chemistry - royal australian chemical...

ALSO IN THIS ISSUE: • One X-ray technique better than two • Haber’s rule and toxicity • Madeira wines worth the wait

in AustraliachemistryJune 2015

chemistryThe sensory world of bees

chemaust.raci.org.au

To discover all your benefits, contact RACI Member Advantage:call 1300 853 352 or visit www.memberadvantage.com.au/raci

Make the most of your member bene�ts

June 2015iS

tock

phot

o/m

embi

o


cover story

22

news & research7 On the market8 News13 Research42 Events42 Cryptic chemistry

members30 New Fellow31 Obituary

views & reviews4 Editorial5 Your say32 Books33 Data & privacy34 Peer review36 Economics38 Environment39 Grapevine40 Postdoc diary41 Letter from Melbourne

22 Exposure time and chemical toxicity: a new approachOver the past century, few scientific relationships have survived unaltered.Haber’s rule has not only survived, it has prospered in its application.

26 New X-ray spectroscopy gives better look at the chemistryof interfacesThe Lawrence Berkeley National Laboratory has combined key features oftwo highly acclaimed X-ray spectroscopy techniques.

The tale in the sting: working and sensory lives of beesBees have a well-earned reputation for pollination and honey-making, buttheir lesser known skills in electrocommunication are just as impressive.

26

18

Fran

k Hur

ley/

Aust

ralia

n W

ar M

emor

ial

iStockphoto/7io

You may have noticed that someone new is steering theResearch section here at Chemistry in Australia. After nine yearsat the helm, Matthew Piggott compiled his final Researchhighlights for the April edition. Matthew joined the magazine’smanagement committee in 2005 and soon after suggestedstarting a Research highlights section: ‘I had always enjoyedreading the Science and Technology Concentrates in C&EN; theResearch column was inspired by that.’ The committee and themagazine have been very lucky to benefit from Matthew’s goodideas and hard work since then.

In Matthew’s first batch of Research highlights, CSIRO’s ChrisElvin and colleagues summarised their research (published inNature, doi: 10.1038/nature04085) into production of asemisynthetic version of resilin, the rubbery cross-linkedprotein found in the legs of some insects (see picture).‘Synthetic resilin has potential for medical use in situationsrequiring a resilient elastomer with a long fatigue lifetime,’ saidthe authors in the February 2006 edition of Chemistry inAustralia (p. 33).

In 2013, Linqing Li and Kristi Kiick at the University ofDelaware reported on recent developments in resilin’sbiomedical applications (ACS Macro Letters, doi:10.1021/mz4002194): ‘The outstanding mechanical propertiesof natural resilin have motivated recent research in the

engineering of resilin-like polypeptide-basedbiomaterials, with a wide range of applicationsincluding use as biorubbers, nanosprings,elements in biosensors, and tissue engineeringscaffolds.’

Matthew thanks those who havecontributed research summaries for publication– particularly those who did so on their owninitiative and who took note of style and wordlength! He is also thankful to the many peoplewho provided positive feedback. Matthewhopes that:

… researchers have valued and will continue to valuethe opportunity to publicise their work among the RACI

community, and that the readers have enjoyed finding out about whatthe heavy hitters are up to. My apologies if I’ve annoyed anyone with myeditorial tinkering, and sorry to those whose work I was unable toinclude.

David Huang, a senior lecturer in the chemistry departmentat the University of Adelaide and treasurer of the RACI’s SouthAustralian Branch, revealed his inauguralResearch highlights in the May edition,and we look forward to many more. Eversince his undergraduate days editingstudent publications at the University ofSydney, David has had an interest injournalism and in science communicationin particular. Compiling the column, hesays, will be a good way to pursue theseinterests, while becoming acquaintedwith the many chemists in Australiadoing cutting-edge research. He thinksthat the section can help to inspirechemists by making them aware of

EDITOR Sally WoollettPh (03) 5623 [email protected]

PRODUCTION EDITORCatherine Greenwood [email protected]

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

PRODUCTIONControl Publications Pty Ltd Ph/fax (03) 9500 0015/0255 [email protected]

BOOK REVIEWSDamien [email protected]

RESEARCH HIGHLIGHTSDavid [email protected]

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

PRESIDENT Paul Bernhardt FRACI CChem

MANAGEMENT COMMITTEESam Adeloju (Chair) [email protected] Hügel, Alan Jones, Amanda Saunders, Colin Scholes, Curt Wentrup

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

© 2015 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproduced whollyor in part without written permission. Further details on thewebsite (chemaust.raci.org.au). ISSN 0314-4240 e-ISSN 1839-2539


Chemistry in Australia4 | June 2015

editorial

Research and reviews roll on

Matthew Piggott David Huang

developments in other fields. David commentsthat the Research highlights section:

… provides an important service by collatingoutstanding new Australian research from across allchemistry disciplines. The scale of chemistryresearch in Australia is small compared with that inmany other countries, and it can be easy to forgethow much excellent research is done here – I thinkit’s important that this excellence beacknowledged.

Those withsharp eyes willhave noticed anew addition toour contactssection: DamienBlackwell is ournew book revieweditor. Damienis the presidentof the RACI’sTasmanianBranch and hasserved on that

branch committee for more than 10 years. ForChemistry in Australia, he is busy sourcingbooks and other resources for review, andfinding homes for them. We are grateful forhis services and those of a good number ofreviewers from a range of professionalbackgrounds.

Damien relishes opportunities to read andwrite, and enjoys the review process andproviding constructive feedback, whatever thesubject matter. He appreciates theopportunity to:

… be exposed to a new group of scientists, theirstyles, interests, interpretation and knowledge ofchemistry.

The research landscape is always changing.Clearly, Matthew, David and Damien want tobe part of this. What’s more, they all enjoyand see the importance of an involvement inthe RACI that is greater than membershipalone. This magazine, the Institute and itsmembers are so much richer for it.

your say

Chemistry in Australia 5|June 2015

Sally Woollett ([email protected])

With thanks to Matthew, David andDamien for their contributions tothis editorial.

Adding colour to Yellowstone’s thermal springsThis is a brief historical comment on the item on the March news item‘Yellowstone’s thermal springs – their colours unveiled’ (p. 8) originally from theAmerican Institute of Physics. It may not only be tourists in recent years whohave changed the colours of the thermal springs with discarded coins anddetritus.

There is the case of R.W. Wood, a brilliant experimental physicist and practicaljoker, throwing a bottle of fluorescein into the Emerald Spring at Yellowstone in1892 when on his honeymoon. As a result, the pool ‘was glowing in the hotsunshine with the brilliance and colour of an emerald’, which amazed the othertourists and the guide (Seabrook W. Doctor Wood, modern wizard of the laboratory:the story of an American small boy who became the most daring and originalexperimental physicist of our day – but never grew up New York: Harcourt, Braceand Company, 1941, pp. 47–8).

William P. Palmer FRACI CChem

Chemists, laborateurs and pharmacistsThe letter from Chris Embery (April issue, p. 5) and the President’s message (Dec2014/Jan 2015 issue, p. 4) reminded me that when I joined the staff of theSouth Australian Brewing Co Ltd in Adelaide in early 1946, it was with the title‘assistant brewer and analyst’. Although the company was then expanding itslaboratory facilities, the title ‘chemist’ was not used (nor was it employed forabout 30 years thereafter), as it was considered that its use may support the thenprevalent, but ignorant, rumours about the existence of ‘chemical beer’. Anothermajor Australian brewing company then used the French term laborateur ratherthan ‘chemist’.

In an association spanning nearly seven decades with the beverage and foodindustries in Australia, plus involvement with RACI and other relevantprofessional associations, I can recall various attempts to improve the generallevel of scientific literacy among the general public and of food and beverageconsumers in particular. There is no doubt that education is the key but obviouslythere is much still to be done to dispel the myths surrounding ‘chemicals’ and todiscourage the use of terms such as ‘chemical free’ and others with similarconnotations. It is encouraging to note from the President’s message that theDecadal Plan for Chemistry, initiated by the Australian Academy of Science’sNational Committee on Chemistry, recognises the importance of education and, touse the President’s phrase, of ‘taking our word back’.

The confusion that still exists regarding the roles of ‘the chemist’ and ‘thepharmacist’ still remains to some extent … but that is another story!

John Harvey FRACI CChem

Colour and cyanobacteriaI enjoyed reading ‘A spectrum of seasonal change’ by Colin Scholes (April issue, p.14). It reminded me of work I did on nutrient-rich eutrophic ponds. The idea was toadd ‘dye’ to inhibit cyanobacteria. We found pine bark leachate absorbs at about thesame wavelength preferred by blue-green algae. I first became interested in this bynoticing that ‘tea-coloured’ waters, as at Tidal River, Victoria, don’t appear to sufferfrom algae blooms. Experiments on a treated wastewater storage lagoon in SouthGippsland found that salinity and pH fluxes, induced by adding sea water, wereeffective in controlling algal densities (August 1997 issue, p. 6).

Max Thomas

Damien Blackwell

your say

6 | June 2015Chemistry in Australia

Pantone coloursMany thanks for your note about Pantone colours in the Aprilissue (p. 4).

The initiation and batch matching of requisite printed coloursto a Pantone standard is a basic in label design and periodicreceipt of the printed labels. There would be many chemists whohave needed to acquire working knowledge of their use in theirday-to-day dealings with marketing personnel and printers forlabels, logos and advertising copy.

Ultimately, Pantone colours rely on the inertness of theircomponents and packaging/containment to maintain theirintegrity, analogous with any other chemical reference standard.As such, their storage conditions must minimise any effects oflight, humidity and heat.

David Edmonds FRACI CChem

Colours and ‘chemical free’Chemistry in Australia of April 2015 is another masterpiece ascollaged by the Editor, Sally Woollett. Members of RACI arefortunate to receive monthly editions of high quality and varietythat will appeal to the whole membership. Personally, I start withIan Rae’s ‘Letter from Melbourne’ and then the obituaries, thisbeing a symptom of my ageing.

None-the-less, over the month I read cover to cover, enjoy andlearn something new.

The cover of autumn leaves includes a purple leaf, which is notas common as the reds, oranges, yellows and browns with whichwe in suburban Melbourne are familiar. This purple colour finds itsway into the editorial where Sally’s favourite colour is Pantone2058. Officially, Pantone 2058 is known as ‘Crocus’ but to my eyesit is strongly reminiscent of the colour mauve (Pantone MauveMist 15-3207 TPX) a popular clothing colour of the 1950s andearly 1960s. Unfortunately, in 2000s Melbourne you can beclothed in any colour as long as it is black (paraphrased fromHenry Ford’s early 1900s famous quote regarding his Model TFord.)

Mauve is virtually unknown to today’s children, and some otherwords from that 1950s era have a completely new meaning asexpressed by Chris Embery in his letter ‘Dangers of “chemical free”’(April issue, p. 5). It makes me wonder what Henry Bolte andArthur Rylah would have done with the book The gay provider byAlan Marshal, published by F.W. Cheshire in 1961 (subtitled TheMyer story, i.e. Myer Emporium), with the present day meaning.

As a chemist of over 50 years in the food and pharmaceuticalindustries, I am extremely perturbed by the highjacking of theancient word ‘organic’. I support Chris completely but we chemistslost the race many years ago. At this time, Standards Australia arereviewing Australian Standard AS6000 – Organic and BiodynamicProducts. This Standard contains lists of food additives that maybe used in manufactured foods that can be approved as ‘organic’even though many of these additives are inorganic or synthetic.

Tony Zipper FRACI CChem

Knowledge versus thinkingProfessor Ian Chubb was quoted in the March issue (p. 32). Ofchemistry: ‘It’s more than a discipline, said Chubb, it’s a way ofthinking.’

This reminded me of Richard Dawkins’ essay ‘Science, Geneticsand Ethics: Memo for Tony Blair’ from about 12 years back (A devil’s chaplain: reflections on hope, lies, science, and love,Mariner Books, 2004). In this essay, Dawkins wrote:

Senior Ministers could be forgiven for seeing scientists as little more thanalternate igniters and quenchers of public panic. If a scientist appears in anewspaper today, it will usually be to pronounce on the dangers of foodadditives, mobile phones, sunbathing or electricity pylons. I suppose this isinevitable, given the equally forgivable preoccupation of citizens with theirown personal safety, and their tendency to hold governments responsiblefor it. But it casts scientists in a sadly negative role. And it fosters theunfortunate impression that their credentials flow from factual knowledge.What really makes scientists special is less their knowledge than theirmethod of acquiring it – a method that anybody could adopt withadvantage.

Later in the same issue of Chemistry in Australia, in ‘Whystudents should study STEM’, Kieran F. Lim writes that: ‘Studyingchemistry develops critical thinking skills such as synthesising andevaluating information, record-keeping and documentation skills,and the ability to interpret data and use evidence to support aline of reasoning.’

In other words, what makes scientists and especially chemistsspecial is less what we know, important though that may be, butrather how we think.

This is now more important than ever because most of theknowledge that used to be the preserve of the scientific researchsection of a university library is now visible to anyone with abroadband connection. Journalists – and politicians – are adept atgrabbing this knowledge, often out of context, for purposes notalways aligned with the welfare of the community or its citizens.This makes it all the more important that, when representing ourprofession, we must not let the media use us as just an ‘expertwitness’, which, in Dawkins’ words, would be ‘as though one metPicasso and devoted the whole conversation to the dangers oflicking one’s brush. Or met Bradman and talked only of the bestbox protector to put down one’s trousers.’

Nigel Simpson MRACI CChem

on the market


ICP-MS technology measures the quantity of ions striking adetector, after the sample is ionised in argon plasma. ThePlasmaQuant® MS series boasts a major technologicaladvancement in its RF generator, producing an extremelyrobust plasma that can handle any matrix but using only halfthe amount of argon gas of competitive ICP-MS.

The PlasmaQuant® MS is a universal workhorse, suitable fora wide range of routine applications in environmental analysis,food safety, agriculture, pharmacy, mining, chemistry andpetrochemistry. The PlasmaQuant® MS Elite is Analytik Jena’spremium offering with unprecedented 1.5 GHz sensitivitymaking it the most sensitive ICP-MS instrument on the marketand up to five times more sensitive than competitive systems.

This incredible sensitivity makes it perfect forsemiconductor and research applications in geochemistry,environmental, materials science and metallomics. It is theinstrument of choice for applications that require specialisedsample introduction accessories, including laser ablation forthe direct analysis of solid samples and liquid chromatography,which offers the capability to measure different chemicalforms of a specific element in a sample. The high sensitivity ofthe Elite model even allows laboratories in the field of single-particle analysis to detect nanoparticles at less than 10 nmdiameter – a limit that, until now, has been difficult to reach.

The twin-position, bench-mounted design offers completeflexibility for customers to configure the system to theirlaboratory requirements. Dual entry ports allow for fast andeasy connection of third-party accessories while the incrediblysmall 0.4 m2 footprint requires very little lab space. ThePlasmaQuant® MS is the only ICP-MS to offer an all-digitaldetection (ADD10) system, providing ten orders of lineardynamic range in pulse-counting mode only. This eliminatesthe need for a regular and inaccurate cross-calibrationassociated with inferior digital-analogue detectors. The ADD10accurately attenuates strong signals without requiring aseparate analogue measurement.

The benefits are exceptional detector life time and fast,accurate multi-element analysis from ultra-trace to majorlevels in a single measurement. For further information,contact MEP Instruments, ph. (02) 9878 6900, [email protected] or visit www.mep.net.au.

The new perspective in ICP-MS

news

Martian weather and soil conditions thatNASA’s Curiosity rover has measured,together with a type of salt found inMartian soil, could put liquid brine in thesoil at night.

Perchlorate identified in Martian soilby the Curiosity mission, and previouslyby NASA’s Phoenix Mars Lander mission,has properties of absorbing water vapourfrom the atmosphere and lowering thefreezing temperature of water. This hasbeen proposed for years as a mechanismfor possible existence of transient liquidbrines at higher latitudes on modernMars, despite the red planet’s cold anddry conditions.

New calculations were based on morethan a full Mars year of temperature andhumidity measurements by Curiosity. Theyindicate that conditions at the rover’snear-equatorial location were favourablefor small quantities of brine to formduring some nights throughout the year,

drying out again after sunrise. Conditionsshould be even more favourable at higherlatitudes, where colder temperatures andmore water vapour can result in higherrelative humidity more often.

‘Liquid water is a requirement for lifeas we know it, and a target for Marsexploration missions,’ said the report’slead author, Javier Martin-Torres of theSpanish Research Council, Spain, andLulea University of Technology, Sweden,and a member of Curiosity’s scienceteam. ‘Conditions near the surface ofpresent-day Mars are hardly favourablefor microbial life as we know it, but thepossibility for liquid brines on Mars haswider implications for habitability andgeological water-related processes.’

The weather data in the reportpublished in Nature Geosciences comesfrom the Curiosity’s Rover EnvironmentalMonitoring Station (REMS), which wasprovided by Spain and includes a

relative-humidity sensor and a ground-temperature sensor. NASA’s Mars ScienceLaboratory Project is using Curiosity toinvestigate both ancient and modernenvironmental conditions in Mars’ GaleCrater region. The report also draws onmeasurements of hydrogen in the groundby the rover’s Dynamic Albedo ofNeutrons (DAN) instrument, from Russia.

‘We have not detected brines, butcalculating the possibility that theymight exist in Gale Crater during somenights testifies to the value of the round-the-clock and year-round measurementsREMS is providing,’ said Curiosity projectscientist Ashwin Vasavada of NASA’s JetPropulsion Laboratory, Pasadena,California, one of the report’s co-authors.

Curiosity is the first mission tomeasure relative humidity in the Martianatmosphere close to the surface andground temperature through all times ofday and all seasons of the Martian year.


NASA Mars rover’s weather data bolster case for brine

The Rover Environmental Monitoring Station (REMS) on NASA’s Curiosity Mars rover includes temperature and humidity sensors mounted onthe rover’s mast. One of the REMS booms extends to the left from the mast in this view. Spain provided REMS to NASA’s Mars ScienceLaboratory Project. The monitoring station has provided information about air pressure, relative humidity, air temperature, groundtemperature, wind and ultraviolet radiation in all Martian seasons and at all times of day or night.

NAS

A/JP

L-Ca

ltech

/MSS

S

Recent figures from the AustralianBureau of Statistics show Australianpharmaceutical exports declined by 18%to $2.9 billion in 2014, compared to$3.6 billion in the year before.

Since 2012, when they peaked ataround $4.3 billion, Australianpharmaceutical exports have declined bymore than 30%.

‘These figures are extremelydisappointing,’ said Medicines AustraliaCEO, Tim James.

‘Pharmaceutical manufacturing isprecisely the sort of activity thatAustralia should excel at. We have ahighly skilled labour force, a world-classinfrastructure, a history of excellence inmanufacturing innovation and, aboveall, a long-standing and well-justifiedreputation for manufacturing safe, high-quality medicines and vaccines.

‘Despite this, new investment inpharmaceutical manufacturing inAustralia remains negligible, whichclearly shows that all these factors aresimply not enough to keep Australiacompetitive.’

Unfortunately, the decline inAustralian pharmaceutical exports comesat a time when the global market formedicines and vaccines is booming. It isalready worth over US$1 trillion per yearin sales, and is expected to nearlydouble in size by 2020.

‘Much of this growth is going to comefrom emerging markets in Asia,’ Jamessaid.

‘But right now, we just don’t have thecorrect policies in place to capitalise onthis growth. If this continues, we willno doubt miss out on this once-in-a-generation opportunity, regardless ofhow good we may look “on paper”.’

Last year, Medicines Australia, inpartnership with AusBiotech, submitteda joint proposal to the AustralianGovernment on steps it should take tobuild a stronger pharmaceuticalsindustry in Australia.

Broadly, the proposal called on theGovernment to:• ensure a stable, predictable and

efficient business operatingenvironment

• strengthen Australia’s intellectualproperty system

• enable growth in Australia’s localbiotechnology sector

• enact globally competitive incentivessuch as tax breaks to encourageinvestment.‘Implementing these policies would

show that the Australian Government isserious about attracting investment andthat Australia is truly “open forbusiness”,’ James said.

‘Globally, the pharmaceutical industryinvests billions each year inmanufacturing. If we want to attract abigger share of this investment, we bemust be proactive, decisive andcoordinated, especially with respect tothe policy environment.’MEDICINES AUSTRALIA


Pharmaceutical exports dive

Relative humidity depends on thetemperature of the air, as well as theamount of water vapour in it. Curiosity’smeasurements of relative humidity rangefrom about 5% on summer afternoons to100% on autumn and winter nights.

Air filling pores in the soil interactswith air just above the ground. When itsrelative humidity gets above a thresholdlevel, salts can absorb enough watermolecules to become dissolved in liquid,in the process of deliquescence.Perchlorate salts are especially good atthis. Since perchlorate has beenidentified both at near-polar and near-equatorial sites, it may be present insoils all over the planet.

Researchers using the High ResolutionImaging Science Experiment (HiRISE)camera on NASA’s Mars ReconnaissanceOrbiter have in recent years documentednumerous sites on Mars where dark flowsappear and extend on slopes during warmseasons. These features are calledrecurring slope lineae, or RSL. A leadinghypothesis for how they occur involvesbrines formed by deliquesence.

‘Gale Crater is one of the least likelyplaces on Mars to have conditions forbrines to form, compared to sites athigher latitudes or with more shading. Soif brines can exist there, that strengthensthe case they could form and persist evenlonger at many other locations, perhapsenough to explain RSL activity,’ saidHiRISE principal investigator AlfredMcEwen of the University of Arizona,Tucson, also a co-author.

In the 12 months following its August2012 landing, Curiosity found evidencefor ancient streambeds and a lakebedenvironment more than 3 billion years agothat offered conditions favourable formicrobial life. Now, the rover isexamining a layered mountain inside GaleCrater for evidence about how ancientenvironmental conditions evolved. JPL, adivision of the California Institute ofTechnology in Pasadena, manages theMars Science Laboratory and MarsReconnaissance Projects for NASA’sScience Mission Directorate, Washington.NASA

Medicinal & Pharmaceutical ProductsPaper, Paperboard & Articles of Paper Pulp, Paper orPaperboard

Professional, Scientific and Controlling Instruments

Machinery Specialised for Particular Industries

General Industrial Machinery & Equipment

Office Machines & Automatic Data ProcessingMachinesTelecommunications & Sound Recording EquipmentElectrical Machinery, Apparatus & Appliances, andElectrical Parts ThereofAircraft & Associated Equipment, Spacecraft, Satellites& Spacecraft Launch VehiclesWine & Other Alcoholic Beverages

Cars, Road Vehicles (incl. Air Cushion Vehicles)

news

Australian smart technology that harvests blast furnace wasteand converts it into a new product to make cement is beingtrialled for commercialisation in China where 60% of the world’siron waste is produced.

The process, known as dry slag granulation, also reduceswater use and greenhouse gas emissions, and is the focus of anagreement signed by CSIRO and the Beijing MCC EquipmentResearch & Design Corporation (MCCE).

The signing of the agreement, to demonstrate CSIRO’s dryslag granulation (DSG) technology at industrial scale, is alandmark for Australia–China research collaboration and forenvironmentally friendly metal production, according to CSIRODirector of the Mineral Resources Flagship, Jonathan Law.

‘Our collaboration is an exciting step towards the uptake ofan innovation with real prospects of transforming theproductivity and environmental performance of global ironsmelting,’ Law said.

‘The benefits from wide uptake of DSG technology on blastfurnaces will be profound in helping the global industry to

reduce water and energy use and greenhouse gas emissionswhile sustaining metal production.’

The DSG technology that is fitted to blast furnaces includesa spinning disc and granulation chamber that separates moltenslag into droplets under centrifugal forces, uses air to quenchand solidify the droplets, and extracts a granulated slag productas well as heated air.

The process produces a ‘glassy’ product that is ideal forcement manufacture, but has significantly lower associatedgreenhouse gas emissions than cement produced byconventional methods.

Air at 500–600°C extracted from the DSG process can beused onsite for drying, preheating or steam generation.

The technology also saves water and eliminates theunderground water pollution that can be associated withalternative wet granulation processes.

‘The benefits each year from full commercialisation andadoption of DSG technology are in the order of 60 billion litresof water, 800 petajoules of heat energy and 60 million tonnes ofgreenhouse gas emissions,’ Law said.

‘Those savings are equivalent to 14% of Australia’s energyuse and about 10% of our greenhouse gas emissions each year.’

In entering the collaboration with MCCE, CSIRO hasrecognised the R&D reputation of the Beijing-based companyand its ability to scale up the technology and introduce it intoChina – where 60% of the world’s 300 million tonnes of ironblast furnace slag is produced each year.

Under the agreement, MCCE is to scale up and demonstratethe technology at industrial scale and, upon success,commercialise it in China and then potentially world wide.

The agreement is the culmination of more than a decade ofDSG technology development by CSIRO and industry partners,including Arrium and BlueScope.CSIRO


Forging a future in green steelmaking

The dry slag granulation rig is fitted to blast furnaces to producegranulated slag and heated air.

As urban residents know, air quality is abig deal. When local pollution levels goup, the associated health risks alsoincrease, especially for children andseniors. But air pollution varies widelyover the course of a day and by location,even within the same city. Nowscientists, reporting in EnvironmentalScience & Technology, have usedsmartphone and sensing technology tobetter pinpoint where and when pollutionis at its worst.

Mark J. Nieuwenhuijsen andcolleagues note that many studies have

investigated people’s exposure to airpollution, which is associated withrespiratory and cardiovascular problems.But they usually create a picture ofexposure based on air pollution levelsoutside people’s homes. This approachignores big differences in air quality inschool and work environments. It alsoignores spikes in pollution that happenover the course of the day, such asduring peak hour. Nieuwenhuijsen’s teamwanted to test technology’s ability to fillin these gaps.

The researchers equipped more than

50 school children with smartphones thatcould track their location and physicalactivity. The children also receivedsensors that continuously measured theambient levels of black carbon, acomponent of soot. Although mostchildren spent less than 4% of their daytravelling to and from school, commutingcontributed to 13% of their totalpotential black carbon exposure. Theresearchers conclude that mobiletechnologies could contribute valuablenew insights into air pollution exposure. AMERICAN CHEMICAL SOCIETY

Smartphones as personal, real-time pollution monitors

A team of scientists from Technische Universität München(TUM) (Germany) and Linköping University (LIU) (Sweden) hasdeveloped a methodology to investigate the equilibriumthermodynamics of single molecules.

In the search for high performance materials for applicationssuch as gas storage, thermal insulators or dynamic nanosystemsit is essential to understand the thermal behaviour of matterdown to the molecular level. Classical thermodynamics averageover time and over a large number of molecules. Within a three-dimensional space single molecules can adopt an almost infinitenumber of states, making the assessment of individual speciesnearly impossible.

The breakthrough study is based on two pillars: a technologythat allows molecules to be caged within two-dimensionalnanopores and extensive computational modelling.

At the Chair of Molecular Nanoscience and Chemical Physicsof Interfaces at TU München, led by Professor Dr Johannes V.Barth, Dr Florian Klappenberger developed the method toproduce high-quality metal-organic networks on a silver surface.The network forms nanopores that restrict the freedom ofmovement of adsorbed single molecules in two dimensions.Using scanning tunnelling microscopy, the researchers were able to track their motions at different temperatures with sub-nanometre resolution.

Parallel to the experiments, the researchers worked with

sophisticated computer models to describe the temperaturedependence of the dynamics of these single trapped molecules.

Comparing experimental and modelled data, the scientistsunravelled that under certain conditions the integral theoryapproaches a simple projection of the molecular positions inspace. This approach is central to statistical mechanics, but hasnever before been challenged to reproduce an experiment, dueto the practically infinite molecular positions and energies oneneeded to consider without the nanoscale confinement.

‘It was extremely exciting to employ two-dimensionalnetworks as a confinement strategy to reduce the availableconformational space of a single molecule, like a chaperonedoes with a protein’, said Dr Carlos-Andres Palma, the leadauthor of the study. ‘In analogy to biology, such a form ofconfinement technology has the potential to establish sensors,nanomachines and possibly logics controlled by and made ofmolecular distributions.’

Applying their knowledge of characteristic equilibriumconfigurations, the researchers carefully modulated thenanopore, thus making a single molecule write letters of thealphabet such as L, I and U, just by fine-tuning thetemperature.

Their work has been published in Nature Communications(doi: 10.1038/ncomms7210).TECHNISCHE UNIVERSITÄT MÜNCHEN


Caging of molecules allows investigation of equilibrium thermodynamics

Evolved Gas Analysis

NETZSCH is recognized world-wide as a technological leader in the thermal characterization of materials. Now celebrating 40 years experience in hyphenation and evolved gas analysis techniques, we offer leading, well-proven coupling systems: the unique SKIMMER® STA-MS Coupling, the capillary coupling for the QMS 403 D Aëolos®, the Perseus® FT-IR coupling and the GC-MS Coupling.

NETZSCH is recognized world-wide as a technological leader in the thermal characterization of materials. Now celebrating 40 years experience in hyphenation and evolved gas analysis techniques, we offer leading, well-proven coupling systems: the unique SKIMMER®

STA-MS Coupling, the capillary coupling for the QMS 403 D FT-IR coupling and the GC-MS Coupling.

Visit us at 35APS

Conference (Booth 6)

www.35aps.org.auNETZSCH Australia Pty Ltd

3/21 Binney Rd Kings Park NSW 2148 Tel: 02 9641 2846 [email protected]

news


Trajan and UTAS secure toppostdoctoral fellows for ASTechTrajan Scientific and Medical (Trajan) and the University ofTasmania (UTAS) have secured three top scientists to overseeinnovative research programs at ASTech, the ARC TrainingCentre for Portable Analytical Separation Technologies,supported by the Australian Research Council (ARC).

ASTech is a collaboration between Trajan and UTAScombining industry knowledge and research to innovate inproduct design, development and manufacturing techniques.

Professor Emily Hilder, ASTech Training Centre Director, saidthat she is looking forward to working closely with the threenew postdoctoral fellows who were selected from a pool ofapplicants from around the world.

Dr Greg Barbante has a PhD in electroanalytical/syntheticchemistry and Honours in the development of sensors based onimmobilised microcrystals, and has recent experience in thefood industry, including HPLC and GC method development, andproject management.

Dr Masoomeh Tehrani Rokh completed her PhD inEngineering in the field of bio-microelectromechanical systemsand microfluidics, a Master of Science in microengineering andnanoelectronics, and has extensive experience inmicrofabrication processes and facilities.

Stephen Tomisich, Trajan’s Chief Executive Officer said, ‘Weare thrilled to have recruited these high-calibre researchers forASTech. Each has unique expertise that will complement R&D atTrajan, and this month we have welcomed Dr Lapierre atTrajan’s global headquarters in Melbourne to commence hisindustry placement.’

Dr Florian Lapierre has a PhD in micro and nanotechnologyin the field of sophisticated microfluidic device design, also aMaster of Science and Technology in microfluidic systems and aMaster of Engineering in scientific measurement and appliedbusiness. Lapierre has worked as an engineer consultant inbiomaterial development and designing digital microsystems forpathogen detection.

Tomisich said the development of new micro-materials couldplay a critical role in next generation portable analyticaldevices.

Hilder encourages scientists to seize the opportunity whileASTech PhD scholarships are still available.

‘Applications will be accepted until all HDR positions havebeen filled, so budding scientists should visit the ASTechwebsite and apply to join us in developing innovativeseparation technologies,’ said Hilder.ASTech

JP vacuum recirculating water pump IP2050 List $3293.34SALE PRICE $1775.82

DK20 digester (heating) 20 place with temperature ramp. ID1705 List $5289.78 SALE PRICE $3990.00

SMS scrubber IS5100 List $1831.72SALE PRICE $987.69

Kjeldahl Digestion system for nitrogen analysis and protein determination.

ADELAIDE08 8186 0523

[email protected]

BRISBANE07 3376 9411

[email protected]:\MARKETING\ADVERTISING\Chemistry In Australia\324-Chem.in.Aust.1.4.15

Stirring & Mixing

Buffer Solutions

Fine Chemicals Water Analysis

Ovens & Incubators Air Sampling Pumps

Weighing & Measuring Glassware

Filtration & Chromatography Plasticware

REF:324

HOBART03 6272 0661

[email protected]

MELBOURNE03 9701 7077

[email protected]

PERTH08 9302 1911

[email protected]

SYDNEY02 9603 1205

[email protected]

Unique twin neck bottle for easy dispensing

TARSONS

research


Yeast-eating bacteriain the human gutYeasts have been a regular part ofour diet since their domesticationsome 7000 years ago. A joint studybetween groups in the US, the UK,Belgium and Canada, and that ofAssociate Professor Spencer Williamsat the University of Melbourne hasworked out how a commoncomponent of the humanmicrobiota, Bacteroidesthetaiotaomicron, acquired thecapacity to use the yeast cell wall asa food source (Cuskin F., Lowe E.C.,Temple M.J., Zhu Y., Cameron E.A.,Pudlo N.A., Porter N.T., Urs K.,Thompson A.J., Cartmell A., Rogowski A.,Hamilton B.S., Chen R., Tolbert T.J.,Piens K., Bracke D., Vervecken W.,Hakki Z., Speciale G., Munōz-Munōz J.L.,Day A., Peña M.J., McLean R.,Suits M.D., Boraston A.B., Atherly T.,Ziemer C.J., Williams S.J., Davies G.J.,

Abbott D.W., Martens E.C., Gilbert H.J.Nature 2015, 517, 165−9). A critical rolein this work was played by the bespokeazasugar inhibitor a-mannosyl-1,3-isofagomine synthesised by the Williamsgroup, which was used in X-raycrystallographic structural studies todetermine on a molecular level how a

glycoside hydrolase enzyme cleavescomplex chains of the polysaccharidemannan found in yeast cell walls. Thediscovery that mannan is a micronutrientdegraded by B. thetaiotaomicron may berelevant to the health-promoting effectsof the human microbiota.

Nanostructured electrodes for efficient water splitting

Electrolytic water splitting holds promisefor large-scale storage of energygenerated from renewable sources, suchas solar and wind, in the form ofhydrogen fuel. But the sluggish kineticsof the oxygen evolution reaction on theanode means that expensive catalystssuch as oxides of iridium (IrO2) orruthenium (RuO2) must often be used tolower reaction barriers. The group ofAssociate Professor Chuan Zhao at the

University of New South Wales hasrecently developed a highly efficientoxygen electrode by electrodepositingamorphous mesoporous nickel−ironcomposite nanosheets directly ontomacroporous nickel foam substrates(Lu X., Zhao C. Nat. Commun. 2015, 6,6616). The hierarchically structuredporous electrode exhibits high catalyticactivity towards water oxidation inalkaline solutions, initiating the reaction

at an overpotential of only 200 mV anddelivering current densities of 500 and1000 mA cm–2 at overpotentials of 240and 270 mV, respectively. The electrodeis also stable to prolonged use at highcurrents. The results suggest theelectrode is the most efficient oxygenevolution electrode in alkalineelectrolytes reported so far and canpotentially be used for industrial waterelectrolysis.

research


Harnessing light for fuel

Researchers at Monash University have made significantprogress towards developing a method of artificialphotosynthesis that could replace the use of fossil fuels in thefuture. Artificial photosynthesis is the industrial process ofpreparing fuels and chemicals from nothing more than carbondioxide, water and sunlight. The researchers, led by ProfessorDouglas MacFarlane, discovered a new way to convert carbondioxide to methanol (Li H., Zhang X., MacFarlane D.R. Adv. Energy. Mater. 2015, 5, 1401077). They created a photo-catalyst based on copper oxide, the surface of which is decorated with tiny carbon dots about 2 nm in size. Thisnano-composite material can directly convert carbon dioxidedissolved in water into methanol, using only sunlight as anenergy source. The key to this process in chemical terms is thedevelopment of catalysts – one to oxidise water and another toabsorb and reduce carbon dioxide. When the catalysts arecoupled with materials that can absorb light energy, fuels suchas methanol can be generated efficiently.

Chirality in solution is controlled simply by molecularstereocentres, while that in crystals has the added complexitythat all molecules in the crystal unit cell must be considered.Crystal packing typically involves centrosymmetricarrangements of enantiomeric pairs, meaning that chiralcrystals are rare. On surfaces, however, self-assembledmonolayers (SAMs) usually pack into units containing internalrotational symmetry, preserving chirality. In addition, thecombined molecule−surface geometry, or the arrangement ofachiral molecules above a surface, can generate chirality.Recently, researchers at the University of Technology, Sydney,led by Professor Jeff Reimers, and at five other institutions(Yan J., Ouyang R., Jensen P.S., Ascic E., Tanner D., Mao B.,Zhang J., Tang C., Hush N.S., Ulstrup J., Reimers J.R. J. Am.Chem. Soc. 2014, 136, 17087−94) combined to observe andcharacterise seven SAMs formed by the butanethiol family onAu(111). Racemic 2-butanethiol mixtures self-assemble, bothdirectly on the surface and on Au-adatom stereocentres, intounits containing 12 chiral centres each, yet this structure isrectangular with an approximate internal symmetry plane,negating long-range expressions of surface chirality. On theother hand, achiral oblate-like t-butanethiol self-assembleswithout chiral head groups into near rhombic shapes withprofound long-range chirality. While the whole surface isracemic, independent large domains are chiral, offering theprospect of chiral catalysis.

Chirality on surfaces unlike that insolution or crystals

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

Polymersomes − vesicles formed by self-assembly of polymeramphiphiles − provide a good platform for targeted drugdelivery and for creating complex (bio)catalytically activesystems for research in synthetic biology and systemschemistry. To realise these applications requires both spatialcontrol over the encapsulation components in thepolymersomes and a means to determine where the componentsare in the polymersomes. Addressing these twin challenges, the

Thordarson group at theUniversity of New South Walesand collaborators recentlyreported the synthesis of aprotein−polymer bioconjugatePNIPAM-b-amilFP497 composedof thermo-responsive poly(N-isopropylacrylamide) (PNIPAM)and a green-fluorescent proteinvariant (amilFP497) (Wong C.K.,Laos A.J., Soeriyadi A.H.,Wiedenmann J., Curmi P.M.G.,Gooding J.J., Marquis C.P.,Stenzel M.H., Thordarson P.Angew. Chem. Int. Ed. 2015, 54,5317–22). Above 37°C, thisbioconjugate forms

polymersomes that can (co-)encapsulate the fluorescent reddrug doxorubicin and the fluorescent pink light-harvestingprotein phycoerythrin 545 (PE545). Using fluorescence lifetimeimaging microscopy and Förster resonance energy transfer(FLIM-FRET), the researchers were able to distinguish PE545protein found only in the polymersome membrane fromdoxorubicin found in both the polymersome core andmembrane.

Capture and sensing of payloads in polymersomes

Merck Millipore is a division of

The new ChromBookAdvance with the world of chromatography in your hands.

COMING SOON!One of the most trusted chromatography resources is now even more resourceful:

Merck Millipore’s new ChromBook features the latest innovations and information for

TLC, HPLC, UHPLC, and sample preparation. Explore our entire range of new and existing

products. Access valuable advice about cutting-edge methods and applications.

Advance with us - hand in hand.

BOOK YOUR COPY NOW!Contact Merck Millipore: 1800 335 571www.merckmillipore.com/chrombook

Advance with the world of chromatography in your hands.

ceful:ceful:

mation for mation for

w and ew and existing xisting

hods and applications.hods and applications.

research


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

The development of renewable energy technologies isvital for meeting the increasing energy demands of themodern world and for lowering greenhouse gasemissions and environmental pollution from fossil fuelcombustion. Towards this end, many approaches toharvesting solar energy have been explored. The dye-sensitised solar cell (DSC) is one promising device thatcan potentially be constructed at low cost and withenvironmentally friendly components. Efforts are beingmade to develop n-type and p-type DSCs that can becombined into high-efficiency tandem DSC devices. Butthe poor efficiency of p-DSCs has hampered theperformance of such tandem devices. The Spiccia andBach groups at Monash University have recently tackledthis problem by developing a new electrolyte for p-DSCsbased on the tris(acetylacetonato)iron(II/III) redoxcouple that better matches the energy levels of the p-typesemiconductor and sensitiser used (Perera I.R., Daeneke T.,Makuta S., Yu Z., Tachibana Y., Mishra A., Bäuerle P., Ohlin C.A.,Bach U., Spiccia L. Angew. Chem. Int. Ed. 2015,

54, 3758–62). The devices made with this redox couple havethe highest efficiency (2.5%) and current density(7.65 mA cm−2) of any p-type DSC reported to date.

New benchmark in p-type dye-sensitised solar cell performance

The generation of acyl anion equivalentsfrom aldehyde-containing materialsunderpins many studies in the field of N-heterocyclic carbene (NHC) catalysis.Recent studies from the Lupton group atMonash University have uncovered apathway that allows esters to provideaccess to acyl anion equivalents as well.The specific reaction proceeds via a novelcycloisomerisation, elimination, redoxisomerisation cascade. Thetransformation is quite general (15examples) and, using chiral catalysts,

allows the synthesis of axially chiralbiaryls via a novel point to axial chiralitytransfer event (Candish L., Levens A.,Lupton D.W. Chem. Sci. 2015, 6,2366−70). The potential of this new

entry to acyl anions is yet to be fullyexploited, and may lead to other novelcomplexity-generating cascades startingfrom ubiquitous ester-containingsubstrates.

Esters provide acyl anion equivalents too

In the May issue, an interestingHighlight on the synthetic uses ofdiethylaluminium azide (Et2AlN3) byMonticelli and Pace (Vienna) summarisesthe formation of tetrazoles and bis-tetrazoles from (di)nitriles, triazoles andbeta-azidoketones (by Michael addition)from alpha-beta unsaturated ketones,beta-azidoalcohols from the ringopening of epoxides, which effectivelycorresponds to the addition of HO–N3 toC=C double bonds. Numerous otherreactions are also described, includingthe formation of acyl azides from esters(by substitution) and of azido-functionalised C60 (by addition). Thereactivity of this reagent arises from acombination of the Lewis acid nature ofAl and the nucleophilic andcycloaddition properties of the azidegroup.

Hypervalent iodine compoundsconstitute another powerful group ofreagents in organic synthesis. AHighlight by Hartrampf and Toombs-Ruane (Munich) describes the use ofdiaryliodonium salts in thedifunctionalisation of alkynes, wherethey act as highly electrophilic aryltransfer reagents. Such reactions yieldinter alia 3-methyleneoxindoles from propargylic amides, 3-alkoxymethylfurans from beta-acylalkenynes, quinolines fromacetylenes and nitriles, and triazolesfrom acetylenes and azides. Many otheruseful reactions are also described.

Imines (Schiff bases) are well-knownand highly useful compounds, e.g. forthe synthesis of secondary (chiral)amines and bio-organic compounds suchas alkaloids. They are usually preparedby condensation of an aldehyde orketone with an amine at reflux, oftenwith the help of a catalyst such as zincor titanium chloride, alumina or coppersulfate. Philip Andrews and co-workers(Monash University) report the rapid andfacile preparation of a variety ofaromatic and heterocyclic, chiral andachiral imines by using microwaveirradiation. The yields are high, oftenquantitative, and the reactions arefinished in a matter of minutes.

The importance of pyrimidines inbiology and in medicinal chemistry iswell established. However, thepreparation of simple 4,6-dihydroxypyrimidines (6-hydroxypyrimidin-4-ones) and thecorresponding 4,6-dichloropyrimidinescan be tedious, requiring the isolation ofhygroscopic intermediates, viz. imidoacid ester and amidine hydrochlorides.Opitz, Sulger, Daltrozzo and Koch(Konstanz and Oldenburg) have nowdeveloped a one-pot, high-yielding (upto 93%), large-scale (1 mol) synthesis of2-substituted 4,6-dihydroxypyrimidinesas well as their conversion to the 4,6-dichloropyrimidines with POCl3 in up to 86% yield on a similarly largescale. These well-worked procedures willbe of interest to synthetic and medicinalchemists. In addition, the mechanism ofthe chlorination reaction wasinvestigated computationally.

June 2015

Aust J Chem

Curt Wentrup FAA, FRACI CChem ([email protected]),http://uq.edu.au/uqresearchers/researcher/wentrupc.html?uv_category=pub

MEPinstrumentsThe right chemistry.

M962 Adv_MEP_NIRSystMasterlab_275x76_20131111.indd 1 12/11/2013 11:33


Working and sensory lives of bees

BY DAVE SAMMUT

stingThe tale in the

According to the United Nations, ‘ofthe 100 crop species that provide90 per cent of the world’s food,over 70 are pollinated by bees’

(bit.ly/1DpiRYF). It’s little wonder, then, thatbees continue to be a subject of study aroundthe world. More surprising, perhaps, is that somuch remains to be learned.

Bee-keeping (apiculture) is believed tohave started as far back as about 4500 yearsago; sculptures in ancient Egypt show workersblowing smoke into hives as they removehoneycomb. In ancient Greece, Aristotle eitherkept and studied bees in his own hives orexamined the observations passed to him bybeekeepers. In doing so, he made some astuteconclusions; for example, that there are threeclasses of bees, one of which is sterile. Alongwith his better observations, he thoughtincorrectly that bees do not make honey andinstead that it is distilled from dew.

In reality, the manufacture of honey by beesis both complex and elegant. Honey varies incomposition depending on many factors (suchas the different species of flower from whichthe inital nectar is collected), but in generalterms it is dominated by two key simplesugars: dextrose (glucose isomer) andlevulose (fructose isomer), constituting over70% by mass. It also contains aromatic volatileoils (giving it rich flavour), mineral elements,some proteins, enzymes, vitamins andcolouring matter.

Worker bees collect nectar from selectedflowers. Containing about 80% water, togetherwith complex sugars, this nectar is stored in aspecial stomach (the ‘honey stomach’) wherethe invertase enzyme secreted by the bee’ssalivary glands begins the process of breakingdown the sucrose in the nectar into simpleglucose and fructose. Some of the glucosereacts with a second enzyme, glucose oxidase,to form gluconic acid and hydrogen peroxide,creating conditions of low pH (3.2–4.5).

sucrose + O2 fructose + glucose

Once the worker bee’s honey stomach isfull, it returns to the hive and regurgitates thepartially modified nectar for a hive bee. Thehive bee ingests this material to continue theconversion process, then again regurgitates itinto a cell of the honeycomb. During theseprocesses, the bees also absorb water, whichdehydrates the mixture.

Hive bees then beat their wings to fan theregurgitated material. As the water evaporates(to as little as around 10% moisture), thesugars thicken into honey – a supersaturatedhygroscopic solution of carbohydrates (plusoils, minerals and other impurities).

Some researchers think that the hive beesinject a venom into each comb, giving thehoney its antibacterial properties; othersdismiss this idea, saying that the highconcentration of sugars means thatfermentation cannot happen. Either way, thereseems to be general agreement that the acidicnature of the honey is hostile to bacteria,mould and fungi.

In its entire lifetime (approximately sevenweeks, as compared to Aristotle’s estimate ofseven years), an average bee will produce lessthan a gram of honey.

But how does the worker bee select itsflowers in the first place? In 2013, ProfessorDaniel Robert and his team at the University ofBristol made a fascinating discovery (Science,doi: 10.1126/science.1230883).

It was already well known that bees generatea positive charge as they move, and mostparticularly as they fly. It was also known thatflowers generate a weak negative charge overtime. Using a Faraday pail (a sort of electricallyshielded bucket, similar to the wire cage in amicrowave oven), Robert and his teammeasured this positive charge on individualbees. They went on to demonstrate that whenthe bee lands on a flower, this charge istemporarily passed to the flower, and that for aperiod of minutes after the visit the flower willhave a measurably more positive charge.


Bees have a well-earned reputation for pollinationand honey-making, but their lesser known skills inelectrocommunication are just as impressive.

iStockphoto/ursusarctos

iSto

ckph

oto/

Ivan

Mikha

ylov

Most importantly, using artificialflowers with a controlled electricalcharge, the Bristol team was able toshow that the bees could sense theelectrical charge on the flowers, andthat they could be trained to use thatcharge to guide their activities. Thiswas a breakthrough – the first time thatelectroreception had beendocumented in an invertebratespecies (see Sensational species box).

It now seems that bees also useelectrocommunication. In a paper tothe Royal Society in 2013, Greggers etal. note that ‘the electric fields emittedby dancing bees consist of both low-and high-frequency components. Bothcomponents induce passive antennalmovements in stationary beesaccording to Coulomb’s law. Bees

learn both the constant and themodulated electric field componentsin the context of appetitive proboscisextension response conditioning.’(Proc. R. Soc. B, doi: 10.1098/rspb.2013.0528)

The ‘waggle dance’ is itself aremarkable note in the journals ofscience. Much like the Rosetta Stoneunlocking the secrets of hieroglyphics,the seminal work of zoologist Karl vonFrisch unlocked in the mid-20thcentury the secrets of the movement ofsuccessful foragers returning to thehive. He correlated the dance todirections on flower patches viarelative position of the sun and thedistance from the hive, with differentdances particular to different beespecies. It was the first demonstration

of non-human communications forlearning, and it won von Frisch the1973 Nobel Prize in Physiology orMedicine. And now we know thatelectrical fields also play their part inthis communication.

However, the waggle dance is notwithout controversy. Some expertsargue that the waggle dance cannotgive guidance on a nectar source, andthat floral odour is actually thedominant method of recruiting bees tothe source. For most of us, this is amatter of nuance. It would seem thatmost scientists would agree that bothmechanisms contribute, and that it isonly the relative weighting that is incontention. For the antagonists, it isoften a matter of polarised principle,even outright hostility.


The multiple senses that humans andanimals possess beyond the ‘standardfive’ are fascinating. In humans, thisincludes mechanical senses for balance(‘equilibrioception’) or for locomotion(‘propioception’), and many more.

Electroreception is the biologicalability to perceive electrical stimuli. Insome species of the animal kingdom,these senses are highly developed –particularly in aquatic or wet terrestrialenvironments where charge is carriedbetter. As an example, some species ofshark can detect DC fields as low as5 nV/cm.

The most common usage is inelectrolocation in predation. Livingorganisms generate small electrical fieldsin the movement of their muscles and in

their nerves, while fish also generatefields from the ion pumps associatedwith osmoregulation at the gillmembrane. Some predators use this todetect their prey (sharks have beenshown to attack any source of anelectric field, which was a problem forearly telegraph cables), while others usethe sense to avoid predators.

This has led to an ‘arms race’, forexample in the evolution among somefish species towards more complex orhigher frequency electrical fields thatare harder for their predators to detect.

Conversely, some species of fishcommunicate by modulating thewaveform of their electrical field, formating and territorial displays.

This electroception is caused by amultitude of biological mechanisms.Sharks use field sensors called theampullae of Lorezini: electroreceptorcells connected to seawater by pores intheir snout and head. Monotremes(particularly the platypus, but also twospecies of echidna) use free nerveendings located in the mucousmembranes of the snout.

In species with ‘activeelectrolocation’, the animal generates itsown electrical field using a specialisedorgan of modified muscle or nerves, andthen modifies the frequency andwaveform in a manner that might beunique to the species or even theindividual.

Sensational species

iSto

ckph

oto/

vlad

oska

n

Electroreception in bees is associated with a collection ofsensory cells in the second segment of the antennae calledthe Johnston’s organ, which detects motion in the flagellum(the final antennal segment). As with other animals, the senseis mechanical, but it represents yet another mechanism forelectroreception. It is a truly wondrous demonstration of theability of evolution to take up every advantage available in thephysical world. And because the presence of the Johnston’sorgan is a defining characteristic that separates the classinsect from other hexapods, it opens the possibility of yetundiscovered behavioural triggers in invertebrates.

Returning to the Bristol study, the researchers found thatthe electrical charge stimulus worked best in combinationwith colour triggers, and this brings me to anotherremarkable aspect of bees and the animal kingdom moregenerally.

The honeybee can see only four basic colours, comparedto the 60 distinct colour combinations from the three primarycolour photoreceptors in humans. Their visible spectrumstretches from about 300 to 650 nm, and they are red-blind. Yetwith their vision in the UV portion of the spectrum, bees cansee a quite remarkable amount of detail in flowers that wecannot, which is obviously an evolutionary response betweenthe two organisms. Indeed, the extensive publications ofProfessor Lars Chittka of Queen Mary University of Londonsuggests that the photoreceptor abilities of ancestral beespre-dated the existence of flowers by more than100 million years, and that the colouration of flowers evolved inresponse to the bees’ ability, rather than the other wayaround.

That there is a topic so thoroughly researched over such along period, and with so many insights yet to offer, is simplydelightful. Given the importance of bees to our global foodsupply, these advances in our understanding are of more thanmere esoteric interest. They might one day become critical toour existence.

Dave Sammut FRACI CChem is principal of DCS Technical, a boutique scientificconsultancy, providing services to the Australian and international minerals, wasterecycling and general scientific industries.


Bee populations, both wild and commercialised, are indecline globally. Current research is largely focused ontrying to identify the causes of decline (called colonycollapse disorder in the US). The main areas underinvestigation are bee parasites (most particularly thevarroa destructor mite), use of pesticides and the build-upof toxins in the foraging environment, loss of biodiversityand foraging rich environments, spread of the Africanisedhoney bee (in the US), and extremes of weatherassociated with changing climates. Work is being done ingene manipulation of honey bees to protect them frommites, as well as research into alternative pollinators thatcan be used should bee populations fail catastrophically.

Some recent good news in Australia is an innovativebeehive design using a slight flexing of a plasticframework to allow honey to flow directly out of the hive(literally honey on tap) for collection. This could haveimplications in the fight to strengthen bee colonies, byallowing more user-friendly beekeeping set-ups for therapidly expanding urban apiarist markets. No smoking orbee suits required!

Chantelle Craig

The cells of the honeycomb fracture during this new type ofprocess, allowing the honey to flow down, but they don’tactually break.

Investigating bee declineThe honeybee can see onlyfour basic colours, comparedto the 60 distinct colourcombinationsfrom the threeprimary colourphotoreceptorsin humans.

Honeybees on the plastic beehive framework.

iSto

ckph

oto/

Ivan

Mikha

ylov

Flow

Med

ia

Flow

Med

ia

Chemistry in Australia22 |

BY DES CONNELL

A new approach

Exposuretime andchemical toxicity

iStockpho

to/khvos

t

The introduction of a newweapon was heralded to theQueen Victoria Rifles in April1915 when the startled

soldiers, resting after being at the front,saw coming at them from the Frenchlines galloping teams of frenziedhorses. The soldiers could see thatsomething terrible was happening inthe ominous green–yellow cloudmoving slowly towards them. It was thestart of one of the first mass gas attacksof the Great War using chlorine, and itbecame the weapon the soldiersfeared the most.

World War I is described by somecommentators as the chemists’ war.The originator of chlorine gas as aweapon of war was Fritz Haber,controversial recipient of the NobelPrize in Chemistry in 1918. This wasawarded for his development of theprocess for fixation of nitrogen fromthe atmosphere to produce cropfertilisers, and greatly accelerated foodproduction. It is possibly the mostimportant industrial process for thehuman race ever devised; it was, andstill is today, a great service tohumanity.

Another result of the involvement ofthe ‘father of chemical warfare’ isHaber’s rule (Haber F. ‘On the historyof gas warfare’, In: Five lectures fromthe years 1920–1923. Springer, Berlin,pp. 75–92, 1924). It is used to predictthe influence of exposure time ontoxicity in medical, occupational andother industrial applications. In recenttimes, the occurrence of toxicchemicals at low environmentalconcentrations and for long periods oftime have become important. Thesenew factors need to be consideredwhen setting environmental andoccupational guidelines for toxicchemicals, thus leading to newrequirements for accounting for theexposure time (Yu Q. et al.Chemosphere 1999, vol. 38, pp. 909–18; Zhao Y., Newman M.C. Environ.Toxicol. Chem. 2004, vol. 23, 2147–53).

Haber’s rule and lethalconcentrationToxicological data is usually reportedas the LD50 or LC50, while the exposuretime to reach the toxicity, often 24, 48or 96 hours, is recorded but fixed andnot considered as a quantifiable

variable (Ashauer R., Escher B. J.Environ. Monit. 2010, vol. 12, pp. 2056–61; Rozman K.K., Doull J. Toxicology2000, vol. 144, pp. 169–78; RozmanK.K., Doull J.J. Pharmacol. Exp. Ther.2001, vol. 296, pp. 663–8). Usuallybroad and imprecise terms such asacute, subacute, chronic andsubchronic are used to describe theexposure time conditions. The lethaltoxicity, at another exposure time otherthan that reported, may be required toset guidelines in air, food, soil andwater. This is usually obtained byextrapolation using Haber’s rule.Haber formulated a rule to do thisextrapolation from observations of theeffects of poisonous gases and used itto calculate the lethal effects in thedispersal of chlorine on the WesternFront. Haber’s rule is usuallyexpressed as:

LC50 × exposure time = constant (K) where LC50 is the lethal concentrationof the toxic chemical to the averageorganism over the time the organism isexposed and the empirical constant Kis related to the organisms beingevaluated, experimental conditionsand units used.


Australian infantry wearing small box respirators. Thesoldiers are from the 45th Battalion, Australian 4thDivision at Garter Point near Zonnebeke, Ypres sector,27 September 1917.

Over the past century, few scientificrelationships have survived unaltered.Haber’s rule has not only survived, it hasprospered in its application.

Fran

k Hur

ley/

Aust

ralia

n W

ar M

emor

ial

Thus a lethal gas with an LC50 of10 mg/m3 taking 24 hours to reachlethality to an average mammal, givesa calculated K of 240. The lethality ofthe gas at 48 hours would be 240/48,which is 5 mg/m3. Other toxicities atother exposure times can be similarlycalculated. The inherent toxicity of thesubstance does not change during theexposure, irrespective of the timeinvolved, but the toxic effects on theorganism have a longer duration withlonger exposure times andconsequently have a lethal toxic effectat a lower concentration.

This rule has been used forevaluation of effects of exposure timeon toxicity for about a century with ahigh degree of success. Many variantsof Haber’s rule have been proposedthat preserve the essential nature ofthe relationship, with the two variables,

toxicity and exposure time, modified insome way.

Haber’s rule has stood the test oftime in setting standards, extrapolatingeffects from chronic to subchronicexposure, setting exposure limits forworkplaces and even settingguidelines for maximum permissiblelimits for chemicals in spaceships.Generally, Haber’s rule has beenextremely valuable with toxicants atrelatively high levels and shortexposure times.

Faults of Haber’s ruleManagement of toxic chemicals hasexpanded over recent decades. Therelatively high exposures withpharmaceuticals as well as workplacesand other industrial applicationsremain important. But theenvironmental occurrence of

chemicals poses new challenges, withlong exposure times and low levels ofexposure. In these situations, Haber’srule has two major faults.

First, according to Haber’s rulewhen the toxicity approximates zero,as occurs in most environmentalsituations, then the exposure timeshould approach infinity since thevalue of K needs to remain constant tosatisfy Haber’s rule – thus zeromultiplied by infinity should give K.This is an inappropriate result, whichdoes not give any useful values in theextrapolation.

Second, there is no limit to Haber’srule – it can be applied to very longexposure times, in fact well beyond thelifetime of any organism (specificallyhumans) being considered. This is alsoinappropriate and yields no usefulresults.


The RLE model ...solves theproblems apparentwith the traditionalHaber’s rule, whichcannot be appliedto long-termexposure tochemicals in theenvironment.

Representation of the RLE model fitted to hypothetical observed data with fish andzooplankton.

iStockphoto/Molekuul

Reduced life expectancy modelOur research (Connell D.W., Yu J. Mar.Pollut. Bull. 2008, vol. 57, pp. 245–9;Verma V. et al. Chemosphere 2012, vol.89, pp. 1026–33) evaluates theimportance and use of the normal lifeexpectancy (NLE) as a totally newvariable in quantifying the effects ofexposure time on toxicity. The newmodel addresses the two major faultswith Haber’s rule. It is based on anobserved negative linear relationshipbetween the lethal toxicity of achemical, LC50, and the naturallogarithm of the exposure time, LT50.Thus it describes the fall in LC50 as theexposure time increases until LC50

decreases to zero and LT50 becomesthe NLE. The organism exhibits areduced life expectancy (RLE) as theexposure time increases (see figure).The model takes the form:

LC50 = –a ln(exposure time, LT50) + bwhere LC50 is the lethal concentrationto the average organism, LT50 is theaverage exposure time for theexpression of lethality LC50 also whenthe LC50 is zero and the LT50 is the NLEand a and b are empirical constants.

Our extensive investigations (VermaV. et al. Environ. Poll. 2014, vol. 185, pp.234–9, 2014; Verma V. et al. ISRNToxicology 2013, doi: org/10.1155/2013/230763) of data from the literature withthe RLE model for fish and marineinvertebrates involving 88 data sets andwith a wide range of organic andinorganic toxicants gave high linearstatistically significant correlations(R2 > 0.8). These plots take the form ofthe hypothetical plot shown.

The NLE introduces a fixed limitingpoint for a species and at the sametime it is a reference point. Thisvaluable reference point is availablewith most data sets where the NLE ofthe test organism is known. It utilisesthe fact that when the exposure to achemical is zero, it follows that the timeto reach lethal toxicity is the NLE.

It should be noted that the toxicity ofthe chemical being considered isconstant all the time although the LC50

values are declining. But the exposuretime increases and is responsible forthe observed change in LC50 of thecompound. In fact, with increasingexposure time, the contribution of theconstant toxicity of the compound tothe observed toxicity (LC50) declinesas the significance of the exposuretime increases. Finally when LC50 is atits minimum, at zero, then the exposuretime is the normal life expectancy.

Use of the RLE modelThe RLE model can be used tocalculate LC50 values for a specificorganism and toxicant at any exposuretime from a set of data comprisingLC50 and corresponding exposuretime. The RLE model is used togetherwith the NLE of the organism beingconsidered to develop the RLEequation for the particular organismand specific toxicant. However, the setof LC50 values and correspondingexposure times are supplemented withthe NLE at an LC50 of zero. Theequation of best fit is obtained for thisdata for a plot of LC50 against ln LT50, asin the graph, which gives values for all

the constants in the RLE equation:LC50 = –a ln(LT50) + b

In this situation, only one actualmeasured data point is needed,together with the NLE, to obtain theRLE equation. Once the RLE equationis obtained, the LC50 can be calculatedat any exposure time with areasonable level of accuracy.

New parameters, newapplicationsThe RLE model is a new approach toevaluating the influence of exposuretime on toxicity. It solves the problemsapparent with the traditional Haber’srule, which cannot be applied to long-term exposure to chemicals in theenvironment. The model has beenproven to be accurate in predicting thechange in toxicity with differentexposure times with a range ofdifferent chemicals and differentorganisms. The NLE is a newparameter that has never been usedfor this purpose before. From a limiteddatabase consisting of a minimum of asingle data point with fish andzooplankton, in addition to the NLE ofan organism, the RLE equation can beobtained. From this, the LC50 at anyexposure time can be calculated. Thenew model is simple and has manyapplications, particularly in relation tohealth risk assessment and the settingof guidelines for exposure to toxicants.

Emeritus Professor Des Connell AM, FRACI CChem isat the Griffith School of Environment, GriffithUniversity, Queensland.



New X-ray spectroscopygives better look at thechemistry of interfaces

BY LYNN YARRIS

The LawrenceBerkeley NationalLaboratory hascombined keyfeatures of twohighly acclaimed X-ray spectroscopytechniques.

Anew technique, developedby researchers working atthe Advanced Light Source(ALS) of the US Department

of Energy (DOE)’s Lawrence BerkeleyNational Laboratory (Berkeley Lab),offers sub-nanometre resolution ofevery chemical element to be found atheterogeneous interfaces, such asthose in batteries and fuel cells. Thisnew technique is called SWAPPS forstanding wave ambient pressurephotoelectron spectroscopy, and itcombines standing-wavephotoelectron spectroscopy (SWPS)with high ambient pressurephotoelectron spectroscopy (APPS).

Researchers working at theAdvanced Light Source (ALS) of the US Department of Energy (DOE)’sLawrence Berkeley NationalLaboratory (Berkeley Lab) havecombined key features of two highlyacclaimed X-ray spectroscopytechniques into a new technique thatoffers sub-nanometre resolution of

every chemical element to be found atheterogeneous interfaces, such asthose in batteries and fuel cells. Thisnew technique is called SWAPPS forstanding wave ambient pressurephotoelectron spectroscopy, and itcombines standing-wavephotoelectron spectroscopy (SWPS)with high ambient pressurephotoelectron spectroscopy (APPS).

‘SWAPPS enables us to study a hostof surface chemical processes underrealistic pressure conditions and forsystems related to energy production,such as electrochemical cells,batteries, fuel cells and photovoltaiccells, as well as in catalysis andenvironmental science,’ says CharlesFadley, a physicist who holds jointappointments with Berkeley Lab’sMaterials Sciences Division and theUniversity of California Davis, wherehe is a Distinguished Professor ofPhysics. ‘SWAPPS provides all theadvantages of the widely usedtechnique of X-ray photoelectron

iSto

ckph

oto/

7io


spectroscopy, including element andchemical-state sensitivity, andquantitative analysis of relativeconcentrations of all species present.However with SWAPPS we don’trequire the usual ultrahigh vacuum,which means we can measure theinterfaces between volatile liquids andsolids.’

Fadley is one of threecorresponding authors of a paperdescribing SWAPPS in NatureCommunications. The paper is titled‘Concentration and chemical-stateprofiles at heterogeneous interfaceswith sub-nanometer accuracy fromstanding-wave ambient-pressurephotoemission’ (doi: 10.1038/ncomms6441). The other twocorresponding authors are HendrikBluhm, with Berkeley Lab’s ChemicalSciences Division, a pioneer in thedevelopment of APPS, and SlavomírNemšák, now with Germany’s JülichPeter Grünberg Institute.

In terms of energies andwavelengths, X-rays serve as excellent

probes of chemical processes. In thealphabet soup of X-ray analyticaltechniques, two in particular stand outfor the study of chemistry at theinterface where layers of two differentmaterials or phases of matter meet.The first is SWPS, developed at the ALSby Fadley and his research group,which made it possible for the firsttime to selectively study buriedinterfaces in a sample with either softor hard X-rays. The second is APPS,also developed at the ALS by a teamthat included Bluhm, which made itpossible for the first time to use X-rayphotoelectron spectroscopy underpressures and humidities similar tothose encountered in natural or

practical environments.‘Heterogeneous processes at

solid/gas, liquid/gas and solid/liquidinterfaces are ubiquitous in moderndevices and technologies but oftendifficult to study quantitatively,’ Bluhmsays. ‘Full characterisation requiresmeasuring the depth profiles ofchemical composition and state withenhanced sensitivity in narrowinterfacial regions at the nanometrescale. By combining features of SWPSand APPS techniques, we can useSWAPPS to measure the elemental andchemical composition ofheterogeneous interfaces with sub-nanometre resolution in the directionperpendicular to the interface.’

SWPS ... made it possible for the firsttime to selectively study buriedinterfaces in a sample with either soft orhard X-rays.

Says Fadley, ‘We believe SWAPPS will deliver vitalinformation about the structure and chemistry ofliquid/vapour and liquid/solid interfaces, in particular theelectrical double layer whose structure is critical to theoperation of batteries, fuel cells and all of electrochemistry,but which is still not understood at a microscopic level.’

Fadley, Bluhm, Nemšák and their collaborators used theirSWAPPS technique to study a model system in which ananometre layer of an aqueous electrolyte of sodiumhydroxide and caesium hydroxide was grown on an ironoxide (hematite) solid. The spatial distributions of theelectrolyte ions and the carbon contaminants across thesolid/liquid and liquid/gas interfaces were directly probedand absolute concentrations of the chemical species weredetermined. The observation of binding-energy shifts withdepth provided additional information on the bondingand/or depth-dependent potentials in the system.

‘We determined that the sodium ions are located close tothe iron oxide/solution interface, while caesium ions are onaverage not in direct contact with the solid/liquid interface,’Bluhm says. ‘We also discovered that there are two differentkinds of carbon species, one hydrophobic, which is locatedexclusively in a thin film at the liquid/vapour interface, and ahydrophilic carbonate or carboxyl that is evenly distributedthroughout the liquid film.’

A key to the success of this study was the use of X-raystanding waves to excite the photoelectrons. A standingwave is a vibrational pattern created when two waves ofidentical wavelength interfere with one another: one is theincident X-ray and the other is the X-ray reflected by amirror. Interactions between standing waves and core-levelelectrons reveal much about the depth distributions of eachchemical species in a sample.

‘Tailoring the X-ray wave field into a standing wave canbe used to achieve greater depth sensitivity inphotoelectron spectroscopy,’ Fadley says. ‘Our combinationof an oscillatory standing-wave field and the exponentialdecay of the photoelectron signal at each interface gives usunprecedented depth resolution.’

In their Nature Communications paper, the authors saythat future time-resolved SWAPPS studies using free-electron laser or high-harmonic generation light sourceswould also permit, via pump-probe methods, looking at thetimescales of processes at interfaces on the femtosecondtime scale.

‘The range of future applications and measurementscenarios for SWAPPS is enormous,’ Fadley says.Reproduced with permission from Lawrence Berkeley NationalLaboratory/Phys.org


By utilising X-ray standing waves to excite photoelectrons, SWAPPSdelivers vital information about all the chemical elements at theheterogeneous interfaces found in batteries, fuel cells and otherdevices. Slavomír Nemšák

SWAPPS measures the depth profiles ofchemical elements with sub-nanometreresolution in the direction perpendicular tothe interface, utilising an X-ray standingwave field that can be tailored to focus onspecific depths, i.e. near the surface or nearthe iron oxide interface. Chuck Fadley

APPS ... made it possible forthe first time to use X-rayphotoelectron spectroscopyunder pressures andhumidities similar to thoseencountered in natural orpractical environments.

Exquisite meals for less

Enjoy a wide range of complimentary meals,

discounts or percentage savings on your next bill. Choose from a variety of

lunch and dining options at over 300 participating

restaurants around the country.

Visit the website below for more details and to view a

complete list of restaurants available in your area.

MAKE THE MOST OF YOUR BENEFITS:

www.memberadvantage.com.au/raci

{ }

Call RACI Member Advantage on 1300 853 352 for more information.

raci news obituary


Anthony O’Mullane was born inCork, Ireland; he received his BScfrom University College Cork in 1997and completed his PhD at the sameuniversity in 2001 in the field of goldelectrocatalysis. He undertookpostdoctoral fellowships atTechnische Universität Darmstadt,Germany (organic electronics),University of Warwick, UK(electrochemical imaging studies)and then in Australia at Monash

University (organic semiconductors, large amplitude Fouriertransformed AC voltammetry). In 2008, he worked briefly as aresearch scientist at CSIRO before taking a position at RMITUniversity where he was then awarded a Vice Chancellor SeniorFellowship. In 2012 he was awarded an ARC Future Fellowship andin 2013 continued this fellowship and started a senior lectureshipat Queensland University of Technology.

O’Mullane’s research is multidisciplinary in nature and includesthe electrochemical synthesis and characterisation ofnanostructured materials such as metals, metal oxides andconducting organic materials; electrocatalysis; catalysis;photocatalysis; lithium metal batteries; liquid metals and inparticular the application of electrochemical methods to variousaspects of physical, chemical and biological science. In essence,his work focuses on applying electrochemical principles tounderstand electron transfer processes that are at the core ofmost technologies, devices or applications. He thoroughly enjoyscollaborative research projects and to date this has led to thepublication of over 100 journal articles.

He and his colleagues were awarded the John A. Brodie Medal(2010) and he recently received an RACI Citation Award (2014)for his contribution to chemistry and the chemistry profession.

O’Mullane served as the RACI ambassador for RMIT during histime there, and also as the secretary (2010–13) and now Chair ofthe Electrochemistry Division of the RACI. He is married to Linda(an economist). They have two daughters Meesha and Maya,Meesha (5) having the current ambition to be a ‘doctor scientist’.

New Fellow

PTYLTDRowe Scientific

www.rowe.com.au

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]

Pledge to Chemists

This is not a “subtle” attempt to obtain more

R.J. Rowe (FRACI)

Notice of Special General MeetingA special general meeting is planned for Thursday 9 July2015 at 7 pm in Lecture Theatre 4, School of Chemistry(Building F11), University of Sydney, NSW 2006.

The agenda will be:1 Welcome 2 Apologies3 Proxies received4 Resolution

Accept the revised constitution 5 Vote6 Result of vote (To be accepted, 75% of the votes must

be in favour.)7 Meeting close

The sole topic of the meeting will be a vote on aresolution to accept the revised constitution.

The revised constitution is included as an insert in thismagazine. It is also available, together with a comparisonwith the current constitution document, on the RACIwebsite at www.raci.org.au/theraci/corporate-governance/notice-of-general-meeting.

The constitutional revision has been formulatedthrough an extensive consultation process within theBoard, the Assembly and the membership in generalthrough a progression of green papers, white papers anddrafts all open for comment.

Eligible voters include all individual members exceptundergraduate students and Associates.

If you are unable to attend the meeting, you can stillvote by use of a proxy form. A proxy form is included as aninsert in the magazine together with a stamped returnenvelope or it is available on the website listed above.

Complete the proxy form and either return it to the CEOat the National Office before 8 July 2015 or give it to acolleague who is attending the meeting.


raci news obituary

It is with great sadness that we note thepassing of George Victor Meehan in theAdelaide Hills on Saturday 15 March 2015.George devoted most of his professionalcareer to James Cook University over fourdecades, and had a distinguished career inboth teaching and research. He is very

warmly remembered by all his students and colleagues.George Meehan was born in Western Australia and did his

BSc and Honours degrees in Chemistry at the University ofWestern Australia. He then moved to the Australian NationalUniversity, where he undertook his PhD in synthetic organicchemistry. He subsequently held two postdoctoral positions atOhio State University and University College London beforebeing appointed to the staff of the University of Strathclyde asa lecturer in organic chemistry (1970–5). In 1976, he returnedto Australia to take up a position as a senior lecturer at JamesCook University – from where he retired as a professor in 2009.

George was a supremely gifted teacher and he was invariablydeeply admired by students he dealt with at both theundergraduate and postgraduate levels. He was uncompromisingabout the standards required at the tertiary level for graduates,and while challenging students, he displayed infinite patienceto ensure they not only reached that standard, but also realisedtheir own talents.

In his research, his primary interests were in syntheticorganic chemistry for specific chemical and biological purposes.The emphasis of his medicinal/bioorganic chemistry work wason the synthesis of molecules that exhibited significantpharmacological activity or were useful as biochemical tools.However, perhaps he was ultimately more widely recognised forhis collaborative work on supramolecular chemistry/molecularand metal-ion recognition with Professor Leonard Lindoy – whowas on the chemistry staff at JCU from 1970 to 1996 and thenat the School of Chemistry, University of Sydney. Thiscollaborative program was substantially funded (>$1 million) bythe Australia Research Council (inter alia) from 1992 until afterhis retirement, and was very productive – with nearly 40 jointpublications and many invitations (usually presented byProfessor Lindoy) for plenary or section lectures at national andinternational conferences.

George Meehan had an encyclopaedic knowledge of syntheticorganic chemistry and he was always a wonderful and verygenerous source of wise information, advice and guidance aboutstrategies in organic chemistry. His record boasts some80 publications – almost invariably in leading internationalpeer-reviewed journals.

George Meehan also provided significant academic leadershipthroughout his career – his voice was always one of adherenceto best practice and the maintenance of the highest academic

standards. Among many contributions, he played an extremelysignificant role in the establishment of the very successfulpharmacy program at JCU, and for a time he had a significantrole in the activities of the Staff Association. George was thequintessential team player.

George was also involved in RACI activities: he was theSecretary of the North Queensland Section 1977–9, and wassubsequently the Section Chairman in the early 1980s. In 1989,he was the Secretary for the National Conference of the RACIDivision of Organic Chemistry, which was held in Townsville, andhe was a regular visitor to primary schools in the region for the‘Chemistry in Schools Program’ run by the Chemical EducationDivision of the Queensland Branch.

On his retirement, George and Susan moved to Adelaidewhere they built a beautiful home in the Adelaide Hills.However, during 2014, George became seriously ill as acomplication of some procedures associated with hiscontraction of emphysema and his health deteriorated all tooquickly. He is survived by his wife Susan – herself a faithfulservant of JCU in administration for many years (particularly theGraduate Research School) – and their four sons – Malcolm,Gareth, Anthony and Leon – and their families.

George Meehan was a very major force in the establishmentof the research profile of James Cook University and there arevery fond memories of his time in Townsville. Vale George – youwere a very good friend and valued colleague. May you rest inpeace.

Emeritus Professor Richard Keene FRACI CChem

George Victor MeehanA gifted teacher

George Meehan had anencyclopaedic knowledge ofsynthetic organic chemistryand he was always awonderful and very generoussource of wise information,advice and guidance aboutstrategies in organicchemistry.

books

Practical three-waycalibrationOlivieri A.C., Escandar G.M., Elsevier,2014, hardback, ISBN 9780124104082, 330 pp.,$176.95, e-book US$150

Quantitative analysis is subject to avariety of constraints, which varyfrom situation to situation, butuniversally has an over-riding aim ofgetting an appropriate answer to achemical problem, in a timely

manner and with minimal effort. Chemical data is veryimportant; considerable effort, time and expense are oftenrequired to get it, so it is important that efficiency ofacquisition and its utility be maximised. Chemometrics offers away to facilitate this, by melding the chemist’s art withprinciples of experimental design and statistical dataprocessing. It is probably fair to say that chemometrics existson the fringes of chemistry. Most chemists know very littleabout it; a good number think it is probably important but lackthe detailed understanding to either use its techniques or graspits applicability; and others view it as ‘black magic’. Further, itusually requires a reasonable level of computer programmingskill and an understanding of difficult concepts in mathematicsand statistics.

Practical three-way calibration, available both as a text andan e-book, is intended as an introductory-level guide toanalytical calibration with three-way instrumental data (forexample, data from a diode array HPLC detector in the form ofwavelength vs signal vs time). The authors claim that priorprogramming experience is unnecessary and that there is noneed to learn programming languages. Freely available softwaresuch as MATLAB (a high-level language and interactiveenvironment that lets you explore and visualise ideas across arange of disciplines from signal processing to finance) and MVC2(model view controller software) is used throughout the textand the authors walk the reader through examples fromanalyses. These are of graduated complexity and theirexplanations are aided by computer screen shots. Themathematics and statistics are kept to reasonable levelsthroughout.

The book begins with a discussion of calibration scenariosbefore investigating the attributes of various forms of data.After introducing the MVC2 software, a series of quite complex

chapters follow, covering, inter alia, factor analysis for tri-linearand non-linear data, multivariate curve resolution, partial least-squares, and three-way/second-order standard additions.Introductory, yes, but these are certainly not trivial concepts.There is danger of reaching erroneous conclusions if theunderlying concepts are not clearly grasped. (If you don’tbelieve me, consider some of the guff people drag out of Excelstatistics routines: the machine spits out the number, so itmust be right and pregnant with meaning!)

Practical three-way calibration is far from an ‘easy read’. Youreally need to work at it, preferably in front of a computer. Ifyou do that, I’m reasonably confident it will enrich youranalytical chemistry perspectives, help you better plan andprocess your experimental data, and enhance the level ofcunning you bring to hunting the analytical snark. For me, atleast, there is a very steep hill to be climbed. The authors areArgentinian and there is a delightful Spanish flavour to theirwriting. They cogently quote Saint Augustine (re time). Let merequote, slightly altered: ‘If no one asks me about it (practicalthree-way calibration), I know what it is, but if I wish toexplain it to him who asks me, I do not know’. The book hasmoved me from total ignorance to educated uncertainty.

R. John Casey FRACI CChem


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

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

Chemometrics [melds] thechemist’s art with principlesof experimental design andstatistical data processing.

We increasingly live in an age of big data, but does that equateto an Orwellian dystopia where ‘Big Brother is watching you’?Are privacy and data sharing directly in conflict, or can anorganisation’s decision to share your personal data becompatible with protecting your freedom and choice?

The European Union is proposing a new Data ProtectionRegulation, which could curb data sharing in Europe, includingfor research purposes. Could legislation that is designed toprotect individuals from unwanted use of their data actuallyundermine the wellbeing of the people it seeks to protect?

At the Wellcome Trust Sanger Institute, big data is our breadand butter. In January 2014, we reached a major milestone,having collected one petabyte (one million gigabytes) ofgenomic data and we continue to collect about one terabyte(one thousand gigabytes) each day.

The data that we collect is used around the world to improveknowledge of human and animal health. We pride ourselves onour expertise in sequencing and analysing genomes. Ourresearch is overwhelmingly supported by charitable and publicfunds, so we believe it right and in the public interest thatothers benefit from the science we create by sharing ourexpertise, resources and the data we generate. Doing greatscience is of limited benefit if others cannot use it.

So, if sharing genomic data is in the public interest wheredoes that leave our participants’ privacy? Our human data isgenerated from volunteers who donate samples. Whether theyare apparently healthy people or people with specific illnesses,they appreciate the fact that their data is beneficial to society.For many participants, they do not simply donate for anindividual project, but instead expect and want us to share thedata we derive from their donation freely with otherresearchers.

Our participants recognise that it is not possible to predictthe future uses for their data but they still consent to and wanttheir data shared for research purposes. This is typically done ina coded anonymised form that prevents researchers fromknowing individuals’ identities.

Alongside consent, the Sanger Institute also operates amanaged system whereby researchers must apply to access data.An application to access data is never judged on the merits ofthe science or whether it competes with our own research, butsimply on whether the applicants are seeking to use data forlegitimate and ethical research purposes.

As we have the consent of our participants to share data, itis not unreasonable to ask why we have managed access.Consent is a fundamental and critical cornerstone of research,the importance of which cannot be underestimated, but

believing that consent completely protects participants fromhaving their privacy breached is, perhaps, a mistake.

Every day people give commercial organisations consent touse their data when they sign up for their services, and yetoften feel their privacy has been invaded if an organisationuses their data in a way they did not expect. This wasexemplified in the backlash that accompanied publication ofthe experiment Facebook carried out on its users. Every userhad given consent but many still felt that Facebook hadbreached their privacy.

At the Sanger Institute, we believe that guarding data frommisuse stands alongside consent as the best means toguarantee we protect our participants’ privacy.

Given that consent is rightly enshrined in research andpermeates our society, it is understandable that the EuropeanParliament put consent at the heart of their proposed DataProtection Regulations, which will include health-related andgenetic data. Under the proposals, individuals need to providepurpose-limited consent for their personal data to be used andthey must re-consent on a case-by-case basis for their personaldata to be shared.

On the face of it, this sounds reasonable, but, in reality,vital research that is legal and ethical would not be possiblebecause of the difficulties of re-consenting thousands ofparticipants each time their data was shared for new research.

We believe that these regulations will make research at theSanger Institute and worldwide extremely difficult in a way thatwould be detrimental to research and health care, but criticallythey also undermine the autonomy of research participantsthroughout Europe. We should all have the right to say how ourdata is used.

For these reasons the Sanger Institute has chosen to supportthe Data Saves Lives Campaign, which aims to persuade the EUto recognise the importance of sharing data for research and torevise its restrictions on research. The Sanger Institute iscommitted to protecting the privacy of our participants,without whom our work would not be possible.

Over the coming months we will campaign to be allowed todo the research that we believe is so important to patients andbeneficial for wider society and in the process we will becampaigning for our participants’ autonomy and their right toself-determination.

Sarion Bowers is the Research Policy Advisor at the Wellcome Trust SangerInstitute. She has a PhD in Biochemistry. Before joining the Institute, she didpostdoctoral fellowships in Leeds and Connecticut. She recently completed an MScin Science and Technology Policy, in which she researched the adoption ofgenomics into the NHS. First published at https://sangerinstitute.wordpress.com/2015/01/28/can-sharing-your-personal-data-protect-your-freedom.

data & privacy


Can sharing your personal data protect your freedom?

peer review

Most academic papers today are published only after someacademic peers have had a chance to review the merits andlimitations of the work. This seems like a good idea, but thereis a growing movement that wants to retort as Albert Einsteindid to such a review process.

Academic review process was different in Einstein’s time. Inhis brilliant career, the only time his work was subjected toblind peer review – the authors don’t know the reviewers andvice versa – he showed contempt for what is now the goldstandard of science. Was Einstein right to be so suspicious ofthe peer-review process? Should we learn from him and begin toquestion the widespread use of peer review in academicscience?

The first part of Einstein’s career was in the German-speakingworld. The German physics journals, in which Einstein publishedhis breakthrough work, didn’t have the same peer-review systemwe use today.

For instance, the Annalen der Physik, in which Einsteinpublished his four famous papers in 1905, did not subject thosepapers to the same review process. The journal had a remarkablyhigh acceptance rate (of about 90–95%). The identifiableeditors were making the final decisions about what to publish.It is the storied editor Max Planck who described his editorialphilosophy as:

To shun much more the reproach of having suppressed strange opinionsthan that of having been too gentle in evaluating them.

Many of the core scientific discoveries were not peerreviewed to modern standards. For example, the publication ofthe foundational paper describing the double helical structureof DNA by James Watson and Francis Crick in 1953 would havebeen jeopardised in the context of the classic review system aswe know it, because of its speculative nature.

At the prestigious journal Nature, the peer-review systemwas only formally introduced in 1967. More recently, thediscovery of distortion in gravitational waves by a telescope atHarvard – which has crucial consequences for our understandingof the formation of the universe – was presented as preliminaryand treated with extreme caution and even sometimes withdenigration, because it had not been peer-reviewed.

American adventureIt was only after Einstein came to the US in 1935 that he cameface to face with the peer-review process. He and his youngercolleague, Nathan Rosen, sent a paper on gravitational wavesto Physical Review, a journal which had established itsreputation as the premier physics journal in the US. The paperhad the potential to be highly controversial as it challenged theidea that gravitation was a wave.

John Tate, the editor of the journal, hesitated over Einstein’spaper for a month. He then sent it to a reviewer for comments –his selected reviewer was probably the famously gossipy HowardPercy Robertson, one of Einstein’s colleagues at Princeton. The

reviewer returned ten pages of comments which cast doubton many of the central claims in the paper. The editorreturned these comments to Einstein, asked him toconsider the issues, and make any changes he sawnecessary. Here is how Einstein reacted:

We (Mr. Rosen and I) had sent you our manuscript for publicationand had not authorised you to show it to specialists before it isprinted. I see no reason to address the – in any case erroneous –comments of your anonymous expert. On the basis of this incidentI prefer to publish the paper elsewhere.

Although he withdrew the paper from Physical Review,Einstein went on to publish it in a much more low keyoutlet, the Journal of the Franklin Institute. However, thepublished version contains substantial revisions. It appearsthese revisions were largely on the basis of a discussion hehad with Robertson at Princeton. The revised version toneddown many of his original huge claims. These revisions mayhave saved him from public embarrassment.

What would Einstein say today?Some might see this as an amusing historical incident. Butwe think it contains some important lessons for scientistsof all kinds today. This is because it reflects the currenttension regarding the peer-review system.

The story reminds us that double-blind peer review isonly a relatively recent invention. For most of history ofscience, scientific advances were judged in a much more openand public fashion. It also shows us that the peer-reviewprocess can provoke displeasure among even the greatest. Itcan mean scientists not listening to criticism. Sometimes theresult is that many ideas don’t see the light of day.

These anecdotal lessons point to wider issues with the peer-review process, which itself hasn’t been studied in much detail.The review process was meant to save scientists from mistakesand public embarrassment. The idea was that peers help toimprove our work, and the review process of high-statusjournals can serve as ‘stamps of approval’ or simply signal ofquality.

But sometimes a collegial discussion rather than formalisedpeer review can be a better way of getting the message across.So far the peer-review process has been largely an item of faith– something that probably produces better science. However,there is a growing body of evidence which is challenging thisnotion.

An extensive review of the literature on peer review in 1998identified problems. They found that there is a low level ofreliability and agreement over the quality of submitted papers,largely because of a lack of objective evaluation criteria. Evenworse, reviewers make mistakes in their evaluation and oftenaccept papers they should have rejected. As a directconsequence, established journals are usually biased againstinnovative work.


Hate the peer-review process? Einstein did too

In our own field of management science, some have claimedthe peer-review system means academic work can simply end uplosing its integrity during the review process, and can result intrivial and boring research.

On a more positive note, when reviews are perceived ofquality by authors, they tend to generate more citations, whichis a measure of the number of times a research paper ismentioned in other journals and is considered a mark of quality.Also, reliability is not necessary for an efficient review process –often it is the process of peer review itself that contributes toimproving the paper. Reviewers play a developmental role in theconstruction of knowledge, and the energy they deploy in thisprocess is primarily driven by moral motives rather than anymaterial interest.

Bad review for peer reviewPerhaps the most gentle solution would be to improve peerreview. There are clearly disagreements about how this might bedone. Some claim the peer-review system needs to become moreobjective through the introduction of clearer criteria and bettertrained reviewers who are able to systematically apply thesecriteria. Others claim that some subjectivity is importantbecause it can stop reviewers herding to established ideas,thereby crowding out alternative and often more innovativeapproaches.

The frustration regarding the peer-review system has led tonew hybrid systems to emerge. For instance, some scientific

communities haveexperimented withmaking reviewingprocess public.

In the hardsciences, there arethose who postpapers online andother scientistsdecide whetherthey are worthbeing cited. PLOSONE publishes anypaper that hasbeen considered as‘technically sound’after a round ofeditorial review,and readers thenjudge the relevanceof the research.Another alternativesystem would be tohave a set ofreviewers rating all

the papers submitted online, and revising their judgement incase of resubmission. The growing number of open accessjournals has raised concerns that peer review would beprogressively abandoned and search engines and metrics willreplace editors and peer reviewers.

Let’s try something newSome, like Einstein before them, think that the peer-reviewsystem should be abandoned in favour of a ‘market of ideas’where the best research would naturally be identified by thecrowd, hence reducing the cost of the review process. There aremany potential dangers of these alternatives to peer review, themost obvious being expanded opportunities for ‘bad science’ tomasquerade as legitimate work. However, given the immensecost and frustrations associated with the peer-review process,we think it may be worth considering alternatives.

Peer reviewing is an important scientific institution. Butthere might need to be a range of forums in which scientificresults and discussion takes place – peer-reviewed journals onlybeing one among a number of options. Such options would thencompete for both the attention of the readers and the bestpapers. We think this mixed scientific landscape would havepleased Einstein.

Andrew Spicer is Professor of Organisational Behaviour, Cass Business School atCity University London. Thomas Roulet is Novak Druce Research Fellow at theUniversity of Oxford. First published at www.theconversation.com.


iStockphoto/mediaphotos

economics

Renewable resources are often touted as the route to a carbon-free economy. In today’s climate of low oil prices, theeconomics of biofuels and biochemicals production needconsideration. Production of ethanol and the conversion ofethanol into ethylene are a useful basis for discussion.

Ethanol is produced by a wide variety of fermentationprocesses, of which the most widespread is the conversion ofcarbohydrates (such as sugar) into ethanol and carbon dioxide.For sucrose, the reaction stoichiometry is:

C12H22O11 + H2O → 4C2H5OH + 4CO2

This route to ethanol is widespread as it is the basis for theproduction of potable ethanol (booze). In most jurisdictions,the product attracts large excise taxes (currently $80/L forwhisky). It is also used in the production of ethanol fuels in theUS and Brazil and at Sarina (using sugar molasses) and Dalby(using sorghum) in Queensland. Note that most Australian fuelethanol is produced as a by-product from starch manufacture atManildra in NSW and this process is not considered here.

One point to note is that a typical fermentation takes placein a relatively dilute solution so that one of the main operatingcosts is the separation of the ethanol from the excess water.

Ethanol can be dehydrated to produce ethylene attemperatures usually over 200°C (500 K):

C2H5OH → C2H4 + H2OThis is an equilibrium reaction (see below) with a large

portion of industrial-grade ethanol being produced by hydrationof ethylene at low temperatures.

Free energy change C2H5OH → C2H4 + H2O

High potable excise results in heavy regulation of industrialethanol, which is generally tax free, and fuel ethanol, which isgenerally taxed at fuel levels ($0.389/L), to ensure theintegrity of the excise system.

Prior to the advent of the petrochemical industry, ethylenewas often produced by dehydration of ethanol and is still foundin small facilities in some countries (India, China) and was once

used in Australia by CSR Chemicals at Rhodes. Recent interest inrenewable plastics has reinvigorated work in the process.

The table gives illustrative economics using sucrose (asmolasses) as the feedstock. The first two columns give scenariosfor two typical scales of operation – capital and operating costsare in 2013 US dollars. Feedstock for this example was priced assugar at $US300/t.

Statistics for ethanol productionFeedstock Molasses mol + sugar LigninEthanol output (ML/year) 56.79 37.86 56.79

Capital cost ($million) 49.63 37.10 65.91

Capital costs (c/L) 11.86 13.30 15.75

Operating costs (c/L) 27.35 29.09 35.70

Feedstock costs (c/L) 51.78 51.78 4.89

Ethanol production costs (c/L) 90.99 94.17 56.34

Gasoline at current oil price (c/L) 43.73

Typical US ethanol traded price (c/L) 40.00

Capital costs ($/t) 150.31 168.55 199.60

Operating costs ($/t) 346.67 368.75 452.47

Feedstock costs ($/t) 656.26 656.26 61.98

Ethanol production costs ($/t) 1153.24 1193.56 714.05

Gasoline at current oil price ($/t) 594.71

The data illustrates that the ethanol production cost is morethan 90c/L, which is more than double the cost of gasoline(petrol) at the current oil price (about $65/bbl for Tapis crude)and the traded price for ethanol on the US market. At thistime, the cost of sucrose ($300/t) is higher than its value asethanol.

Because of the impact on the use of arable land for fuelproduction forcing increases in food prices, there is much effortin developing non-food feedstock such a lignocellulose (e.g.wood fibres, corn stover, bagasse). There is a paucity ofinformation on the cost of this process but in the last columnof the table I have placed some indicative costs for a similaroutput. There are three main points:• Capital costs are higher due to a more complex process and a

lower overall efficiency. Large volumes of primary feedstockwill require additional processing such as drying andshredding. Also specialist enzymes are needed for theprocess, which will be produced on-site in a separate facility.

• Operating costs are higher, reflecting a more complexprocess, which will include the disposal of significantvolumes of waste material

• Feedstock cost is not zero, as might be assumed. Proposedsources will require collection and transport to the facility.The transport cost in energy terms limits the scale of theoperation to a relatively small facility so that economy ofscale is limited. The notionally free feedstock may have avalue (such as mulch), which will have to be recompensed insome way.


Biofuels and biochemicals

Assuming a value of $20/t for the cost of the feedstock anda 65% efficiency in the process, then production costs arereduced to 56c/L, which is still higher than the price of ethanoland gasoline at current oil prices. Without on-going subsidy,this revolutionary new route only makes sense at significantlyhigher oil prices. The sensitivity of the cost of production tofeedstock price is shown.

Ethanol production cost versus feedstock price.

Rather than use ethanol for a relatively low value commoditysuch as fuel, what about conversion to higher value ethylene?The salient economics are illustrated.

With a typical ethylene value of about $1300/t, ethanolprices have to be below about $600/t to make this route viable.As noted from Figure 2, this is only likely to be achieved bynew (unproven) routes using low-cost lignocellusosic feedstockwith cost below $40/t.

An alternative view is that using ethanol priced at $1000/tto give ethylene at $2000/t, the difference (approximately$700/t) is the premium a user would have to pay to use‘renewable’ ethylene for ‘renewable plastics’.

Although there is much interest and political will to developand promote ethanol as a renewable fuel, this economicanalysis shows that, without high government subsidies such astax breaks, grants and fuel mandates, the current technology isonly viable at high oil prices (>$100/bbl). At current oil andsugar prices, the level of subsidy required is very high andwould present a major hurdle for private investment in thissector.

This study also shows that new routes using lignocellulose asa feedstock would also require high oil prices to succeed. Atpresent, the technology is marginally viable at best and stillrequiring a subsidy at the current oil price.

Converting ethanol to ethylene is marginal unless theethanol was available at energy equivalent prices when theproduction cost would be similar to the product of ethylenefrom ethane by steam cracking (May issue, p. 36).

Using the route to produce renewable ethylene and hencerenewable plastics implies a premium of at least 50% relative toconventionally produced products.

New website, same great content

Access features, news and views from the latest issue and from our chemistry archives.

Visit our new online home at chemaust.raci.org.au

iSto

ckph

oto/

mce

rova

c

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

Sensitivity of ethanol production cost to ethanol price.

environment

Television shows with a forensic science theme are a populargenre at the moment. The combination of ‘high-tech science’,the nerdy/edgy lab experts and the standard mystery solved in55 minutes is grabbing the attention of TV audiences around theworld. In the real world, the field of environmental forensicshas become an important set of tools for environmentalregulation and enforcement of environmental compliance.Besides the trendy high tech, there is a lot of sound, basicscience that also goes into nabbing the environmental baddies.

In my time at EPA Victoria, the Environmental Chemistryteam was an integral part of gathering the evidence that wouldstand up in Court and identify the guilty parties. EPA’s fieldstaff had an important role to play, too, because the integrityof the samples they collected, and the ability to demonstratecustody of those samples through the analysis chain, wascritical in establishing facts beyond reasonable doubt.

In one case, the field team investigating a fish kill in anurban creek used chemical analysis to identify that the fish haddied from ammonia poisoning. The source was not obvious,there being no discoloured discharges from the stormwatersystem to provide any clues. One of the chemistry teamrecognised that fertilisers are sources of ammonia, so the fieldstaff searched for warehouses and other storages that mighthave been holding fertilisers. This identified one premises thathad been storing urea in bulk, in stockpiles on the floor of alarge shed. Somehow, the powder made its way into thestormwater system and hydrolysed, releasing ammonia into thecreek. In this case, it was the chemical reasoning about thepossible source that drove the good outcome (at least from theperspective of nabbing the culprit).

The major part of EPA's work involved GC-based analysis ofhydrocarbon mixtures. This is hardly surprising given thewidespread use of petroleum mixtures and the highly mobilenature of the liquids themselves. Hydrocarbon ‘fingerprinting’ isthe main game here, and it even takes its name from anotherwell known forensic science technique. The overall envelope ofa GC trace can be a good starting point to try and either match

a suspected source sample with one from the environment, orrule out possible sources. High-resolution GC enables severalmarker compounds to be targeted, and measurement of theirrelative abundances enables a high level of certainty to beachieved in matching samples. We typically used GC-FIDtechniques to achieve a match, but occasionally the addeddiagnostic power of GC/mass spectrometry came into play.

While it might be possible to use GC techniques to matchpetroleum samples with a high degree of certainty, one needs agood idea of where to look for a source in the first place. Whena marine oil spill washed up on Phillip Island, impacting onVictoria’s famous little penguin colony, finding a source mighthave been a daunting prospect. Bass Strait is wide and wild,and the currents are strong. However, in this case, the Bureauof Meteorology and the Australian Maritime Safety Authority(AMSA) were able to apply computer modelling to track thepath of the petroleum mass washed up on the beach. Thechemical fingerprint indicated how long the spill had been inthe environment, and tracking of the winds and currentestablished, in concert with satellite signals that track vessels,the one ship that had been in the likely source zone at thetime. AMSA intercepted the ship at its next Australian port ofcall and seized its log, which showed that the bilge tanks hadbeen cleaned illicitly in the location and at the time modellinghad predicted.

Like satellite imagery, conventional aerial photography canbe used for surveillance and environmental monitoring. InLombardy, Italy, a multi-year program of aerial surveillanceusing multispectral infrared and visible imaging has been usedto map densely populated areas for the presence of asbestoscement roofing materials. By examining the images from twodifferent points in time, the regional EPA could identify thehouses from which asbestos cement materials had beenremoved. Staff then visited houses to confirm that theasbestos-containing materials had been disposed of properly.From my observations of rural housing in Russia, a similarapproach might be applicable there if the authorities were soinclined. Asbestos cement seems to have been a popular roofingmaterial, possibly in the Soviet era, but there is a trend ofreplacing it with coated steel sheeting, often in bright colours.When I saw the apparent trend, my immediate thought wasabout what had happened to the waste materials.

One of the most effective tools in environmental forensics isthe dog-walking citizen. Any number of environmental spillsand other incidents, not to mention even more sinisteroffences, are first brought to light by those civic-minded peoplewho value canine companionship and fresh air. Which just goesto show that it doesn’t have to be all high tech and nerdy labgeeks in order to find the guilty party.

Paul Moritz MRACI CChem is a Principal Environmental Scientist with DouglasPartners, and an EPA-appointed Environmental Auditor in Victoria and theNorthern Territory. He is also a dog owner who walks by the local creek.


Whodunnit?

Abestos cement roofing, Uglich, Yaroslavl Oblast, Russia.

The general knowledge crossword in Melbourne’s Sunday Ageoccasionally seeks a word for a ‘heating process used in wineproduction’. While there are perhaps a few options, the one thatcame to my mind initially was the production of Madeira,although the crossword compiler required the specific name of‘estufagem’ for the heating process. In reality, there are twoversions of the estufagem process as well as another heatingstrategy known as ‘canteiro’.

Madeira wine comes from the island of the same name, partof the Portuguese archipelago in the north Atlantic Ocean. Thecapital, Funchal, is located at latitude 32°N. For comparison,this is similar to Rottnest Island in our hemisphere. On theother hand, Funchal is about a 90-minute flight from Lisbonand is in fact closer to the African coast than mainland Europe.The island area is around 800 km2 (references vary!), andimportantly for grape production it is hilly with most of thisarea at slopes over 25%. This presents a challenge toviticulture.

The vines are planted on terraced land, with about1700 hectares under vine. The actual holdings are small, withthe average around 0.3 hectare, requiring wineries to purchasegrapes from many growers. The common trellis used is a pergolasystem, with the vines fruiting below wires running betweenposts at 1–2 metres above the ground. Some farmers will evenplant vegetables for domestic use under the vines – a great wayto make use of the limited space.

Mechanisation is a challenge and most work, includingharvesting, is done by hand. The older practice involvedcrushing the grapes on site and transferring the must intogoatskin vessels of about 70 litres volume. These vessels wouldthen be carried by hand, often across the carrier’s back, alongthe narrow pathways between the terraces to the winery. Thejourney may be up to 20 kilometres. Check out bit.ly/19ZQTYOand the following page for some great images. Trucks are nowused to transport the grapes.

The initial part of the winemaking process is similar to thatfor fortified port wine. After the grapes are crushed, thefermentation is allowed to continue until the selectedsweetness level is achieved. Fermentation may be performedeither in stainless steel vats or in oak casks. The fermentationis stopped by the addition of neutral alcoholic spirit around96% strength. As less ‘natural’ alcohol is produced in theshorter fermentation for sweeter wines, more spirit is requiredto achieve the desired final alcohol concentration around 19–20%. This results in greater dilution of the wine compared tothe drier styles. Bual and Malvasia (sometimes called Malmsey)grape varieties tend to be used for the sweeter wines and maybe fermented on skins for more effective extraction of phenoliccompounds. The longer fermentation results in a drier wine andthis is normally performed ‘off-skins’. Verdelho, Sercial and TintaNegra Mole varieties are more commonly used for the drierwines.

The uniqueness in the production of Madeira wines comesfrom the heating process employed after the fermentation andfortification steps. Heating is utilised to enhance the ageingand maturation of the wine. The estufagem process involvesplacing the wine in large stainless steel tanks and heating thewine to between 45°C and 55°C for at least three months, afterwhich it is allowed to cool and then aged in old oak casks. Avariation of this process uses casks in a warm room at 30–40°Cfor at least six months to achieve the same degree ofdevelopment. Wines destined for the upper end of the marketgo through the canteiro process that involves the wine in 480-litre pipes (oak barrels) being placed under the eaves in winecompany lodges in Funchal. Heating is by the sun only and thematuration takes at least two years, although some may be leftunder the eaves for 20 years or longer.

Serendipity played a significant part in the development ofthis winemaking process. Tradition has it that a ship loadedwith Madeira on its way to England deviated via the Indies.When the wine was opened, it was regarded as the ‘best ever’and so a sea voyage was introduced as standard practice. Aftersome time, it was realised that perhaps heating of the wine inthe ship’s hold as it passed over the Equator may have been thebasis for its development and thus heating in the wineryreplaced the ship voyage. Exposure of Madeira to heat andoxygen (through ingress via barrel staves) means that the winewill not oxidise when opened and so will keep well for years, ifone can wait that long!

grapevine


The wine of Madeira

Geoffrey R. Scollary FRACI CChem ([email protected])was the foundation professor of oenology at Charles SturtUniversity and foundation director of the National Wine andGrape Industry Centre. He continues his wine research at theUniversity of Melbourne and Charles Sturt University.

What to tryThe wines from Madeira are not common in Australia, butthey have a significant historical and internationalreputation. Tradition has it that Madeira wine was used forthe toast at the signing of the US Declaration ofIndependence. A pipe was sent to Napoleon Le Premier inexile, although he apparently declined to open the cask.For those readers who remember Flanders and Swann,Madeira seems to be favoured by roués (bit.ly/1CNHTjN).

My experience with these wines is limited to those madefrom Verdelho. The off-dry versions are suitable as aperitifwines. The nose tends to show caramel, smokiness andmaybe dried stone fruits while the palate normally showsgood acid structure to hold the wine through a long finish.A 500-millilitre bottle of a 10-year-old wine is about $50.If you are keen to try an aged wine, the Solera 1898 isavailable as a medium dry wine at $1350 (750-millilitrebottle), although one website was offering a 10% discountfor a dozen purchase!

An enormous, 3-storey tall blue plastic bear cups his hands around hiseyes and presses his face up against the glass of the Denver conventioncentre, trying to peer inside. What he would have seen, had his plasticeyes worked on the 28th of August would have been ten thousandchemists from all over the world gathered together to talk about theirresearch during the 242nd American Chemical Society (ACS) NationalMeeting.

It was with these words that I began my report to the RACI onmy 2011 experience at the ACS. It was a memorable trip andremains one of my most fruitful conference experiences. I was aPhD student and filled with enthusiasm and awe at the breadthof research that was being undertaken in the field of chemistry.

Two weeks ago, I found myself at the ACS again, this time asa postdoctoral researcher. By sheer coincidence, it was againheld in Denver, so it was a good opportunity to see what hadchanged in the last 1300 days and what hadn’t.

The first thing that struck me was just how competitive thefield is now that I am a postdoctoral researcher. As a PhDstudent, the atmosphere seemed to be more benign – I was,after all, in a cohort of relatively inexperienced researchers. As a postdoc, I am in a far more brutally competitive cohort. My peers are postdocs looking towards the next stage of theircareer. This inevitably means an assistant professorship – a position for which there is intense and seeminglyinsurmountable competition.

Sharing the experiences of two of my almost-peers may giveyou an idea of what the competition is like. (I say ‘almost-peers’ because they are a couple of years ahead of me with theircareers.)

The first researcher graduated from the same group as I didand went on to postdoc for one of the top five polymerscientists in the US. In his three years with the group, he co-authored over 30 peer-reviewed papers. To put this numberin perspective, I authored seven in my three and a half years as a PhD student, so he did very well indeed. When he landed ajob, I was happy for him; he is clearly one of the bright youngminds of polymerchemistry. Then Ifound out thathis advisor (theaforementionedtop-five scientist) wrotehim 40 reference letters beforehe secured a job. 40! That is astaggering number. Especially sinceyou consider that I am approximately athird as productive as he is (publication-wise). Does this mean my referees will have towrite me 120 letters of reference?

The next story is a little more positive.The researcher graduated from a well-respected group and spent a year with astart-up and then 18 months

postdoccing before landing his assistant professorship. Heapplied for 20 jobs and received nine offers. Much better, right?Ah, but he did his postdoc at Caltech. In the US, Caltech carriesa lot of weight and, in addition to this, his advisor also activelyworked to get him a job.

I write about these colleagues because it may be interestingfor young PhDs to know what lies ahead in the job market. It isan especially sharp contrast with the process of finding apostdoc: I was working at the labs of my first-choice supervisor12 months after approaching him!

While this may sound discouraging for aspiring researchers,there is good news. The assistant professors at the conferencewere a really supportive bunch. Each of them seemed genuinelywarm and cordial towards their peers. Even more encouragingwas the respect shown by the established professors towardsthe young up-and-comers. It seems that the assistantprofessorship is a much more difficult pond to get into than thepostdoctoral one, but once you make it there, the fish are allpretty friendly and the bigger fish aren’t looking to gobble youup.

I’ve moved from a small pond in New Zealand to a larger onein Australia to a larger one still in Europe. Now I look across the

Atlantic to see an apparently enormous one inthe US. The barrier to entry looks

high indeed, but I hope I havewhat it takes to make it. Andwith luck, 1300 days aftertoday, the big blue bear may

see an enthusiastic NewZealander addressing the ACSyet again, this time as anassistant professor!

The author is a small fish in Lausanne,Switzerland, and is aware of the ironythat he wishes to swim in a pond in

plain view of a giant blue bear.

postdoc diary

Chemistry in Australia| June 2015

1300 days later

40

It seems that the assistantprofessorship is a much moredifficult pond to get into thanthe postdoctoral one, butonce you make it there, thefish are all pretty friendly andthe bigger fish aren’t lookingto gobble you up.

iStockphoto/Diane Labombarbe

In 1934, publisher Maurice G. Henderson produce a volumeentitled 500 Victorians, labelled as the Centenary Edition. Itwas not the latest edition of a regular publication but a one-offto take advantage of interest aroused by the centenary ofsettlement of the colony. It was normal for people to pay to beincluded in publications like this, but nothing in the bookalludes to this and there was no press coverage that I couldfind.

All sorts of worthies were included, with photographs oftheir heads placed on top of sketched bodies wearingappropriate clothing, mostly suits. I was interested, of course,to see if there were any chemists. Indeed there were, and Ifound four. They were Professor Sir David Orme Masson (‘you willneed several APCs before tackling Sir David’s literature’), AlbertCherbury David Rivett, Masson’s successor in the Melbournechair but by 1934 the CEO of CSIR, and Arthur Victor Leggo,metallurgist, chemical manufacturer and merchant. I was awareof these three, but the remaining chemist was unknown to me.

He was Neville Burton Currey, who was educated at BrightonGrammar, served in the Great War and ‘on return founded thechemical works of which he is proprietor’. In 1917–19, he was adriver in a Signal Company in France. His membership of severalclubs was mentioned, as well as his recreations – golf, yachting,aviation and tennis, each of which was illustrated by a littlecartoon. There was no evidence of technical or universityeducation; records at the National Archives of Australia showthat he applied, as an ex-serviceman, for assistance inundertaking a course in gold assaying with Mr W. Levy ofMelbourne but there is no evidence that this request wasgranted or that he did undertake such training that could havebeen the basis for a chemical business. It was noted that hisfather was Registrar of Titles and Registrar General of Victoria,so it seems unlikely that there was a family business for him totake over.

The 1934 volume gave his birth year as 1898, and his WorldWar I service record shows that he was 19 years old when heenlisted in 1917. His World War II record gives the birth year as1905. This may have been adjusted so as to make him seemunder 40 years of age when he enlisted, because the correctdate was implied upon his death in 1969 at age 71. During thissecond period of service, he faced a court martial in December1942 but no details of the charge and the outcome areavailable.

From 1921 until the late 1930s, Currey was listed indirectories as a chemical manufacturer with an office in a citybuilding but no factory was listed. No advertisements or listing

in directories gave any clue as to what Currey’s companymanufactured, so I spent some time hunting around to see whathe was up to.

There is one clue about what his chemical company wasdoing. In 1927, describing himself as a manufacturing chemist,Currey applied for an Australian patent for ‘a process andapparatus for decorating purposes’. It concerned the decorationof a glass container such as ‘a fancy shaped bottle’ or a potteryobject by coating it with a coloured film like that formed by asolution of shellac and ‘gamboge saffron or the like’ in clearvarnish. Patterns in a variety of colours are formed bybrushwork and a clear outer coating was to be applied toprotect the design. A sketch of a typical product was includedin the application. The patent was granted in 1928.

More robust materials such as ceramics are decorated bychina painters, often using flower motifs, and this art draws ona culture going way back into history. The pigments, mostlymetal oxides, are mixed with liquids and painted onto theceramic. The liquid may be oil, often a mixture of mineral oiland an unsaturated vegetable (drying) oil, but water or glycolscan be used and even glue or milk. The paint is allowed to dryand then the object is fired at 600–700°C. Several layers maybe applied, with successive firings, to build up a three-dimensional decoration. While unglazed material can bepainted, most china painters prefer to work with glazed pieces.Dilute hydrofluoric acid was used to prepare the surface beforeapplication of the paint, but increasing hazard classification hasmade this acid almost impossible to purchase by hobbyists, socleaning with alcohol, mainly to remove fingerprints, has tosuffice. I see from recent press coverage of some antiqueglassware that painting could even be done on the inside ofvessels.

Similar techniques were used to prepare most of the ‘stainedglass’ that we see in decorative windows in churches and otherplaces. I had always imagined that the glass was coloured(tinted) by including the metallic oxides or salts in the originalmelt. Some of it was made that way but much of it had thecoloured layer painted after it was cut to size and shape andbefore it was fired to ‘fix’ the pigment. The more modernwindows I have seen make use of tinted glass in bright colourswith better light transmission, but the old techniques are stillused for special pieces.

letter from melbourne


Neville Currey: interwar chemist?

Ian D. Rae FRACI CChem ([email protected]) is a veterancolumnist, having begun his Letters in 1984. When he is notcompiling columns, he writes on the history of chemistry andprovides advice on chemical hazards and pollution.


cryptic chemistry

Across1 Combine hydrogen, thorium,

protactinium, nitrogen and a hydrocarbonmixture. (7)

5 Oi! Catch! Fumbled! What a shambles! (7)

9 (CH3)3N+(CH2)2OHX− 618310. (7)

10 New relay behind bismuth film twomolecules thick. (7)

11 Fifty-fifty is fair. (7)12 Confused if Lusitanian comes back

holding anion. (7)13 Piddle in the street? Nice! (5)14 Adept at organising titanium, carbon,

iron, neon, iodine and fluorine. (9)16 New niche in coal producing dyestuff. (9)19 Little one’s cat gets into the arsenic! (5)22 Yank to admire and beautify Spooner

macromolecule. (7)24 It’s late in the day to aim for treating

11 Across. (7)25 Sent out diet met change. (7)26 Triangular one, dope, with xenon and

iodine mixed in. (7)27 Indicators in glass bottles. (7)28 Perhaps iron in a place where one feels

comfortable. (7)

Down1 Clue: sun explosion in the middle. (7)2 Bear show. (7)3 Travel grant – one of three. (7)4 Eyelet can filter C2H2. (9)5 Dice, perhaps, changes 2 into 8. (5)6 It describes a group attached to

CH2=CHCH2– in a legally licensedbusiness. (7)

7 Your old place for digging up 5-methyluracil. (7)

8 Contemporary flow. (7)15 Less room: points to carbon allotrope. (9)16 Machines modified p score. (7)17 Chilling O2 in the hold. (7)18 Passivity of Iranite reaction. (7)19 Expert pitch for compound. (7)20 Crack if hard water follows oxygen

radical. (7)21 Imply offer. (7)23 Bumps small numbers over Dextrose

Equivalent. (5)

events

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

18th International Conference on OrganometallicChemistry Directed Towards Organic Synthesis(OMCOS-18)28 June – 2 July 2015, Barcelona, Spain www.omcos2015.com

11th International Symposium on Ionic Polymerization5–10 July 2015, Bordeaux, Francehttp://ip15.sciencesconf.org

35th Australasian Polymer Symposium13–15 July 2015, Gold Coast, Qldwww.35aps.org.au

12th International Conference on Materials Chemistry(MC12)20–23 July 2015, York, UKwww.rsc.org/events/international

24th International Symposium: Synthesis in OrganicChemistry20–23 July 2015, Cambridge, UKwww.rsc.org/events/international

IUPAC 201548th General Assembly 6–13 August 2015, 45th World Chemistry Congress 9–14 August 2015,Busan, Koreawww.iupac2015.org

13th Conference on Laser Ablation (COLA-2015)31 August – 4 September 2015, Cairns, Qld http://cola2015.org

13th Annual UNESCO/IUPAC Workshop andConference on Macromolecules and Materials7–10 September 2015, Port Elizabeth, South Africahttp://academic.sun.ac.za/unesco

22nd International Clean Air and EnvironmentConference 20–23 September 2015, Melbourne, Vic. http://casanz2015.com

4th Federation of Asian Polymer Societies –International Polymer Congress5–8 October 2015, Kuala Lumpur, Malyasia www.4faps-ipc.org.my

2015 Sustainable Industrial Processing Summit andExhibition9 October 2015, Turkeywww.flogen.org/sips2015

Pacifichem 201515–20 December 2015, Honolulu, Hawaiiwww.pacifichem.org

RACI events are shown in blue

For further information about advertising in our print magazine or online, contact:Marc WilsonGypsy Media Services0419 107 [email protected]

2015 media guidenow available

iStockphoto/Jirkab

2015 NATIONAL AWARDS

www.raci.org.au/awards

The RACI is a professional membershiporganisation and one of the mostimportant duties of the organisation isthe recognition and promotion of thecontributions and achievements of our members.

There are a range of prestigious awardscovering a broad range of areas fromschool education to applied researchthat are aimed at the full range ofmembers from Post Graduate Studentsto Distinguished Fellows.

These awards are open to all membersof the RACI who meet the specificaward requirements. Some can beapplied for while others requirenomination by third parties.

The awards are listed on the website atwww.raci.org.au/awards together withthe criteria requirements and proposedmethods. Any other information can berequested from [email protected] orby contacting the RACI National Officedirectly on (03) 9328 2033.

Presentation of the awards will be at aspecial dinner held in November 2015.

SUBMISSIONS CLOSE AT 5 p.m. (EST)ON 30 JUNE OR 31 MAY FOR POST GRADUATE STUDENTS.

iStockphoto/choness

chemistry - royal australian chemical...

Documents