chemistrychemaust.raci.org.au/sites/default/files/pdf/2018/CiA_Feb 2018.pdf · Editor at wools@ westnet.com.au. Visits and verses Thank you for another year of Chemistry in Australia

• Pushing the boundaries of microscope resolution• Metal–organic frameworks: a ‘top ten’ emerging technology• The stories your chemistry teacher wouldn’t tell you

chemistry

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in AustraliaFebruary 2018

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Getting to grips withneuroplasticity data

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6February 2018

24


16Making connections: from neuroplasticity data totreatmentA treasure trove of existing and emerging medical research findingsbeckons chemists to effect ground-breaking solutions to a wide arrayof medical issues.

cover story

20 A cool visualisation breakthrough: the 2017 Nobel Prize inChemistry. Part 1The limits of microscopy resolution have been smashed as part of workrecognised by the 2017 Nobel Prize in Chemistry.

24 Metal–organic frameworks: from laboratory to factoryOnce thought of as the ‘gunk in the bottom of the flask’, metal–organicframeworks have emerged as a potential wonder material. Marta Rubio-Martinez and Matthew Hill present an Australian perspective.

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Chemistry in Australia4 | February 2018

editorial

Part of my role as editor is commissioning contributors –making sure that we have enough content, as well as a goodrange of it. To start the new year, I’d like to report on a fewmovements and milestones within the pages of Chemistry inAustralia.

Entrepreneur and technical consultant Dave Sammut haswritten more than 40 feature articles since he commencedcontributing them in 2013. An active member of the RACI, Davewas thrilled to be involved in the 100 Reactions project duringthe RACI’s centenary, and he is committed to helping youngscientists transition from university to careers as part of theRACI’s mentoring program. I am very grateful for his strong andenthusiastic support of the magazine.

Dave is co-authoring this year’s features about the recipientsof the 2016 Nobel Prize for Chemistry while our usualcontributor, Peter Karuso, is taking a sabbatical. Petervolunteered to write Nobel prizewinner profile pieces for themagazine in 2009 and has been going strong ever since. He’sintroduced us to some very fine chemists and fascinatingchemistry along the way. I wish him well on his sabbatical.

Also taking a break is environment consultant Paul Moritz.Writing the environment column since 2012, he has alsocontributed book reviews and a feature article on environmentprotection (November 2003). Paul has written more than30 opinion pieces, and the editorial team particularlyappreciates the time he has taken to complement his writingwith interesting photos.

Science communicator Jeremy Just has been writing his‘science for fun’ column since the beginning of last year. Jeremyis right at the end of his PhD, finishing off his thesis in organicchemistry. During his PhD studies, he has been investigatingthe use of a benchtop espresso machine to extract a diverse

range of biologically interesting organic molecules from plants.The ultimate goal of this research is to develop a rapid andefficient extraction method (April 2017). He can regularly beseen around Tasmania presenting science shows and workshops,and in the media. Jeremy says he ‘appreciates the opportunityto write general interest pieces for Chemistry in Australia asanother outlet for engaging Australians in science’.

You may well remember contributions from a ‘mystery’ PhDand then postdoc diarist until mid-2016. That contributorwas … cue drumroll … John Moraes. Writing from New SouthWales and then from Switzerland and the US, John shared somecandid accounts of his highs and lows as a chemistry PhD andpostdoc, including the ‘gentle art of quitting’ (August 2016).That was his final contribution, in which his byline said that hewas ‘trying to break into the corporate world’. Here’s a recentreflection and update from John:

I found writing for Chemistry in Australia a valuable way to ruminate inpublic about the interesting career trajectory I had taken – from PhDstudent to postdoc to stay-at-home-dad to job seeker to corporate 9-to-5’er. I tried to provide insights into those particular snapshots of my lifeand guidance for those about to chart similar waters. It was fun. I hopeit was useful. I now work for Nike in the USA. I don’t do much withchemistry, but absolutely feel that each step I took in the circuitousjourney was invaluable and helped me do what I do. And do it well.

These and all of our contributors are the pulse of ourmagazine. I admire all of you for sharing your knowledge andopinions with readers.

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

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© 2018 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproduced whollyor in part without written permission. Further details on thewebsite (chemaust.raci.org.au). ISSN 0314-4240 e-ISSN 1839-2539


Sally Woollett ([email protected])

Movements and milestones

your say news

Chemistry in Australia 5|February 2018

Natural organic compounds thatcontain fluorine are rare because livingorganisms – with a few exceptions –do not produce them. US scientistshave now genetically engineered amicrobial host for organofluorinemetabolism, allowing it to produce afluoridated intermediate known as adiketide. As reported in AngewandteChemie (https://doi.org/10.1002/anie.201706696), the diketide couldthen be used as a monomer for the in vivo production of fluorinatedbioplastics.

Unlike nature, chemists use fluorineoften. Teflon coatings for pans andwater-repellent Gore-Tex jackets, bothbased on polytetrafluoroethylene,immediately spring to mind. Fluorineis also found in many agrochemicals,and about 20–30% of modernpharmaceuticals, ranging fromantimalarial and cytostatic drugs toinhalation anaesthetics, bloodsubstitutes and liquid ventilationagents. Organofluorine molecules arealso used in liquid crystals fordisplays, as well as in ozone-friendlyrefrigerants and propellants.

Given the potential for livingsystems to produce highly complexchemical compounds, researchersworking with Michelle C.Y. Chang atthe University of California, Berkeley,aimed to manipulate the biosyntheticmachinery in cells to use simplefluorinated building blocks to makenew organofluorine target molecules.

To achieve this, they introducedgenes that code for three particularlyefficient enzymes from a variety ofother microorganisms into Escherichia

coli to construct the diketidebiosynthesis pathway. These enzymesare able to use fluorine-containingderivatives of their normal substrates.In addition, it was also necessary tointroduce a gene for a transportprotein that carries fluoromalonate –as fluorine-containing startingmaterial – into the cell. The enzymesallowed the cells to use thebiosynthesis pathway to makefluoromalonyl coenzyme A and convertit to the 2-fluoro-(R)-3-hydroxybutyrate diketide in high yield.

The researchers introduced yetanother gene for an enzyme used bymany bacteria to makepolyhydroxyalkanoates (PHAs), whichare polyesters used to store carbonand energy. Biodegradable PHAs areused in the production of bioplasticsfor applications such as foodpackaging and medical implants. Thenew, genetically engineeredmicroorganisms incorporated thefluorinated diketides into the PHAsthey produced, generating polymerscontaining 5–15% fluorinatedmonomers. The fluorinated bioplasticswere less brittle than fluorine-freePHAs. Controlled incorporation offluorinated monomers could allow fortargeted variation of the properties ofbioplastics.

The researchers also hope to usethe key component fluoromalonylcoenzyme A to produce a broadspectrum of small fluorinatedmolecules in living cells forpharmaceutical applications.

Angewandte Chemie International Edition

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

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

Visits and versesThank you for another year of Chemistry inAustralia and in particular the November issue.I found many interesting articles, including thereport on Sir John and Lady Cornforth (p. 16).This reminded me of his visits to theDepartment of Organic Chemistry (as it wasthen) at the University of Melbourne and thememorable poem, by Sir John, about Australiaand Professor Arthur Birch of ANU. You mayknow it, but if not the first verse goes likethis:

That outpost of empire Australia,A land of the strangest mammalia,The kangaroo rat, the blood sucking batAnd Arthur J Birch inter alia.

David Kelly FRACI CChem

Fluorine-containing moleculesfrom cell culture

news


A special kind of sliced apple is now for sale at select USsupermarkets, one that won’t turn brown when cut, bitten orbruised.

Arctic® apples have been developed by Canadian biotechcompany, Okanagan Specialty Fruits Inc. (OSF). OSF is the firstcompany to license CSIRO’s non-browning technology.

Their first product is snack-sized bags of fresh Arctic® Goldenapple slices, with more non-browning varieties expected infuture years, including Granny Smith and Fuji.

Company founder Neal Carter began working on the apples inthe mid-1990s.

‘I came across research from CSIRO that had managed to“turn off” browning in potatoes’, Carter explained.

‘As an apple grower, I was very aware that appleconsumption had been declining for decades while obesity rateshad simultaneously been sharply rising.

‘My wife and I felt that we could help boost appleconsumption through a similar biotech approach with apples, asnon-browning apples would be more appealing and convenient.

‘We felt this could also significantly reduce food waste, asnearly half of all apples produced end up wasted, many due tosuperficial bruising’, he said.

While there may be other sliced apple products already onthe market, these are often coated with vitamin C and calciumto prevent browning and to preserve crispness, and this canchange their taste.

Apples and other fruit and vegetables turn brown after theyare cut or damaged because of a naturally occurring enzyme(polyphenol oxidase or PPO) that reacts with other componentsin the fruit cells when these cells are ‘broken’, producing abrown pigment.

CSIRO scientists constructed an anti-PPO gene which, wheninserted into plants, blocks the production of PPO and thereforestops the browning.

Spoilage due to browning costs food-processing industriesworldwide millions of dollars each year in wastage and costlychemicals to prevent the reaction.

This non-browning technology has potential to reduce waste,not only in apples and potatoes but also in other importanthorticultural crops, such as beans, lettuce and grapes whereproduce with only small injuries could still be sold.

CSIRO

Turning off the browning reaction

The anti-PPO gene blocks the production of polyphenol oxidase and therefore stops browning. © Okanagan Speciality Fruits


When warm candy cools and solidifies,the mass of thick, viscous liquid sets tohard candy – an edible glass.

To physicists, glass is not just thestuff that we drink out of or lookthrough. It is, more broadly speaking, afluid that sets as a solid withoutcrystallising. In a glass, molecules arearranged randomly, rather than in anordered crystal lattice.

But what actually happens during thesetting process? How do the mechanicalproperties change when viscous liquidscool and transform into glass?

This is what physicists at the researchcentre Glass and Time at RoskildeUniversity (RUC), Denmark, are trying tofind out in collaboration with scientistsfrom the Massachusetts Institute ofTechnology in the US.

Seven experiments plannedThey designed seven experiments tomeasure the viscosity of the liquid as itcooled down, which are now published inthe scientific journal PNAS.

‘We’re now able to measure themechanical properties – flow properties –in a much larger area than was possiblebefore. It’s taken many years and a lot ofwork to reach this point’, says leadauthor Tina Hecksher, an associateprofessor at the Department of NaturalScience and Environment at RUC.

It is not easy to measure how fluidsbehave as they become increasinglyviscous. There’s a huge differencebetween measuring a thin liquid and onethat is just about to turn to glass. Itrequires advanced measuring equipment,which the scientists first need todevelop.

‘The viscous liquids’ dynamicproperties are extremely dependent ontemperature. But we used a host ofdifferent methods to measure a widerange of temperatures’, says Hecksher.

Better cell phones andmedicinesUnderstanding this transition has manyapplications; for example, in the

manufacture of solid glass in consumerelectronics, such as smartphones and flatscreens. But there are other less obviousapplications, says Hecksher.

‘There’s a lot of research into glassformation in medicine. It’s easier for thebody to dissolve medicine in glass formthan medicine in the crystalline form, soit will be interesting to find out how wecan produce medicine as a glass insteadof crystals’, she says.

Understanding the setting andformation of glass can also helpgeophysicists understand how magmaflows and sets. The applications arenumerous, but the basic research andtheory needs to come first.

Viscous liquids resemble eachotherThe scientists studied silicone oil, but inprinciple, they could also have studiedhoney, tar, or another liquid that sets toglass as the temperature falls.

‘All liquids can be supercooled. Theycan all form glass and behave surprisinglysimilarly when cooled’, says Hecksher.

But not all liquids behave in exactlythe same way, she says. ‘It would be niceto have a universal theory forsupercooled fluids. But perhaps we

should develop a theory for particularsimple fluids, which can be adjusted invarious ways for more complex fluids.’

This is the hypothesis that Hecksherand colleagues will investigate.

‘We’ll try to find a theory for thesimplest fluids, such as the silicon oilthat we have used, and perhaps this canbe the starting point. But theories needto be tested and this is what we’ve nowshown we can do’, she says.

Nice piece of workThe results will be compared withtheories of what happens when fluidsbecome more viscous.

Theoretical physicists needexperimental basic research such as this,says Paolo Sibani, lecturer at theDepartment for Physics, Chemistry, andPharmacy at the University of SouthernDenmark.

‘It’s vital to develop new experimentaltechniques as they’re doing in Roskilde.And theoretical physicists like me usethese experimental results to developtheories. We need results that span overmany orders of magnitude and it’s alwaysa challenge. What they’ve done here isvery nice’, says Sibani.Science Nordic/Henrik Bendix

Scientists get to grips with a tricky liquid

iStockphoto/aronbrand

news

February 2018

Scientists at the US National Institute ofStandards and Technology (NIST) havedeveloped a laboratory instrument thatcan measure how much of the carbon inmany carbon-containing materials wasderived from fossil fuels. This will open theway for new methods in the biofuels andbioplastics industries, in scientificresearch and environmental monitoring.Among other things, it will allow scientiststo measure how much of the CO2 in theatmosphere came from burning fossilfuels, and to estimate fossil fuel emissionsin an area as small as a city or as large as acontinent.

This is possible using carbon dating,but it requires extremely precise – andexpensive – measurements. The newinstrument, developed by NIST chemistsAdam Fleisher and David Long and basedon cavity ringdown spectroscopy (CRDS)technology, promises to dramaticallyreduce the cost of those measurements.This is described in the Journal ofPhysical Chemistry Letters (doi:10.1021/acs.jpclett.7b02105).

The key to these measurements iscarbon-14, a radioactive (yet harmless)isotope of carbon that is formed in theupper atmosphere. Carbon-14 is unstable,with a half-life of 5730 years.

But carbon-14 is extremely rare, andto use it for identifying fossil fuels,scientists need to be able to measure itat concentrations as low as one part in

ten trillion, which requires an extremelysensitive measurement technique and aparticle accelerator to separate carbon-14 from carbon-12. The CRDS instrumentthat Fleisher and Long have developedcan sit on a laboratory benchtop and isrelatively inexpensive to operate.

CRDS instruments analyse gases bydetecting the wavelengths of light theyabsorb.

To measure the amount of heavy CO2

in a CO2 sample, the sample is injectedinto the instrument’s measurementcavity, which is a tube with mirrorsinside at either end. A laser of the exactwavelength that only heavy CO2 absorbsis then shot into the cavity. As the laserlight bounces between the mirrors, someof its energy is absorbed by the gas. Thegreater the absorption, the greater theconcentration of heavy CO2.

To achieve the required sensitivity,Fleisher and Long enhanced existingCRDS technology by engineering a systemthat chills the cavity to a uniform –55°Cand minimises temperature fluctuationsthat would throw off the measurement.

This and other improvements boostedthe instrument’s sensitivity enough foraccurate carbon dating.

Biofuels and bioplastics would beburnt, and the resulting CO2 collected foranalysis. This would allow you to test afuel mixture to determine what fractionof it is biofuel. In the airline industry, for

example, this would be useful becausesome countries require that aviation fuelsinclude a specific biofuel percentage.Such tests could also be used to verifythat bioplastics, which sell for apremium, do not contain petroleum-derived compounds.

To estimate fossil fuel emissions in ageographic area, air samples would beanalysed for the atmospheric CO2. Areaswith high fossil fuel emissions, such ascities and industrial zones, will havebelow-normal concentrations of heavyCO2.

‘Fossil fuel emissions dilute theconcentration of heavy CO2 in the air’,said Fleisher. ‘If we can accuratelymeasure that concentration after it’sbeen diluted, we can calculate how muchfossil fuel emissions are in the mix.’

A report from the National Academy ofSciences estimated that 10 000 samples ayear, collected at carefully chosenlocations around the US, would beenough to estimate national fossil fuelemissions to within 10% of the actualvalue. Such a system of measurementscan increase the reliability of nationalemissions estimates. This would beespecially useful in parts of the worldwhere high-quality emissions data arenot readily available.

‘There is a need for this type ofmeasurement in many industries’, Fleishersaid. ‘We’ve demonstrated a path tomeeting that need in a cost-effectiveway.’

NIST

New method for identifying carbon compounds derived from fossil fuels

This NIST instrument that enablesoptical measurement of ‘heavy’ carbondioxide (14CO2), showing theinstrument’s ultra-stable optical cavityand cold sample cell.Rich Press/NIST

February 2018

A little-studied member of theperovskite family of materials couldfind use in a range of electronicdevices, after researchers at KingAbdullah University of Science andTechnology (KAUST), Saudi Arabia,discovered the secret of its strongphotoluminescence.

Perovskites are a wide group ofmaterials that are known to haveremarkable optical and electronicproperties. Perovskites with thegeneral formula ABX3, and particularlythe perovskite methylammonium leadtrihalide, have attracted almost allthe research attention thanks to theirgreat promise as low-cost, high-efficiency solar cell materials.

Other members of the perovskitefamily and perovskite derivatives arealso worthy research subjects, saysMichele De Bastiani, a postdoctoralresearcher in Osman Bakr’s group atKAUST.

De Bastiani and his colleagueshave been testing Cs4PbBr6, aperovskite of the A4BX6 branch of thefamily. This material is noted for itsstrong photoluminescence – theability to absorb light at onewavelength and re-emit it at another.

The material’s potentialapplications include colour-convertingcoatings on LED light bulbs, lasersand photodetectors. But to be able tofine-tune the material’s optoelectricproperties for each application,researchers need to solve the mysteryof why the perovskitephotoluminesces so strongly.

‘We investigated the structural andoptoelectronic properties of Cs4PbBr6

to understand the origin of itsphotoluminescence’, De Bastiani said.Subjecting the material to a barrage

of tests, the team discovered thatwhen a Cs4PbBr6 crystal was heated to180°C, its photoluminescence wasirreversibly destroyed.

Photoluminescence is a two-stepprocess: absorption of light generatesa pair of quasi-particles calledexcitons within the perovskite, whichmust recombine to re-emit the light.Using temperature-dependent X-raydiffraction to track structural changesto the material as heat was applied,the team discovered that at 180°C,CsPbBr3 nanocrystals form within themineral.

The heat-induced structuralrearrangements that create thesenanocrystals also swallow naturaldefects in the original crystal wherebromine atoms were missing, theresearchers concluded. These brominevacancies act as traps for passingexictons. Confined in these traps, theexcitons are much more likely torecombine and emit light.

‘Now that we have thisfundamental understanding, our nextstep is to move on to potentialapplications’, De Bastiani said. ‘Theunique photoluminescence manifestedby Cs4PbBr6 makes these perovskitescompelling materials forelectroluminescence devices, lasersand light converters.’

Meanwhile, many other little-explored members of the perovskitefamily with interesting properties arewaiting to be revealed, De Bastianiadded. ‘One example is CsPb2Br5, asingle crystal we recently synthesisedfor the first time with unseenoptoelectronic properties.’

King Abdullah University of Science andTechnology

Missing atoms in a forgottencrystal bring luminescence

YEARS

on the market


South Australian company Frontier Microscopy has developed afast and accurate way to test for airborne asbestos fibres,potentially making life safer for thousands of Australian familiesand workers.

Using artificial intelligence, advanced robotic microscopy andcloud-based software, this ground-breaking system known asMarvin will revolutionise the way the world monitors, detectsand then stores the results of asbestos air monitoring ondemolition and construction sites.

Frontier Microscopy Managing Director Jordan Gruber saysthere are two key components to the technology: a roboticmicroscope analysis system and a software management suite.

The management suite is a secure web and mobile softwarethat has been designed for day-to-day asbestos air monitoringoperations. It significantly increases air monitoring jobefficiency by automating field data collection on demolition andconstruction sites, laboratory analysis, reporting and clientcommunication.

Gruber said: ‘We are currently piloting the management suitewith Greencap, Australia’s largest risk management andcompliance company. Cutting edge technology is being appliedto improve compliance, reduce risk and simplify informationcapture during air monitoring during asbestos remediation.’

‘Asbestos is still a major issue across Australia, with one inthree public buildings estimated to contain asbestos-basedbuilding materials. Asbestos-based materials must be respected,or else asbestos fibres can become airborne and pose seriousrisk to workers and the general public.’

About six times faster than a human, Marvin – which ispatent pending – analyses air samples using a custom-builtrobotic microscope. The robotic microscope system takes severalhundred photographs across an entire air filter sample in lessthan a minute. The images are then automatically uploaded to

cloud software where they are analysed for signs of asbestos. ‘For labs there are significant benefits, as Marvin eliminates

the manual processing of dangerous minerals and screens airsamples for asbestos fibres in a fraction of the time it takeshumans’, Gruber said.

Marvin is expected to become commercially availableworldwide in the next few months, following an extensivevalidation testing program in a commercial laboratoryenvironment. In the meantime, air samples can be manuallyanalysed through the management suite.

For more information, [email protected].

Revolutionary SA asbestos testing tech set for world stage

In response to changes in the ownershipstructure of the company and thesuccessful expansion of its businessoperation, MEP Instruments has changedits name to Metrohm Australia andMetrohm New Zealand.

As of 1 January 2018, the distributorof leading analytical technologysolutions started operating under thename of Metrohm, its sole parentcompany. The change reflects the closeintegration of the Australian and NewZealand operation under the globalMetrohm brand.

Metrohm is a global market leader inthe fields of titration and voltammetry,

and a trend-setting innovator in ionchromatography, online analysis andlaboratory automation, NIR Ramanspectroscopy and electrochemicalsolutions for research and training.

MEP Instruments Australia and NewZealand was established by MetrohmSwitzerland together with Anton PaarAustria nearly 20 years ago to strengthensupport and service for their customerbase in these countries.

The tremendous success over the pastyears and the enthusiastic acceptance bythe scientific community in the regionhave led to the decision to change thename to Metrohm to reflect the

commitment to the growing customerbase in the region and to establish AntonPaar Australia and New Zealand as aseparate entity.

Along with the name change, thecompany will adopt the corporateidentity, including logo and visualidentity of the parent Metrohm AG. AllMEP/Metrohm office addresses and phonenumbers will remain the same acrossAustralia and New Zealand.

For more information, visitmetrohm.com.au andmep.metrohm.com.au.

MEP Instruments becomes Metrohm Australia, Metrohm New Zealand

Scanning electron micrograph of asbestos fibres.Courtesy of the US Geological Survey

news


Researchers have developedmachine learning to scan tens ofthousands of job ads and found alarge hidden job market for PhDgraduates.

The project, led by theAustralian National University(ANU) and CSIRO’s Data61,developed a job-searching machineto help universities preparegraduates for non-academic workand show industry the value of PhDgraduate research skills.

One of the lead researchers, Dr Will Grant from ANU, said themachine read about 30 000 jobads, many of which were for non-academic work, and assessed thelevel of research skills required foreach job.

‘The PhD was originallydesigned to train the nextgeneration of academics, but mostgraduates today find jobs outsideof academia’, said Grant from theAustralian National Centre for the Public Awareness of Science.

‘The machine found a large hidden job market in Australia forpeople with PhDs, with half of the job ads scanned specifyingthe need for a high level of education, including research skills.’

Grant said the job market was considered hidden becauseemployers did not use ‘PhD’ as a keyword in ads.

He said highly skilled researchers working in a wide varietyof industry sectors were important to Australia’s futureeconomic prosperity.

‘We taught the machine to analyse job ads and tell us whatskills were most important to employers. The problem is thatindustry employers in Australia – particularly in manufacturing,

transport, logistics, marketing and communication – may not beaware that PhD graduates have the skill set they’re looking for’,Grant said.

He said Australian universities must do more to prepare PhDgraduates for work outside of the higher education sector, whileemployers needed to be more receptive to people with PhDs.

‘PhD programs still tend to favour skills required for anacademic career over those demanded by industry’, Grant said.

‘There also seems to be a lack of trust in the PhDqualification as producing work-ready employees.’

Co-researcher Adjunct Professor Hanna Suominen, a naturallanguage processing expert from CSIRO’s Data61, co-inventedthe machine-learning algorithm and is optimistic about thepotential of this tool to help find work for PhD students.

‘Our researchers will continue to develop the machine into aweb portal to support PhD graduates in their search for work’,Suominen said.

The machine could be refined and used to track changes inindustry demand for Australia’s research skilled workforce.

‘It has the potential to connect PhD graduates with idealjobs they may not have otherwise come across or considered.’

The research team has expertise in computer science,research education, linguistics and social science.

ANU

Machine learning uncovers large hidden job market forPhD graduates

PTYLTDRowe Scientific

www.rowe.com.au

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

Suppliers of:

ADELAIDE08 8186 [email protected] BRISBANE07 3376 [email protected] HOBART03 6272 [email protected] MELBOURNE 03 9701 [email protected] PERTH08 9302 [email protected] SYDNEY02 9603 [email protected]

CERTIFIED REFERENCE MATERIALS

iStockphoto/Murat Gocmen

research


Venom-derived peptide toxins provide an abundant pool ofmolecules with diverse biological functions. Researchers fromthe University of Queensland and James Cook University haverecently discovered another function of a large family ofcysteine-rich peptide toxins from the marine cone snail Conusmiles (Jin A.-H., Dekan Z., Smout M.J., Wilson D., Dutertre S.,Vetter I., Lewis R.J., Loukas L., Daly N.L., Alewood P.F. Angew.Chem. Int. Ed. 2017, 56, 14 973–6). Conotoxin Φ-MiXXVIIAcontains a unique cysteine-rich motif comprising threeconsecutive cysteine residues and four disulfide bonds, which

the researchers named as a new conotoxin framework XXVII (C–C–C–CCC–C–C) belonging to a new conotoxin superfamily G2. The researchers synthesised Φ-MiXXVIIA by usingregioselective formation of 4 S–S bonds and determined itsunique tertiary structure by 2D NMR spectroscopy. They foundthat the novel toxin is a structural mimic of the N-terminaldomain of granulin, a human growth factor protein. Overextended periods, Φ-MiXXVIIA promotes cell growth andinhibits apoptosis, suggesting it acts as a granulin mimic.

Uncovering activity of novel toxin

The cycloaddition betweenallylic cations and dienesprovides rapid access toseven-membered rings.Recently, researchers fromthe University of Missouri-Columbia, USA, and theUniversity of Queenslandhave examined a newsubstitution pattern of oxidopyridiniumions as a driving force for this reaction,in which these zwitterions act as dienesto produce the 7-azabicyclo[4.3.1]decanering system in one step (Fu C., Lora N.,Kirchhoefer P.L., Lee D.R. Altenhofer E.,Barnes C.L, Hungerford N.L.,Krenske E.H., Harmata M. Angew. Chem.

Int. Ed. 2017, 56, 14 682–7). Thissubstructure is found in a number ofdifferent alkaloids. An intramolecularversion of the reaction was alsoestablished. Density functional theorycalculations showed that a concertedmechanism is favoured over a range ofother mechanistic possibilities.

Regioselectivities were also generallyhigh. The work holds promise for thesynthesis of new molecular scaffolds toexploit unexplored chemical space as wellas for the total and analogue synthesis ofbiologically active compounds.

Rapid route to bicyclic nitrogen-containing frameworks


Efficient light-induced ligation protocolsare valuable tools for functional materialsdesign. The teams of Christopher Barner-Kowollik and James Blinco, at theQueensland University of Technology andthe Karlsruhe Institute of Technology,Germany, and Michelle Coote at theAustralian National University haveinvestigated two highly efficientphotoligation reactions involvingphotoenols and nitrile imines in acombined experimental and theoreticalstudy (Menzel J.P., Noble B.B., Lauer A.,Coote M.L., Blinco J.P., Barner-Kowollik C.J. Am. Chem. Soc. 2017, 139, 15 812–20).A unique tunable laser system was used toirradiate samples containing either o-methylbenzaldehydes ordiphenyltetrazoles and N-ethylmaleimideat varied wavelengths and constant photoncount to produce action plots of reactivityversus wavelength. The quantum yield ofthe nitrile-imine-mediated tetrazole ene

cycloaddition was estimated to be higherthan 0.55 ± 0.06 at 285nm, whilephotoenol-ligation proceeded withquantum yields up to 0.91 ± 0.10,supporting theoretically establishedmechanisms via conical intersections. Acombination of density functional theoryand multi-reference calculations with

precision photochemical analysis providedinsight into the mechanisms and optimisedreaction conditions for photoligationprotocols. These findings will help todesign advanced photoresists in whichdistinct material properties are encodedwith different colours of light in 3D laserlithography.

Light, reactivity, action!

Low-valent iron centres are critical intermediates in chemicaland biochemical processes. An international collaboration ledby Professor Carsten Streb of the Institute of InorganicChemistry at Ulm University, Germany, and Professor Alan Bondand Dr Jie Zhang of the School of Chemistry at MonashUniversity has led to the discovery of the first example of alow-valent FeI centre stabilised in a high-valentpolyoxometalate framework (Anjass M.H., Kastner K., Nägele F.,Ringenberg M., Boas J.F., Zhang J., Bond A.M., Jacob T.,Streb C. Angew. Chem. Int. Ed. 2017, 56, 14 749–52). Detailed

electrochemical and electron paramagnetic resonance studiesand theoretical analyses provided insight into the reversibletwo-electron reduction of the native FeIII species and theelectronic features of the resulting FeI unit. Initial stability andreactivity analyses showed that the materials design approachcould open new avenues for reductive electron transfer catalysisby polyoxometalates to achieve small-molecule activation andreversible electron storage for battery electrodes and molecular-magnet applications.

Stabilising low-valent iron

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research


Aged catalyst improves alcoholoxidationThe selective oxidation of a primary alcohol to an aldehyde is afundamentally important transformation in synthetic organicchemistry. Although many different reagents perform this typeof oxidation, synthetic chemists tend to rely on only a few ofthese compounds in practice. Prominent among this suite is theLey–Griffith catalyst TPAP (n-Pr4N[RuO4]), which is used incombination with the co-oxidant N-methyl morpholine N-oxide(NMO). The mechanism of this reaction has remained unknownsince the seminal work of Ley and Griffith was published morethan 30 years ago. Collaborators from the Universities ofQueensland, Western Australia and Barcelona, Spain, thoroughlyexamined this reaction by using UV–visible, EPR and 99Ru NMRspectroscopy, as well as isotopic labelling, in an effort tounravel the underlying mechanism (Zerk T.J., Moore P.W.,Harbort J.S., Chow S., Byrne L., Koutsantonis G.A., Harmer J.R.,Martínez M., Williams C.M., Bernhardt P.V. Chem. Sci. 2017, 8,8435–42). Their study unearthed the key finding that freshlyprepared TPAP performs differently from the commerciallyavailable (or aged) catalyst. After a slow induction period withthe fresh catalyst, the oxidation by-product water inducespartial decomposition of n-Pr4N[RuO4] to insoluble RuO2.Serendipitously, small amounts of this RuO2 impurity in agedTPAP enhances the rate of oxidation so that no inductionperiod has been previously observed.


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.

Aromatic indiumThe chemistry of very low oxidation-statemain group compounds has rapidlydeveloped over the last two decades.One of the most formative early resultsin this field was Schnöckel’s synthesis ofthe remarkable aluminium ‘metalloid’cluster anion [Al77{N(SiMe3)2}20]

2–.Although gallium analogues have sincebeen prepared, related indium clusters ofa similar size have remained staunchlyelusive. In their latest collaborativestudy, the teams of Professors CameronJones at Monash University and SimonAldridge at the University of Oxford, UK,have rectified this situation with thesynthesis of the indium metalloid cluster[In68(boryl)12]

– (boryl = –B(DipNCH)2,Dip = C6H3Pri2-2,6) and the related planarfour-membered cyclic dianion[In4(boryl)4]

2–, via the reduction of borylboron(III) halide complexes(Protchenko A.V., Urbano J.,Abdalla J.A.B., Campos J., Vidovic D.,Schwarz A.D., Blake M.P., Mountford P.,Jones C., Aldridge S. Angew. Chem. Int. Ed.2017, 56, 15 098–102). The clustercomplex contains three concentric‘spheres’ of indium atoms,In12@In44@In12(boryl)12, with56 indiums only having bonds to otherindium centres (average In oxidationstate about 0.19). It is essentially awell-defined ‘cut out’ of indium metalwith a boryl ligand coat. The smaller In4

system is formally a 2π-electron cycle,which DFT studies show to have aromaticcharacter. Such compounds could shedlight on the mechanism of indium metaldeposition in, for example,microelectronic devices.

In 1876, there were no effectivetreatment options for commonbacterial infections, which wereoften lethal in the era before

antibiotics. That year, John Tyndallpublished his findings that penicillinkilled bacteria but his paper wasignored. In 1929, Alexander Flemingpublished his finding on penicillin andlikewise it was initially ignored – until1938 when Howard Florey cameacross his paper and decided to act.Until Florey proved otherwise, theprevailing attitude was thatantibacterial drugs were a delusion. Asimilar attitude prevails today inrelation to cures for neuroplasticity-related issues.

Until recently, neuroplasticity – thebrain’s ability to re-wire itself, in effectaltering its own genetic operation –was firmly believed to be non-existentand impossible in adults. Like manywidely held beliefs, it has now beenshown to be false. We now know thatmany serious conditions couldpotentially be relieved or remedied bypromoting, assisting and/or guidingthe brain to re-wire itself and yet it is

still a prevalent widely held convictionthat drugs directing neuroplasticchanges are a delusion.

The harsh reality is that there are noeffective pharmacological means atpresent to neither significantly assistnor reverse existing damage, let alonecure the underlying causes of a widearray of intellectual disability,dementias, neurodevelopmentaldisorders (including autism and Downsyndrome), age-dependentneurodegenerative diseases(including Alzheimer’s and Parkinson’sdisease) and many other neurological-related applications.

Current pharmacological tools inpsychiatry are effectively limited tosymptom relief but are not inthemselves curative. The current drugsoften help and are needed formanagement and for other therapiesto have a chance to work (e.g.psychotherapy). Schizophrenias, OCD,ADHD, anxieties and phobias, damagedue to child abuse, neglect and traumaas well as many others, all potentiallyfall within the scope as beingamenable to neuroplastic

pharmacological curative tools yet tobe created.

Additionally, injuries and afflictionsrelating to neural wiring such as visionimpairment (whether it is congenitalblindness, macular degeneration,injury or optical nerve atrophy),hearing impairment (either congenitalor injury related), motor control(disease or injury), epilepsy andnumerous others are currently beyondour ability to cure.

The potential scope of applications ismuch wider and can apply to healthynormal people such as enhancement oflearning abilities (similar to that seen invery young children).

In the wider community (as well aswithin professional circles) there is awidely held hope that one day a‘miracle’ discovery will be made andthen these issues will be adequatelydealt with. Reality and historicalprecedents say otherwise.

The disconnect between researchand application, and thus a hurdle onthe path to change, can be consideredin terms of the maturity of technology,or technology readiness level (TRL).


BY MOTTY SOBOL

MakingconnectionsFrom neuroplasticity data to treatmentA treasure trove of existing and emergingmedical research findings beckonschemists to effect ground-breakingsolutions to a wide array of medical issues.

The mythology that medicalresearchers on their own and/orpharmaceutical giants will make thishappen is fervently clung to by many.

No one in the private sector paidany attention to Tyndall’s (TRL1) norFleming’s (TRL1) work until HowardFlorey serendipitously found Fleming’spaper and showed that it works inpractice having directed the effortsthat isolated the active compound,purified it and manufactured insufficient quantities to conduct initialclinical experiments (TRL3). Only thendid industry (prodded heavily by theUS government of the day due to itsprojected immediate wartime value)come on board and in record timebring it to TRL9 within four years.Nominally it takes 10–20 years totransition drugs from TRL3 to TRL9.

A golden opportunity forchemists in academiaWithout chemists, especially tenuredacademics who in spirit and positionare similar to Florey (who was ableand willing to obtain and commitresources and skills to try somethingabsolutely new and unproven) taking aleading role, medical theories anddiscoveries (TRL0–2) will very likelycontinue to be made but historycontinues to repeat as these arefrequently seemingly ignored becausethey are not a viable commercialproduct (TRL9 or at the very leastTRL3) as yet.

History and current practiceremains that pharmaceuticalcompanies do follow medical researchand do conduct their own researchinternally (and/or sponsored);however, there is no denying that theindustry has historically andconsistently shown an apparently verystrong preference to ‘ambulancechase’. To minimise their riskenvelope, they wait for someone elseto make a commercially valuableproven product and then buy them out,copy them or use that as a ‘lead’ toeither explore or use combinatoriallibraries to try structurally related

analogues. The prominent firms at thetime all missed the boat in terms ofboth opportunity and staggeringprofits with cytokines (the geneticsignalling molecules initiallycomprising G-CSF and GM-CSF) forcancer applications because it wasoutside the usual expectations forpharmacological entities.

Attitudes matterThe limiting step in paradigm changeis perceptions and attitudes. If youfervently believe that it can’t be done,then why would you even try?

It would be very reasonable toassert that unless another ‘Florey’comes along and takes the results ofexisting medical research results andtransitions one or more of these intoworking prototype(s) that will provethe concept (at least to TRL3), then it ishighly unlikely we will see the oft-hoped-for ‘miracle cure(s)’.

To date, very little attention isseemingly being paid by appliedchemists to a mountain of high-qualitydata (mostly TRL1) that hints atappropriate targets for drug designand development in the areas ofdementias, neurodevelopmentaldisorders, psychological andneurological disorders, blindness,deafness and learning issues, whichare all associated with neuroplasticity.Few chemists in academia andindustry take much notice of researchoutside of their chosen areas ofinterest, and genetic research is oftenviewed as not being ‘chemicallyrelevant’.

Genetic experiments revealtargets for drug designOncology (cancer) research has mademajor contributions to date, butperhaps the most overlookedcontribution is also the most important

Oncogenes are an inherently inbuiltsystem of ‘master regulator genes’.When these go faulty, the result iscancer. They exist to control, monitorand regulate the operation of all othergenes. They do this using a system of


concept00TRL

laboratory experiments/

clinical observations11TRL

initial working prototypes22TRL

proof of concept33TRL

commercial productdevelopment44TRL

regulatory preclinical data55TRL

regulatoryrequired

clinical trials66TRL

regulatory approval77TRL

initial sales and clinical usage88TRL

proven value andadopted as standard

clinical practice99TRL

Technology readiness level (TRL) rangesfrom concept stage (0) to adoption asstandard practice (9).

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receptors and messenger/signallingmolecules. Thus, any research thatshows activity/benefit by switching ‘on’or ‘off’ various genes by means ofgenetic experiments using vectors(genetically modified viruses thateither introduce and paste code or cutcode out or a mix thereof) cantranslate to targets for drug design anddevelopment.

Every successful geneticexperiment medical researchers reportis an alert to the existence of targetsthat are pharmacologically amenable togetting the same end result usingappropriately designed drugs. Theprecise biochemical mechanisms maynot be known as yet, but there ispotential to design drugs that eithermimic or duplicate the messages orselectively block the relevant receptors.The key to success is knowing what thetargets actually are.

Knowing the precise andcorrect target is critical: thecase of serotoninSerotonin (5-hydroxytryptamine or 5-HT) modulates cortical function viawidely projecting axons, which act ona diversity of receptor subtypes.Serotonin receptors are highlyheterogeneous and they have beenregrouped within seven differentfamilies (5-HT1–5-HT7). With theexception of the 5-HT3 family, which isa ligand-gated ion channel, all othersare G-protein coupled receptors, witheach family sharing structural,pharmacological and transductionalcharacteristics. 5-HT receptors havebeen implicated in the regulation ofseveral psychiatric and neurologicaldisorders related to serotonergicneurotransmission, and specificreceptor subtypes have recently beenassociated with either thepathogenesis or the treatment ofmigraine headache. Current evidencecontinues to support the use ofselective serotonin reuptake inhibitorsas first-line pharmacologicinterventions for OCD. Neuroplasticitymodulation and enhancement via 5-HT

agonists may well have a very usefulrole to play in chronic fatiguesyndrome, fibromyalgia and irritablebowel syndrome as well as otherimplicated medically unexplainedsymptoms.

Following the amazing success of 5-HT3 agonist ondansetron at changingthe face of medical treatment ofnausea and vomiting, attention turnedto a spectrum of 5-HT receptors aspotentially useful targets for drugdesign and development.

Between 2000 and 2007 Glaxo (UK)published their efforts to develop anovel (hopefully blockbuster class)rapid-acting antidepressant, havingpinned their hopes and efforts onserotonin reuptake via a well-designedagonist initially for 5-HT1B, then a dual-acting 5-HT1A/5-HT1B agonist (TRL5). Arecent paper by Melburnian medicalresearchers suggest they may wellhave had far better results if theytargeted 5-HT2A receptors instead. It’snow been demonstrated that 5-HT2A

agonists enhance functionalconnectivity between hierarchicalbrain networks, and modulate theinfluence of neural activity from lower-order upon higher-order regions(TRL1). The emerging data suggeststhat there may well be a useful role forthese agents in the treatment for majordepression, anxiety and drugaddiction and in particular in someproblematic circumstances wherecurrent treatment options are limited,prognosis is unfavourable, datasuggests scant, if any, objective benefitof current therapy options andclinicians have historically adopted adistrustful attitude towards thesedifficult-to-treat patients.

Separating fervently held beliefsfrom objective facts is critical. Thisapplies equally to the medicalresearchers conducting the geneticexperiments and clinicians who treatdiseases and conditions and tochemists who can assist bytransitioning medical research datainto practical pharmacologicalsolutions.

In schizophrenia for instance,initially the genetic operating basiswas dismissed because theassumptions about which genes wereresponsible was out by a country mileand the conceptual basis itself was fartoo simplistic to prompt a search in theright direction.

Further studies revealed thatschizophrenia is not one disease butseveral genetically distinct ones (andhence the way drugs work will differamong these). It is now known that atotal of 42 genetic clusters working intandem are responsible for thesymptoms of eight distinct disorders,all falling under one clinical label. Sofar, this new data has not seeminglyaffected how psychiatrists prescribedrugs or how they treat these patients.

Beyond the 5-HT receptor class,there are a myriad of potentialtargeting systems emerging frommedical research results.

Neuroplasticity in adults ispossibleNeuronal plasticity peaks early in lifeduring critical periods and normallydeclines with age. Neuroscientistsrecently showed that it’s possible toreturn some of this plasticity to the


The skeletal formula of serotonin,C10H12N2O, and the human 5-hydroxytryptamine (serotonin) receptor 2A. DrLee/CC0

brains of mice by tweaking a singlegene (TRL1) (doi: 10.1073/pnas.1700866114). They targeted theexpression of the Arc protein andgenetically deleted its coding fromDNA. This presents an enticing novelmolecular target that could be used tofight age-related cognitive decline inhumans. Moreover, the neuroscientistswere able to restore the plasticity inthe visual cortex of eyes of adult mice,potentially providing a gateway todeveloping means to restore sight,heal macular degeneration andcorrect age-related visual deficiencies.There are no effective treatment toolsat present, and chemists are notableby their absence in this area.

The same result hadserendipitously been obtainedpreviously when neuroscientists(neuropsychiatrists) used a widelyprescribed antidepressant drug calledfluoxetine ‘off-label’ (TRL1) (doi:10.1126/science.1150516). Theseresearchers were able to restore thevision of adult rats while in the processof opening the door to unravelling newmechanisms for the therapeutic effectsof antidepressants and for thepathophysiology of mood disorders.

Alessandro Sale, the co-author on thismajor paper was also the editor andco-author of the first chapter ofEnvironmental experience andplasticity of the developing brain (seereview December 2017/January 2018,page 32.)

A significant number of similarlyidentified targets have been reported.For example, the gene Lsampregulates emotional and socialbehaviour (TRL1) and could potentiallybe the gateway to cures in a range ofpsychiatric illnesses and drugdependency.

The potential targeting informationavailable is at times very precise. Forexample, medical researchers arepinning down specific key moleculesin the development and pathogenesisof emotion-related behaviour. Oneexample is netrin-G1 which is aglycosyl-phosphatidylinositol-anchored synaptic adhesion moleculewhose deficiency results in impairedfear-like and anxiety-like behavioursunder specific circumstances. Geneticdeletion of netrin-G1 in corticalexcitatory neurons resulted in alteredanxiety-like behaviour, but intact fear-like behaviour, whereas loss of

netrin-G1 in inhibitory neuronsresulted in attenuated fear-likebehaviour, but intact anxiety-likebehaviour.

From assumption toopportunityWe’re starting to unravel the geneticsof pathology in mental health anddegenerative diseases among aplethora of neural-wiring-relatedapplications potentially amenable viatargeting the receptors used in thecommand and control of thesepathways. This is the point where a gulfexists between existing medicalresearchers and those who cantransform their discoveries intopractical solutions. Many of our mostcherished and widely long-heldassumptions are proving to be false.We’ve never seriously looked atneuroplasticity because we haven’tbelieved the possibilities.

‘Use it or lose it’ is the coreoperating principle of neuroplasticity.The same applies to these current andemerging golden opportunities.

Dr Motty Sobol FRACI CChem is a Neupogen awardrecipient (oncology research) and consultant toindustry (chemical and allied industries).


The Ancient Roman philosopher Seneca proposed that a humanembryo is an adult in miniature and thus the task ofdevelopment is simply to grow bigger. This idea was soappealing that it persisted for almost 2000 years. Only recentlywas brain development found to be a series of stages that canbe broadly divided into two phases:1 a genetically determined sequence of events in utero that

can be modulated by maternal environment2 a time (which is both pre- and post-natal in humans) when

the connectivity of the brain is very sensitive, not only tothe environment but also to the patterns of brain activityproduced by experiences. More importantly, however, it is now recognised that

epigenetic changes, which can be defined as changes indevelopmental outcomes, including regulation of geneexpression, are based upon mechanisms other than DNA itselfand that gene expression can be altered by specific experiences,and this in turn can lead to organisational changes in thenervous system.

Neuroplasticity is now known to be affected by:

Brain development and epigenetic change

experience (both pre- and post-natal)psychoactive drugs (e.g. amphetamine, morphine)

gonadal hormones (e.g. oestrogen, testosterone)anti-inflammatory agents (e.g. COX-2 inhibitors)

growth factors (e.g. nerve growth factor)dietary factors (e.g. vitamin and mineral supplements)

genetic factors (e.g. predisposition, strain differences, genetically modified mice)

disease (e.g. Parkinson’s disease, schizophrenia,epilepsy, stroke)

stress (physical and/or psychological)brain injury and trauma

Science is not the lonelyprofession that it used to be.Gone are the days of themisanthrope academics

locked away in their ivory towers, insingle-minded pursuit of arcanescience. In the modern world, wholegroups of academics cram into theirivory towers, collaborating to createthe next leaps forward in scientificunderstanding. In 1675, Sir IsaacNewton wrote to Robert Hooke: ‘If Ihave seen further than others, it is bystanding upon ye sholders of giants’.Even then, he was adapting words thatwere already centuries old.

How, then, do we recogniseachievement in the new era of

science? Over the last 50 years, therehas been a steady growth of the NobelPrize in Chemistry being awardedjointly, and most particularly in thelaurels being shared by the mandatedmaximum of three researchers. From1968 to 1977, three researchers sharedthe prize just once. By contrast, the2017 winners collected the eighthinstance of a triple-shared prize in thelast decade.

In 2017, the world’s most famousprize for scientific merit was awardedto three researchers – JacquesDubochet (University of Lausanne,Switzerland), Joachim Frank (ColumbiaUniversity, USA) and RichardHenderson (MRC Laboratory of

BY DAVE SAMMUTAND CHANTELLE CRAIG

The 2017 Nobel Prize in Chemistry. Part 1

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The limits ofmicroscopyresolution havebeen smashed aspart of workrecognised by the2017 Nobel Prize inChemistry.

Molecular Biology, UK) – ‘fordeveloping cryo-electron microscopyfor the high-resolution structuredetermination of biomolecules insolution’.

This relatively new science for thevisualisation of active molecules iscreating significant excitement at thebiochemical frontier. As just oneexample, the technique has alreadybeen used to create high-resolution,3D images of the Zika virus in itsnatural state, identifying targets for avaccine.

As is becoming common in modernscience, the story of this breakthroughis one of separate, complementarydevelopments coming together tocreate something outstanding.

The scienceLet’s start with the basics. For thepurposes of this article, I’m going tofollow the Royal Swedish Academy ofSciences in describing a fairly broadrange of molecules, biologicalmacromolecules and complexesunder the generic term ‘particle’.

The structure of particles influencestheir activity. This is particularly thecase with biologically active particles,for which the structures can get reallycomplex. Much more than just theissue of potential chirality of simpleorganic molecules, the complexity ofparticles only grows when you start toconsider issues such as the folding ofproteins (see May 2017, p. 26), or thephysical interactions between particlesand their environment.

Learning about the structure ofthese particles tells us a great dealabout their behaviours. Perhapsmost famously, the 1962 Nobel Prizefor Physiology or Medicine wasawarded to Watson and Crick ‘fortheir discoveries concerning themolecular structure of nucleic acidsand its significance for informationtransfer in living material’. Theirdiscovery crucially relied on X-raycrystallography results generatedby Rosalind Franklin, who was onlyposthumously recognised for hercontribution to this seminal work (seeAugust 2014, p. 19).

Conventional microscopes fail atresolutions less than 400nanometres,because molecules such as proteins aresmaller than the wavelength in thevisible spectrum. As demonstrated byWatson, Crick and Franklin, X-raycrystallography can assist with thevisualisation of particles. X-raycrystallography was also key to the1962 Nobel Prize in Chemistry, for MaxPerutz and John Kendrew’s studies of thestructures of globular proteins.

However, X-ray crystallographysuffers two substantial drawbacks.First, it only works for materials thatwill form crystals, which eliminates asignificant portion ofbiologically active samples.And second, even when acrystal can be formed, this isoften only possible bychanging the matrix and/orstate of the particle, so that thebiological function or activitycan’t be assessed in context.

Nuclear magneticresonance spectroscopy canassist in the characterisation ofsamples that are non-crystalline, but it is limited tovery small particle sizes.Anything so large as aribosome or an ion channel isprohibitive, let alone full cells.


Over the last few years, researchers have published atomic structures of numerouscomplicated protein complexes. From top to bottom: a protein complex that governs thecircadian rhythm; a sensor of the type that reads pressure changes in the ear and allows usto hear; the Zika virus.© The Royal Swedish Academy of Sciences

An earlybreakthrough inmicroscopy camewhen it was foundpossible to producean image of anobject by using anelectron beam.

So an alternative technique was stillneeded. An early breakthrough inmicroscopy came when it was foundpossible to produce an image of anobject by using an electron beam.With a significantly shorterwavelength, electrons offer atheoretical resolution as fine as about0.1 nanometres, subject to quantumeffect limitations.

Ernst Ruska constructed the firstelectron microscope in 1933, for whichhe (jointly) won the Nobel Prize inPhysics in 1986. He went on to takepart in the development of the firstcommercial mass-produced electronmicroscopes, which many consider tobe the major breakthrough for thisanalytical technique.

However, electron microscopy (EM)also has a number of significantdrawbacks. It has suffered long-termproblems with sample preparation andstability, signal quality, and dataanalysis, and many of these problemswere widely considered to bepotentially insoluble.

Samples must be very thin to limitmultiple electron scattering events,preferably only a single layer of theparticles of interest. As well as this, evenin crystalline samples the particlesthemselves can move due totemperature changes or interaction withthe electron beam, and the movementfurther limits the resolution of theimages. This effect is then influenced orlimited by the speed of the detector.

And the problem is exacerbated fornon-crystalline, asymmetric, randomlyoriented particles.

Furthermore, EM requires vacuumconditions, which tends to vaporisewater from samples, and which in turncan completely change their structureand/or chemistry. For EM to have wideapplicability, it needed a technique topreserve water in the particles.

In transmission EM (of which cryo-EM is an improved version), only aportion of the high-energy electronsinteract with the particle, yielding lowcontrast and in turn requiring high-intensity electron beams. But suchintensive beams commonly destroybiological samples, and so theresearcher was faced with the trade-off


13th–14th centuries

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Microscopy through the ages

First scanning electron microscope built by Ernst Ruska. It transmitsa beam of electrons across specimen surface.

Lenses developed for use in spectacles.

First microscope made by Dutch lens grinders Hansand Zacharias Janssen by placing two lenses in a tube.

Cryo-electron microscopy allows high-resolution structure determination of biomolecules. NobelPrize in Chemistry awarded to Jacques Dubochet, Joachim Frank and Richard Henderson.

Scanning tunneling microscope invented by Gerd Binnig and Heinrich Rohrer. It can give 3D images down to the atomic level.

First transmission electron microscope builtby Ernst Ruska. Using electrons, rather thanlight, greatly improves resolution.

Phase-contrast microscope invented by Frits Zernike, which could study colourless and transparent biological materials.

Ultramicroscope developed by Richard Zsigmondy, which could study objects below the wavelength of light.

Ernst Abbe’s mathematical formula correlating resolution to the wavelengthof light made it possible to calculate theoretical maximum resolution.

Compound microscope developedby Galileo Galilei.

Robert Hooke published his microscope studies,including of cork, in Micrographia.

Spherical aberration reduced by Joseph Jackson Lister, who combinedseveral weak lenses to give good magnification with no blurring.

Living cells seen by Anton van Leeuwenhoek using a simple, single-lens microscope.He achieved up to 300 times magnification of blood, insects and microorganisms.

Technical advances improved microscopes and they became more common.

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between potential sample damage andlimitation of resolution. EM has untilnow been generally only considered tobe applicable to ‘dead’ samples.

Ultimately, this is a problem ofsignal-to-noise ratio. These effectstypically limited EM to resolutions of afew nanometres, whereas cryo-EMpotentially offers an extra order ofmagnitude of resolution.

Lastly, there are all the limitations ofthe data capture and analysis. Thestructure of the particles beinganalysed is three dimensional, and sothe techniques that have beendeveloped have had to be able tocapture and then transform theelectron scattering data, particularlygiven the complexities of low signal-to-noise ratio, randomly orientedparticles, and the transformation of 2Dsections into 3D visualisations.

The instrumentCollectively, the 2017 Nobel Prizerepresents the pinnacle ofaccumulated developments overdecades, with individual inspiration

and dedication that has combined tocreate a new analytical capability withrevolutionary implications.

Cryo-EM uses the previously-unknown ‘vitrified’ state of water belowaround –160°C to effectivelyencapsulate and protect biologicalparticles, both preserving them duringanalysis, and allowing virtually ‘in situ’states to be analysed. It then appliessome very sophisticated data captureand modelling to create very high-resolution visualisations.

One of the most important aspectsof cryo-EM is its ability to analyse verysmall sample quantities, effectivelytaking it closer to single particleanalysis. But the technique is alsoversatile across a wide particle sizedistribution, from nano-scale tomacromolecule complexes well over500 000 daltons. In 1995, Hendersonanticipated that enzymes might beanalysed to as little as 52 000 daltons,and this has improved with ongoingdevelopments in the technology.

Having come far from its earlydescription as ‘blobology’, cryo-EM

offers an unprecedented degree ofresolution. In 2015, Dr SriramSubramaniam, of the National CancerInstitute’s Center for Cancer Research,imaged the enzyme betagalactosidase at a resolution of just0.22 nanometres (bit.ly/2jPTway).

The technique is already proving tobe a valuable tool across a range ofbiological fields: botany,biotechnology, zoology,pharmaceuticals, health care andcosmetics. Understanding howbiomolecules function and interact isfundamental to the development ofnew innovations in any of thesesciences. At this level of detail andresolution, it offers a powerful tool forunderstanding biochemistry in itsdynamic states.

In the next article, we’ll look at theindividual contributions fromDubochet, Frank and Henderson.

Dave Sammut FRACI CChem and Chantelle Craig arethe principals of DCS Technical, a boutique scientificconsultancy, providing services to the Australian andinternational minerals, waste recycling and generalscientific industries. Part 2 of this article will bepublished in the March issue.


The resolution progression of cryo-EM, illustrated by a representation of glutamate dehydrogenase with an increasing level of detail from leftto right. For a protein of this size, 334 kDa, the 1.8 Å resolution to the right (38) could only be achieved after 2012/13. After an image by V. Falconieri (Merk A. et al. Cell 2016, vol. 165, pp. 1698–1707). Illustration: © Martin Högbom, Stockholm University.

Metal–organic frameworks(MOFs), also known asporous coordinationpolymers, were first

discovered by Professor RichardRobson at the University of Melbournein 1989. Consisting of metal atoms orclusters joined to one another byorganic molecules, their crystallinestructures have unprecedentedsurface areas and uniform pore sizes.They may be capable of drasticallyenhancing the efficiency of a raft ofprocesses that include separation,storage, detection and release of

target molecules. MOFs have beenselected by the World EconomicForum’s Expert Network and GlobalFuture Councils in collaboration withScientific American and its Board ofAdvisors as one of the top tenemerging technologies of 2017 fortheir ability to harvest clean waterfrom the air using no energy at all. Thetechnology has been successfullytested by researchers from theUniversity of California Berkeley, incollaboration with MIT, with a proof-of-concept device using a zirconium-based MOF, which showed that one


From laboratoryto factoryOnce thought of as

the ‘gunk in thebottom of the flask’,metal–organicframeworks haveemerged as apotential wondermaterial. MartaRubio-Martinezand Matthew Hillpresent anAustralianperspective.

Metal–organicframeworks

K. Lee, J. Howe and J. Neaton, Molecular Foundry at Berkeley Lab/UC Berkeley

kilogram of the material could collectnearly three litres of fresh water perday – enough to supply drinking waterfor one person – from very dry air witha humidity of just 20%.

However, questions have arisenregarding the time taken for thetantalising properties reported underlaboratory conditions to be realised inapplied settings. Notably, thecomparable material family of zeolitestook several decades to findapplication, and MOFs are significantlymore complex and varying materials.Nevertheless, in the past couple ofyears, the hurdles standing in the wayof MOF commercialisation have beenbrought down, and new products areemerging.

The major challenge in makingMOF application feasible is the cost-effective manufacture of MOFs on alarge scale. Although many differentMOF types with tailored functionalities

have been developed in the laboratory,typically each of them requires aspecific synthetic method or at leastspecific details. These laboratoryreactions are quite slow, lasting up toseveral days, and yield only a fewmilligrams of high-quality crystals. Toadd to the challenge, these processescannot be simply scaled up to producemore material. MOF crystals need asurface to nucleate, and using a largerreactor vessel dramatically reducesthe surface to volume ratio, slowingdown the synthesis or yielding poor-quality materials.

The use of solvents is anotherproblematic aspect; many laboratorysyntheses require large amounts ofsolvents, which are costly to obtain andcostly to process as waste materials.Scaled up, these approaches would beeconomically unviable.

These hurdles have motivated manyresearchers and engineers to explore

and develop novel and commerciallyviable routes to produce MOFs in anefficient, reproducible and cost-effective way.

Two promising strategies aremechanochemistry and flowchemistry.

The central idea behindmechanosynthesis is to promotechemical reactions by milling orgrinding solids with no or minimalamounts of solvents (see image belowleft). This synthetic approach isrestricted to the synthesis of only a fewtypes of MOF structures, but is themost environmentally friendly processfor producing MOFs, and couldsignificantly lower the cost ofproduction.

Flow chemistry, on the other hand,is a continuous processing technologythat originated in the pharma andagrochemical sectors in the last twodecades and which CSIRO has


Left: MOF water-harvesting device, composed of a MOF layer and a condenser. The highporosity of the MOF layer allows water to be captured from the ambient air. By placing thedevice in the sun, the MOF is heated and releases the captured water, which then condensesand is ready for collection. Right: Image of the device built for extracting drinking water fromthe air. First published in Rubio-Martinez M. et al. New synthetic routes towards MOF production at scale. Chem. Soc. Rev.,2017, vol. 46(11), pp. 3453–80.

From left to right: Mechanochemical synthesis of MOFs with a twin screw extruder. The CSIRO flow reactor capability used to fabricate MOFsat the kilogram scale. Seven kilograms of copper-based MOF synthesised by CSIRO flow reactor in six hours.First published in Rubio-Martinez M. et al. New synthetic routes towards MOF production at scale. Chem. Soc. Rev., 2017, vol. 46(11), pp. 3453–80.

... in the pastcouple of years, thehurdles standing inthe way of MOFcommercialisationhave been broughtdown, and newproducts areemerging.

adapted as a new method to produceMOFs (see middle image bottom ofpage 25). Contrary to batch reactions,in a flow chemistry set-up, thechemical reactions occur in acontinuously flowing stream in a tubeor pipe rather than in a reactor vessel,solving the problem of surface area tovolume ratio. This new method allowsprecise control over the reactionparameters and delivers an enormousthroughput while maintaining theversatility to produce many typesof MOFs. Reaction times in a flowreactor are dramaticallyreduced from days tominutes, without any loss inquality.

These two novelapproaches to large-scaleproduction are a completegame changer for MOFs,opening the way forcommercial application thatdepends on a kilogramscale and above.

Despite these promisingadvances in productionmethods, MOFs still remain aniche product in commercialmarkets. This is in part due to the highcost of production, caused byexpensive solvents and raw materials,but it is also a market phenomenon. Atthis stage, there is a low overalldemand, which is typical for researchapplications, and commercial MOFsynthesis is limited to small-scalebatch production. Most MOFs areretailed at the gram scale by chemicalsuppliers such as BASF and STREM,and the cost is prohibitive for mostindustrial applications that requiremuch larger amounts.

However, a recent study by MosaicMaterials, a spin-out from theUniversity of California, incollaboration with the Ford MotorCompany, reported that this scenariowould dramatically change oncemarket demand picks up. Theircomplete techno-economic analysesof four different MOFs with potentialfor hydrogen and natural gas storage

assumed a high production of2.5 Mkg/year. The study shows that, inthis case, MOFs can be produced atscale economically if opportunities forfurther cost reduction are employed,such as using cheap and recyclableMOF precursors, reducing the amountof solvent and waste, and low energyconsumption. In essence, this means areduction from thousands of dollars toprices between $35 and $71 perkilogram, making the many potentialapplications feasible on a largecommercial scale. Owing to the manyapplications, the growing market forMOFs will push MOF suppliers forfurther cost-efficiency to remaincompetitive. MOF production at scaleis already underway, which will help

secure customer confidence and openthe door for other MOF-basedproducts in the mid to long term.

The first industrial companyinterested in MOFs was BASF, whichhas been exploring this topic for thelast 15 years. During this time, thechemical giant has been working withleading researchers in the field andhas developed a product portfolio ofdifferent MOF applications as well asselling six MOF products under the

product names Basolite® andBasosiv™ to universities and

companies for researchpurposes.

Since the first patentwas filed in 1995 by the

Nalco chemicalcompany in the US,

commercialisation ofMOFs has progressedslowly. The first MOF-based productsentered the marketmore than 10 yearslater in 2016 by MOF

Technologies and NuMatTechnologies. MOF

Technologies, from Queen’sUniversity Belfast, developed a systemcalled TruPick in collaboration with thefruit and vegetable supplier DeccoWorldwide Post-Harvest Holdings. Theproduct is a micro-adsorbent thatholds methylcyclopropene – a gas thatblocks the post-harvest ripening offruit and vegetables, extending thestorage life and quality of many fruitsand vegetables. Another MOF-basedproduct called ION-X, developed byUS spin-out company NuMatTechnologies, was launched last year.These gas cylinders are based on aproprietary set of MOFs for storinggases such as arsine, phosphine andboron trifluoride, which are importantas dopants in the electronics industry.

In both cases, the companies werespun out of universities but otherinitiatives are also working towards thecommercialisation of MOFs. Forexample, MOFapps aims to bringresearch and industry together by


The microporous molecular structure of azeolite, ZSM-5. This aluminosilicate zeolitehas a high silicon and low aluminiumcontent. Thomas Splettstoesser/CC BY-SA 4.0

… zeolites tookseveral decades tofind application,and MOFs aresignificantly morecomplex andvarying materials.

chemistryin Australia

MEDIA KIT

2018chemaust.raci.org.au

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

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

identifying opportunities anddeveloping commercially viableapplications in the areas of gasstorage, industrial cooling, toxic gasprotection and health care. From anAustralian perspective, CSIRO hascreated the spin-out entity MOFWORX,which is actively developingtechnology to directly capture carbondioxide from the atmosphere for amyriad of uses. The potential for suchtechnologies is based upon thediscovery and development ofcontinuous flow-based MOFproduction, underpinning the ability toaccess commercial scales of materialin an economically viable fashion.MOFWORX will continue as a

production house, developing MOF-based technology, targetingproduction in Australia.

Recent developments in the large-scale production and commercialapplication of MOFs leave the researchfield at a fascinating juncture. In futureyears, as more MOF-based productsfind their way into the marketplace,previously unknown challenges andopportunities will be surely uncovered.For chemistry researchers, this willspur additional fundamental researchchallenges. Scale-up production, whileextremely promising, requires furtherdevelopment to improve efficiency andthe overall economics. Chemists whoare able to transition production tosustainable starting materials andsolvents will find huge traction.

While many MOFs may appear fit-for-purpose, it is inevitable that new

characteristics will be uncovered whenthey are put to the test in the field.From an Australian perspective, thereis a remarkable strength ofresearchers in the field, going rightback to the original inventor, and theteam is globally recognised. They arewell placed to lead in these newresearch opportunities as they arise,with the MOF2018 conference inAuckland an opportunity for this workto be showcased to the globalcommunity. Partnership withcommercial interests in Australia, suchas MOFWORX and other partners, is akey step to both enhancing scientificresearch and finding impactcommercially.

Dr Marta Rubio-Martinez is a research scientist atCSIRO. Professor Matthew R. Hill is a principalresearch scientist at CSIRO and associate professor atMonash Chemical Engineering. A reference list isavailable from the author.


Left: TruPick technology from MOF Technologies based on NT-7815 micro-adsorbent forextending the storage life and quality of many fruits and vegetable. Right: Gas storage tankION-X technology developed by NuMAT for storing speciality gases used in the electronicsmanufacturing industry. First published in Rubio-Martinez M. et al. New synthetic routes towards MOF production atscale. Chem. Soc. Rev., 2017, vol. 46(11), pp. 3453–80.

The study showsthat, in this case,MOFs can beproduced at scaleeconomically ifopportunities forfurther costreduction areemployed ...

obituary


Dr Peter Smith was a much loved and revered figure in theclose-knit Tasmanian chemistry and science communities. Achampion for the advancement of science, and a most generousyet unassuming philanthropist, Peter died on 2 July 2017, aged93.

Peter was born 30 June 1924, an only child. Young Peterexcelled at primary school and later studied at the HobartTechnical High School. Upon completion, he found employment,working as a laboratory assistant for an arc weldingmanufacturer (1940–6). During this time, he studied part-timein the evenings at the Hobart Technical College, achievingdiplomas in both chemical engineering and metallurgy (1945),and ultimately a Diploma of Applied Chemistry (1948). He hadappointments with the Australian Aluminium ProductionCommission (1946–7), Murex Australasia – Chemical andMetallurgical Laboratories (1947–51), and then as an examinerat the Australian Patents Office in Melbourne and Canberra(1951–2).

He returned to Hobart, taking up a position as laboratorydemonstrator in chemistry at the University of Tasmania in1952, studying part-time for a BSc (awarded 1956, Honours1957). Granted leave, he enrolled for his PhD at University

College London, supported by a Du Pont Scholarship. Workingunder the supervision of Professor R.S. Nyholm, Peter wasawarded his PhD in 1962 for his work entitled ‘Aspects of thechemistry of molybdenum halides’. This interest in molybdenumchemistry stayed with him throughout his career.

Returning to the University of Tasmania, Peter progressedfrom lecturer (1962) to senior lecturer (1966) and ultimatelyreader (1971), serving for a time as Acting ChemistryDepartment Head (1981–2). Peter was a committed teacher,with responsibilities typically focusing around his expertise inclassical inorganic and solid state chemistry. However, he wasalso innovative and forward thinking, modernising thecurriculum in the inorganic program, as well as introducing newemerging topics such as Analytical Chemistry, Industrial andApplied Chemistry, and Chemistry for Engineers.

His research was productive, with a focus on the chemistryof intermediate oxidation state compounds of molybdenum,chromium, tungsten, vanadium and titanium, with particularreference to preparative, structural, magnetic and spectroscopicproperties of some halides and pseudo-halides. This work provedfruitful, with around 40 papers being published, stemming fromhis supervision of approximately 25 honours and PhD students.

Peter W. Smith OAMGenerous and distinguished inorganic chemist


Recognising the importance of spectroscopy and instrumentationto university research, Peter was a key driver for theestablishment of the Central Science Laboratory (1974).

Following his formal retirement in 1989, and with concernsabout the future supply of scientists in Tasmania and Australia,Peter established his undergraduate scholarships in PhysicalSciences at the University of Tasmania in 2002. A generousscholarship, Peter was at times supporting as many as10 recipients. To date, approximately 30 students have benefitedfrom Peter’s generosity and support.

Outside the university, Peter made many profoundcontributions to professional life in Tasmania. Foremost amongthese was his support for the RACI. Peter joined the Institute as aStudent member in 1940 and rose to Fellowship in 1972. He was aformer Branch Secretary, Vice-President and two times President inthe 1960s and 1980s. He was awarded a National Citation for hiscontributions to the profession in 1988, and was an Honorary LifeMember. It was a privilege for some members of the local Branchto celebrate with Peter on the occasion of his 75th year ofmembership recently.

Peter also contributed in many other areas. He was a LifeMember of the RSC (joining 1957), an office bearer and PastPresident of The Royal Society of Tasmania, an Honorary LifeMember of ANZAAS (joining 1942), a much loved and distinguishedEmeritus Fellow at Jane Franklin Hall residential college, a Branch

member and State Chair of AUSIMM (joining 1969), and Tasmaniandelegate to national council of AINSE (1982–9).

In his later years, Peter’s many contributions were recognisedand honoured through receipt of a University of TasmaniaDistinguished Alumni Award (2005), an Honorary DSc (2011,coinciding with 50 years of Chemistry at the Sandy Bay campus),and in 2012 a Medal of the Order of Australia (OAM) ‘for servicesto science, education and philanthropy’.

Peter never married, but in numerous conversations made clearhe was never lonely. The countless students that came under histutelage, his many colleagues, and his vast array of friends werehis ‘family’ whom he kept in close contact with. Deeply loyal, hevalued each, and kept close tabs on the lives of countless many.In return, Peter was embraced, honoured and cherished intobroader family circles.

Peter is fondly remembered and held in the highest esteem byTasmanian chemists across many generations. What set him apartfrom other educators was his consistent, sincere interest in thewelfare of those students he taught or was associated with. Heknew names, knew where each came from, met families, and wasinterested in individual journeys. He gave encouragement and,when necessary, rebuke to help make each student work and studyharder. He organised excursions to Tasmanian chemical industries,helped students find vacation employment, and demonstrated theimportance of contributing to a professional society. He wasgenerous with his time and resources, and genuinely cared for thewellbeing of all.

The Australian chemical landscape has changed with thepassing of Peter Smith. However, he has left us an amazingexample, and an amazing legacy. We are thankful for his life andcontributions, ever proper, ever distinguished, ever a scholar.

Ashley Townsend FRACI CChem, Jak Denny MRACI CChem, Eoin Breen andBrian Yates MRACI CChem

What set him apart from othereducators was his consistent,sincere interest in the welfareof those students he taught orwas associated with.

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.

raci news


Jennifer Martin FAA is Director of the Griffith Institute forDrug Discovery (GRIDD, formerly Eskitis Institute). GRIDD ishome to Compounds Australia, the nation’s compoundcollection, and NatureBank – a unique drug discovery platformbased on natural product extracts and fractions that have beenderived from Australian plants, fungi and marine invertebrates.GRIDD also boasts unique resources for bioaffinity screeningand high throughput screening/high content imaging.

Martin is one of Australia’s foremost crystallographers,having made pioneering discoveries in protein crystallographyand structural biology, specifically in the field of redox biologyand drug discovery. She was the first to report a structure of anoxidative protein folding catalyst and to identify theevolutionary link between protein reductases and bacterialprotein oxidases. She has reported structures of more than 130 proteins and protein–inhibitor complexes.

Martin is a former ARC Laureate Fellow, ARC ProfessorialFellow, NHMRC Senior Research Fellow and ARC Queen ElizabethII Fellow. She holds BPharm (Gold Medal) and MPharm degreesfrom the Victorian College of Pharmacy, and was an 1851Scholar during her PhD research at the University of Oxford. She

is currently President of the Asian Crystallography Association,and a member of the Executive Committee of the InternationalUnion of Crystallography.

Since establishing her laboratory 25 years ago, Martin hastrained a generation of structural biologists. She is a strongadvocate for women in science, and a founding member of theAustralian Academy of Science ‘Science in Australia GenderEquity (SAGE)’ Committee that is implementing the AustralianAthena SWAN pilot. She is a member of the NHMRC Women inHealth Science Committee and was awarded the 2017 WunderlyMedal of the Thoracic Society for her work in gender equity.

Martin is passionate about raising awareness of science, andwas inducted as a Bragg Member of the Royal Institution ofAustralia in 2017 for her contributions in this area. Theseinclude establishing Ångstrom Art to use stunning scienceimages on free postcards; lobbying Australia Post to release a2012 stamp of Lawrence Bragg in the centenary year of Bragg’slaw; and lobbying the Royal Australian Mint to issue a coinfeaturing crystallography in 2014, the UNESCO InternationalYear of Crystallography.

New Fellow


Joseph Bevitt MRACI CChem is the inaugural recipient ofANSTO’s Excellence in Science Communication and OutreachAward, for his skills in translating complex scientific ideas andconcepts to broad audiences.

The Excellence in Science Communication and OutreachAward was introduced by ANSTO in 2017 to recognise anindividual who has made an effort to inspire and nurture thefuture generation of scientists and engineers.

As ANSTO’s Research Office Manager, Joseph is passionateabout showcasing ANSTO’s capabilities to students and tappingtheir curiosity to consider potential careers in the area ofscience, technology, engineering and mathematics (STEM).

Michael Druce received the Sustained Contribution to ANSTOAward for his key role in Australia’s advancement andmanufacturing of molybdenum-99. This parent isotope oftechnetium-99m is used in many nuclear medicine procedures

to diagnose diseases such as heart disease and cancer and todiagnose skeletal injuries. Druce was involved in thedevelopment of ANSTO’s 99mTc generator.

Jessica Veliscek-Carolan received the ANSTO Early CareerAward for her role in looking for improvements in the safe andsustainable management of radioactive waste.

The Australian Centre for Neutron Scattering SampleEnvironment team received the George Collins Award forInnovation for their ability to provide innovative solutions forchallenging neutron beam experiments.

ANSTO CEO Dr Adi Paterson said it was a real privilege towork among such a talented cohort of individuals. ‘Our peopleare our greatest asset and it’s important to our organisation tocelebrate their achievements and motivate them to be the best.’

ANSTO

Joseph Bevitt receives new ANSTO research award

books


Perfluorinatedchemicals:contaminants of concernCheremisinoff N.P., ScrivenerPublishing (John Wiley & Sons), 2016,hardback, ISBN 9781118363538,272 pp., $321.95

Talk about good timing! Dr NicholasCheremisinoff (an experiencedchemical engineer and technicaleditor of more than 145 books sincethe early 1990s) has provided yetanother valuable guide to theenvironment industry. He hasdelivered another ‘primer’ with the

right balance of the fundamental chemistry and environmentalscience of an emerging contaminant group, against practicalguidance and related case studies.

Typical of such an emerging contaminant, the fluorine-basedpolymer group was initially described as ‘perfluorinatedchemicals’ (or PFCs) as the book title notes, but theterminology for the environmental contaminant has quicklyevolved to PFAS, now encompassing the broader range of bothper- and poly-fluorinated alkyl substances. Cheremisinoff greatlyhelps to clarify such definitional issues, noting:

PFASs comprise a large group of chemicals that are both chemically andthermally stable and are both lipophobic (have no affinity for oils) andhydrophobic (have no affinity for water), making them very useful insurfactants and as polymers. However, PFASs are composed of two mainparts; one that is formed out of a hydrophobic alkyl chain and ahydrophilic (strong affinity to water) functional group. A total of 146perfluorochemicals and 469 fluorochemicals are potentially able todegrade to PFCAs. The most investigated classes of PFASs are theperfluorocarboxylate acids (PFCAs) and perfluoroalkyl sulfonic acids(PFSAs). The most studied PFCA compound is perfluorooctanoic acid(PFOA) and for PFSA it is perfluorooctane sulfonate (PFOS).

PFAS is a highly topical, front-page issue across Australiaand internationally, primarily due to the wide-spread historicaluse of these compounds, especially in aqueous fire-fightingfoams (AFFF), for which PFAS compounds were an importantingredient. Again, Cheremisinoff notes:

The most investigated classes of PFAS are the perfluorocarboxylate acids(PFCAs) and perfluoroalkyl sulfonic acids (PFSAs). The most studied PFCAcompound is perfluorooctanoic acid (PFOA) and for PFSA it isperfluorooctane sulfonate (PFOS).

Indeed, because of its persistent, bioaccumulative and toxic(or PBT) characteristics, PFOS became a designated persistentorganic pollutant, joining the better-known ‘dirty dozen’identified at the 2001 Stockholm Convention.

Cheremisinoff’s book is an excellent primer for environmentalscientists and engineers currently involved in the assessment andmanagement of this vexing and ubiquitous contaminant group.The book’s well-designed table of contents takes readers fromdefinitional challenges, through the vast uses of this group ofcomplex chemicals, through the ‘supply chain pathways’, to itshuman and environmental risks and associated regulatory agencyconsiderations. The latter part of the book provides an overviewof treatment technologies and it rounds out with four casestudies of PFAS-contaminated sites (all in the US).

Perhaps it was due to the rapid publication of this book tomeet market demands, but one minor complaint in my readingof this book was the frequent duplication of information. This ismost evident in relation to chapters associated with the healthrisk studies (Chapter 4), regulatory framework (Chapter 7) andthe case studies (Chapter 10), although perhaps it was theauthor’s plan to design these chapters to be able to be read inisolation, resulting in such duplication.

Of course, the pace of international research anddevelopment for PFAS has been nothing less than astonishing,and so it is to be expected that a book on PFCs would bequickly superseded. However, the currency of Cheremisinoff’sbook remains valid, especially in relation to the fundamentalchemistry of this complex contaminant. Like any emerging

A family tree of perfluoroalkyl and polyfluoralkyl substances


contaminant, standards, advisories and restriction (Chapter 7)and treatment options/technologies (Chapters 8 and 9) havebecome quickly dated and should be read with caution in lightof significant international changes, especially in the last12 months.

While not meaning to diminish the substantial value of thisbook, I wanted to identify two notable omissions. The first (atleast in my biased analytical chemist’s mind) was the lack ofdiscussion of the analytical chemistry for this complex group ofcompounds, especially in relation to the challenges associatedwith analysing environmental levels for such a ubiquitouscontaminant, as well as increasing interests in PFAStransformational and precursor compounds. The rapiddevelopment of analytical methods for total organic fluoride(TOF) and the total oxidisable precursor assay (TOPA) arequickly emerging to address so-called ‘hidden PFAS’, especiallywhen the comprehensiveness and adequacy of remedialtechnologies are being evaluated. The second notable omissionconcerns linking of the compounds’ environmental chemistrywith their ‘fate and transport’, although this issue istangentially discussed in Chapter 6 (‘Supply Chain and Pathwaysto Contamination’). A second edition of the book would benefitfrom the development of a conceptual model that bringstogether the complex real-world environmental characteristicsfor these compounds.

Given the substantial international level of interest in PFAS,a second edition will probably be welcome. Such a revisioncould include updating of the compounds’ regulatory status,more details on the increasing variety of remedial technologiesfor water, groundwater, soil and structures, and the addition ofmore case studies (noting that Australia has a wealth ofexamples to draw upon). As noted, the very recent andsignificant developments in analytical chemistry and a furtherexpansion of the compounds’ fate and transport may also provesagacious for a second edition (please?)

In conclusion, I strongly recommend Cheremisinoff’s ‘primer’for those environmental chemists, environmental engineers,environmental regulatory agencies and the wider communitywho are involved in PFAS, as a very useful fundamental guide.The sheer novelty of this emerging contaminant groupcontinues to cause confusion in relation to fundamentalchallenges such as terminology and basic chemistry andCheremisinoff’s book may help to address these issues andperhaps allow the debate to move into finding solutions tothese vexing contaminants.

Ross McFarland MRACI CChem

Strange chemistry:the stories yourchemistry teacherwouldn’t tell youFarmer S., Wiley, 2017, paperback,ISBN 9781119265269, 364 pp.,$78.95Strange chemistry: the stories yourchemistry teacher wouldn’t tell you isan exploration of science in the realworld that is as gritty as it isinformative. If you always wanted tolearn the secret ingredient in Coca-Cola, the most toxic substance on Earth, or the most expensive,this book is a good place to start. In an effort to connectchemistry theory with the real world, these stories were created aspart of author Steven Farmer’s experiences teaching organicchemistry to university students. He had begun to include one ofthese real-world stories in each class, and then students started toadmit that the stories were the only reason they attended classes.

An introductory chapter covers chemistry basics for anyonewithout a science background, or for those of us who are a bitrusty on organic chemical structures. The book’s remainingchapters, including ‘Why oil is such a big part of our lives’, ‘Whyold books smell good’ and ‘The poisons in everyday things’ containa series of related stories. The book’s stories also draw on popularmedia, including the TV series Breaking Bad, a program that hashad a significant impact on how chemistry is viewed in society.

The book’s pages are marked not only by chapter but also bystory title, making it easy to flip through and find a good story.Despite this abundance of informative and entertaining stories,the book does not fall into the category of relaxing bedtimereading. However, for anyone interested in the science behind aspecific story, the reading list at the end of each chapter offersthe opportunity for further research on the topic. These readinglists are impressive – varying from books and journal articlesthrough to recent US Government studies and publications.

One of the very few drawbacks of Strange chemistry is howthe impact of many stories is reduced by the extensive use oftrademark chemical names. Many of these brand names (forhousehold chemicals and pharmaceuticals) are unfamiliar,diverting the reader towards Google to try and pick upmomentum. Unless you have spent time in the US or are veryfamiliar with these trademark names, some stories are achallenge to follow. The US-based statistics in many stories (notall of them recent) are also at times quite distracting.

Strange chemistry is not a cover-to-cover read, with thedetails of some stories being enough to make you put downyour glass of wine or your coffee cup (at least temporarilyanyway). Nonetheless, it’s a great option for anyone looking foran entertaining story for a perhaps captive audience.

Samantha Profke MRACI

John Wiley & Sons books are now available to RACI members at a25% discount. Log in to the members area of the RACI website,register on the Wiley Landing Page, in the Members Benefits area,search and buy. Your 25% discount will be applied to yourpurchase at the end of the process.

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

Students often have an intrinsic belief in the infallibility oftextbooks. It is in the textbook and so it must be right. Thesestudents worry when different textbooks give differentinformation. For example, the production of adenosinetriphosphate (ATP) in aerobic respiration is a key process inbiochemistry. The reported number of ATP molecules producedper glucose molecule ranges from 30 to 36 in differenttextbooks. Some authors who write more than one textbookgive different numbers in different books, published in thesame year. Some books explain why there is uncertainty in thenumber, while others do not.

ATP production involves several interlinked steps, and someof these steps have alternative, parallel pathways that vary inthe number of H+ and/or other intermediates involved.

Earlier studies tried to study each step and each pathwaywithin each step separately and obtained a maximum possiblenumber of ATP produced per glucose molecule for eachindividual step or pathway. Then, assuming that if each step orpathway operated independently and at optimum efficiency, theresearchers just added the maximum numbers for each separatestep or pathway. This is the theoretical maximum number(approximately 40) in old textbooks. This is a theoreticalmaximum, not a real yield. Each pathway is linked to otherpathways, so optimising one pathway decreases the efficiencyof some other pathway, meaning this maximum possible numberof ATP molecules produced per glucose molecule is notachieved.

In maths terms, this theoretical maximum is an upper boundor over-estimate. Scientists have tried to lower this upperbound in an attempt to get the lowest upper bound (decreasethe over part of the over-estimation), which should (hopefully)be a better estimate for the real number.

More recent studies have tried to look at all steps andpathways in combination, to get a more realistic yield. Theissue is whether laboratory conditions correspond to realphysiology or biochemistry. As laboratory conditions are alteredto better correspond to real physiology or biochemistry, theyield number is continually being revised downwards: 38, 36,34, etc. Some latest reports have this number at 30 (or perhapseven 28). And there might be some disagreement aboutwhether a particular set of test conditions corresponds better orworse to real physiology or biochemistry, meaning that some ofthe newer, lower numbers are not widely accepted.

Real processes are complex and have real-world limitationsthat limit the yield. This is true in all areas of science andtechnology, including chemistry.

Rote learning the number of ATP produced per glucosemolecule is counter-productive because there is littleunderstanding. (Changing what students should learn may haveimplications for the type of questions that can be asked in anexamination, but that is a discussion for another occasion.)

What is more important is that students develop ‘anunderstanding of the nature of scientific inquiry’, to be able ‘toevaluate and debate scientific arguments and claims’, and ‘toappreciate the dynamic nature of science knowledge’(quotations from the Australian Curriculum: Science).

The fact that different textbooks have reported differentestimated numbers of ATP produced per glucose molecule is agreat example of how knowledge in science has evolved andcontinues to evolve in response to new evidence anddiscoveries. The various estimated numbers demonstrate thestrengths and limitations of science as evidence-basedconclusions continue to evolve based on new evidence.

Instead of focusing on a single number that is the mostcurrent estimate of the number of ATP produced per glucosemolecule, students should focus on the fact that the downwardrevision of this number over time is a demonstration of thetestable and contestable nature of science and the processes ofscience, including chemical science.


education

ATP and the textbook trap

The fact that differenttextbooks have reporteddifferent estimated numbersof ATP produced per glucosemolecule is a great exampleof how knowledge in sciencehas evolved and continues toevolve in response to newevidence and discoveries.

38, 36, 34 ATP ...

iStockphoto/TefiM

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


Introducing students (and non-scientists) to the concept ofchirality is a fundamental aspect of science education. This ofteninvolves a discussion of chirality in nature and the implicationsof this molecular asymmetry, using real-world examples.Consistent with these objectives, one of the first laboratoryexperiments that second-year undergraduate chemistry studentsundertake at the University of Tasmania involves the steamdistillation of R-(+)-limonene from lemons and oranges. R-(+)-Limonene is the major enantiomer present in these citrus fruits.As part of this exercise we have been somewhat surprised to findthat some secondary sources (correctly) state that R-(+)-limonene is the major enantiomer present in oranges, while(incorrectly) claiming that S-(–)-limonene is the major enantiomer present in lemons.Moreover, it is also often erroneously suggested that R-(+)-limonene is responsible for the distinctive smell of oranges,while S-(–)-limonene is responsible for the characteristic odour oflemons.

It is difficult to pinpoint the origins of the myth that orangesand lemons contain opposite enantiomers of limonene in highenantiomeric excess. A 2004 review article, which discusses thistopic, indicates that this may have originated from a paperpublished in Science in 1971 by Friedman and Miller. These

researchers refer to two papers andsuggest that these reports provideevidence that R-(+)-limonene from

orange oil and S-(–)-limonenefrom lemon oil were used as

starting materials in thesemisynthesis of natural products

R-(–)- and S-(+)-carvone,respectively. Interestingly, neither

of the papers cited by Friedman and Millerdiscusses the synthesis of S-(+)-carvone from

S-(–)-limonene or the use of lemon oil as a starting material.To this day, some chemistry textbooks still state that R-(+)-limonene is predominantly found in oranges while S-(–)-limoneneis predominantly found in lemons, as does a webpage on theofficial website of the US National Museum of History –Smithsonian.

R-(+)-Limonene is often obtained from orange peel and it isdescribed as possessing an orange or citrus odour. However, it isproposed that the components of orange oil that are responsiblefor this characteristic orange smell comprise less than 0.1% ofthe oil. This is consistent with the observation that high-purityR-(+)-limonene features a harsh turpentine odour. Notably, S-(–)-limonene has been described as having a harsh turpentineodour with a lemon note. Unfortunately, the myth that R-(+)-limonene is responsible for the distinctive smell of oranges,while S-(–)-limonene is responsible for the characteristic odour oflemons, has also permeated the literature. Currently, this includeschemistry texts, peer-reviewed articles, and, surprisingly, the‘Information for the Public’ section for the 2001 Chemistry NobelPrize on the official Nobel Prize website. Although these sourcesdo not specifically state that S-(–)-limonene is the majorenantiomer present in lemons, the mischaracterisation of theodour profiles of limonene enantiomers may lead people to makesuch an inference.

Relative to other myths that persist in the secondaryliterature, the above-mentioned issues arguably represent ratherbenign errors. However, by directly addressing and drawingattention to this particular issue, we aim to remind the chemicalcommunity (and highlight to students) how easily mistakes andmisconceptions can propagate in science, and society moregenerally. This also reinforces the importance of testing theory inthe laboratory and the need to preserve this feature at the coreof chemical education, both now and in the future.

Christopher T. Desire MRACI (Australian Centre for Research on SeparationScience), Ross M. Deans, Robert A. Shellie MRACI CChem (Australian Centre forResearch on Separation Science), Jason A. Smith MRACI CChem and Alex C.Bissember MRACI CChem are at the School of Physical Sciences – Chemistry,University of Tasmania. Robert Shellie is now at Trajan Scientific and Medical,Ringwood, Victoria.

Oranges, lemons and limonene:addressing surprisingly persistent and enduring myths

... the myth that R-(+)-limonene is responsiblefor the distinctive smell oforanges, while S-(–)-limonene is responsiblefor the characteristic odour oflemons, has also permeatedthe literature.

iStockphoto/Kelenart

economics


One of the main hopes for continuing the use of fossil fuels isthat carbon dioxide resulting from combustion can be depositedin deep geological strata – so-called carbon geosequestration.In past issues of Chemistry in Australia, I have described thetechnology and economics of removing carbon dioxide from gasstreams in the hydrocarbon processing industry and how theseproduce a concentrated stream that can be geosequestrated. Ihave also described the difficulties and costs of extractingcarbon dioxide from flue gases, particularly from gas and coalpower-generating facilities. There are also technology and costissues associated with carbon dioxide disposal in storagefacilities that need to maintain their integrity for hundreds ofyears.

The basic theory of carbon geosequestration comes fromwork in enhanced oil recovery (EOR) using carbon dioxide. Inone method of EOR, carbon dioxide is injected into an oilreservoir, where it dissolves in the oil, lowering the oil’sviscosity and allowing freer flow of oil to the producing well.For this to work, there has to a source of carbon dioxide, oftenremote process plants which means piping to the oil-field overlong distances. This practice gives some reassurance thatcarbon dioxide pipelines and pipeline networks can beconstructed safely and carbon dioxide transmitted over longdistances. This is an important demonstration because mostcarbon dioxide emissions are remote from geological structuressuitable for disposal.

An EOR project at Weyburn in Canada obtains carbon dioxidefrom a large lignite coal-to-gas plant in Dakota in the USA(Dakota Gasification Company). The EOR gas also containshydrogen sulfide, which is also injected and disposed in the EORproject. The pipeline system for this is over 300 kilometreslong. This project demonstrates that pure carbon dioxide is notrequired for geosequestration. The table lists methods that havebeen considered for long-term carbon dioxide disposal togetherwith the typical pressure required to maintain carbon dioxide inthe liquid state.

Methods for long-term carbon dioxide disposalMethod Pressure required (bar)Deep un-minable coal beds 80–100

Enhanced oil recovery 150–160

Deep saline aquifers 150–180

Abandoned oil and gas wells 150–180

Deep sea disposal 310 (3 km water depth)

Data source: Saxena and Flintoff, Hydrocarbon processing, December2006

The methods listed are considered viable methods fordisposing of carbon dioxide. In deep coal beds, the carbondioxide is absorbed by the coal. In EOR, some of the carbondioxide returns via the producing well dissolved in the oil butsince the carbon dioxide is a valuable commodity, it isrecovered and re-injected. Carbon dioxide can also be disposed

of in deep sea trenches of static water and the like where thegas dissolves and remains in the cold water.

Deep saline aquifers and abandoned oil and gas facilities arethe most studied. There are several issues to be considered. Asnoted above, the best sites are often remote from the emissionspoint, requiring a gas transmission pipeline, and becausecarbon dioxide is a heavy suffocating gas, leakage, especiallynear urban areas, will be cause for concern. Another issue is thedissolution of minerals causing, in the long term, caving andpotential collapse and leakage from the storage site. The mainworry is limestone (a very common mineral) but other mineralscould also be attacked over the long times required for storage.

One of the main difficulties is identifying potential sites. Fora greenfield site that is required to geosequestrate theemissions from a large coal-fired power station, the rate ofcarbon dioxide injection may be more than 10 million tonnesper year. Furthermore, this rate will be constant for the life ofthe power station. The rate of injection may be quite high on anewly drilled well but as more carbon dioxide is pushed downthe well, resistance will build up and the rate will fall. This isillustrated in the graph. The top line shows an ideal situationwhere the rate of injection falls little with time but the morelikely situation is with the lower lines. For a geologicalstructure that is tight (highly compacted), resistance toinjection may increase dramatically with time and in order tomaintain a constant high injection rate thousands of wells mayhave to be drilled over the life of the project (lower line). Thisis analogous, but the inverse of, the production of gas fromtight reservoirs or shale where many wells have to be drilled tomaintain a constant overall production rate because theproduction rate of the individual wells falls dramatically withtime.

Injection rate impact of reservoir properties.

The middle line on the graph is the intermediate case whereincreasing resistance can be overcome by drilling less but stillhundreds of wells over the course of a major project. Thegeology will determine if a few or many wells will have to bedrilled but whatever the case, it is certain that ageosequestration project will require an extensive area if largevolumes of carbon dioxide from major power-generatingfacilities are to be disposed of; some estimates are in thethousands of square kilometres

Carbon dioxide disposal

1.2

Time

Relat

ive in

jectio

n ra

te

hundreds of wells

tens of wells

thousands of wells

10.80.60.40.2

0

February 2018

So, for a carbon dioxide geosequestration project, assumingthe costs of carbon dioxide extraction and compression is paidby the emitter (EOR experience indicates that this may be atleast $20/tonne), the additional costs will be for transmissionto the geosequestration site, possibly further compression costsat the injection site, and the cost of the well (typically $2–5 million each).

As can be deduced from the above, a major demonstration ofthis aspect of the carbon geosequestration will be costly. In asmall project in Australia, the CO2CRC has demonstrated theinjection of 65 000 tonnes of carbon dioxide in a depletednatural gas reservoir in the Otway basin in Victoria. The projecthas gone on to inject carbon dioxide into saline formations andto monitor movement of the gas in the underground reservoirs.A commercial carbon dioxide gathering system and pipelinenetwork has been proposed for Victoria in the La Trobe Valley(known as CarbonNet) with carbon dioxide beinggeosequestrated in depleted oil and gas reservoirs in Bass Strait.

One of the largest projects is by Chevron in the Gorgon LNGproject in north-west Australia. The LNG facilities on BarrowIsland use gas from the offshore Gorgon gas field, whichcontains about 14% carbon dioxide. This is extracted prior toLNG production and is injected to a depth of two kilometresunder the island using three compressor stations and nineinjection wells supplemented with six waterproduction/injection wells and two wells for surveillance. Theproject is said to dispose of 3.4 million tonnes of carbondioxide per year when fully operational. However, this will onlydispose of 40% of the facility emissions; most of the rest willprobably be emitted in flue gas from power generation facilitiesto drive the refrigeration plant.

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

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... the best sites are oftenremote from the emissionspoint, requiring a gastransmission pipeline, andbecause carbon dioxide is aheavy suffocating gas,leakage, especially nearurban areas, will be cause forconcern.

science for fun


The history of civilisation as we know it would have been quitedifferent without the love affair between metallic iron and non-metallic carbon. A red-hot charcoal fire containing somenuggets of iron ore ushered in the Iron Age.

Ellingham and Gibbs free energyReducing iron ore to iron is possible because of a set of quirkychemical reactions, which can be shown on an Ellinghamdiagram. The diagram is named after Harold Ellingham (1897–1975) – a British chemist who first constructed the diagram in1944. The diagram’s use was explained by Ray Hodges in part 7of his ‘Back to basics’ series (June 2012, p. 28).

The horizontal axis is temperature and the vertical axis is∆G° (Gibbs free energy), named after Josiah Willard Gibbs. Justas the bigger the voltage of a battery the bigger the energy itwill deliver, the bigger the (negative) ∆G, the bigger the drivingforce for that reaction. Why negative? Sorry, the field justdeveloped this way. The diagram shows that this driving force(think voltage) often changes strongly with temperature.

For any two reactions at a particular temperature, the onewith the larger (negative) ∆G° will reverse the one with smaller(negative) ∆G°. This has an exact parallel with battery voltagesexcept that ∆G° in an Ellingham diagram has a very largedependence on temperature.

Talking about the voltage analogy, there is a direct correlation:∆G° = –nFE°

where n is the number of electrons, F is the Faraday constantand E° is the standard electrochemical potential. Forelectrochemical half-reactions, the reaction with the higher E°drives the reaction with the lower E° backwards.

Thus, the relative amount of electrical energy needed torefine metals electrochemically (at room temperature) parallelsthe ∆G° value for that metal.

Our interest here is in the reduction of iron oxide by carbonand its oxides and this occurs above about 720°C. Thereduction reactions are the three reactions involving carbon andoxygen:[1] 2CO + O2 → 2CO2

[2] C + O2 → CO2

[3] 2C + O2 → 2CO[1] + [3] = [2]

• Note that the lines for ∆G° for CO and CO2 cross at around710°C.

• The equilibrium equation is 2CO ⇌ C + CO2 and is determinedby equation [3] above 710°C and by equation [2] below710°C.

• The dotted line is a composite curve connecting these tworeactions.

• Above 710°C, CO is more stable than CO2 and carbon dioxidewill ‘gasify’ carbon.

• Below 710°C, CO can disproportionate into CO2 and C (butthis requires a catalyst).

• In practice, the gas CO generally does the contact work ofreducing iron ore.

Kinetics overrules equilibriumThe Ellingham diagram shows the species at equilibrium. If thetemperature is decreased suddenly, the time to reach a newequilibrium can be infinite. If the gases cool quickly, as in theexhaust from the hot cylinders of a car or from a gas-firedkitchen range, carbon monoxide is stable and remains in theburnt gases along with carbon dioxide, in spite of the lowertemperature. Carbon monoxide poisoning can and does occur.

This was dramatically illustrated by Australia’s biggestindustrial accident. On 31 July 1902, an explosion killed96 men and boys in a coal mine at Mt Kembla in New SouthWales. Firedamp (mainly methane from the coal seams) in air atlevels between its explosion limits catches fire when exposed toa naked flame. Afterdamp (mainly carbon monoxide) is found inthe residual cooling gases.

Beware the occasional explanation that carbon monoxide isproduced when there is insufficient oxygen. While it is true thatthe carbon dioxide–monoxide equilibrium is shifted to producemore monoxide at lower oxygen concentrations, this is relativelyquite small compared to when a high temperature equilibriummixture is cooled and locked in at ambient temperatures.

With increasing temperature, one line in the Ellinghamdiagram slopes up, another slopes down and the third ishorizontal. The equilibrium of a reaction that produces more gasmolecules than it starts with shifts to the right with increasingtemperature. The equilibrium of a reaction that produces fewermolecules than it starts with shifts to the left with increasing

Ellingham and the iconic reactions of iron

Free energy as a function of temperature for three carbon and oxygenreactions and one iron and oxygen reaction. Graph created from data fromIves D.J.G., Monographs for teachers, No. 3, The Chemical Society (London), 1969

temperature. And a reaction in whichthere is no change remains virtuallyunchanged with temperature.

Gases are more disordered than solids(or liquids) and this drive to disorder(entropy ∆S°) is the major temperaturevariable component of the chemicaldriving force ∆G° in the Ellinghamdiagram. The Ellingham diagram isdetermined by the equation ∆G° = ∆H° – T∆S°.

Now for a phase diagramDon’t faint, yet.

In the diagram below, keep your eyespeeled along the red line separating allliquid from solid plus liquid. This linereaches a minimum at the yellow dot. Thisoccurs at a composition with a minimum and sharp melting point,just like a pure chemical. Carbon in iron can knock down themelting point from 1500°C to around 1100°C, making things a loteasier for blacksmiths at the start of the Industrial Revolution.

Now, look down.To make steels, the amount of carbon in cast iron has to be

reduced by burning it off. However, this also raises the meltingpoint so it is easy to see why steel production came much laterthan iron production.

Think wrought iron and samurai swords. The beating andfolding of the steel allows the carbon to come in contact withair and thus be burnt off. Iron becomes steel as the carboncontent is reduced from 4% to 2% and below.

Remember, phase diagrams only represent equilibriumsituations.

Consider any region in the diagram that represents a solidcomposition. If this material is suddenly quenched in water,this solid compound at equilibrium at high temperaturesremains stable and non-equilibrium at ambient temperatures.

If clean water is dropped onto hot iron, the water justbounces off as bubbles (try this on your ironing iron). But dipthat red-hot samurai sword instead into cold urine and theliquid sticks (don’t try this) and the cooling is more efficient.Some iron nitride is produced on the surface, which provides ahard edge.

Adding chromium and nickel to steel makes stainless steel.Since the mid-20th century, many exotic metals have been addedto form the stable rusty Corten™ (weathering) steel, currently the‘metal de jour’ of sculptors by the sea and elsewhere.

Wood and trees in air are kinetically stable. A red-hotcigarette butt allows this system to move to thermodynamicequilibrium; that is, to carbon dioxide and water vapouraccompanied by an output of extreme heat.

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.


Iron iron–carbon phase diagram.

Abetxuko Bridge – a weathering steel bridge by J. Sobrino in Vitoria, Spain. Pontis21/CC BY-SA 3.0

liquid

eutectic

cast ironsteels

eutectoid

1800

1400

1000

600

200

solid

solid

1130°C

723°C

solid + liquid

solid + Fe3C

ferrite + Fe3C

liquid + Fe3C

Carbon content (%)

Tem

pera

ture

(°C)

0 1 2 3 4 5 6

ferrite

austenite

grapevine

Some years ago when I had my first opportunity to teachoenology in the Erasmus Mundus Master Vintage program, I cameacross the term ‘vin de voile’. My initial reaction was to ask if thiswas a term applied to wine that created some sort of religiousexperience, but quickly came to learn that it was the French termfor wine developed under a film or ‘flor’ yeast. The role of filmyeast in the production of fortified dry white wines such as finoand manzanilla was well known to me, but the use of this type ofyeast for ageing unfortified white wines was rather a surprise.

My first experience of dry, unfortified white wine developedusing a film yeast was in Hungary. When I was teaching in theVintage Master program at Corvinus University of Budapest,each Friday was set aside for an excursion to a wine region. Inthe Tokaj region, I was introduced to Szamorodni száraz. Apartfrom not being able to pronounce the name, I had somedifficulty adjusting to the colour, aroma and palate of the wine.One fundamental issue was simply the presence ofacetaldehyde, commonly used in the ‘New World’ as an indicatorof a wine spoilt through oxidation. The grapes, mainly theFurmint cultivar, can give a wine of up to 14% alcohol. Withoutfurther alcohol addition, the wine is allowed to develop inbarrel under the film or veil yeast. The descriptor of ‘biologicalageing’ for this process is now in common use: biological, asthe film yeast is active in development of the wine.

The wine of this style that perhaps is more widely knowninternationally is vin jaune (yellow wine) from the Jura regionof France. Savagnin grapes, which can yield up to 14% potentialalcohol when fermented to dryness, is the cultivar used for theproduction of vin jaune. The film yeast activity is critical to thiswine style.

The image shows a vin jaune wine undergoing its ‘biologicalageing’. The thin film of yeast sits on the surface, creating the veil

or voile effect. The barrel is a 228-litre aged oak barrel, selectedso that it does not impart oak character to the wine. Theheadspace above the film allows contact with air, creating aerobicconditions, while anaerobic conditions exist under the film. Whilethe wine in this image appears to exhibit a brown colour, the bestwines are golden to deep gold in colour; hence the name vinjaune. Regulations require that a vin jaune is aged for six yearsand three months after grape harvest before it can be bottled.Some younger voile wines are aged for two and a half years only.Traditionally, a squat 620-millilitre bottle is used.

The successful development of vin jaune is very muchdependent on good cellar hygiene as well as the quality of theflor, film, veil, voile, vellum yeast – all these adjectives areused in discussions of the yeast in the literature. My experiencein the production of ‘apera’ wines, the name we now use forfino, was to try and maintain a permanent flor or film andremove wine or add new wine under the film with minimaldisturbance. In the Hungarian and French styles of unfortifiedwines, the film yeast is allowed to develop over time in thebarrel. For this to be successful, sugar fermentation must becomplete and preferably malo-lactic fermentation finished. Thedeveloping film yeast then moves from fermentative tooxidative metabolism. This is a long story, about which I willwrite in a subsequent issue.

Major chemical changes occur during the ageing under veilprocess. Acetic acid (commonly referred to as ‘volatile acidity’)and acetaldehyde initially increase and then decrease inconcentration. Both compounds along with glycerol are utilisedin various metabolic processes linked to the ageing process; forexample, condensation of glycerol with acetaldehyde can leadto the formation of acetals. Perhaps the most notable chemicalchange is the formation of sotolon from α-ketobutryic acid andacetaldehyde (Thuy et al. J. Agric. Food Chem. 1995, vol. 43,pp. 2616–19.). Sotolon is a powerful impact aroma compoundthat has a love it/hate it response by tasters. Its aroma iscommonly ascribed to curry, burnt honey and fenugreek. Agedwines show a marked increase in neutral polysaccharides(Santos et al. Vitis 2000, vol. 39, pp. 129–34), which add tothe viscosity and length of the mouthfeel.

Finding the traditional Jura wines in Australia can be achallenge with often only the younger two and a half year agedwines being available. The wines are great as an aperitif, andgo brilliantly with Comté cheese, a so-called ‘terroir cheese’made from unpasteurised cow’s milk in the Jura region. Asimple alternative, however, is to go to Kangarilla Road wineryin McLaren Vale and get the 2015 The Veil (bit.ly/2BhSA21). Apleasant way to commence 2018.


Wine under veilAr

naud

25/

Wik

imed

ia

Major chemical changesoccur during the ageingunder veil process.

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 dandelion, Taraxacum officinale, flourishes in my garden but Ienjoy the bright yellow flower so much that I often wait until theweed is in full flower before digging it out. I can’t enjoy it forlong because the fluffy seed head soon appears and the wind-blown seeds are sown to generate the next crop of dandelions. Thecommon name of this plant is said to be derived from the Frenchdent de lion – tooth of the lion – which refers to the shape of theleaves. I wondered what the French thought about this, but I gota surprise when I consulted my mini-Larousse and found pissenlitthat translates as pee-the-bed.

That’s what we called it when I was a child. It was widelybelieved, at least among my peer group of neighbourhood kids,that picking the flowers, certainly holding a bunch of them,would inevitably lead to a nocturnal accident. I can’t rememberany evidence for this belief and I recall that I, even then abudding scientist, picked a few flowers and dared the plant todo its worst. Nothing untoward happened.

The purported diuretic effects of the dandelion could hardlyhave arisen from bunches picked by innocent children or thegardeners cursing its presence in their lawns so I undertook alittle literature research. It revealed that various bits of theplant had been used for hundreds if not thousands of years infolk medicine and that diuresis was indeed among itspharmacological properties. The roots contain a number ofsesquiterpene lactones and their glycosides, some triterpenesand phytosterols, and flavones. The aerial parts have flavones,too – hence the bright yellow colour – along with fructans,polyphenols and derivatives of hydroxy benzoic acids. It’s notclear exactly which of these could be responsible, but anaqueous extract of the leaves is certainly diuretic. The leavesand stems are also very rich – 5% and 8% respectively - inpotassium.

Physiological effects produced by plants are nothing new, ofcourse, but this was literally a ‘backyard’ example. Toxicitycausing fatality would have to be the most extreme of thephysiological effects, and just short of that the strange effectsproduced by opioid alkaloids can be quite scary. There are someless well known – but appreciated if you’ve been there – effectsof the opioids, such as their propensity to induce constipation.

I turned to Chemistry in the market place (sixth edition, BenSelinger and Russell Barrow, 2017) – CiM6, as the authors callit – to check out my asparagus knowledge. When we eat

asparagus, the cyclic disulfide contained in it,asparagusic acid, is converted in the body to thiolsthat are rapidly excreted in the urine, giving it astrong, unpleasant smell. It was my understandingthat only some people’s metabolism worked that wayso stinky pee wasn’t guaranteed, but Ben and Russellare up to date with the four classes of asparaperson:those who excrete but can’t detect, neither excretenor detect, detect but don’t excrete, detect andexcrete (the category in which both authors, and I,

fall). A game of perms and pongs, to paraphrase thosemathematics lectures.

Inulins are fructans, sugar polymers consisting of chains offructose units with some glucose end groups, which areregarded as ‘dietary fibre’. They are soluble, so ‘fibre’ seems tobe stretching it a bit (no pun intended), but that’s the waydietary nomenclature works. Health food shops stock dietaryfibre concoctions, and you can find them in the ‘alternative’section of most pharmacies. That’s for deliberate ingestion, butinadvertent ingestion can occur, too, if the food contains thecarbohydrate inulin. Inulin makes up about 75% of the tubersof the Jerusalem artichoke Helianthus tuberosus – nothing to dowith Jerusalem and not even an artichoke. Once planted, thesethings grow like weeds in Melbourne gardens and producekilograms of tubers that are edible, with a sweet, delicateflavour ... but watch out. I used to be able to eat them with noill effects, but now in my mature years even a small amount ofJerusalem artichoke produces copious amounts of intestinal gas,courtesy of an over-active biome.


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.

Plants to watch out for

The purported diuretic effectsof the dandelion could hardlyhave arisen from bunchespicked by innocent childrenor the gardeners cursing itspresence in their lawns so Iundertook a little literatureresearch.

iStockphoto/igaguri_1

cryptic chemistry


Across1 Made Spooner very busy. (9)6 See 28 Across, 2 Down and/or

25 Down.9 Sneer at iodine trapping scale. (5)10 Rent permit. (3)11 Al2SiO4(F,OH)2 is best from beginning to

end. (5)12 Benzene, for example, is like clockwork

around oxygen. (9)13 Calls may be 12 Across. (5)14 Less sugar here? (5)16 C4H4S is not 12 Across. (9)19 Pick 10 Across cosine error. (9)20 Our inclusion of a metalloid

surface. (5)21 Bring together a band. (5)23 Gathering one tricep hurt. (9)26 Born earlier; back in the days when

secured loans were safe. (5)27 Even anomers get used in

spectroscopy. (1.1.1.)28 & 6 Across Make up proteins from

calcium, molybdenum, iodine andsilicon. (5,5)

29 1613117 compounds. (5)30 Bones of knees lost flexibility. (9)

Down1 See 15 Down.2 & 6 Across Chair stood to reveal the most

hydroxylated of the set. (5,5)3 Flame with oxygen every so often

outside the ring. (9)4 Silly radical: R3Si–. (5)5 Enticed to circumvent discovery. (9)6 Looking for posterior. (5)7 Bumping up against pigment in

transition. (9)8 Scopes how big they are. (5)15 & 1 Down Old capillaries clot badly: size

is important and so is a phaseboundary. (9,9)

16 Episulfides near this iodine reaction. (9)

17 PH3 happens to react with HO–. (9)18 Destroy or reuse on invalid. (9)21 Cultivates sprouts. (5)22 Scrutinises small apertures. (5)24 Change of direction: hyperbola,

perhaps. (5)25 & 6 Across Iron lost as NaI modifies C

compounds containing both =CNH and–COOH groups. (5,5)

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

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

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chemistrychemaust.raci.org.au/sites/default/files/pdf/2018/CiA_Feb 2018.pdf · Editor at wools@ westnet.com.au. Visits and verses Thank you for another year of Chemistry in Australia