right) and PhD student Zhe Jai (left).

A FeSiBCuNb metallic glass.

news


Scientists concerned that global warmingmay release huge stores of methane fromreservoirs beneath Arctic tundra anddeposits of marine hydrates – a theoryknown as the ‘clathrate gun’ hypothesis –have turned to geologic history to searchfor evidence of significant methanerelease during past warming events.

However, a study published in Nature(http://doi.org/10.1038/nature23316)suggests that the last ice age transitionto a warmer climate some 11 500 yearsago did not include massive methane fluxfrom marine sediments or the tundra.Instead, the likely source of rising levelsof atmospheric methane was tropicalwetlands.

While this certainly is good news, thestudy also points at a larger role ofhumans in the recent methane rise.

‘Our findings show that naturalgeologic emissions of methane – forexample, leakage from oil seeps or gas

deposits in the ground – are muchsmaller than previously thought’, saidEdward Brook, co-author and OregonState University paleoclimatologist. ‘Thatmeans that a greater percentage of themethane in the atmosphere today is dueto human activities, including oil drilling,and the extraction and transport ofnatural gas.’

The study suggests that humanemissions of geologic methane may be asmuch as 25% higher than previousestimates. Although not as abundant ascarbon dioxide, methane is a much morepowerful greenhouse gas and thereforethe rising levels are an importantcontributor to global warming.

‘This means we have even morepotential to fight global warming bycurbing methane emissions from ourfossil fuel use’, said lead author VasiliiPetrenko, an associate professor of earthand environmental sciences at the

University of Rochester.Anthropogenic methane emissions are

the second largest contributor to globalwarming after carbon dioxide, but therehas been uncertainty as to the source ofthat methane and whether it haschanged over time, Brook noted. The newstudy sheds light on the issue byanalysing levels of atmospheric methanefrom the last deglaciation in air bubblesthat have been trapped in pristine icecores from Antarctica’s Taylor Glacier.

The researchers were able to estimatethe magnitude of methane emissionsfrom roughly 11 500 years ago bymeasuring radioactive carbon isotopes inmethane, which decay fairly rapidly.Methane released from those marinehydrates and permafrost is old enoughthat any 14C originally present has nowdecayed away.

They found that the amount ofmethane from ancient ‘14C-free sources’

Methane from tundra, ocean floor didn’t spike during previous naturalwarming period

Researchers sample along a transect at Taylor Glacier in Antarctica, with Friis Hill on the left and the Asgard mountain range in thebackground. Courtesy Hinrich Schaefer


was very low – less than 10% of the totalmethane – during the entire range ofsampling, from 11 800 to 11 300 yearsago.

‘A lot of people have painted theArctic as a methane time bomb’, Brooksaid, ‘but this shows that it may be morestable than we thought. Past performanceisn’t always a predictor of the future, butit is a good analogue. We should be moreconcerned about anthropogenic sourcesof methane into the atmosphere, whichcontinue to increase.’

The levels of 14C in the ice coressuggest that the increase in methaneduring the last deglaciation had anothersource – likely from tropical wetlands,said co-author Christo Buizert, OregonState University.

‘Methane is not stored in the tropicsfor long periods of time, but producedevery day by microbial activity inwetlands’, Buizert said. ‘We know fromother studies that rainfall increased inthe tropics during the last warmingperiod, and that likely created morewetlands that produced the additionalmethane.’

Atmospheric methane has increasedfrom 750 ppb in the year 1750 to morethan 1800 ppb today – mostly fromanthropogenic sources, especially leakage

from fossil fuel production, the creationof rice paddies, and cattle ranching, theresearchers say.

‘All of the natural gas that we mine isvery old and leaking inevitably occursduring that process’, Brook said. ‘Naturalgas is considered a cleaner energy sourcethan coal, but it can be a significantproblem depending on how much of themethane is leaking out.’

The key to documenting the source ofatmospheric methane is the pristine icecores of Taylor Glacier in Antarctica,where dry, windy conditions have allowedthis ancient ice to be slowly brought tothe surface. One reason scientists had yetto pin down the sources of methaneduring the last ice age is that the amountof 14C is so small, it takes enormousamounts of ice to get enough air tomeasure the isotope.

It takes some 900 kilograms of ice,running a melting instrument over threedays, to get enough air to produce onesample of measurable 14C. Drilling downin the centre of the ice sheet to find thatmuch ice from the end of the last ice agewould be prohibitively costly and labour-intensive, but the unique conditions atTaylor Glacier – pushing that old icetoward the surface – made it possible.

By Mark Floyd, Oregon State University

ChemRN – a newnetwork dedicated tochemistryElsevier has announced that SSRN, itsworking paper repository and preprintserver, has launched the ChemistryResearch Network – ChemRN.

The launch of ChemRN follows hoton the heels of the launch in June2017 if BioRN, SSRN’s new networkdedicated to biology and its firstoutside the social sciences. BioRNalready has nearly 5000 papers livefrom approximately 6500 authors.

Gregg Gordon, Managing Director ofSSRN, said: ‘The launch of ChemRN ispart of our strategy to extend theexpertise and knowledge we have inbuilding community-driven networks tobenefit even more people in theresearch community.’

Chemistry researchers can shareideas and other early stage research,including posting preprints andworking papers on ChemRN. Users canquickly upload and read papers forfree, across all of chemistry, includingthe fields of energy, environmental andmaterials sciences. It allows users toquickly upload and read abstracts andfull text papers, free of charge.

A preprint is the author’s ownwrite-up of research results andanalysis that has not been peer-reviewed, nor had any value added toit by a publisher (such as formatting,copy-editing and technicalenhancements). A preprint server, orworking paper repository as they arealso known, allows users to sharethese documents.

SSRN has been serving the researchcommunity since 1994 and wasacquired by Elsevier in May 2016. Sincejoining Elsevier, SSRN has completelyredesigned its website, making itcleaner and easier to use. It has alsolaunched full-text search. SSRN is nowworking towards deeper integrationwith Elsevier’s other research products,particularly Mendeley’s referencemanagement software and Pure’sresearch management system.

on the market

... a greater percentage of the methanein the atmosphere today is due tohuman activities, including oil drilling,and the extraction and transport ofnatural gas.

news


Australia’s only Nobel Prize-winner in Chemistry, Sir JohnCornforth, died four years ago, the year after his wife Rita, alsoa University of Sydney chemistry alumnus, passed away – andto mark what would have been his 100th birthday, Googlecreated a ‘Doodle’.

The Doodle was developed for the homepage ofGoogle.com.au and was also run in various countries around theworld; beyond Australia, countries that opted in saw the Doodlefrom 12 am to 12 midnight in their local time on7 September 2017.

Going deaf from an early age, John Cornforth replacedlectures with textbooks and relied on Rita to lip-read and assistcommunication in sign language.

University of Sydney historian, Associate Professor JuliaHorne, said much had been written about Sir John’sachievements, and the important role of his wife and fellowresearcher, Lady Cornforth, was also acknowledged: ‘Someawards have recognised his wife also, for example theUniversity-wide Rita and John Cornforth Medal’, Horne said.

Sir John was an inspired science communicator and gainedhis Nobel Prize for his work on the stereochemistry of enzyme-catalysed reactions, contributions which, as the Guardianstated, stimulated studies on the mechanism of a variety ofenzyme-catalysed reactions, many of which are importanttargets in drug discovery.

University of Sydney Vice-Chancellor and Principal Dr MichaelSpence said the Cornforths personified the university’s traditionof life-long learning and research excellence.

‘The Cornforths made a remarkable contribution to the worldand it was perhaps Sir John’s determination to consult primarysources, and celebrate science as an ongoing endeavour, thatmade his work so precise and compelling’, Spence said.

Head of the School of Chemistry Professor Philip Gale said hefirst became acquainted with Sir John’s earlier work as a youngstudent at Oxford.

‘As a young DPhil student at the University of Oxford, I wasaware of Sir John’s work early work on phenol-formaldehydemacrocycles. It’s a great honour to lead the School of Chemistry

at the University ofSydney whichprovided Sir Johnwith his firstexperiences oforganic chemistry’,Gale said.

Dean of theFaculty of ScienceProfessor TrevorHambley said:‘Having had thegood fortune to bepresent at Sir John’slecture to mark the75th anniversary ofthe RACI, I canattest to what anextraordinaryintellect he was.’

Sydney biologist Dinah Hales remembers Sir John as aremarkable uncle whose career took him, along with Rita aspostgraduates on scholarships, to Oxford University: ‘He was avery active man … he liked to bushwalk, climb mountains andwas also a chess champion’, said Hales, who has retired fromher role as associate professor at Macquarie University.

‘He also helped me in my research, sending me samples ofcompounds and explaining aspects of steroid biology andchemistry’, Hales said.

John Cornforth Jnr, a retired engineer living in Switzerland,previously described in a speech to the Royal Society ofChemistry how his father’s scientific training permeated otheraspects of his life.

‘He had a somewhat scientific attitude to gardening – hewould always read the literature and then experimenthimself … his interest in garden produce tended to stop at thekitchen door (but resume at the dining table).’

Eldest daughter Brenda Osborne, a retired generalpractitioner from the UK, added that herfather was a loving family man who alsohad a great passion in poetry: ‘He had agift of being able to read a poem perhapsonly once and be able to recite itthereafter word perfect.’

Sir John and Lady Cornforth aresurvived by their children John CornforthJnr, Philippa Cornforth and BrendaOsborne.

University of Sydney

Google Doodle honours Australia’sNobel Prize-winner in Chemistry

Rita and John Cornforth. University of Sydney

Google


research

Single crystals are typically brittle inelastic materials: whenstruck or bent, they usually crack, shatter or deform irreversibly.Now, researchers at the Queensland University of Technologyand the University of Queensland have grown single crystals ofa well-known coordination compound, copper(II)acetylacetonate, that are flexible enough to be reversibly tiedinto a knot while maintaining crystallinity (Worthy A.,Grosjean A., Pfrunder M.C., Xu Y., Yan C., Edwards G.,Clegg J.K., McMurtrie J.C. Nat. Chem. 2017,https://doi.org/10.1038/NCHEM.2848). Mechanicalmeasurements indicate that the crystals exhibit an elasticitysimilar to that of soft materials such as nylon, and thus theydisplay properties associated with both hard and soft matter.Using the Australian Synchrotron, the researchers mapped thechanges in crystal structure that occur on bending, anddetermined with atomic precision the mechanism that allowsthe crystals to bend. Under strain, the molecules in the crystalreversibly rotate, and thus reorganise to allow the mechanicalcompression and expansion required for elasticity whilemaintaining the integrity of the crystal structure. Six otherexamples of flexible crystals were also identified.

Flexible crystals tie current thinking in knots

A large family of naphthoquinonemeroterpenoids with potent antibioticactivity, including the napyradiomycins,are biosynthesised fromtetrahydroxynaphthalene (THN) by marinebacteria. However, the prenylsubstitution pattern of thenapyradiomycins, such asnaphthomevalin, contradicts theexpected nucleophilic reactivity of THN.Intrigued by this, researchers at theUniversity of Adelaide and the Scripps

Institution of Oceanography, UC SanDiego, USA, collaborated to investigatethe biogenesis of the napyradiomycinsand discovered a biosynthetically uniqueα-hydroxyketone rearrangement thatexplains the unusual substitution pattern(Miles Z.D., Diethelm S., Pepper H.P.,Huang D.M., George J.H., Moore B.S. Nat.Chem. 2017, https:/doi.org/10.1038/NCHEM.2829). First, a thermal α-hydroxyketone rearrangement wasdeveloped by organic chemists at the

University of Adelaide in a biomimetictotal synthesis of naphthomevalin. Thistotal synthesis provided access toproposed biosynthetic intermediates,which aided the discovery by biochemistsat the Scripps Institution ofOceanography of a bacterial enzyme thatcatalyses the 1,2-shift. Computationalstudies were also conducted to givefurther insight into this mechanisticallyand biosynthetically interestingrearrangement.

Paradigm shift in marine natural product biosynthesis

research


Molecular structures with 1D channels, known as nanotubes,have potential applications in gas sorption, separation andstorage. Recently, Brett Paterson, Brendan Abrahams, PaulDonnelly and colleagues from the University of Melbourne usedhost–guest interactions to direct the assembly of coordinationcomplexes into nanotubes that can act as hosts for smallmolecules (Paterson B.M., White K.F., White J.M.,Abrahams B.F., Donnelly P.S. Angew. Chem. Int. Ed. 2017, 56,8370–4). Two different ZnII complexes of glyoxal-bis(4-phenyl-3-thiosemicarbazone) were prepared from the same startingmaterials by altering the synthetic conditions. When the

complex was prepared in dimethylsulfoxide, a triangular prismstructure formed, involving three ZnII centres and three bridgingligands. In contrast, discrete square coordination nanotubeswith four ZnII centres bridged by four ligands were formed bysimply adding the linear small molecules acetonitrile (CH3CN),carbon dioxide (CO2) or carbon disulfide (CS2). The linearmolecules template the formation of the square coordinationnanotubes and are included as guests within the channels. Thetemplate can be removed and the hollow nanotubes can adsorbtwo molecules of CO2. These approaches could be useful forselective molecular recognition and capture.

Templating coordination nanotube assembly

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., Chem. Sci.) are encouraged to contribute generalsummaries, of no more than 200 words, and an image to David.

Our 2018 media kit is now available atchemaust.raci.org.au.

For further information,contact Mary Pappa: [email protected], (03) 9328 2033

After more than 18 months in the role of editors-in-chief ofAustralian Journal of Chemistry and handling a large number ofsubmissions, we have been periodically both startled andbemused by fortunately rare examples of poor behaviour on thepart of authors. The pressure to publish in a Western journal ofestablished international repute remains very high for manyscientists, but particularly for those hailing from countrieswhere research funding and defined career paths remaindifficult. This has led to recourse by some authors to dubious orunethical means to have their submissions accepted and CVscorrespondingly enhanced. Here are some examples that one orthe other of us has had to deal with (including with otherjournals that we are associated with).• Authorship changes after provisional acceptance of a paper.

On more than one occasion, after the corresponding authorhas been notified of provisional acceptance of theirmanuscript subject to revision, the revised manuscript iseventually returned together with a covering letter outliningthe minor editorial changes and corrections that have beenmade. These have been accompanied by a statement that thechanges have necessitated the addition of one or moreauthors. It is nearly always clear to us that the manuscriptchanges were so minor as to make it impossible that anynew contribution was provided by the proposed newauthor(s). There have been reports of some authors makingthe provisional acceptance letters an opportunity to sell co-authorship places on revised manuscripts (M. Hvistendahl,Science 2013, vol. 342, pp. 1035–1039). We usually refuse toaccommodate such requests unless major revisions wereundertaken in which additional studies were indeedperformed and reported by the new authors.

• Withdrawal of an accepted manuscript. After much effort hasbeen spent in sourcing suitably qualified reviewers, who,themselves, then spend a great deal of time preparingcomprehensive assessments together with a recommendationof provisional acceptance subject to revision, thecorresponding author then notifies us that a decision hasbeen made by their department to send the revised (and nowscientifically much-improved and fully English-edited) workas a new manuscript to another journal, often one with a

higher impact factor. This is despite agreeing at the time ofthe original submission to have the work published in ourjournal (subject, of course, to suitable revision andacceptance). Such behaviour is particularly galling, giventhe waste of the editors’ and reviewers’ considerable effortsduring the manuscript handling process. Naturally, theauthors are blacklisted from making future submissions.

• Simultaneous submissions to journals. On one occasion, areferee in Japan notified us that a manuscript he had agreedto review was identical to another by the same authors thathe was reviewing for a different journal. On questioning thecorresponding author, the excuse was given that it was theresult of a ‘clerical error’ by the department’s secretary, whosent the manuscript simultaneously to different journals. Itwas evident that, in this case, a multiple submission was aneffort to increase the chances of acceptance of themanuscript by any forum. Needless to say, it was rejected byour journal and the authors are now permanently blacklisted.Fortunately, Australian Journal of Chemistry has a very

efficient publishing office (CSIRO Publishing), which, togetherwith its vigilant editorial board, continues to be wise to theseunethical efforts to secure publication in our journal. Yet, wewill undoubtedly continue to be surprised by original efforts to‘bend’ the author submission procedures.

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

aust. j. chem.


The editors’ experiences (part 1): (lack of) author ethics in journal publishing

The RACI’s centenary this yearis a milestone – a uniqueopportunity to recognisewhat RACI has accomplished

and to acknowledge its ongoing roleand responsibility in the future ofchemistry, both nationally andinternationally.

In 2019, the International Union ofPure and Applied Chemistry (IUPAC)will likewise celebrate 100 years. TheUnion was formally registered on28 July 1919. A steering committee setup by the IUPAC Bureau has outlinedthe following vision for the centenary,providing the following backgroundand offering initial ideas. Subsequently,a formal IUPAC100 managementcommittee has been established.Members at large, includingindividuals and national adheringorganisations such as RACI, are invitedto become involved in the variousevents and activities that are planned.

BackgroundAs the curtain rose on the 20th century,chemistry was already a maturescience and a thriving industry. Butcommunication within the industry wasdifficult. There were few generallyaccepted norms for the naming ofchemical compounds and chemistsroutinely did so according to their own

personal preferences, resulting inmultiple names for a single, uniquecompound. This lack of a universallyaccepted language in chemistrycreated a major barrier to the sharingof information, ultimately hinderingefficient research and the rapidadvancement of scientific discovery.Aware of this major barrier to thegrowth of scientific knowledge, agroup of eminent chemists andvisionaries from France, Belgium, Italy,the UK and the US gathered in 1919 tocreate IUPAC.

The IUPAC founders were alsoaware that chemical instrumentationand methodologies were continuouslyevolving towards greater precisionand that more tools were beingdeveloped to assess the chemical andphysical properties of substances.Therefore, IUPAC was given thecharter not only to create anomenclature that would facilitatecommunication within the chemistrycommunity, but also to developstandards and norms for thecalibration and normalisation ofchemical substances.

What in 1919 perhaps seemed adistant and unachievable goal is todaya reality. Thanks to the efforts of alegion of chemists over many decades,advances in scientific research have


IUPAC’sCreating the common language of chemistry

Preparations for thecentenary of IUPACin 2019 are alreadyunder way, reportsMary Garson.

centenary

escalated due to the creation of universallyaccepted standards, terms and nomenclature.

IUPAC as a creator of the commonlanguage of chemistryConceived as an international organisation,IUPAC was born in the aftermath of WorldWar I – an event that negatively affected thepublic’s perspective of science in general, andof chemistry in particular, leading them toquestion the peacetime role of chemistry andthe societal benefits that it provides. Throughthe organisation of regularly scheduledscientific meetings worldwide, IUPAC hasnurtured an international community that hasdealt with all aspects of chemistry, pure as wellas applied.

One hundred years later, IUPAC and thefield of chemistry jointly face many interwovenchallenges such as globalisation, the energycrisis, climate change and other environmentalchallenges. The IUPAC Centenary offers anopportunity not only to commemorate thiscentury-old organisation, but also to rethinkhow IUPAC can better promote and advancethe evolving field of chemistry, particularly aswe move into the era of ‘big data’. It is anopportune time to take a critical and ambitiouslook at IUPAC in order to prepare the globalchemistry community for the future, and toengage effectively with the next generation ofchemists who will lead our science forward.

Chemistry is a major contributor to the well-being of humankind, from the ongoingevolution of better and more effectivemedicines to the production of safe, cleanwater. Some of its major breakthroughs such asthe fixation of nitrogen to make fertiliser or thesynthesis of nylon as a new material havegreatly contributed to health and security, butthere are still major challenges to be met. Fromsocietal challenges such as climate change toalternatives to fossil fuels, chemistry has asignificant role to play in the invention of newsolutions for a better and more sustainablefuture for all. Today’s United NationsSustainable Development Goals(https://sustainabledevelopment.un.org/sdgs)are both a call to and a source of inspiration forchemists. IUPAC, as the internationalorganisation of chemistry, should play a majorrole in creating the platform providing theresources and the network for delivering theneeded solutions more effectively and in a


Friedrich August Kekulé was head of the committeethat began, in 1860, to formulate an internationalnaming system for organic compounds. IUPAC isone legacy of this collaboration.Williams Haynes Portrait Collection. Chemical Heritage Foundation

IUPAC’s early historyIUPAC was formed in 1919 by chemists from industry and academia, whorecognised the need for international standardisation in chemistry.

The standardisation of weights, measures, names and symbols isessential to the well-being and continued success of the scientificenterprise and to the smooth development and growth of internationaltrade and commerce.

This desire for international cooperation among chemists and facilitationof the work of the international, but fragmented, chemistry community werethe earliest characteristics of the Union. Even before the creation of IUPAC,a predecessor body, the International Association of Chemical Societies(IACS), had met in Paris in 1911 and produced a set of proposals for thework that the new Association should address.

These included:• nomenclature of inorganic and organic chemistry• standardisation of atomic weights• standardisation of physical constants• editing tables of properties of matter• establishing a commission for the review of work• standardisation of the formats of publications• measures required to prevent repetition of the same papers.

Although 1911 might now seem an early date for chemists to starttalking about the possibility of and need for international collaborationand standardisation, the first international attempt at organising organicchemical nomenclature – the Geneva Nomenclature of 1892 – grew out of aseries of international meetings, the first of which was organised by Kekuléin 1860.

iupac.org

collaborative and open manner. IUPAC’s legacy is very rich and one

that should be celebrated. After acentury of activity and growth, IUPAChas helped to shape a very dynamicfield of knowledge. Chemistry hasreinvented itself several times since1919, reorganising its structurethrough the creation of newsubdisciplines, fostering new topics atthe crossroads of well-rootedspecialties, and forgingmultidisciplinary communities for theresolution of contemporary problems,

such as the creation of new materialsand environmental studies. Along withits constant effort to shape andconstantly improve the language ofchemistry to reflect newdevelopments, IUPAC has also beeninstrumental in the support ofeducation and in the global growth ofchemistry. IUPAC remains anindispensable resource for chemistry.

Events and activitiesIUPAC has made a formal submissionto UNESCO to request the inclusion of28 July in their calendar of anniversarydates for 2019; the executive board ofUNESCO will advise its decision onthis anniversary date duringOctober 2017.

In July 2019, the global chemistrycommunity will meet in Paris for theWorld Chemistry Congress (WCC)and General Assembly of IUPAC. Thisis not a coincidence! When offering thevenue, French colleagues made thepoint of wanting to celebrate IUPAC’scentenary in the City of Light. The

organisers of the 2019 WCC planseveral events to celebrate the IUPACCentenary, including sessions focusedon IUPAC’s role in the evolution ofchemistry, the revolution ofinstrumentation in chemistry,education and training in chemistry,and some of the scientists who haveworked for IUPAC.

Other activities and events that areplanned include:• the celebration of IUPAC’s role in

creating the common language ofchemistry: This is envisaged as akey theme of the Centenaryactivities. Since the 150thanniversary of Mendeleev’speriodic table will also take place in2019, this will also be highlighted inthe celebration. An online globalcompetition centred on periodictable trivia is planned and will reacha global audience of young studentsin a way that will be attractive tothem, and that will give visibility tothe work of IUPAC over the last100 years.


Inaugurated in 1974, the Palais des Congrès de Paris is the venue for the 2019 World Chemistry Congress and General Assembly of IUPAC.

After a century ofactivity andgrowth, IUPAC hashelped to shape avery dynamic fieldof knowledge.

iStockphoto/rglinsky

• a video to gather, share, andvisualise the history of IUPAC: Thiswill document the manycontributions made by thisinternational organisation increating a common language forchemistry, providing objectivescientific expertise, and developingthe essential tools for theapplication and communication ofchemical knowledge for the benefitof humankind and the world.

• web stories: A series of 25 webstories will further highlight some ofthe essential tools and activities thathave been created by IUPAC, andwill highlight how these tools arecurrently being used by scientistsaround the world every day. Typicalexamples include InChI identifiers,Commission II – Atomic Weights,the various ‘colour’ books such asthe Green Book on quantities,symbols and units used in physicalchemistry.

• interactive periodic table: A group ofyoung chemists will work under theIUPAC banner to increase theparticipation of early careerchemists in IUPAC through storiesof 100 influential chemists (fromhigh school to established careerscientists). One idea they have,again linked to the 150thanniversary of the periodic table, isto create an interactive periodictable organised by ‘jobs’ related tochemistry. Each ‘element’ will be a

portrait of a person who workswithin the field of chemistry, andwill address the diversity ofchemists and/or students ofchemistry worldwide.

• social media outreach: The youngchemists group, working inassociation with IUPAC, also aims toincrease the use of social media asan outreach tool within IUPAC andsimilar chemistry organisations, andto increase the awareness of thegeneral public of how chemistry isintrinsically part of their everydaylife. More than ever, globalorganisations such as IUPAC needto engage better with thecommunity of chemists whorepresent the future of thediscipline.

• logo competition: Prior to theCentenary, students worldwidewere invited to design a logo aspart of the celebration, and thesuccessful entry was then reworkedby a graphic designer (see imageon page 20).

• virtual handshake: Using socialmedia, IUPAC members andchemists worldwide will create avirtual handshake during a globalbreakfast to be held in May 2019 asa prelude to the main celebrationsin July. In this activity, ‘WomenCelebrating a Chemical Moment inTime’, women chemists andchemistry students from around theworld will network by VOIP, Skype,

social media and/or blogs. Somebreakfasts will choose to have paneldiscussions or guest speakers. Awebsite with the video on thehistory and language of IUPAC, andalso for sharing footage, photos andstories post-events, will provideinformation for organisers of thevarious individual breakfast events.

• education and professionaldevelopment: If funding can beobtained, a summer school in 2019aims to teach green chemistry toyoung postgraduate and graduatechemists from the developingcountries, in particular from Africa.

The way forwardThe website for the IUPAC100Celebrations (www.iupac.org/iupac100)will be launched during the latter partof 2017. The IUPAC100 celebrationswill provide a unique opportunity forIUPAC and all its members to highlightthe importance of chemistry in aninternational setting, and to previewthe role of chemistry in the next100 years. It will be excellent ifAustralian chemists joined in! How willyou celebrate?

This article contains content originally published inthe September–October 2016 issue of ChemistryInternational, and has been updated with contentprovided by individual members of the IUPAC100Management and Planning Committee; thiscommittee is chaired by Professor Mary Garson FRACICChem, University of Queensland, together with Dr Laura McConnell, Bayer Corp., USA.


IUPAC President, Natalia Tarasova, says, ‘In2019, we will pause to celebrate oursuccesses and give serious deliberation asto how IUPAC can best continue in the yearsahead to serve as an advocate for the freeexchange of scientific information for thebenefit of humankind worldwide. While thiscelebration is just one moment in time, wehope that it will have a lasting impactthrough events that will advocate the valueand importance of science literacy tostudents worldwide, inspire youngergenerations of men and women to becomethe innovative chemists of the 21st centuryand beyond, and have a positive influenceon the public’s perception of science ingeneral and chemistry in particular.’ Courtesy IUPAC

For the past ten years, it hasbeen the responsibility ofEuropean chemicalcompanies to ensure that their

products do not contain substancesthat are harmful to human health or tothe environment. To a large extent, thesystem depends on trust and now itappears that this trust has beenmisplaced.Chemical companies inEurope do not adequately report theharmful effects that their productscould inflict on people and theenvironment. This means that we maybe exposed to various types ofdangerous substances, such asendocrine disrupting chemicals –substances that may interfere with the


Chemical companies

fail to comply with EU regulations

BY JOHANNE UHRENHOLTKUSNITZOFF AND IDA ERIKSEN

Chemical companies are required todocument that their chemicals are safebut the majority withhold or submitincomplete information to the Europeanauthorities, allowing dangeroussubstances to stay on the market.

iStockphoto/aaron007

hormone system with negative side-effects for people and the environment.

So says Henrik Holbech, from theEuropean Chemicals Agency’s(ECHA) expert group on endocrinedisruptors. The information thatchemical companies are obligated tosubmit to the agency about harmfulsubstances in their products is oftenmissing or wrong, he says.

‘Unfortunately I can’t give concreteexamples since the expert group’swork is confidential. But overall a lot ofstatutory data are missing. There’s alsoexamples of data sitting with thechemical companies from studies thatthey conducted, but haven’t sharedbefore we force them to do so. It’s veryfrustrating and a big problem forregulating harmful substances’, saysHolbech.

In 2016, an ECHA test revealed that72% of company reports were missingimportant information on substancesthat they produce or import. Screeningby German authorities in 2015 showedthat just one of 1814 so-called ‘datapacks’ that companies had submittedmet the authority’s requirements.

‘An obstacle to protectingpublic health’The situation is so bad that the directorof ECHA, Geert Dancet, sent an emailto the chemical industry in April 2017,demanding an immediateimprovement so that the authoritiescould do their job.

Dancet wrote that ‘the failure ofcompanies to comply with therequirements of EU chemicalslegislation is a fundamental obstacle toECHA’s efforts to protect publichealth.’

If companies do not improve, thenthis will have severe consequences, hewarns.

‘The current data is simplyinsufficient to make a well-foundedassessment of the risk of a chemical.This has two significant consequences:we waste our time hunting harmlesssubstances and, far worse, may notprioritise the most worryingsubstances.’

The extent of this lack of informationon chemicals in the market placesurprises the Danish ConsumerCouncil THINK Chemicals.

‘It’s unacceptable that companiesreport insufficient information on anyeffects of these substances, as the spotcheck shows. This must be thefoundation of the EU’s work onchemicals, and it’s the companies’responsibility. They owe us consumers,who eventually buy their goods, to liveup to that responsibility’, says projectmanager Stine Müller.

Scientific data omittedEuropean companies have beenobligated to submit all available andrelevant scientific data to ECHA since2007. This applies to chemicals thatthey produce themselves or importfrom other parts of the world.

But when the experts, includingHolbech, reviewed the data packs itseemed that ‘very often’ crucialscientific data on chemicals aremissing.

‘In the meantime we see that suchdata already exists, but the companiesdon’t share it, and this is especiallyproblematic if they show harmfuleffects’, says Holbech.

‘I don’t think that chemicalmanufacturers are trying to put harmfulsubstances out into the market place.It’s probably more about takingadvantage of the political uncertainty

that still exists around many of thesepotential endocrine disruptingsubstances’, he says.

Danish Environment Agency: itdoes not look like an honestmistakeThe Environment Agency in Denmarkis well aware of the problem, saysMarie Louise Holmer, who works withendocrine substance regulation inDenmark.

Chemical companies regularly tryto avoid testing their chemicals byposting earlier decisions for othersubstances.

Her colleague, Magnus Løfstedt,who is responsible for the DanishEnvironment Ministry’s adoption ofREACH legislation, suggests that someof the failures may be honest mistakes,but this is still problematic.

‘I don’t want to argue that the rulesare clear and we certainly findcompanies that trade in good faith,despite not complying with all therules. But from this study on the qualityof the data packs that they mustsubmit, many companies clearly evadethe rules regarding standardinformation requirements’, saysLøfstedt.

Many companies do their bestChemical manufacturers andimporters in Denmark are aware thatdata packs are not as good as theycould be. But this does not mean thatpeople are cheating the system, saysKarin Klitgaard, head of environmentalpolicy from the Confederation ofDanish Industry.

‘It’s not our experience that the datapacks are deliberately neglectful. Our


For endocrine disrupters such as bisphenol A(pictured), companies are obligated toconduct a single test if they produce orimport more than 1000 tons of thesubstance a year. Therefore, it is importantthat companies reveal all existing scientificdata on the effects of endocrine disrupters.

In 2016, an ECHAtest revealed that72% of companyreports weremissing importantinformation onsubstances thatthey produce orimport.


The European Chemicals Agency (ECHA)has added the substanceperfluorohexane-1-sulfonic acid to theCandidate List of substances of very highconcern (SVHCs). Entries for bisphenol Aand four phthalates have been updatedto include endocrine-disruptingproperties for human health. TheCandidate List now contains174 substances.

Perfluorohexane-1-sulfonic acidbelongs to the group of per- and poly-fluoroalkyl substances (PFASs). Thisidentification is part of a regulatoryactivity, targeting this large substancegroup with the aim of clarifying theconcerns and regulating the substances,as necessary. The aim is also to avoidundesired substitution with other PFASs.Several PFASs have already beenidentified as SVHCs, one group (PFOA andrelated substances) is now restricted, onerestriction is under preparation and manyassessments are underway.

The bisphenol A entry was updated toreflect an additional reason for inclusiondue to its endocrine-disrupting propertieshaving adverse effects on human health.Bisphenol A was included in theCandidate List in January because of itstoxicity to reproduction.

The entries for benzyl butyl phthalate,bis(2-ethylhexyl)phthalate, dibutylphthalate and diisobutyl phthalate werealso updated because the EuropeanCommission has decided on theirendocrine-disrupting properties.

The Candidate List is a list ofsubstances that may have serious effectson human health or the environment.Substances on the Candidate List are alsoknown as ‘substances of very highconcern’. The aim of publishing such alist is to inform the general public andindustry that these substances arecandidates for possible inclusion in theAuthorisation List. Once they are on theAuthorisation List, industry will need toapply for permission to continue using

the substance after the sunset date.Companies may have legal obligations

resulting from the inclusion of thesubstance in the Candidate List. Theseobligations may apply to the listedsubstance on its own, in mixtures or inarticles. In particular, any supplier ofarticles containing a Candidate Listsubstance above a concentration of 0.1%(weight by weight) has communicationobligations towards customers down thesupply chain and consumers.

In addition, importers and producersof articles containing the substance havesix months from the date of its inclusionin the Candidate List (7 July 2017) tonotify ECHA. Information on theseobligations and related tools areavailable on ECHA’s website.

European Chemicals Agency. A table of changes isavailable at https://echa.europa.eu.

ECHA headquarters in Helsinki. Kaihsu Tai/CC BY-SA 3.0

Changes to ECHA Candidate List

The Candidate List is a list ofsubstances that may have seriouseffects on human health or theenvironment.

members spend an enormous amountof energy correctly registering andreporting substances. No one wants tomake mistakes and send harmfulsubstances out into the market place’,she says.

In fact, companies want morecontrol over the data packs, saysKlitgaard.

‘Those who don’t do it rightundermine the entire system andmake the rest look bad. So we wantECHA to reveal the data packs thatdon’t meet their requirements andenforce the rules better’, she says, andadds that REACH legislation wasdesigned to prevent substances being

sold if there was not enoughinformation regarding their effects.

Only 5% of data have beencheckedRight now, ECHA cannot do much toencourage companies to improve theirdata reporting, says Holbech.

ECHA have spot checked just 5% ofcompany reports and so there areprobably many more undetectedincidences. By the time ECHAbecomes aware of any potentialharmful effects, the products arealready on the market, he says.

Hence, the Danish ConsumerCouncil THINK Chemicals would also

like to see the rules tightened, thoughthey regret that such steps arenecessary.

‘The REACH requirements shouldcertainly be met and if they’re not, thenthe EU should have tools to ensure thatthey are. But it is of course sad that ourauthorities need to use extra time andresources to control rather than workmore pro-actively for consumersafety’, says Müller.

Johanne Uhrenholt Kusnitzoff and Ida Eriksen areregular contributors to ScienceNordic. Originallypublished as part of a series on endocrine-disruptingchemicals: http://sciencenordic.com/endocrine-disrupting-chemicals. Reused withpermission.


Secure a piece of chemical historyRemember the RACI now and in years to come with this limited edition publication celebrating the Institute’s centenary year.

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

160 pages of perspectives, profiles, facts and photos tell the story of RACIfrom 1917 to today.

November 2017

Professor Mark Buntine, Centenary Congresschair, speaking at the welcome reception. Photographer at Large

The first female presidents of theAsian Federation for MedicinalChemistry. Associate ProfessorRenate Griffith (right), AFMC presidentin 2016 and 2017, and chair of theorganising committee forAIMECS2017 at the CentenaryCongress, is handing over the flag tothe next president, Professor Esin Aki-Yalcin from Turkey. Esin will becomepresident of AFMC next year andorganise AIMECS2019 in Turkey.Courtesy Renate Griffith

The opening ceremony, in one of theplenary halls. Photographer at Large

The RACI Centenary Congress was aconfluence of chemistry, creativity andcamaraderie. It was also a time forcolour, collaboration and celebration.

from the Centenary Congress

Chemistry in Australia28 |

November 2017

Professor Frances Arnold, plenary speaker:‘This was a great meeting – I really enjoyedbeing in Melbourne, and the science wassuper. Here’s a photo of three of your plenaryspeakers (from left): Dr Laura Kiessling,Professor Frances Arnold, Professor MollyStevens) enjoying dinner at Il Cantuccio on mybirthday!’ Courtesy Frances Arnold

A winter theme at theCentenary CongressCelebration dinner.

Visualisation of RACI100tweets during the Congress. Stuart Palmer

Photographer at Large

Micahel KAssiou

Chemistry in Australia 29|


The perfect complement to a conference. Photographer at Large

The first female president of RACI’s first 100 years, Dr Doreen Clark(right), with Dr Vicky Gardiner, who will be the first female presidentof RACI’s second 100 years. Courtesy Vicki Gardiner

Chemistry goes on ice for an evening. Photographer at Large

One of the awards presented at the Academic Sharp Brain event.Photographer at Large



Student and poster sessionsattracted plenty of interest. Oliver Jones

How many Fellows can you fit on anescalator? Photographer at Large

Professor MartynPoliakoff (at theMelbourneMuseum),keynote speaker:‘Great conference,fantasticorganisation but Ionly saw onekangaroo!’Martyn Poliakoff

RACI: a century of bonds, published as part of centenarycelebrations and given to Congress delegates. Photographer at Large


The RACI Victorian Branch’s Women inChemistry (WinC) committee is one of themost active groups of the branch,regularly running networking and careerdevelopment events throughout the year.At the recent RACI Centenary Congress inMelbourne (23–28 July 2017), WinC hadan active presence throughout theconference. They held two events overthe course of the week, and found theengagement with local, interstate andinternational colleagues to be highlyrewarding.

The first event was a dinner on theMonday night of the conference, held ata local South Wharf restaurant alongMelbourne’s Yarra River. More than 50guests joined WinC for the evening, withspecial presentations from five of thecongress’ plenary and keynote speakers:Laura Kiessling (University of Wisconsin),Sally Brooker (University of Otago),Vivian Yam (University of Hong Kong),Andrea Robinson (Monash University) andZaiping Guo (University of Wollongong).Each of the speakers provided anecdotes

of their research experiences,highlighting ‘not to give up too easily ortoo early’, ‘be passionate’ and the‘importance of a supportive network’.Overall, it was an enjoyable and inspiringnight for all in attendance, and afantastic networking opportunity for thestudents and early career researchers,who spent the evening in conversationwith both the speakers and members ofthe WinC committee.

The second WinC event was a‘Supporting Women in Chemistry’discussion panel, held on the Thursdayafternoon. Guest speakers on the panelwere Dr Marguerite Evans-Galea (IndustryMentoring Network in STEM), Dr AnnabellaNewton (Victorian WinC committee) andDr Katherine Locock (RACI EquityCommittee). Each of the speakers gave anoverview of the activities of theirrespective support networks, includingupcoming events, and then participated ina rigorous Q&A session with the audience.This was the first event for which WinClive-tweeted updates for those whocouldn’t attend the event in person, whichwas filled to capacity. In addition toWinC’s own online engagement, it wasgratifying to see that guests at the panelevent also contributed their thoughtsusing the same hashtag, #supportWinC.Following from this social media success,in future the RACI-VIC WinC committeewill continue to use this hashtag topromote their events.

The WinC committee wish to thankthe RACI Congress organisers for helpingto facilitate inclusion of these twosuccessful events in the program. If youwish to engage with the RACI-VIC WinCcommittee, keep watch for the hashtag#supportWinC; or if you wish to be addedto the WinC mailing list, please [email protected]. To stay apprised ofall their upcoming events, visitwww.raci.org.au/branches/vic-branch/women-in-chemistry-group. TheWinC committee is pleased to welcomeall members of the scientific communityto attend their events, which are notexclusively aimed at women or chemists.

Dr Susan Northfield MRACI is Secretary for RACI-VICWomen in Chemistry Committee.

Supporting women in chemistry

Guests at the RACI Congress Women inChemistry dinner, held at South Wharf.

Guests for the ‘Supporting Women in Chemistry’ panel event, joined by members of theWinC committee. Back (from left): Yvonne Mah, Marguerite Evans-Galea, Annabella Newton,Amy Heffernan, Katherine Locock. Front (from left): Belinda Abbott, Susan Northfield.



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What is your best method and is it disclosed in yourpatent?Dr David Herman, FB Rice

A requirement for obtaining a validAustralian patent is that thespecification must disclose the ‘bestmethod’ known to the applicant ofperforming the invention. epurpose of the best methodrequirement arises from the quidpro quo of the patent system – thatthe applicant must disclose the

most effective means of performing an invention for the public to beable to research and develop further following its publication and tobe commercially free to use once the granted monopoly expires, andthat the applicant does not omit information that gives the bestresults.

So what does disclose the ‘best method’ exactly mean? Givenfailing to do so can render a patent invalid in Australia, it is essentialthat this requirement is properly understood.

What is the best method?e best method is related to the nature of the invention.Importantly, the best method is not determined with sole referenceto the claims. If the claims of the invention relate to a product per se(i.e. a chemical compound), the specification may still need toinclude the best method for the product’s manufacture, along withthe applicant’s best version of the product.

In particular, if there are numerous possible methods formanufacturing the product, which may vary the properties of theproduct, the applicant is required to disclose the best method theyuse to make the product. is may, for example, be a new method ofisolating the product per se, or could merely be one optimised singlestep in what otherwise would be a routine procedure; for example,the selection of a specific drying temperature when makingpharmaceutical tablets by conventional processes.

ere is no need to explicitly state in the patent specification that‘the best method known to the applicant is ...’, or if more than onemethod is included, to indicate which method is the best, provided itis disclosed in some shape or form.

When is the best method assessed?e best method requirement is assessed on the basis of theapplicant’s knowledge at the time of filing the complete application.is will include the knowledge of the inventors and any othercontributors to the research. Should a better method be developedprior to filing the complete application (i.e. during the priorityperiod), it must be included in the complete specification. ecomplete specification does not need to be amended if a bettermethod is developed aer the complete specification filing date.

Can the best method be added in later?Australian patent law now prohibits any amendment that extends thedisclosure of a patent specification. Put simply, an amendment toinclude something new about how to perform the invention is notallowable.

Australia is now out of step with other countries on this best methodrequirement. A common strategy overseas may be to pursue the bestproduct in one patent and its best manufacture method for making itin a separate patent. A best manufacturing method may also wish tobe retained as a trade secret or in-house knowledge. However, in viewof Australia’s requirements, withholding the best method from apatent application runs a risk of it being found invalid. For more information, email [email protected].

science ↔ society


In 2016, conservative, pro-Brexit, British politician MichaelGove announced that people in England ‘… have had enough ofexperts with organisations from acronyms saying that theyknow what is best and getting it consistently wrong’.

In the US, Donald Trump famously doesn’t believe any expertwho doesn’t agree with him. Our most recent former PrimeMinister Tony Abbott has also been accused of having trustissues.

Growing distrust of experts is linked with changing social andpolitical climates. But it also stems from misunderstandings aboutwhat experts are, and what their obligations to society entail.

At their heart, criticisms of experts often imply that they areservants, commodities or so vested in their field they can’trelate to reality.

To restore trust in experts, we need to remember they are,first and foremost, human beings.

How detractors define and judge expertsIt’s probably safe to assume politicians are working from arelatively simple definition of ‘expert’, such as: ‘an expert is aperson with specialist knowledge not commonly held, or likelyto be understood, by a layman’.

When people like Trump make assertions about the right andproper role of experts in public conversations, they appear to

have an implicit list of infringements that experts must nevertransgress.

Expressing values or opinionsDetractors claim that when speaking as an expert, the thingsyou say in public should be untainted by your values andopinions. In essence, you should be a passive conduit forinformation or facts.

University of Colorado Professor Roger Pielke offers a subtledisdain for experts occupying this position when he critiquesthe ‘stealth issues advocate’, a role ‘characterised by the expertwho seeks to hide his/her advocacy behind a facade of science,either pure scientist or science arbiter’.

Deviating from the straight and narrowCritics of experts believe that should you even appear todeviate from your role as a neutral presenter of facts (forexample, by offering policy advice), you are no longer an expertand/or cannot be trusted.

This is typified by Myron Ebell when he was head of DonaldTrump’s Environmental Protection Agency transition team. Hesaid:

[…] whenever you hear an environmental expert, think that he is anurban eco-imperialist.

Rejection of the ‘expertariat’: In June 2017, the Trump administration formally advised the United Nations of their intention to withdraw fromthe Paris Agreement. The Paris Agreement was reached by heads of delegations at the 2015 United Nations Climate Change Conference inParis (pictured). Presidencia de la República Mexicana/CC BY 2.0

Distrust of experts happens when we forget they arehuman beings


Making mistakesThose who criticise experts assert that if you get somethingwrong, you are no longer an expert and/or cannot be trusted.Myron Ebell referred to experts as ‘the expertariat’, saying:

The people of America have rejected the expertariat, and I think withgood reason because I think the expertariat have been wrong about onething after another, including climate policy.

All of these criticisms forget one thing: experts are humanbeings.

To suggest that the benefits of expertise can be delivered‘value-free’ is naive. Like all people, experts are influenced bypolitics and biases, emotions and beliefs. They are motivated,active agents who create, process and communicate knowledge.Experts are not passive conduits.

The reality of the expertTo consider the role of experts in public debates, I’m drawing onmy own area of expertise: science communication. In the spiritof this article, I should note that I claim expertise here basedon nearly 20 years of university-based research, practice andteaching as well as my experience providing consultancies inAustralia and around the globe.

In my realm, the most interesting grist for discussionsaround experts and trust turns up wherever science-related (butnot always science-based) assertions are flung around incontests over socially contentious issues.

Climate change action, the acceptance of geneticallymodified foods, and compulsory childhood vaccination are threeclassic examples where this regularly plays out in public.

Of course, in examples like these, the role of expertise is notstraightforward. For starters, exactly what constitutes pertinentspecialist knowledge is itself up for debate.

Scientific aspects of disagreements about climate change,genetic modification or vaccination are regularly accompaniedby arguments grounded in social, political, economic and

religious concerns. And well they should be – these are not uni-dimensional issues. It’s not simply a matter of ‘getting someexpertise’; it’s also about working out which expertise isrelevant, and to whom.

In an ideal world, the evidence-based assertions of expertswithstand evidence-based challenges, and are modified wherethey are found wanting. It’s through the open, honest,systematic contest of ideas among experts that the best ideasemerge.

Clearly, the place of the expert in public conversations onthese issues depends on many factors: the goal(s) of theconversation; the knowledge, interests and positions of theparties involved; and importantly, the types of people whomight be ‘listening in’.

But more, it should also depend on what the expertsthemselves want to achieve. Like anyone else, experts havetheir own motives, even when overtly wearing their expert hat.

Traditionally, an expert’s motivation for participating inpublic conversations as an expert will be rooted in a desire toinform, guide, advise or warn based on their specialistknowledge.

But equally – and often simultaneously – they could bedriven to participate because they want to engage, inspire orentertain. They themselves may also hope to learn from theirparticipation in a public conversation.

Or maybe they just want to be noticed (and there’s nothingwrong with that).

So, what’s the place of experts in publicconversations?Assessing the actions of experts using criteria that downplay,and even ignore, the fact that they are people makes it easierto admonish them and dismiss their expertise because they dareto have opinions, to make mistakes, or to pick a side.

US Navy Professor Tom Nichols says we live in:

[…] a manic reinterpretation of ‘democracy’ in which everyone musthave their say, and no one must be ‘disrespected’.

This is a place where, at the extremes, positions put forwardby experts are deemed suspect because they come from experts.

In a world where facts and logic are considered malleable,and where powerful, influential interest groups cast doubt onthe notion of expertise itself, it’s the place of the expert inpublic conversations to help turn this tide.

It’s my opinion that the expert should strive to be seen asmore human, to embody at every opportunity their position as apart of society, as a person who has interests and opinions andalso expertise.

How they choose to do this, however, should be up to them.

Rod Lamberts is Deputy Director, Australian National Centre for Public Awarenessof Science, Australian National University. First published atwww.theconversation.com.

Detractors claim that whenspeaking as an expert, thethings you say in publicshould be untainted by yourvalues and opinions. Inessence, you should be apassive conduit forinformation or facts.


Central to many of the approaches to greenhouse gas mitigationis the removal of carbon dioxide from gaseous emissions so itdoes not add to the greenhouse burden of the atmosphere.When extracted, the gas can be sequestrated in deepunderground storage facilities. In the extreme, there are nowseveral proposals to extract the gas from the atmosphere forgeo-sequestration. Here I will discuss the current practice andeconomics of carbon dioxide separation from streams of mixedgases in industry.

Carbon dioxide is found as a waste (unwanted) gas in a widevariety of streams in the hydrocarbon processing and chemicalindustry and many different methods are used to remove it.Generally, removal is accomplished by process plant asillustrated below. The gas to be treated flows into the base oftower A at pressure and rises against a descending stream ofabsorbent. The treated gas (carbon dioxide depleted) exits thetop of the tower. Absorbent loaded with carbon dioxide exitsthe base of the tower and is pumped to a regenerator tower B

where the carbon dioxide is desorbed from the absorbent, oftenby boiling the absorbent by means of a heater C, and exits thetop of the tower. Regenerated absorbent is pumped to the topof tower A.

Most commonly, absorbent regeneration is accomplished byheat (boiling the absorbent), and to optimise efficiency of theprocess the streams passing between the towers pass throughheat-exchangers.

The choice of absorbent (process) is determined by thenature of the gas being treated. Some processes use physicalabsorbents with the rate and efficiency of absorption of carbondioxide being determined by Henry’s law. The table listscommon components in gases to be treated, together with theirnormal boiling points – the value for carbon dioxide iscomputed. For design purposes, the process is built around theremoval of a key gas (carbon dioxide) to a specified level. As aconsequence, to a first approximation, gases present withhigher boiling point are also removed. For example, in the case

H2 20.4

N2 77.4

CO 81.7

O2 90.2

CH4 112

CO2 (computed) 175C2H6 184.6

C2H2 188.4

H2S 213.5COS 223

C3H8 231.1

NH3 240

i-C4H10 261.4

SO2 263.2

n-C4H10 272.7

CH3SH 279.1

NO2 294.3

HCN 299

i-C5H12 301

CH3CH2SH 308.2

n-C5H10 309.2

CH3SCH3 310.5

CS2 319

n-C6H14 341.9

C6H6 353.2

c-C6H12 353.8

n-C7H16 371.6

H2O 373.2

n-C8H18 398.8

iStockphoto/nielubieklonu

Separating CO2 in industry

economics

Carbon dioxide removal from industrial gases.

Boiling points of gases pertinent to CO2 removalGas Boiling point (K) Gas Boiling point (K)


of carbon dioxide removal, any hydrocarbons present with ahigher boiling point will also be stripped from the gas.

An early process (RectisolTM) uses methanol, which is chilled(to typically –40°C) so the process requires refrigeration plant.This process is good at handling highly fouled gases fromgasifiers and the like and is able to strip out high-boilinghydrocarbons and tars. The choice of a low-boiling solvent suchas methanol facilitates separation from these materials andmethanol recycle. Originally used in coal gasifiers, such aprocess would be used to clean gases from bio-gasification ofrenewable feedstock such as wood waste and bagasse. Newerprocesses use higher boiling solvents to avoid the refrigerationrequirement or mixed absorbents to improve selectivity.

To a large extent, membrane processes operate in a similarmanner, as shown in the following diagram. High-pressurecarbon-dioxide-containing gas enters one side of a unit separatedinto two by a membrane. Carbon dioxide ‘dissolves’ in themembrane and passes through the membrane to the low-pressureside of the unit. Adequate separation efficiency is improved byoperation of multiple units in series and recompressing andrecycling the tail gases. Problems arise when the gas to betreated contains higher boiling compounds that also dissolve anddegrade the membrane, such as aromatics. This has occurred incarbon-dioxide-rich natural gas in central Australia.

In many instances, hydrogen sulfide removal is also requiredalong with the carbon dioxide. As the table shows, hydrogensulfide will also be removed with physical absorbents. However,both of these gases are acid gases and there are a large numberof processes that use this fact to improve removal efficiency byusing an alkaline absorbent. These processes get over thelimitations of Henry’s law absorption capacity and kinetics bychemically reacting the acid gases. As will be appreciated, thechoice of absorbent is limited by the need to form a salt thatcan be easily reversed in the regenerator:

CO2 (or H2S) + absorbent → absorbent–CO2 + heat

Application of heat in the regenerator liberates the acidgases. Alkanol amines are widely used for removing carbondioxide and hydrogen sulfide from natural gas, heavierhydrocarbons being first removed upstream so they do notinterfere with the process.

Another absorbent used is hot potassium carbonate (theBenfield process), which forms a bicarbonate upon contact withcarbon dioxide. This process is commonly used in ammoniasynthesis plants where ample steam is available for processoperation (near 100°C) and absorbent regeneration. Overall, theprocess is less energy intensive than amine or physical solvent-type processes, and ammonia synthesis gases (nitrogen andhydrogen) are effectively insoluble in the hot potassiumcarbonate solution, which minimises losses.

The economics of gas treatment and the choice of theprocess to be used are strongly dependent on the nature of thegases to be treated. At one end of the spectrum is the Rectisol-type process, which can, more or less, treat any gas. Minimisinglosses and extracting and separating unwanted products such ashydrocarbons and tars requires a lot of process equipment andhence high capital cost. At the other extreme, chemicalabsorption processes are well established for treating gaseswith relatively few unwanted species.

Most natural gas contains some carbon dioxide. This isusually extracted and exhausted to the atmosphere. Onlyrecently as fields higher in carbon dioxide are developed havethere been proposals for carbon dioxide geo-sequestration. Forexample, at the Gorgon field in Western Australia (10–20%carbon dioxide), the developers (Chevron) remove and geo-sequestrate carbon dioxide so that the final gas meetsspecifications for production of LNG or pipeline transmission toPerth (typically 2% carbon dioxide). However, high carbondioxide content fields in central Australia (25% or more carbondioxide) and newer developments in Bass Strait (Kipper >10%CO2) still exhaust extracted carbon dioxide to the atmosphere.

Difficulties of mass carbon dioxide removal are illustrated bythe case of the East Natuna gas field in the Indonesian sectorof the South China Sea (the West Natuna field provides gas toSingapore). The East Natuna field is one of the largestundeveloped gas fields known. It was discovered in 1973 and isthought to contain over 200 Tcf (trillion cubic feet) of gas,unfortunately with a carbon dioxide content of about 70%(volume), which has so far precluded its development. Proposalsto develop the field have gone through many iterations withone proposal to lower the carbon dioxide content by membranesand re-injecting the carbon dioxide requiring double the usualoff-shore facilities (dedicated off-shore carbon dioxide removaland geo-sequestration platforms).

In a later issue, I will discuss some matters relating tocarbon dioxide removal from flue gas prior to geo-sequestration.

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

Membrane processes.

science for fun


When did you last change those little plastic cages of camphoror naphthalene hanging in the depths of your cupboard? Ifyou’ve forgotten, chances are they’ll be empty, and the mothsand silverfish have moved in.

These pure compounds convert readily at room temperaturefrom solid to vapour without forming a liquid; that is, theyhave a high vapour pressure. This is why they are effective atdeterring insects. Why do they have this high vapour pressure?Well, these molecules are compact and globular, and as youraise the temperature they start to rattle around fairly freely inthe solid phase. As a consequence, they don’t need much moreenergy to escape as a vapour.

How do we know this? We measure the heat absorbed by thesolid as a function of temperature and note how much heat isabsorbed as we slowly warm the sample. This tells us at whattemperatures different modes of molecular movement start (andthus absorb more energy). When the material reaches its

melting point, not much more energy is needed to actuallycause it to melt – it has a low enthalpy of fusion. In practice,it is easier to check this by starting from the melt and monitora cooling curve versus time.

Camphor belongs to a group of substances called plasticcrystals. It is soft and waxy and can be cut with a knife. It wasused as a plasticiser for nitrocellulose in producing one of thefirst mouldable plastics, celluloid. The first movie films wereproduced on so-called ‘nitro’ film, which sadly has mostlydeteriorated. Celluloid dolls are collectors’ items. Celluloid’slast major use, for table tennis balls, is also dwindling infavour of polymer balls.

Old camphor packets carried a warning that the camphorshould not be used in the presence of naphthalene because itis liable to melt. What is this threatened melting? A eutecticdiagram illustrates what happens.

The data for the diagram is obtained by starting withcamphor (shown on the right), measuring the melting pointand then adding naphthalene, checking the melting point ofthe mixture after each addition. We see how the melting pointdecreases. We then do the same with pure naphthalene (shownon the left) and adding camphor.

Close to the vertical axes, where the additions are small, theregions are labelled ’a’ and ‘b’ and we are dealing with solidsolutions of camphor in naphthalene or naphthalene incamphor of various compositions.

Further out, with more additions, are regions labelled ‘a andL’, and ‘b and L’. The a and b are again solid solutions of

Based on P.M. Robinson, H.J. Rossell and H.G. Scott, Binary phasediagrams of some molecular compounds – I. Mol. Cryst. Liq. Cryst.1970, vol. 10, pp. 61–74.

In the bad old days, the molecular mass of organiccompounds was determined by dissolving a known amountof the compound in molten camphor, freezing it, grinding it,and then measuring the new lower melting point. This iscalled the Rast method.

The lowering is a colligative property; that is, it dependson the number of moles of the added compound. You knowthe mass you have added, so you can obtain the molecularmass. The melting point is no longer sharp. Consistency isneeded when deciding which point to accept as the meltingpoint because there is a range between first starting to meltand finally all melted.

Old camphor packets carrieda warning that the camphorshould not be used in thepresence of naphthalenebecause it is liable to melt.

Sublime science meets eutectics

iStockphoto/epantha


variable composition but are now mixed with a liquid solution.Above that is a pure liquid solution. These latter curves meet ata fixed point at an intermediate composition called the eutecticpoint.

Thus there are three compositions with a sharp meltingpoint: pure naphthalene, pure camphor and the eutecticmixture. Below the horizontal line through the eutectic, there isonly a mixture of solids.*

The depression of freezing point in the a and b regions isused in a process called the Rast method of determiningmolecular mass.

If the vapours of camphor and naphthalene came in contactin your cupboard and condensed on your clothes, there wouldbe a low melting point mixture of crystals and liquid. Thisexplains the warning on the old labels. Unlike the naturalmaterial, synthetic everyday camphor contains borneol and thushas a lower melting point. This means various melting pointscan be less than indicated on the diagram.

A concoction of camphor with additives is the basis of anintriguing 1860s weather forecaster (prognosticator) called astorm barometer or chemical weatherglass, of dubiousperformance.

Ben Selinger FRACI CChem is Emeritus Professor of Chemistry at ANU and, alongwith ANU colleague Associate Professor Russell Barrow, released the sixth editionof Chemistry in the marketplace (CSIRO Publishing) in June 2017. For moreinformation, visit www.publish.csiro.au/book/7366.

Admiral Robert FitzRoy, promoting the storm barometer in the1860s, proclaimed that ‘if fixed, undisturbed, in free air, notexposed to radiation, fire, or sun, but in the ordinary light of a well-ventilated room or outer air, the chemical mixture in a so-calledstorm-glass varies in character with the direction of the wind, not itsforce, specially (though it may so vary in appearance only) fromanother cause, electrical tension’. ReneBNRW/CC BY-SA 3.0

• In three narrow, tall jars, place some caged naphthalene,some caged camphor and some caged camphor andnaphthalene mothballs together. Seal the jars and placethem in the sun for a day or so. Note what you see.

• You should see the sublimation and deposition ofcrystals on the sides of the glass, different shapes forthe two different compounds.

• The jar with both camphor and naphthalene contains amixture; check the melting point by placing the jar in alarger jar filled with water at around 30°C. The crystalswill melt and, on moving out of the sun, may freeze (asa white amorphous solid).An unrelated question is why the material sublimes from

the holders and deposits on the inside of the glasscontainer. Glass is transparent for much of the solarradiation whereas the chemical cages and their contentsabsorb and will be warmer than the glass walls. Thisexplains the movement and crystal deposition on the innerglass surface. It also shows that garden greenhouses don’twork due to the (atmospheric) greenhouse effect. Air insidea car gets hot in the sun but the windscreen doesn’t.

Experiment: caged chemicals

*For a more detailed interpretation of phase diagrams, see Chemistry in themarketplace sixth edition, appendix 5, phase diagrams, and check out the tour ofthe phase diagram for lead and tin, that in principal is the same as for camphornaphthalene. The latter diagram, shown on page 463, is over-simplified.

grapevine


I have encountered many different approaches to wine tastingsince my first serious involvement after my doctoral studieswhen the attitude was something like ‘cheap is all I can afford,so it must be good’. I did meet one PhD student who tried toquantify this approach by calculating the dollars per each per cent alcohol so that low-priced high-alcohol wines scoredwell. One winemaker, when discussing whether the 20-point or100-point scoring scale should be used, claimed that he used a2-point scale: 1 if the wine went down and 2 if it stayed down!

On the more serious side, I have always been intriguedwhen, in a tasting session with flavour chemists, theiremphasis is only on the aroma of the wine. They spendconsiderable time trying to identify the aromas and then applydescriptors. They then go on to the next glass without eventasting the first one. When I ‘nose’ a wine, I am checking to seeif the aroma is OK and does not show spoilage characters.Essentially, if it smells like wine, then I taste. If overly spoilt, Igenerally will not taste because the time required to remove theresidual aroma and taste sensations can be too long.

All this is by way of introducing the concept of mouthfeel.Until recently, most of mouthfeel research has focused on redwine, with an examination of the polyphenolic content in relationto astringency and bitterness being one major and ongoingresearch effort. I suspect that there has been some prejudicetowards red wines because these are commonly perceived as morecomplex than white wines. The opinion of many is that a whitewine is what one drinks before red wine! Perhaps the subtlety ofgood white wines is not apparent to consumers of big red wines(here I am showing my own prejudice).

The state of knowledge on white wine mouthfeel has recentlybeen reviewed by Richard Gawel and Paul Smith from theAustralian Wine Research Institute with Sara Cicerale and RussellKeast from Deakin University (Crit. Rev. Food Sci. Nutr. 2017,doi: 10.1080/10408398.2017.1346584). Commencing with asummary of the physiology of mouthfeel perception, the reviewcontinues with a discussion of the association between mouthfeeland wine composition. Ethanol and pH/acidity are two factorsthat exert a significant influence on mouthfeel, while a range ofmedium-to-low-concentration compounds may exert an effecteither individually or through interactions with other compounds.

The mouthfeel responses can be broadly classified as warmth,prickling and spritz as well as the tactile sensations of viscosity,astringency and bitterness with sweetness for some styles.Ethanol can produce a warm mouthfeel, changing to prickling asits concentration increases. High acid wines may also exhibitprickling and spritz. Phenolic compounds elicit an astringentresponse as well as bitterness in some instances. Recent researchon polysaccharides indicates that this class of compounds caninfluence astringency through an interaction with phenoliccompounds, although most studies are on red, rather than white,wine. Glycerol, the third most abundant compound in white wine,is often assumed to influence viscosity, although the research isconflicting, perhaps to some extent because of the sweetness ofglycerol itself.

Viscosity is a good example of the challenge in linkingmouthfeel to wine components. While the physical viscosity ofwine can be readily measured, tasters focus on what can betermed ‘oral viscosity’ as reflected in ‘the ease with which theliquid flows between the upper surfaces of the tongue and thepalate’. Oral or perceived viscosity generally appears to correlatewith a wine’s measured physical viscosity (around 0.15mPa/s).Gawel et al. note that increasing wine pH leads to a higherperceived viscosity. A small pH change is unlikely to changephysical viscosity, so the higher mouthfeel viscosity perceptionwould appear to be related to other, not yet, recognised effects.

One of the complexities associated with profiling mouthfeelis the influence of retronasal aroma sensation. Essentially,aromas can be sensed by orthonasal (sniffing in) and retronasal(breathing out) routes (see Shepherd in Flavour, 2015, vol. 4,p. 19, doi.org/10.1186/s13411-014-0030-9). This is especiallysignificant in wine because the volatility of several aromacompounds is enhanced by the warmer temperature in themouth. While detailed studies of the retronasal effect in wineare limited, one by Anthony Sereni, James Osborne andElizabeth Tomasino from Oregon State University examined thelink between retronasal sensing and mouthfeel perception inChardonnay (Beverages 2016, vol. 2, p. 7,doi: 10.3390/beverages2010007). The trick in theseexperiments is to taste wine in the ‘normal way’ and repeat thetasting wearing a nose clip, the type of clip used in swimming.The results of the Sereni et al. study showed that there was adefinite influence of retronasal aroma on mouthfeel perception,although the nature of the interactions and their link to winecomposition remains an open question. There is undoubtedlysome great research opportunities here.

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.

The mouthfeel responses canbe broadly classified aswarmth, prickling and spritz aswell as the tactile sensationsof viscosity, astringency andbitterness with sweetness forsome styles.

Mouthfeel of white wine

In 1952, the Botanic Garden in Melbourne welcomed an unusualvisitor. He was Ronald Melville, a botanist who had recentlybeen appointed to the Australasian Section of the Royal BotanicGarden, Kew, an appointment he held until his retirement in1968. ‘Retirement’ did not mean ceasing work as a taxonomist,of course, and he practised his craft until shortly before hisdeath in 1985 at age 82.

During his year in Australia, he was said to have collectedmore than 20 000 specimens. Many of them must have gone toKew, but there are 9216 of his specimens in Australian herbaria,2979 of them Victorian. Only 1716 of the Victorian ones areheld here in Melbourne, along with 1675 from other states andterritories. I gleaned this information from the wonderfulAustralasian Virtual Herbarium (https://avh.chah.org.au), towhich I was directed by local experts.

Melville had been at Kew, working in the Museum Section,since he was awarded his PhD degree in 1934 for studies ontomato seedlings. His thesis topic is a true indicator thatMelville was no mere theorist but, rather, a practical man withwide interests in nutritional and economic botany, as shown inhis 1948 book The story of plants and their uses to man. Beforethese interests flowered (pun recognised), however, in the late1930s he established himself as a specialist on the taxonomy ofelms (genus Ulmus), starting with those in Britain but rangingfurther afield to the Eastern Mediterranean and the Himalayas.

During World War II, he was Kew’s nominee on severalnational committees, among them the Vegetable DrugsCommittee of the Ministry of Health. Supplies of vitamin C werethreatened and so Melville was detailed to work with Dr MagnusPyke in a search for alternative (to citrus) sources of thisessential food component. They examined walnuts, coniferneedles and various fruits and edible plants, before concludingthat rose hips were the best source. So rosehip syrup was bornand its production was undertaken by the Rose Hips ProductsAssociation, for whom Melville served on the ScientificCommittee.

During the war, Melville also served in the Home Guard, andwas a member of the local St John’s Ambulance Brigade andsecretary of the Twickenham Allotments and GardensAssociation and then the Allotments Committee of theTwickenham Borough Council. Home gardens and allotmentsmade valuable contributions to wartime food supplies and thelocals would have been delighted to have such an expert intheir midst.

As if all this committee work were not enough, Melvilleserved on committees of the Twickenham and Thames ValleyBeekeepers Association and took a keen interest in bees andbeekeeping. He published several scientific articles on hisalmost-a-hobby, including one in Nature in November 1944 inwhich he described an investigation into suburban honey thathad a strange taste. It came from an apiary in Kensington, notfar from Kensington Gardens, and was collected in 1943. ‘The

first impression on tasting it’, he wrote, ‘was of a mild floralbouquet, but this was followed by a persistent after-tastereminiscent of cats’. Maybe he meant ‘cat’s pee’. On diluting thehoney and centrifuging, the pollen that the bees had gatheredwith the nectar settled out, and Melville showed that 44% ofthe total came from the tree of heaven, Ailanthus altissima. Thenext most abundant contribution was from the sweet chestnut,Castanea sativa. On storage, the honey gradually lost the ‘cat-like’ flavour, and what remained was ‘a delicious muscatelflavour’. ‘Honey is usually eaten within a short period of itsproduction’, the ever-practical Melville wrote, ‘but as with winesand cheeses it would pay to store some kinds until the flavourmatures’. Among the many constituents of Ailanthus that havebeen identified, the only one that I thought might beresponsible was 2,6-dimethoxybenzoquinone.

In the late 1950s, Melville became interested in thedevelopment of flowering among Palaeozoic plants,concentrating on Glossopteris. This is a ‘marker’ plant for theGondwanaland continent and fossil leaf impressions can befound in Southern Australia as well as in South America, Indiaand Madagascar. I remember a geology excursion to BacchusMarsh, 60 kilometres west of Melbourne, where there areoutcrops of Permian sediments bearing Glossopteris andGangamopteris leaf impressions.


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.

Melville and the Great Honey Hunt

Ailanthus altissima flowers. CC BY-SA 3.0

cryptic chemistry


Across1 Gas centres on leachate enveloping

restricted toners. (8)6 Repair needed after three elements

added at the end. (6)9 Customer holds money over

lithium. (6)10 It’s in your DNA; pace, develop. (8)11 Getting out, paces gin

consumption. (8)12 There’s new compounds. (6)13 Sulfur blends odours. (6)15 Mixup backed in finding red rosidae

flowers. (8)17 Increases loans. (8)20 Copies pictures. (6)22 The French pursue a faux pas three

times. (6)24 577528616 lights. (8)26 Human tie to C2H7

+. (8)27 R2C=N• found over in northerly Nimitz

Glacier. (6)28 Symbols of carbon bases. (6)29 Intenser reaction generated

intermediates from azides. (8)

Down2 Maintains grips. (5)3 Complete in general. (7)4 Nitric’s in 15 Across by its very

nature. (9)5 Promised joke when in troubled

need. (7)6 Afterward could be honest if rhenium is

added. (5)7 More lend support. (7)8 Meddle to bury two metals. (9)14 Referee rated room review. (9)16 One of us cites tin’s reaction. (9)18 Lug in software which pops up. (7)19 Wise guy weaves on looms. (7)21 15 Across need in a nucleobase. (7)23 Vents: bad times! (5)25 Form of nitrogen in which conduction is

due to the movement of electronsrather than positive holes. (1–4)

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

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

QACS 2017 – Qld Annual Chemistry Symposium27 November 2017, Queensland University of Technology,Brisbane, Qldraci.org.au/events/event/qacs-2017-qld-annual-chemistry-symposium

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

Christmas HLM Awards and Retirees Lunch11 December 2017, Graduate House, Carlton, Vic.raci.org.au/events/event/christmas-hlm-awards-and-retirees-lunch

6th International Conference and Exhibition on MaterialsScience and Chemistry17–18 May 2018, Rome, Italymaterialschemistry.conferenceseries.com

ALTA 2018 – Nickel-Cobalt-Copper, Uranium-REE & Gold-PMConference & Exhibition19–26 May 2018, Perth, WAaltamet.com.au/conferences/alta-2018

AOCRP-5 – 5th Asian & Ocean Regional Congress onRadiation Protection20–23 May 2018, Melbourne Vic.aocrp-5.org

Macro 18 – World Polymer Congress1–5 July 2018, Cairns, Qldmacro18.org

8th International Conference on Environmental Chemistryand Engineering20–22 September 2018, Berlin, Germanyenvironmentalchemistry.conferenceseries.com

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