managing the burden of ballast water

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in AustraliaAugust 2017

chemistryStowaways:managing the burden of ballast water

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18Stemming the flowAn international convention for managing ships’ ballast water toprevent the arrival of invasive marine species is about to comeinto force.

cover story

22 Getting a reaction: 100 ways to reach outDave Sammut was thrilled to share a set with two of his science heroes whilefilming experiments for the RACI Centenary project 100 Reactions in 100 Days.

26 Phytochemistry of Australian plants: a new databaseThe creators of a new phytochemical database describe its development andtheir continued efforts to cover the many thousands of Australian plant species.

Chemistry in Australia4 | August 2017

from the raci

On 22 April this year, a March for Science was held in 600 citiesworldwide in attempts to have scientists of all disciplinesrecognised for what they do and to ensure science is funded torequired levels. There were 12 sites in Australia, includingTownsville where I attended along with several hundredinterested scientists and the public. While this event may havesprung to life after science funding cuts in the US and wasinitially a political protest, organisers began to realise theweight behind the scientific movement worldwide and itmorphed into a rally for recognition.

The March for Science was a global event bringing togetherpeople from all walks of life who say we need more evidenceand reason in our political process. Public discovery,distribution and understanding of scientific knowledge ascrucial to the freedom, success, health and safety of life on thisplanet was championed.

March for Science is a non-partisan group, marching topromote stable public science funding, open communication ofscience, evidence-based policy, and greater scientific literacyand education in critical thinking.

The aims of the march were around fostering a flourishingculture of robust scientific pursuit, ensuring that the knowledgegained through science is used for the public good, andimproving the public’s relationship with the scientific processand a universal literacy in science.

Among its endeavours, March for Science Australia calls forworld-class science education and teaching of critical thinkingskills in Australian schools, and a well-informed community.March for Science supports initiatives to promote:• broad public knowledge and discussion of scientific work and

science education that teaches children and adults to thinkcritically, ask questions and evaluate truth based on theweight of evidence

• open communication• decision-makers genuinely considering all the available

evidence when formulating policy• long-term public investment in scientific research by the

Australian government, to provide researchers with thestability needed to plan and execute large-scale projects

• investment in basic research as a matter of priority.

There has been a shift in recent years towards a focus oncommercialising research. This is an essential area but cannotcome at the expense of basic, or ‘blue-sky’, research (researchfor which the applications are not immediately obvious).

Anyone who values the role of science in society wasencouraged to take part in the March for Science.

The RACI was reasonably quiet during this March for Sciencecampaign. While we do not want be get heavily involved in thepolitics of other countries, I believe the RACI should be thevoice of chemistry in Australia. Scientists have struggled for solong to ensure funding investments are made to support theirendeavours, and this campaign may be the start of somethingbigger for which I feel the RACI should have a voice.

The march is complete for 2017 and now there is a call toact on outcomes of discussions, workshops etc. held during themarch. Look for ‘March for Science’ on Google, Twitter andFacebook. We should be supporting such ambitious activitiesaround the globe and I encourage chemists and their sciencecolleagues to get behind this movement.

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

PRODUCTION EDITORCatherine Greenwood [email protected]

ADVERTISING SALES Mary Pappa Ph/fax (03) 9328 2033/[email protected]

PRODUCTIONControl Publications Pty Ltd [email protected]

BOOK REVIEWSDamien [email protected]

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

PRESIDENT Peter Junk FRACI CChem

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

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

© 2017 The Royal Australian Chemical Institute Inc. unlessotherwise attributed. Content must not be reproduced whollyor in part without written permission. Further details on thewebsite (chemaust.raci.org.au). ISSN 0314-4240 e-ISSN 1839-2539


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

From the President

http://chemaust.raci.org.au

Chemistry in Australia 5|August 2017

your say

Aberdeen alumniI greatly enjoyed Ian Rae’s piece in the June issue (p. 41)about Alexander Findlay and other chemists, having beenassociated with the University of Aberdeen. I might be able toadd to its content by pointing out that James Clerk Maxwell(1831–79) was Professor of Natural Philosophy at MarischalCollege, Aberdeen, at the time of its merger with King’s Collegeto form the University of Aberdeen. He is remembered andhonoured as a physicist, but his endeavours did take him intophysical chemistry. The best-known example of this is theMaxwell distribution, which every chemistry student is taughtabout in the physical chemistry component of his or her course.

I experienced quite a surge of nostalgia when I saw thephotograph of Marischal College in Ian’s article, havingmemories of visits there for two reasons: examinationinvigilation and degree ceremonies. Nowadays, only one wing ofMarischal College is used for university purposes. The restcomprises the Aberdeen City Council Headquarters, anarrangement that has been in place since 2011.

Clifford Jones FRACI CChem

Soil lead levelsThe work done by the Macquarie University team on leadconcentrations in Sydney backyards (June p. 34) is anadmirable example of chemistry being applied for the publicgood. However, it seems Mark Taylor’s team might bemisapplying the soil Health Investigation Levels (HILs) listed inthe National Environment Protection (Assessment of sitecontamination) Measure 1999 (‘the NEPM’), which sets thestandards for conducting contaminated site investigations inAustralia (it was updated in 2013). They write of the‘300 mg/kg Australian health guideline’ for lead in soil. Thevalue of 300 mg/kg is the HIL applicable for low densityhousing and other sensitive sites (e.g. primary schools,childcare centres). However, the NEPM explicitly states:‘Investigation and screening levels are not clean-up or responselevels, nor are they desirable soil quality criteria’.

The HILs were set on the basis of a number of assumptionsabout human exposures and the characteristics of thecontaminant in solution. These include: home-grown fruit andvegetables represent less than 10% of the total amountconsumed; the lead in soil is only 50% bioavailable; and ablood lead concentration of 10 mg/dL is the target that shouldnot be exceeded. The NHMRC has more recently revised this lastvalue to 5 mg/dL. These are among the range of factors to beconsidered if lead (or other contaminant) concentrations exceedthe relevant HIL.

The NEPM provides additional guidance about how the HILvalues should be applied. It suggests that where a HIL isexceeded, the 95% upper confidence limit of the meanconcentration, the standard deviation of results, and themaximum concentration also be considered. Under somecircumstances, it may be acceptable to allow soil with

individual sample concentrations up to 250% of the HIL toremain on site. Therefore, in the data provided by Taylor’s team,many of the soil samples taken in backyards and vegetablegardens, and with lead concentrations greater than 300 mg/kg,might be acceptable for on-site use.

The article is right to point out that that airborne lead andlead-based paint on the site can contribute to elevated leadconcentrations in soil. However, caution also needs to beexercised in importing ‘clean garden soil’ into garden beds.Occasionally, these soils from garden suppliers have aproportion of sewage treatment plant sludge incorporated in themix, and elevated concentrations of metals can be present.

Paul Moritz FRACI CChem

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

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news


US Chemical SafetyBoard facesuncertain futureUnder US President Donald Trump’s proposed2018 budget, the world’s only independentbody dedicated to investigating chemical-related industrial accidents would be abolished.A story in Chemical & Engineering News(bit.ly/2rRSygE) revisits why the US ChemicalSafety & Hazard Investigation Board wasinitially created, its accomplishments and whatexperts say about its potential demise.

Jeff Johnson, a special correspondent toC&EN, notes that the board – also known as theChemical Safety Board, or CSB – was called forin the 1990 legislative overhaul of the Clean AirAct. But the board lacked the necessary supportfrom presidents George H.W. Bush and BillClinton, so industrial chemical accidentinvestigations were delegated to otheragencies. But stalled investigations into a 1995explosion at a New Jersey facility that killedfive workers and destroyed surroundingbusinesses led to pressure from unions,community groups, the state’s governor and asenator to fund the CSB. In 1998, the boardopened its doors.

Since then, the CSB has investigated some130 accidents, and has produced more than90 accident reports and about 40 safety videos.The board has positively influenced industrialand chemical safety in the US and elsewhere,industrial accident experts told C&EN, and witha budget that has never exceeded $12 millionin any given year, they say that’s a good deal.

American Chemical Society

Last year, an investigation by the US Chemical Safety Board warned that regulatorychanges to date do not sufficiently empower the regulator to oversee industry efforts toprevent another disaster like the Deepwater Horizon rig explosion and oil spill in 2010.DVISHUB/CC-BYSA2.0

Without CSB carrying out independent,non-judgemental investigations, USchemical and petrochemical industrieswould be without one of the key toolsthey need to reduce the risk ofcatastrophic accidents.Ian Whewell, former HSE director of offshore safety, US Health and Safety Executive

I am encouraged thatassessment of some grantsunder the newarrangements will beblinded to gender, age,career stage and institution.Andrew Holmes FRACI CChem, President, Australian Academy ofScience

Changes to NHMRCfunding announcedThe National Health and Medical Research Council (NHMRC) hasannounced changes to its grant funding program that supportsAustralia’s health and medical researchers. The NHMRC’srestructured program will include four types of grants, andlimits will be placed on the number of grants an individualresearcher can apply for or hold. Assessment of InvestigatorGrants and Synergy Grants will focus mainly on track record,and assessment of Ideas Grants will focus primarily on thescience, innovation and significance of the proposed research.

National Health and Medical Research Council


The Institution of Chemical Engineers (IChemE) Safety Centreand the Safety Institute of Australia have published two newchapters in the Occupational Health and Safety Body ofKnowledge (www.ohsbok.org.au). The launch followed18 months of collaborative working, aimed at closing theknowledge gap between health and safety professionals andprocess safety engineers.

Completed by a cross-discipline team of both IChemE SafetyCentre (ISC) members and Safety Institute Australia (SIA)members, the chapters were launched in April. They focus onprocess hazards in the chemical industries, and process safetymanagement respectively.

There were 178 workplace safety incidents reported inAustralia last year according to SafeWork Australia. Seventeenof these occurred in the process industries, which includeschemicals, oil and gas, pharmaceutical production and foodproduction.

IChemE Safety Centre Director, Trish Kerin, hosted the launchwith a webinar entitled ‘An Introduction to Process Safety’.

‘The collaboration between ISC and SIA has been a positivestep in closing the gap between process safety and moregeneralist health and safety roles … A basic knowledge of

process safety is essential to improving your safetycompetencies more generally, whether you work in the processindustries or not.’

Pam Pryor, Registrar of the Australian OHS EducationAccreditation Board, custodian of the OHS Body of Knowledge,said, ‘These new chapters are a fantastic addition to the Body ofKnowledge. The evidence is clear; all health and safetygeneralists should have a basic knowledge of process safety,particularly when they are operating in high-risk environments.I am confident that this development will be essential toclosing the current gap of knowledge, and in turn reduce thenumber of incidents, not only in Australia, but on a globalscale’.

Institution of Chemical Engineers

IChemE Safety Centre to publish insight in Health andSafety Body of Knowledge

Pam Pryor and Trish Kerin at IChemE’s annual safety conference, Hazards Australasia 2016.

news


A study from Indiana University, USA, hasfound evidence that extremely smallchanges in how atoms move in bacterialproteins can play a big role in how thesemicroorganisms function and evolve.

The research, published in Proceedingsof the National Academy of Sciences (doi:10.1073/pnas.1620665114), is a majordeparture from prevailing views about theevolution of new functions in organisms,which regarded a protein’s shape, or‘structure’, as the most important factorin controlling its activity.

‘This study gives us a significantanswer to the following question: How dodifferent organisms evolve differentfunctions with proteins whose structuresall look essentially the same?’ said DavidGiedroc, Lilly Chemistry Alumni Professor,who is senior author on the study.

The study also provides new insightsinto how microorganisms respond to theirhost’s efforts to limit bacterial infection.

‘What we’ve shown is atomic-levelmotional disorder – or entropy – canimpact gene transcription to affect thefunction of proteins in major ways, andthat these motions can be “tuned”evolutionarily’, said Daiana A. Capdevila,

a postdoctoral researcher in Giedroc’s lab,who is first author on the study. ‘Thismay allow bacteria to rapidly evolve newways to overcome medical treatmentsince atomic motions can be optimisedfor function more easily than a physicalstructure.’

In the battle between bacterialinfection and modern medicine, she saida key step is ‘mapping’ the enemy’sterritory. Unravelling the molecularstructure of proteins that trigger themechanisms that thwart the humanimmune system informs the design ofnew drugs. However, this approach isbased on the assumption that a protein’sshape fundamentally controls itsbehaviour.

It also assumes proteins are rigid. Thenew study shows protein function isbetter understood by studying thestructure’s internal atomic motion.

Specifically, Giedroc and colleaguesanalysed the protein CzrA that controlshow bacteria regulate zinc levels, animportant ability that providesmicroorganisms the power to resist thehuman immune system. Zinc regulationallows the body to fight off infection by

either flooding invaders with zinc,causing cellular death or completelystarving them of the element, which alsokills infectious agents.

Through the use of NMR spectroscopy,the scientists measured the movement ofatoms in CzrA and identified those mostaffected by zinc. They then ‘swapped’these atoms with different amino acidsand found that the protein almostcompletely lost the ability to regulatezinc levels in cells. The experimentrevealed unexpected areas on themolecule that appeared to play a role arole in zinc regulation, despite theirphysically distant location on the protein‘map.’

‘There’s no way anyone could havepredicted these areas played a role inzinc regulation by simply looking at theprotein structure,’ Giedroc said. ‘Once youknow where these “hot spots” arelocated, however, it’s theoreticallypossible to design a small molecule ordrug to produce the same effect as ouramino acid-swapping experiment – thatis, to essentially shut off the protein.’

In fact, this is one of the mainconcepts behind a powerful new class ofdrugs called ‘allosteric drugs’, so namedbecause they’re designed to affect areason a protein – called allosteric sites –that enhance or regulate the primaryfunction of the protein, such as zincbinding, without directly targeting thepart of the protein that controls theprimary function.

‘This is really about thinking aboutthe functions of proteins in the contextof a network – not simply targeting asingle strategic point but rather lookingat the system holistically,’ Giedroc said.‘And this particular study shows the mosteffective way to gain this deeperknowledge requires going beyond themolecular level in proteins to understandhow atomic motion plays a role infunction – after which you can startapplying that knowledge to designingmore effective drug-based therapies.’Indiana University

Atomic-level motion may drive bacteria’s ability toevade immune system defences

A scanning electron micrograph of Staphylococcus aureus. The scientists conducted theirexperiments on S. aureus, a common cause of skin, sinus and lung infections.Janice Haney Carr, Centers for Disease Control and Prevention/Wiki

Research that aims to reduce the risk ofmine tailings failure and a project toimprove understanding of the ecologyand hydrology of streams in arid areas aretwo new research projects at theUniversity of Western Australia to receiveFederal Government funding.

Professor Andy Fourie, from the Schoolof Civil, Environmental and MiningEngineering, and his team will use a$630 000 grant plus $720 000 cash and$540 000 in-kind support from partnerorganisations to develop techniques topredict and mitigate the risk of failure inmine tailings storage facilities.

Dr Pauline Grierson and Dr GregSkrzypek, from the West AustralianBiogeochemistry Centre within UWA’sSchool of Biological Sciences, will use a$620 000 grant plus $400 000 cash and$800 000 in-kind support from partnerorganisations.

They will work with researchers fromRio Tinto and the National Centre for

Groundwater Research and Training atFlinders University to investigate howsurface groundwater affects the ecologyof ephemeral streams, with a focus onthe Pilbara region of northwesternAustralia.

‘Findings from the study will be used

in conjunction with monitoring programsto help prevent and mitigate unwantedenvironmental outcomes of mining andother land management on groundwaterresources and ecological values of theseimportant ecosystems,’ Dr Grierson said.

University of Western Australia

August 2017

Research at the University of Pittsburgh, USA, into a moreenergy-efficient catalytic process to produce olefins couldinfluence potential applications in diverse technology areasfrom green energy and sustainable chemistry to materialsengineering and catalysis.

‘Carboranes: the strongest Brønsted acids in alcoholdehydration’ (Catalysis Science & Technology, doi:10.1039/C7CY00458C) was authored by Giannis Mpourmpakis,assistant professor of chemical and petroleum engineering, PhDcandidate Pavlo Kostetskyy and undergraduate student NicholasA. Zervoudis.

‘Carboranes are one of the strongest known acids, but littleis known about how these molecular catalysts can dehydratebiomass-derived alcohols’, Mpourmpakis explained. ‘Ourcomputational research not only detailed the mechanism underwhich alcohols dehydrate on these catalysts, but mostimportantly we developed linear relationships between theenergy input needed to observe dehydration of alcohols and thealcohol characteristics.’

According to the paper, ‘these obtained relationships areespecially relevant to the field of solid acid catalysis, a widelystudied area with a vast range of industrial applications,including the formation of olefins (polymer building blocks)from biomass-derived alcohols as well as fuels and chemicalsfrom sugars and polyols’. The group’s research focused on

primary, secondary and tertiary alcohols, and revealed the slopeof linear relationships depending on the reaction mechanism.

‘This research is important because now experimentalistshave a way to identify the reaction followed when differentalcohols dehydrate’, Mpourmpakis said. ‘Because this processinvolves biomass-based production of polymers, we canpotentially create a more sustainable and energy-efficientprocess.’

University of Pittsburgh

o-CarboraneWikicommons

A more energy-efficient catalytic process to produce olefins

New projects at UWA: mine tailings and groundwater

Ephemeral stream in the Hamersley Range, in the Pilbara region.Alexandra Rouillard


news

SESAME, the Middle East’s first majorinternational research centre for scienceapplication research, was inaugurated on16 May. It will see scientists from acrossthe region and beyond work side by sidein researching the peaceful uses ofnuclear technology. The InternationalAtomic Energy Agency (IAEA) has beenclosely associated with the project and isan observer on the SESAME council.

The facility will foster innovativescientific and technological research inareas ranging from biology, archaeologyand medical sciences to studying thebasic properties of materials science,physics, chemistry and life sciences.

‘This centre, it is hoped, will alsoprevent and reverse the “scientific” braindrain and encourage scientists tocontribute to the development of thepeople of the region’, said KhaledToukan, Chairman of Jordan AtomicEnergy Commission. As a scientific andcultural bridge between diverse societies,

this centre of excellence is open to allscientists from the Middle East andelsewhere, he added.

SESAME is modelled on CERN(European Organization for NuclearResearch) and was developed under theauspices of the United NationsEducational, Scientific and CulturalOrganization (UNESCO).

Scientists and engineers from Cyprus,Egypt, Iran, Israel, Jordan, Pakistan, thePalestinian Authority and Turkey – thecurrent members of SESAME – have beeninvolved in the preparatory work at thefacility since 2004.

At the heart of the facility is aSynchrotron-light for ExperimentalScience and Applications (i.e. SESAME),which is capable of generating intenselight beams for advanced scientific andtechnical research. It belongs to thefamily of synchrotron facilities.

‘SESAME is an achievement both interms of science and international

relations and its success is due to theinterest and confidence of all involved’,Toukan said. ‘The support provided by theEuropean Commission, as well as variousinternational and national laboratoriesand organisations including the IAEA iswell recognised.’

As a first step towards commissioningthis synchrotron facility, the precisetesting and circulation of the beam lightin the ‘storage rings’ has beensuccessfully achieved in the 2.5 GeV(gigaelectronvolt) compact high-performance light-source machine. Theaim of this Centre is to have 24beamlines covering a wide range ofscientific applications. Two of thesebeamlines – the infrared and the XRF (X-ray fluorescence) – have been installedand are ready for producing photons.

The multipurpose infrared beamlinewill be used for a number of applicationssuch as biological and materials sciencestudies.

The facility will enable visitingscientists, including university studentsand researchers, to participate inexperiments on synchrotron radiationsources, analyse the data obtained andacquire and share scientific expertise andknowledge, Toukan said.

The facility’s managers plan to take upjoint projects with other internationalsynchrotron radiation laboratories todevelop and improve features ofbeamlines around specific scientificresearch projects, as well as undertakeprojects involving SESAME members inareas such as environmental and culturalheritage studies tracing the origin ofmaterials.

The IAEA has helped in the successfulcommissioning of the SESAME magnets,hands-on training in areas such asbeamlines technology, installation, andtesting of equipment in a highperformance synchrotron radiationresearch centre, Toukan said.

International Atomic Energy Agency

Middle East’s first synchrotron opens in Jordan

Infrared beamline scientist Dr Gihan Kamel checks particle analysis data at SESAMEInternational Research Centre, Jordan. Dean Calma/IAEA


Internationalprize for PhDstudentResearch into canola processing and theeffect on bioactive components in the oilhas earned a Charles Sturt University(CSU) PhD student internationalrecognition.

Ms Clare Flakelar MRACI (pictured withher award), who is a member of theGraham Centre for Agricultural Innovation,was presented with a student excellenceaward at the American Oil Chemists’Society conference in Florida, USA.

Her research examines how canola oilprocessing affects the concentration ofbioactive compounds.

‘Many bioactive components in canolaoil are linked to beneficial health effects’,Flakelar said. ‘For example, commercialcanola seed contains lutein, a bioactivecompound with the potential to preventmacular degeneration.’

‘But these components, particularlycarotenoids, tocopherols and sterols, arereduced or eliminated entirely duringcurrent commercial oil production.

‘My research involves assessing thebehaviour and influence of certainfactors on these bioactive components,primarily the effects of genotype, thestorage of seed and oil, and theprocessing from seed to oil.

‘My goal is to provide industry with

some of the information they need topursue the retention or enhancement ofbioactive compounds in end-product oilfor consumer health benefit.’

Flakelar said it was a thrill to bepresented with the award and to presenther research at the conference.

Her research is supervised byAssociate Professor Paul Prenzler fromCSU’s School of Agricultural and WineSciences.

‘This award is open to postgraduatestudents from all over the world,’ Prenzlersaid. ‘Not only is this award well

deserved for Clare’s hard work, but it alsoshows that the Graham Centre has thecapacity to undertake world-classresearch in oils chemistry.

‘Clare has already published her workin some of the best food chemistryjournals, and there are more high-qualitypapers to come. On top of this academicsuccess, she has developed strong linkswith oil processors in Australia who arevery excited about the possibilities herresearch opens up to develop newproducts.’

Graham Centre for Agricultural Innovation

Crayola is introducing a new blue crayon colour inspired by thediscovery of a ‘new to the world’ blue pigment. YInMn Blue, thevibrant pigment discovered in 2009 by chemist Mas Subramanianand his team at Oregon State University, is the inspirationbehind Crayola’s newest crayon colour.

On 1 July, Crayola released the top five blue crayon colournames. Consumers can vote for their favourite colour and viewthe real-time, daily voting results at Crayola.com/NewColor.Voters will be entered for a chance to win one of six grand prizesof an all-expense paid trip for four to the Orlando CrayolaExperience and a daily prize of the award-winning Crayola AirMarker Sprayer.

Crayola will unveil the new blue crayon colour name and thesix grand prize winners in early September 2017.

Crayola

New Crayola blue inspired by discovery of YInMn pigment

news


Plutonium discovery lightsway to clean up nuclearwastePlutonium has long been part of many countries’ nuclear energystrategies, but scientists are still unlocking the mysteriesbehind this complicated element and seeing how they can useheavier nuclear elements to clean up nuclear waste.

Now, new research by Florida State University ProfessorThomas Albrecht-Schmitt shows that plutonium doesn’t exactlywork the way scientists thought it did. The findings willcontribute to his team’s efforts to develop technologies toclean up nuclear waste. The work was published in NatureChemistry (doi: 10.1038/nchem.2777).

Albrecht-Schmitt and a team of researchers have beenstudying plutonium for almost two decades to understand howit behaves chemically, and how it differs from lighter elementssuch as iron or nickel. To Albrecht-Schmitt’s surprise, aplutonium–organic hybrid compound that his team assembledin the lab behaved much like compounds made with lighterelements.

‘What makes this discovery so interesting is that the material– rather than being really complicated and really exotic – isreally, really simple’, Albrecht-Schmitt said. ‘Your imaginationgoes wild, and you think: “Wow, I could make that class ofcompound with many other types of heavy elements”. I coulduse other heavy elements like uranium or maybe evenberkelium.’

The team observed that electrons were shuttling back andforth between two different plutonium ions.

The movement of electrons between two positive ions is anaction that typically happens between ions of lighter elementssuch as iron, which is why lighter elements are often used in

biology to accomplish chemical reactions.Albrecht-Schmitt said his team immediately realised there

was something unique about the compound they hadengineered in the lab simply because of its colour.

‘Plutonium makes wild, vibrant colours’, Albrecht-Schmittsaid. ‘It can be purple, it can be these beautiful pinks. It can bethis super dark black-blue. This compound was brown, like abeautiful brown chocolate bar. When we saw that colour, weknew something was electronically unusual about it.’

Albrecht-Schmitt’s work is part of his lab’s overall mission tobetter understand the heavier elements at the very bottom ofthe periodic table. Last year, he received $10 million from theDepartment of Energy to form a new Energy Frontier ResearchCenter that will focus on accelerating scientific efforts to cleanup nuclear waste.

‘In order to develop materials that, say, trap plutonium, youfirst have to understand at the most basic level, the electronicproperties of plutonium’, Albrecht-Schmitt said. ‘So that meansmaking very simple compounds, characterising them inexquisite detail and understanding both experimentally andtheoretically all of the properties you’re observing.’

Albrecht-Schmitt and his research team have conductedsimilar work on the elements californium and berkelium.

Florida State University

Thomas Albrecht-Schmitt is the Gregory R. Choppin Professor ofChemistry at Florida State University. Bill Lax/Florida State University

EPP Group reacts to impending US withdrawal from Paris AgreementUS President Trump’s decision towithdraw from the Paris Agreement onfighting climate change has been metwith regret by the EPP Group in theEuropean Parliament.

‘Trump’s decision is a sad one, but Iam certain that the Paris Agreement andthe worldwide efforts to fight climatechange will survive Donald Trump. Europeand the rest of the world need to give astrong signal. We need to fulfil ourcommitments and continue theinternational process on climatemitigation. At the same time, it is moreimportant than ever to protect Europeanindustry when it produces to the bestpossible environmental standard’, said

Peter Liese MEP, the EPP Group’sSpokesman on Environment and Health.

‘Trump’s decision cannot be legallybinding before 2020. Who knows ifPresident Trump will still be in office atthat time? Many parts of the UnitedStates, for example California, will stillcontinue to reduce greenhouse gasemissions. The European Union and allthe other partners in the agreement arecommitted to continuing with theircommitments and the internationalprocess despite Trump’s decision’, saidLiese.

As for the reform of the EuropeanEmissions Trading Scheme (ETS), Lieseinsists that companies producing

according to the best technology are notburdened by the EU ETS. ‘I sincerely hopethat the Council adopts the amendmentsthat the European Parliament alreadyadopted with a broad majority. We haveto consider further action such as aborder tax adjustment if the measures areinsufficient. If US companies now benefitbecause they have no more climateobligations, such a measure should notbe ruled out’, the EPP Group MEPconcluded.

EPP Group Editor’s note: The EPP Group (EuropeanPeople’s Party group) is the political groupin the European Parliament comprisingdeputies (MEPs) from the member partiesof the European People’s Party.


Light initiates many chemical reactions. Experiments at theLaser Centre of the Institute of Physical Chemistry of the PolishAcademy of Sciences (IPC PAS) and the University of Warsaw’sFaculty of Physics have for the first time demonstrated that byincreasing the intensity of illumination, some reactions can besignificantly faster. Here, acceleration was achieved using pairsof ultrashort laser pulses.

In order to thoroughly investigate the nature of theprocesses involved, ultra-short consecutive pairs of laser pulseswere used, and an increase in the rate of reaction between themolecules was observed by up to several dozen per cent. Theobservations of the Warsaw scientists have been reported inPhysical Chemistry Chemical Physics (doi: 10.1039/c6cp08562h).

‘Our experiments provide fundamental knowledge about thephysical processes that are important for the course ofimportant light-induced reactions. This knowledge canpotentially be used in many applications, especially whendealing with high-intensity light sources. These include, amongothers, various microscopic imaging techniques, ultra-fastspectroscopy as well as photovoltaics, particularly if light-focusing devices such as solar collectors are used’, said DrGonzalo Angulo (IPC PAS).

In light-induced reactions, a photon with the appropriateenergy excites a molecule of dye. When there is a molecule ofquencher near the excited molecule, an interaction takes place:there may be a transfer of energy, an electron or a proton,between the two reactants. Reactions of this type are commonin nature. A good example is electron transfer inphotosynthesis, which plays a key role in the formation of theEarth’s ecosystem.

A factor that can influence the acceleration of reactions isthe intensity of the light that initiates them. In order to studythe nature of the processes taking place, the Warsaw chemistsused laser pulses lasting femtoseconds instead of thetraditional continuous stream of light. The energy of theimpulses was adjusted so that, under their influence, the dyemolecules moved into the excited energy state. The pulses weregrouped in pairs. The interval between pulses in a pair wasseveral dozen picoseconds (trillionths of a second) and wasmatched to the type of reacting molecules and the environmentof the solution.

‘The theory and the experiments required care and attention,but the physical idea itself is quite simple here’, noted JadwigaMilkiewicz, a PhD student at IPC PAS. ‘In order for the reaction

to occur, there must be a molecule of quencher near the light-excited dye molecule. So, if we have a pair of molecules thathave already reacted with each other, this means that they wereclose enough to each other. By increasing the number ofphotons in time, we thus increase the chance that if, after thereaction, both molecules have managed to return to theirground state, the absorption of a new photon by the dye hasthe potential to initiate another reaction before the moleculesmove away from each other in space.’

The course of reactions in solutions depends on many factorssuch as temperature, pressure, viscosity or the presence of anelectric or magnetic field. This research has proved that thesefactors also influence the acceleration of the chemical reactionthat occurs with an increased intensity of illumination. Undersome conditions, the acceleration of the reaction wasunnoticeable; under optimal conditions, the rate of the reactionincreased by up to 25–30%.

‘In our experiments so far, we have concentrated on light-induced electron transfer reactions; that is, those which changethe electrical charge of the molecules. However, we do not seeany reason why the mechanism we have observed could notfunction in other variations of these reactions. So, in the nearfuture, we will try to confirm its efficacy in energy transferreactions or in reactions involving also proton transfer’, saidAngulo.

Institute of Physical Chemistry of the Polish Academy of Sciences

With more light, chemistry speeds up

Some chemical reactions can be accelerated by increasing theintensity of illumination – this has been demonstrated byresearchers from the Institute of Physical Chemistry of the PolishAcademy of Sciences in Warsaw. IPC PAS, Grzegorz Krzyzewski

news


Sandia National Laboratories researchers Prashant Rai (left), HabibNajm (centre) and Khachik Sargsyan discuss mathematicaltechniques used to study the behaviour of large molecules atquantum scale. Dino Vournas

Researchers at Sandia National Laboratories in the US havedeveloped new mathematical techniques to advance the studyof molecules at the quantum level. Mathematical andalgorithmic developments along these lines are necessary forenabling the detailed study of complex hydrocarbon moleculesthat are relevant in engine combustion.

Existing methods to approximate potential energy functionsat the quantum scale need too much computer power and arethus limited to small molecules. Sandia researchers say theirtechnique will speed up quantum mechanical computations andimprove predictions made by theoretical chemistry models.Given the computational speed-up, these methods canpotentially be applied to bigger molecules.

Sandia postdoctoral researcher Prashant Rai worked withresearchers Khachik Sargsyan and Habib Najm at Sandia’sCombustion Research Facility and collaborated with quantumchemists So Hirata and Matthew Hermes at the University ofIllinois. Computing energy at fewer geometric arrangementsthan normally required, the team developed computationallyefficient methods to approximate potential energy surfaces.

A precise understanding of potential energy surfaces, keyelements in virtually all calculations of quantum dynamics, isrequired to accurately estimate the energy and frequency ofvibrational modes of molecules.

‘If we can find the energy of the molecule for all possibleconfigurations, we can determine important information, suchas stable states of molecular transition structure orintermediate states of molecules in chemical reactions’, Raisaid.

Initial results of this research were published in MolecularPhysics (doi: 10.1080/00268976.2017.1288937).

‘Approximating potential energy surfaces of bigger moleculesis an extremely challenging task due to the exponential increase

in information required to describe them with each additionalatom in the system’, Rai said. ‘In mathematics, it is termed thecurse of dimensionality.’

The key to beating the curse of dimensionality is to exploitthe characteristics of the specific structure of the potentialenergy surfaces. Rai said this structure information can then beused to approximate the requisite high dimensional functions.

‘We make use of the fact that although potential energysurfaces can be high dimensional, they can be wellapproximated as a small sum of products of one-dimensionalfunctions. This is known as the low-rank structure, where therank of the potential energy surface is the number of terms inthe sum’, Rai said. ‘Such an assumption on structure is quitegeneral and has also been used in similar problems in otherfields. Mathematically, the intuition of low-rank approximationtechniques comes from multilinear algebra where the function isinterpreted as a tensor and is decomposed using standardtensor decomposition techniques.’

The energy and frequency corrections are formulated asintegrals of these high-dimensional energy functions.Approximation in such a low-rank format renders thesefunctions easily integrable as it breaks the integration problemto the sum of products of one- or two-dimensional integrals, sostandard integration methods apply.

The team tried out their computational methods on smallmolecules such as water and formaldehyde. Compared to theclassical Monte Carlo method, the randomness-based standardworkhorse for high-dimensional integration problems, theirapproach predicted energy and frequency of water moleculesthat were more accurate, and it was at least 1000 times morecomputationally efficient.

Rai said the next step is to further enhance the technique bychallenging it with bigger molecules, such as benzene.

Sandia National Laboratories

Maths techniques to improve computational efficiency in quantum chemistry

A depiction of random two-dimensional slices of a 12-dimensionalfunction for determining energy and frequency corrections of aformaldehyde molecule. Sandia National Laboratories

research


Unusual C–H activation mechanisms

Fast route to tailor-made proteinsA renaissance in the use of largepolypeptides and proteins as therapeuticagents has led to significant interest insynthetic technologies to rapidly andefficiently access these biomolecules.Peptide ligation methods haverevolutionised protein science andprovided an avenue to make polypeptidesand proteins with tailor-mademodifications to maximise specificity andactivity or to probe biological function.One of the key problems remaining in thefield is that it still takes an unacceptablylong time to synthesise a given protein.Professor Richard Payne and co-workersat the University of Sydney have recentlydescribed the development of a one-potligation–deselenisation technique ataspartate and glutamate residues thatenables the synthesis of native proteinswith unprecedented speed (Mitchell N.J.,Sayers J., Kulkarni S.S., Clayton D.,Goldys A.M., Ripoll-Rozada J.,

Pereira P.J.B., Chan B., Radom L.,Payne R.J. Chem 2017, 2, 703–15). Thekey feature of the method is that boththe ligation and deselenisation reactionsproceed rapidly and cleanly withinminutes and are compatible for use inone-pot synthesis. The teamdemonstrated the utility of the technqiue

by synthesising several protein targets,including three tick-derived thrombininhibitors that could be assembled,purified and isolated for biologicalinterrogation within a few hours. Themethod serves as a powerful means toaccess synthetic proteins, includingtherapeutic leads.

A versatile method for the direct C–Hsilylation of (hetero)aromaticcompounds, developed by the Grubbs andStoltz laboratories, makes use ofpotassium t-butoxide as a cheap,environmentally friendly catalyst (Nature2015, 518, 80–4). Exactly how thistransition-metal-free transformationoccurs has remained a mystery. Now, ateam of chemists from the US, Germanyand Australia propose two distinctmechanisms for the C–H silylation inback-to-back papers in the Journal of theAmerican Chemical Society (J. Am. Chem.Soc. 2017, 139, 6867–79; Banerjee S.,Yang Y.-F., Jenkins I.D., Liang Y.,Toutov A.A., Liu W.-B., Schuman D.P.,Grubbs R.H., Stoltz B.M., Krenske E.H.,Houk K.N., Zare R.N. J. Am. Chem. Soc.2017, 139, 6880–7). Unexpectedly,experiment and theory support bothmechanisms: a homolytic pathwayinvolving silyl radical addition followedby ipso-H abstraction and a heterolyticpathway involving heteroarene

deprotonation by a hydridic intermediate.Intriguingly, calculations reveal that anovel cubane-like KOtBu/HSiR3-derivedhydride may be involved in both

pathways. These studies point to usefulnew mechanistic paradigms for C–Hactivation by the environmentallyfriendly, earth-abundant KOtBu.

research


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

Why bull ant stings are painful

Venom-derived peptide toxins provide an abundant pool ofmolecules with diverse biological functions. Researchers fromthe University of Queensland, Monash University and theKolling Institute of Medical Research have recently discovered anew pain-causing peptide (D-myrtoxin-Mp1a) from the jackjumper bull ant Myrmecia pilosula with very unusual structuraland functional properties (Dekan Z., Headey S.J., Scanlon M.,Baldo B.A., Lee T.-H., Aguilar M.-I., Deuis J.R., Vetter I.,Elliott A.G., Amado M., Cooper M.A., Alewood D., Alewood P.F.Angew. Chem. Int. Ed. 2017, doi: 10.1002/anie.201703360). D-Myrtoxin-Mp1a is a 49-residue antiparallel heterodimericpeptide with a unique framework comprising two non-identicalchains connected by two disulfide bonds. Remarkably,combining the individual synthetic chains resulted in the self-assembly of Mp1a without employing directed disulfide bondformation. 2D-NMR analysis revealed a well-defined and uniquestructure containing a pair of antiparallel a-helices. Dualpolarisation interferometry showed strong interaction withsupported lipid bilayers and insertion within the bilayers ofboth mammalian and bacterial membranes. Mp1a also displayedbroad-spectrum antimicrobial activity, with the highest potencyagainst Gram-negative A. baumannii (MIC 25 nM). Injection of10 µM of Mp1a into the paws of mice elicited spontaneous painand mechanical allodynia (pain caused by mild mechanicalstimuli such as a light touch), indicating that the peptide isthe probable cause of the bull ant’s painful stings.

on the market


Wiley and CAS to deliveradvanced predictivecheminformatics capabilitiesto researchers worldwideJohn Wiley and Sons, Inc. and CAS, a division ofthe American Chemical Society, have announced apartnership that will accelerate the evolution ofpredictive synthesis by enriching Wiley’sChemPlanner technology with the most accurateand complete chemical information from CAS.

Rapid advances in the fields of predictiveanalytics, artificial intelligence and machinelearning offer tremendous opportunity to enhancethe way scientific information is queried andanalysed. ChemPlanner’s state-of-the-artcheminformatics technology helps chemists findthe best selection of diverse and viable routes fortheir synthesis, increasing their efficiency andcreativity when developing new molecules.

As an innovative provider of sophisticateddigital information solutions, CAS will enhanceChemPlanner with a wealth of additional reactioncontent and associated references, includingreactions from patents. Integrating more than 10times the reaction content and offering valuablenew features suggested by current ChemPlannerusers, including stereoselective retrosyntheticprediction and customisable relevance ranking,this powerful new version of ChemPlanner will bedelivered exclusively in SciFindern, a new researchexperience from CAS that exponentially elevatesscientific discovery.

‘The integration of the rich CAS contentportfolio will greatly enhance the quality andscope of ChemPlanner’s predictions, as well as theutility of the resulting synthetic routes to helpresearchers overcome synthesis challenges faster’,said Dr Matthew J. Toussant, senior vice presidentof product and content operations, CAS. ‘CAS has astrategic focus on leveraging emerging machinelearning and predictive technologies to acceleratethe pace of scientific research, and this is ourinitial step in that evolution.’

‘Wiley is thrilled to collaborate with CAS and tomake ChemPlanner accessible to hundreds ofthousands of researchers worldwide’, said JayFlynn, SVP & MD, Research Publishing, Wiley. ‘CASis big data for chemistry, making this marriage ofbest-in-class content and technology a naturalpartnership. Our goal is to provide powerful, data-driven content that helps chemists solve globalchallenges.’

Successful lean manufacturing principles are increasingly beingadopted in the laboratory environment. The challenge is tounderstand how best to put Lean Laboratory into practice in aparticular workplace.

A two-part webinar series by METTLER TOLEDO, ‘Employing aLean Lab Approach to Optimize Lab Processes’, co-presented bylean laboratory expert Erwin Studer, explains the concept of LeanLab and how it can be applied to established laboratories or thedesign of a new laboratory. Lean methods help to ensure thatlaboratory processes are clearly defined, structured and controlledto deliver more consistent and predictable laboratory performance.This generates a detailed understanding of lab capacity andresourcing requirements and leads to a positive impact on leadtime and costs, productivity and right-first-time.

Part 1 ‘Work Smarter, Not Harder’ introduces the basic conceptsof Lean Laboratory and explains the 10 areas to consider inassessment of the current status of a lab. These are used to guidethe improvement of existing processes. It is often the simplest orsmallest changes that can bring about the most significantimprovements.

Part 2 ‘Improve Productivity’ goes deeper into value streammapping and performance management. Advice is given on how toidentify value-adding or unnecessary steps in a workflow, using theexample of sample preparation for analysis. This allows participantsto identify the issues that could have the biggest impact onimproving lab productivity. Measuring the impact using a number ofkey performance indicators is also discussed.

Watch these recorded webinars now at www.mt.com (click onEvents & Expertise).

For more information, visit METTLER TOLEDO at www.mt.com.

Lean Laboratory webinar: optimisinglab processes

The diversity of marineecosystems evolved, not justby the physico-chemicalcharacteristics of regional

water bodies, but also by thebiogeographic isolation of coasts byoceans and seas. From the timemariners first set to sea, their vesselsbecame a vector for the globaldistribution of species, bothintentionally, for example food cropsand domestic animals, andaccidentally, for example terrestrialweeds and rodents. Introductions ofalien species in the marineenvironment are often less obvious,but ships have facilitated themovement of species for centuries. Asurvey of alien marine species in Port

Phillip Bay, Victoria, in 1999documented 160 species consideredlikely to be alien, which represented13% of the known marine flora andfauna in the bay.

Although some marine aliens wereknown to have been in Australia sincegold rush times, the evidencesuggested a new pulse of arrivals inthe latter decades of the 20th century.Of particular concern in the 1990s wasthe arrival and rapid populationgrowth of a number of species,including the Northern Pacific seastar(Asterias amurensis) in Hobart’sDerwent River and Port Phillip Bay, theAsian kelp (Undaria pinnatifida) insoutheastern Tasmania and Port PhillipBay, and the black-striped mussel


Stemmingthe flow

An internationalconvention formanaging ships’ballast water toprevent the arrivalof invasive marinespecies is about tocome into force.

BY JOHN LEWIS

Stemmingthe flow

(Mytilopsis sallei) in Darwin Harbour.There were also concerns about themovement of toxic dinoflagellates –microalgae that can bloom to cause‘red tides’ that can lead to paralyticshellfish poisoning from eatingmussels and oysters that have fed onthese algae.

Ballast is used in ships to providestability and to compensate for weightchanges in cargo loads, and from fueland water consumption. In the days ofsail, rocks collected from seashoreswere commonly used as ballast but,with the introduction of steel-hulledships, ballast tanks for holdingseawater ballast became the norm.Ballast water is taken aboard as shipsunload, and discharged as ships load.With Australia’s trading patterns, bulkcarriers that export raw materials suchas coal, iron ore, oil and gas woulddischarge ballast in the Australianports of call, and container ships andvehicle carriers that importmanufactured goods would take upballast prior to departure.

In the late 1980s, Australia, togetherwith Canada, raised concerns onballast water at the InternationalMaritime Organization (IMO) MarineEnvironment Protection Committeeand, in 1991, the committee adoptedthe non-mandatory InternationalGuidelines for preventing theintroduction of unwanted aquaticorganism and pathogens from ships’ballast water and sediment discharges.Continued review of the issueconsequently led the IMO to adopt thelegally binding InternationalConvention for the Control andManagement of Ships’ Ballast Waterand Sediments (‘the BWMConvention’) on 13 February 2004.

The BWM Convention included atwo-stage introduction of managementmeasures: first, up until at latest 2016,ships would be required to meet aballast water exchange standard(Regulation D-1), then, after this, shipswould have to meet a ballast waterperformance standard (Regulation D-2). Regulation D-1 required ships on

international voyages to exchangeballast water taken up in ports withopen ocean water with an efficiency ofat least 95% volumetric exchange.Regulation D-2 requires ships to havea ballast water treatment systeminstalled that will ensure that ballastwater discharged contains:• less than 10 viable organisms per

cubic metre greater than or equalto 50 micrometres in minimumdimension

• less than 10 viable organisms permillilitre less than or equal to10 micrometres in minimumdimension

• indicator microbes concentrationsas a human health standard of:– toxicogenic Vibrio cholera less

than one colony-forming unit(cfu) per 100 millilitres

– Escherichia coli less than 250 cfuper 100 millilitres

– intestinal enterococci less than100 cfu per 100 millilitres.

As with all IMO conventions, entry-into-force of the BWM Conventionwould be 12 months after a requiredminimum number of IMO MemberStates ratified the Convention and, forthis Convention, the requirement wasnot less than 30 States, the combinedmerchant fleets of which constitutednot less than 35% of the gross tonnageof the world’s merchant shipping.Acceptance of the convention byStates was slow, and the requirementwas only met in September 2016, sothe date for entry-into-force of theconvention is 8 September 2017.However, it should be noted thatballast water discharge frominternational ships arriving inAustralian ports has been managedsince 2001 under the Australian BallastWater Management Requirements thatrequire deep ocean ballast waterexchange.

Meeting the D-2 standard for ballastwater treatment systems (BWTS) ischallenging because of factorsincluding the range of organisms to berendered non-viable, the volume ofwater to be treated, the water


(top) The Northern Pacific seastar (Asteriasamurensis) and (bottom) the Asian kelp(Undaria pinnatifida) arrived in Australia inthe 1990s and quickly establishedthemselves.

Ballast water istaken aboard asships unload, anddischarged asships load.

chemistry and quality, which mayencompass salinity ranges fromfreshwater to fully marine and highwater turbidity, and that the standard isa discharge standard, meaning thatorganisms are not able to regrow in thetanks during the voyage. The IMOrequires that a commerciallydeveloped BWTS is approved by a flagadministration in accord with IMOguidelines that require land-basedtesting ship-board trials and, forsystems using active substances,approval of environmental impact ofdischarged ballast water by theMarine Environment ProtectionCommittee. At the end of 2016, some68 systems had received typeapproval certification in line with IMOrequirements, 30 of which made use ofactive substances.

Treatment systems generallyinclude a two-stage process: physicalsolid–liquid separation to separatesuspended solid material, includinglarger organisms from the intake water,then disinfection to kill or inactivatemicroorganisms.

The physical solid–liquid separationphase can employ hydrocycloneseparation or surface filtration,sometimes with upstream addition ofchemical flocculants or coagulants toincrease the efficiency of particleseparation. Filtration systems can usediscs or fixed screens with automaticbackwashing. The hydrocyclonesystem of high-velocity centrifugalrotation can be more effective thanfiltration.

Disinfection can involve physicalmethods, or the addition or generationof active substances. Physical methodsinclude UV irradiation, cavitation,deoxygenation and heat. UVirradiation is a widely used method for

industrial and municipal watertreatment. A technological challengefor UV application was the need forwater clarity to enable UV penetrationthrough the full treatment pipe orvessel diameter. However, this hasbeen overcome in the development ofsome systems through effectivefiltration of water prior to thedisinfection stage. Ballast water canalso be passed though the reactorduring deballasting, but without theneed for filtration, to kill any organismsthat may have regrown during thevoyage.

Deoxygenation of the water will killorganisms within several days, butthere is a heightened risk of anaerobiccorrosion of tank walls by sulfate-reducing bacteria, the human healthrisk of the deoxygenated tank headspace if hatches are opened, and theenvironmental risk from the release oflarge volumes of deoxygenated waterinto a recipient water body. Cavitation,generated ultrasonically or by gasinjection, disrupts organism cell wallsbut has been found to require


A container ship berthing at Swanston Dockin the Port of Melbourne. Ballast water, andsometimes unwanted marine species, aredischarged from a ship as it loads.

Treatment systemsgenerally include atwo-stage process:physical solid–liquid separation ...then disinfection

additional treatment systemsdownstream for total efficacy. Heat haslimitations in the requirement for thelethal temperature to be maintainedover an extended period of time andthe risks that sub-lethal temperaturescould enhance bacterial growth.

Chemical disinfection usingoxidising biocides is the other widelyused approach, with different systemsusing chlorination, electrochlorination,chlorine dioxide, ozonation, paraceticacid and/or hydrogen peroxide. As isthe case for UV radiation, chlorinationsystems are widely used for thetreatment of municipal and industrialwaters. In natural waters, the biocidaleffect is achieved by a sodiumhypochlorite solution producingdifferent oxidising compounds. Freechlorine, or free available chlorine, ispresent as an equilibrium mixture ofhypochlorous acid and hypochloriteions, which are both oxidants, but thelatter is far less effective than theformer. For ballast water treatment,sodium hypochlorite can be generatedelectrochemically directly from

seawater or, in freshwater or lowsalinity waters, from stored brine.

Ozone is a stronger oxidant thanchlorine and can decompose highmolecular weight organic substancesto produce low molecular weightcompounds such as aldehydes andcarboxylic acids. Ozone decomposesrapidly with a half-life in pure water ofa few hours, but with a half-life ofminutes in raw water due to reactionwith organic matter.

A drawback of both chlorinationand ozonation systems is the formationof by-products that can includehalogenated methanes, hydrocarbons,amines, acetonitriles etc. The risks ofresidual oxidants in discharge ballastwater causing environmental damagein the receiving waters can requireneutralisation of residual chemicalsprior to discharge, which can beachieved, for example, by dosing withsodium bisulfate.

An added complication for theinstallation of a BWTS is that the USCoast Guard has set more stringentstandards than the IMO on the

performance of a BWTS and US-typeapproval of systems is required forships operating in US waters. The USCoast Guard regulations requirecompliance at the first dry-dockingafter 1 January 2016 and at delivery fornew builds. However, the first US-typeapproval of a BWTS was not issued untilDecember 2016 and only two moresystems have been approved since.

With entry-into-force of the BWMConvention, ships not already fitted witha ballast water treatment system will berequired to do so by 2021. Estimates ofthe number of ships needing retrofitBWTS installations over the next fiveyears vary from 35000 to 120000 ships.One calculation based on the lowernumber, and an estimate that there are250 shipyards worldwide capable ofdoing the work, results in each yardhaving to install a system every 16days.Installation of a BWTS can cost up toUS$5 million per ship.

Quite a task …

John A Lewis is Principal Marine Consultant, ES LinkServices Pty Ltd, Castlemaine, Victoria.


A small container ship under way off Singapore. Singapore is the second largestcontainer port in the world (behind Shanghai), and Melbourne is the largest in Australia.


Dave Sammut wasthrilled to share aset with two of hisscience heroeswhile filmingexperiments for theRACI Centenaryproject 100 Reactionsin 100 Days.

From the youngest age, I lovedwhat science had to offer me.Beyond learning, science wasinspiration, and imagination.

The RACI’s Centenary project ‘100Reactions in 100 Days’ has allowed meto fulfil the dreams of a little boy whosat glued to the television through thepeak of the Curiosity Show years (seebox). As it was for so many buddingscientists of my generation, hosts DrRob Morrison and Dr Deane Hutton(pictured above) fanned the flames ofmy early science interest.

The projectLed by Dr Nathan Kilah of theUniversity of Tasmania, the RACI’s 100Reactions in 100 Days seeks to createengaging YouTube content for thenewest generation of scientific minds.The videos are being created by RACIscientists around Australia, often justwith webcam and smartphone.

It’s an opportunity for our members‘to celebrate the centenary, to highlightyour work, and to demonstrate youroutreach abilities to a globalaudience’. Aiming at a wide audience,

100 waysto reach out

Getting a reaction

the project invites members to createvideos up to five minutes long, ‘with afocus on inspiring engagement andenthusiasm for chemistry’(www.raci.org.au/raci-news/100).

From the first email invitation tomembers, I was enthusiastic about theproject. I put the resources of the teamat my organisation, DCS Technical,behind it, and we got to work ondeveloping our contribution to theproject.

My starting point was to reach outto Dr Rob Morrison. Rob had writtensome columns for Chemistry inAustralia a few years ago (2009–2012).At the time, I had sent Rob a ‘fan boy’email, and he had been generousenough to reply.

Rob responded to my invitationimmediately and enthusiastically, onbehalf of both himself and Deane. Iwas transported. The idea that I couldcollaborate with my childhood heroeswas a gift to my younger self that Iwould never have dared to dream of.

Creating contentIn consultation with Nathan Kilah(keeper of the master list ofexperiments, to minimiseduplications), we prepared a list of10 experiments for the project. Thereare so many experiment options thatare interesting and highly visual, and Iwas delighted with Rob and Deane’sidea to reprise a couple of theexperiments from the Curiosity Showdays.

We eventually settled onexperiments with acid–base chemistry(dissolving egg shells, and creating‘rubber bones’), gases (helium andliquid nitrogen) and a couple ofspectacular flame experiments withhydrogen generation and fireworkchemistry. The full set is available onthe RACI’s YouTube channel.

We reached out to other scientistsand institutions, to see who wanted tocollaborate. So many people have putup their hands to volunteer space,resources and support, it wasgratifying to receive such enthusiasm –

with that enthusiasm all the greaterwhen we mentioned Rob and Deane’sinvolvement.

The challenge was not in findingsupport, but in finding mutuallycompatible dates to bring all theoffered resources together. It was alogistical exercise, but eventually theteam was brought together for twodays of filming in May 2017.

The shootThe team and I went a bit overboard. Ifwe were going to film with theprofessionals, then we were going totry to make a professional showing ofourselves. As we say in ‘the biz’ – donot try this at home.

The shoot, involving about 10people, was organised for threelocations over two days: the NationalMeasurement Institute and FledgeInnovation Labs at the joint CSIRO siteat Lindfield, New South Wales, and atUniversity of Technology, Sydney.

Our volunteer video professionalbrought enough cameras so that wewould shoot everythingsimultaneously – the wide shots, the

‘talking head’, the close-ups, even a‘go pro’ camera taped to the ceiling.That made filming considerablysimpler, because we didn’t have torepeat the reactions to get the differentviews. There was lighting. There weremicrophones. It was an electricityutility’s dream.

For each experiment, we startedwith a series of rehearsals, testing thesequence and timing of the actions,and giving the camera crew an


Curiosity ShowCuriosity Show was a seminalAustralian science-based programbroadcast from 1972 to 1990, andit now lives on at YouTube.

The Curiosity Show websitestates that the show ‘… was anationally broadcast science andtechnology television program foryoung people, including segmentson natural history, astronomy,music, technology and puzzles. Itis remembered for its emphasis onhow to make working machinesand models from everydaymaterials around the home. Morethan 500 programs were produced, with a total of around 5000 segments’.

The show could be likened to the American series Mythbusters, with fewerexplosions and more science. Anecdotally, the creator of Mythbusters, producer PeterRees, was a fan of Curiosity Show during his formative years growing up in Sydney.

After the end of Curiosity Show, Rob and Deane have continued to be active inscience communications, with extensive science writing and speaking engagementsthat continue to this day.

The challenge wasnot in findingsupport, but infinding mutuallycompatible datesto bring all theoffered resourcestogether.

Curiosity Show in the 1970s.

opportunity to adjust and optimisetheir shots and angles. Then beingrelatively well prepared, we could filmmost of the experiments in just acouple of takes.

And so filming began. Deane wasthe first on the schedule, and hearinghim say the immortal words ‘Why didthis happen? I’m glad you asked!’ wasa nostalgic thunderbolt.

Even though we were relatively wellorganised, the filming of each 3–5-minute video took more than anhour. And that was when everythingwent well. We lost quite a bit of time onthe first day of the shoot when thingswent awry.

In shooting the fireworks chemistryvideo, we made a last-minute decisionwith our hosts to change the order offilming. It seemed a good idea to use

the darker of two rooms available tous, to better bring out the visuals as wediscussed the way different metals areused to generate colours in fireworks.Rob was using cornflour as the carrier,then mixing various metal powdersand ‘puffing’ them into a flame. Theresulting flash was spectacular, with asmall associated puff of smoke anddust. It was all safe and benign, buthindsight provides wonderful clarity,and in hindsight the better-ventilatedroom would have been the betterchoice.

We’d made it through the rehearsaland most of the filming. As Robopened his mouth to say the final linein the script ‘… and now we’d betterstop, before we set the fire alarms off’,the wailing began. I’d like to take thisopportunity to reiterate our apology to

the professional scientists of NMI andCSIRO for the interruption to their day.

Throughout the shoot, it waswonderful to see how manyestablished scientists clustered outsideat each location, whispering excitedlywhile waiting for an opportunity to sayhello and ‘thanks for everything youdid’. Rob said that it can be a littlesobering when a middle-aged personenthuses about what a fan they were asthey grew up, but there were plenty ofexamples of that during the two daysof filming. The sense of fun and theunderlying admiration wereabundantly evident throughout theexperience.

The highlight for me was theopportunity to actually get on camerawith my heroes. My acting wasterrible. I forgot my lines. I stood there


Dr Rob Morrison filming at the National Measurement Institute.

grinning like an idiot, just thrilled to bethere. And I don’t mind any of that. Iwas living the dream. So where do Iaudition for Mythbusters?

Getting involvedI’ve written this piece because I’d liketo encourage you to create somethingof your own, and because it was somuch fun to do that I just have to tellsomebody.

RACI members around Australia stillhave time to get involved. 100Reactions in 100 Days will beextensively promoted during NationalScience Week (12–20 August), withsome awards for the best student film.Please contact Nathan Kilah([email protected]) to talkabout ideas.

Here is what I learned duringfilming.• You don’t have to do a full

professional shoot. A webcam ormobile phone is fine.

• Planning is critical. From location, toresources, to script, know what youintend to do and what’s required.

• Pay attention to lighting. Haveenough natural and warm light tobring the video to life.

• Ideally, have a reasonablyuncomplicated backdrop. Try not tomake the shot too ‘busy’.

• Eliminate background sound anddistractions.

• Have a rehearsal, and run throughthe experiment a few times so thatthe whole crew is familiar with thesequence.

• Consider mixing up your views –close up, wide, ‘talking head’,overhead, whatever makes the finalproduct more dynamic andinteresting.

• Even basic editing takes a lot oftime – hours per minute of video –but the results are definitelyworthwhile.

Dave Sammut FRACI CChem is principal of DCSTechnical, a boutique scientific consultancy providingservices to the Australian and international minerals,waste recycling and general scientific industries.Special thanks to Dr Rob Morrison and Dr DeaneHutton, DCS Technical Pty Ltd, Fledge InnovationLabs, National Measurement Institute, SamanthaOhlsen Photography, University of Technology Sydneyand Warren Lewington.


Dr Deane Hutton preparing to film at Fledge Innovation Labs, with Dave Sammut just happy to be there.

Phytochemical studies ofAustralian plants increasedmarkedly in the early 1940s,during World War 2, when it

became important to search for newsources of potentially useful drugs. Asignificant outcome was the large-scale production of theanti-seasickness compound hyoscine(a tropane alkaloid), which wasisolated from the Australian plantDuboisia myoporoides. Hyoscine wasused during World War 2 on theAustralian, British and Americanwarships.

After the war, what became knownas the Australian PhytochemicalSurvey was intensified by CSIR (laterCSIRO). Several chemists wereemployed full-time on this project.Chemists in Australian universities alsobecame actively involved in whatbecame a major collaborative effort –the collection and identification of

plant species beingorganised and providedby CSIRO. The involvementof CSIRO in the survey ceasedin the mid-1970s, and since thattime there has been relatively lessphytochemical work done bychemists in Australianuniversities.*

Details of the outcome of theAustralian Phytochemical Surveywere published in the book Plantsfor medicines: a chemical andpharmacological survey of plants inthe Australian region (D.J. Collins,C.C.J. Culvenor, J.A. Lamberton, J.W.Loder and J.R. Price, CSIROPublishing, 1990). ‘In the Australianregion’ refers to the fact that several ofthe plant species studied werecollected in New Guinea. The


The creators of anew phytochemicaldatabase describeits development andtheir continuedefforts to cover themany thousands ofAustralian plantspecies.

BY DAVID COLLINS AND DONALD MCGILVERY

Phytochemistryof Australian plantsA new database

*For a historical account of the Survey, see Price J.R., Lamberton J.A. and Culvenor C.C.J., ‘The AustralianPhytochemical Survey: Historical Aspects of the CSIRO Search for New Drugs in Australian Plants’, HistoricalRecords of Australian Science, 1993, vol. 9, pp. 335–56.

iStockphoto/levkr

bibliography in thisbook comprised2022 phytochemicalpapers that were

publishedbetween 1940and 1987.

In 2003, acomputerised

version of thisbibliography, updated

to the year 2000, waspublished by CSIRO

Publishing as a CD-ROM – PhytoChemAustralia: a database on Australian plantchemistry 1940–2000 (D.J. Collins andC.C.J. Culvenor). In this database, eachof the compounds isolated/identifiedwas listed in the bibliographic entryfor a given research paper, togetherwith an assignment of compound type.This database was fully searchable forauthors, plant families, genera andspecies, and for compound names andcompound types. But the lack ofstructural formulas and compounddata meant that this database hadlimited usefulness, and it wasjustifiably criticised on this basis.

The present database (freelyavailable at ausphytochemistry.monash.edu) is a major extension ofthe foregoing database, but containsthe very important addition of fieldsthat include the structural formula,molecular formula, molecular weight,accurate mass, Chemical Abstracts

(CAS) Registry Number, andsystematic name of every

compound that has beenisolated from/identified in

Australian plants. Allof these items are

fully searchable.Given the historydescribed above,only researchpapers published

since 1940 areincluded (see box,

p. 28, for other criteria).

Structure and content The presentation of the data

from a given reference is in card-style format. Searches may be madeon authors, plant names (family, genusand species), and on compounds. Forcompounds, the search options arecompound type, name, molecularformula, molecular weight, accuratemass, and CAS Registry number.

Every compound entered in thedatabase is accorded a compoundtype. Those most frequently foundinclude ‘monoterpene’,‘sesquiterpene’, ‘triterpene’, ‘flavone’,‘flavonol’, 'iridoid glycoside', ‘alkaloidquinoline’, ‘alkaloid indole’ and‘flavone glycoside’. With the exceptionof the carboxylic acid group, there isno indication of functionality in the‘compound type’ – for example onecan do a ‘Find’ on ‘triterpene acid’. Inthe case of complex polycycliccompounds, the assigned ‘compoundtype’ is not systematic, butdescriptively indicative by thequalification of a recognisable sub-structure: for example, alkaloid indole,tetracyclic. There is an alphabeticallyindexed list of compound types thatmay be browsed.

The detailed molecular data for aspecific compound that is listed withina given reference may be accessed byclicking on the name of thatcompound. This updates all of the datain the Compound Details box at thebottom of the screen: the name asgiven in the paper, molecular formula,

molecular weight (four decimalplaces), accurate mass (four decimalplaces), CAS Registry number,systematic name as given bySciFinder, and structural formula. All ofthese criteria are individuallysearchable; for example, one can‘Find’ all of the compounds in thedatabase with a chosen molecularformula. One can also do a ‘Find’ onthe numerical value of molecularweight, or accurate mass, providedthat four decimal places are used. Itshould be noted that because of therelatively recent revision of atomicweights, the molecular weight for agiven molecular formula will differ inthe third and/or fourth decimal placesfor entries made in the databasebefore and after that revision. A ‘Find’on an accurate mass value wouldusually be more appropriate.


The database ...contains the veryimportant additionof fields thatinclude thestructural formula,molecular formula,molecular weight,accurate mass,CAS RegistryNumber, andsystematic nameof everycompound thathas been isolatedfrom/identified inAustralian plants.

Present contentThe database containsinformation from 8446 scientificjournal articles, and includesdata for 14 656 differentchemical compounds. Thesecompounds have been isolated,identified and characterisedfrom 10 450 different species ofAustralian plants. Thesenumbers will grow automaticallyas new data is recorded. Givensome 20 000 vascular plantspecies have been identified inAustralia, and several thousandlower plants (2000 algae andlichens; 550 ferns; 1000 mosses;and 11 800 fungi), there is muchmore work to be done!

Future data acquisitionData acquisition will continue,and the updated version will becontinually available online.Several mainstreamphytochemical and relatedjournals are scanned regularlyfor new data, but we are awarethat there must be many morerelevant references, especiallyby international chemists, thatare yet to be found and‘extracted’. New data (relevantreferences) is also acquired bySciFinder searches onarbitrarily chosen plant species,or on specific senior authorsknown to be active inphytochemical research.

We welcome advice of errorsand omissions, so that theappropriate corrections andadditions can be made. A SendComment button is available onthe HELP page atausphytochemistry.monash.edu.

David J. Collins FRACI CChem compiled thephytochemistry database and is HonoraryAdjunct Senior Research Fellow, School ofChemistry, Monash University.Donald C. McGilvery, who developed thedatabase, is Lead Operator, AustralianSynchrotron.

Chemistry in Australia28 |

Criteria for database inclusion1 Only research papers published since 1940 are included.2 The designation ‘Australian plant’ is based on two major publications. One is the Census of

Australian vascular plants, by R.J. Hnatiuk, Australian Government Publishing Service, 1990(Number 11 of The Australian flora and fauna series, produced by the Bureau of Flora andFauna, Canberra). The other botanical authority used is the set of volumes (36 publishedso far) in the series Flora of Australia. In addition to the strictly indigenous flora, theforegoing volumes also include some overseas plants (names marked with an asterisk inthe above publications) that have been naturalised in Australia: such plants are includedin this database.Many of the plants that are indigenous in northern Australia are also indigenous in someother countries, particularly in Asia, including India, Japan and China, but also in othercountries. Most of the recent studies on ‘Australian plants’ are by chemists working inthose countries. We are aware that many more relevant phytochemical studies byinternational chemists have yet to be found and included. This is being done progressivelyby the arbitrary choice of plant species for systematic searches using SciFinder. Also,because many of the species of Eucalyptus have been adopted and cultivated by othercountries, most of the recent work on the eucalypts is by overseas chemists. There is anongoing search for relevant papers of this type that have yet to be included.

3 Papers that primarily describe pharmacological studies are not generally included, butpapers that describe both the isolation and the results of pharmacological studies ofbiologically active compounds are relevant, and are included.

4 Phytochemical work described in patents is not included – only studies published inscientific journals are included in this database.

5 In those studies where several species of a given genus are examined, only the data forthe Australian species is included.

6 In publications that describe the isolation/characterisation of compounds from more thanone plant species, the compounds are not ascribed to a particular species. One needs toconsult the paper for that detail.

7 In the case of essential oil analyses, the arbitrary choice has been made to include onlythose components that constitute 1% or more of the oil. Specific percentages are notgiven, but components of 20–40% are given an asterisk, those of 40–80% are given adouble asterisk, and those of more than 80% are given a triple asterisk. One can do a find,for example on 1,8-cineole***, to find all of the plants that have given essential oils richin that compound.

8 The compound names entered into the database are usually those used by the author(s) ofa given paper, except for the occasional correction of a typographical/spelling error. Theresult is that some compounds will be found under different names. This particularlyapplies to variability in the derivatisation of trivial names – especially in the naming ofglycosides. For example, quercetin 3-O-a-D-glucopyranoside will also be found asquercetin-3-glucoside, quercetin-3-O-glucoside, isoquercetrin etc. For each of theseentries, the Compound Data File contains the systematic name as given by SciFinder –namely, 2-(3,4-dihydroxyphenyl)-3-(b-D-glucopyranosyloxy)-5,7-dihydroxy-4H-1-benzopyran-4-one.The duplicates/replicates of a given compound may be found by doing a ‘Find’ with theCAS Registry Number.

9 Articles that review the phytochemistry of specific species or genera are included in thedatabase, but the numerous compounds listed in the review article are not included in thedatabase entry. All of the compounds included in such a review should be found in thedatabase entries for the various original research papers. Reviews are included primarily fortheir bibliographic value.

10 Papers that only report total group analyses – such as ‘total phenolics’ or ‘total alkaloids’ –are not included; only papers that report specifically identified compounds are included.

11 Papers that describe experiments on the tissue culture of plants are not included.

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books

Food safety: innovativeanalytical tools forsafety assessmentSpizzirri U.G., Cirillo G. (Eds), Wiley, 2016,hardback, ISBN 9781119160557, 480 pp.,$321.95

The preface to Food safety: innovativetools for safety assessment announcesthat this is the first in a proposed seriesof compilations regarding food science ingeneral. The present volume explores theuse of modern techniques for theanalysis of food constituents orcontaminants or, in one case, deliberate

additives. It is not for the general reader, though each chapterintroduction is itself excellent reading. Rather it suits thosefamiliar with ‘cutting-edge’ methods and who wish to reviewtheir application to foods.

The book is well presented and, considering the authors arefrom 12 countries, only one of which has English as its firstlanguage, quite readable.

The book’s editors hail from the Department of Pharmacy,Health and Nutritional Sciences at southern Italy’s University ofCalabria.

The introduction ‘Food Analysis: a Brief Overview’ walks thereader through available techniques and applications.

Chapter 2, the only chapter featuring deliberately addedsubstances, deals with methods to detect and measure artificial(non-nutritive) sweeteners such as saccharin. Methods includesample clean-up, HPLC and capillary electrophoresis, the lastable to detect four added sweeteners simultaneously.Considering the evident expertise of the authors, the overviewwould have benefitted from ‘fleshing out’ to greater depth.

Current official (US) methods for lipids are reviewed inChapter 3, along with current advances in sample preparation,automation and detection. These include a section on infrared(FTIR) methods. The authors stress the importance (at leastwithin the US) of AOAC methods; these, by definition, are wellvalidated through sample exchange programs, an importantfeature where analyses do not have analytes with absolutevalues but depend in part on the methods themselves.

Chapter 4 covers analyses for substances that are markers forallergens present in foods. Here we enter the realm of the mostmodern analytical chemistry and biochemistry. Methods arechiefly immunochemistry, mass spectrometry and genomicamplification to detect and measure the protein, peptide or DNAmarkers of interest. An excellent final section explains therequired parameters for method validation and an extensivetable lists the allergens available to spike samples for thispurpose.

Chapter 5 deals with methods to detect, identify andquantify characteristic fragments of genetically modifiedorganisms (GMOs). The authors dedicate the first 12 pages to a

remarkably clear introduction to the history, scope of and needfor GMOs and an introduction to the methods. The next 40 or sopages cover essentially ‘textbook’ DNA and protein-basedmethods, with some new twists, and the last ten pages covernewer, and an almost bewildering array of, biochemicalmethods. The most recent emphases are on speed of operationand the ability to detect multiple genetically modifiedelements: one GM corn variety has six different enhancements!

The analysis of antioxidant substances in foods is thesubject of Chapter 6. Extraction methods are thoroughlyexamined; analysis is mostly by chromatography. A bibliographyof 235 references up to 2015 provides an excellent base fromwhich to explore the methodologies.

Chapter 7 features a useful overview of pesticide residues infood and food products and of appropriate analytical methods.For each step, the principle and its applications are given andexamples provided. The range and complexity of methods forextraction, separation and detection is quite astonishing and allare well referenced. The emphasis is on modern techniques,especially those that are rapid. An interesting example is theuse of a single hanging drop of solvent that is exposed, in asealed chamber, to an aqueous liquid extract containing thedesired pesticide. The drop is then withdrawn and injected intoa GC for separation! So much for serial extractions in separatingfunnels!

Free amines as indicators of food spoilage are covered inChapter 8. This chapter discusses chromatographic methods foridentification and determination of biogenic amines in foods ofanimal origin. Free amines and amino acids are naturallypresent in foods, but amine concentration can increase due tothe decarboxylation of amino acids by the action ofmicroorganisms or from steps in food processing. Thus, ifinterpreted cautiously, free amine can be an indicator of foodspoilage, particularly spoilage of animal products. The chapterdiscusses extraction and the applicable chromatographictechniques for particular food groups, and an extensivesummary table is provided.

Food allergies are surprisingly common, requiring dependableand sensitive analytical methods for their detection andmeasurement, especially in regard to the cautionary labelling offoods. The authors of Chapter 9 compare protein-based methods(immunological assays) with extraction followed by massspectrometry, the latter being far more specific, but expensive.They then discuss an alternative approach to assay for DNAmarkers using PCA, a very sensitive, though indirect, method.

Extensive tables list current methods using immunochemistryfor detection and measurement as well as using immunosensorsfor detection only. The latter have the potential to enhance thespeed of analysis (and therefore reduce analysis time) and arealso discussed in Chapter 11. The field of immunochemistry isadvancing very quickly, many of the references being dated2005–2015.

Food-borne viruses are unwelcome visitors to the humanbody. Chapter 10 covers detection of food-borne viruses such as


• The declining art of scienti"c glassblowing• Andrew Holmes celebrates RACI’s centenary and 50 years of membership• Peter Doherty on marching for science

chemistryFrom Gothic to the GPO:a Melbourne architectural tour for Congress delegates


in AustraliaJuly 2017

chemistryFrom Gothic to the GPO:a Melbourne architectural tour for Congress delegates

Your member magazine Read the latest issue of Chemistry inAustralia in advance of the print edition.

Archive accessBrowse or search our index from 2003, ortrack down back issues from 2014 on.

Features and advertisingFind out about contributing a featurearticle or contact us about advertising.

There’s more to explore atchemaust.raci.org.au

norovirus and hepatitis A. Sensitive methods are needed herebecause the infective dose can be as low as ten particles. Onecurrent issue is how to distinguish infective from non-infectiveparticles. Here, cell culture is the soundest method in principlebut limited in range and often extremely difficult. So molecularmethods, such as polymerase chain reaction to concentrate theanalyte, are more often used. This chapter is very clearlywritten and generously referenced, the most recent item beingdated 2015.

Chapter 11 covers biosensors in general. It explains thatlarge-scale agriculture and processing have brought new safetyconcerns and with these the need for specific, sensitive and, ifpossible, rapid methods. Tables and detailed sections givemethods where biosensors can be used to detect foodcomponents and contaminants. In these, recognition sites fromorganelles, cell receptors, enzymes and antibodies to tissuesand even tailored molecules feed various transducers to deliveran electrical signal that can be measured. Biosensors may evenappear in ‘smart’ packaging – packaging with built-in indicatorsfor temperature or other indices of interest.

A final, short chapter reviews immunoassay methods in foodanalysis, though much of the detail appears in earlier chapters.

Overall, this is a potentially valuable reference tool,spanning a wide variety of analytical topics of interest toanyone working or planning to work at the leading edge of foodchemistry or biochemistry.

Bruce Graham 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.

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education

The chemical sciences is one of 22 Fields of Research (FOR)assessed against world standard benchmarks as part of theAustralian Research Council’s Excellence in Research for Australia(ERA) exercises. Data are available from three exercises conductedin 2010, 2012 and 2015. Details of the exercises and primary dataused are available from the ARC website (www.arc.gov.au/era-reports). In the June issue (p. 38), the chemistry disciplineperformance was benchmarked against four other science FORs.

Universities report their research activities in eight four-digitchemistry subdiscipline categories, 0301–0307 (see table) and0399. Category 0399 (designated ‘Other Chemical Sciences’) is amiscellaneous collection of data. This category has not beenincluded in this comparative study because of variability incontent sources between reports. All research outcomes are,however, included in any two-digit 03 chemical sciences figurespresented.

Performance by subdiscipline and universities are rated on ascale of 1 to 5 – from well below to well above world standard.The number of universities submitting research for evaluation ineach of the subdisciplines in 2015 is shown in the table alongwith the average national rating.

Some 26 of Australia’s universities submitted chemical sciencesresearch for evaluation. Physical and structural was the mostwidely researched subdiscipline. By contrast, theoretical andcomputational was actively researched in only five universities.Chemical sciences in aggregate and all subdisciplines, with theexception of organic, were assessed at above world standard (>4).The highest ranking was awarded to macromolecular andbiomolecular at 4.75.

The aim of the presentation in the present report is to provideinsight into the relative performance Australia-wide of the sevenmain subdisciplines using data from the 2015 and 2010 reports.Data on six parameters are reported to the ARC. Three have beenevaluated here: the number of fulltime researchers (FTE) in theprevious year, the research output over a six-year period and theresearch income over a three-year period. To simplify thepresentation, the quantitative data for these parameters havebeen normalised to the performance for analytical. The relevantanalytical chemistry values in the 2015 ERA report are: FTE 167.6,research output 1897.3, research income $41.65million. Thecorresponding 2010 values are: FTE 157, research output 1883,research income $37.58million. The values for the otherdisciplines may be obtained directly from the ERA reports or

derived using the analytical chemistry values and information inthe graphs.

Subdiscipline performances – 2015 ERA reportThe analysis presented in the first graph reveals that thediscipline of medicinal and biomolecular had the largest numberof FTE researchers (57% more than analytical). Physical andstructural, and organic also had more researchers than analytical.The smallest subdiscipline was theoretical and computational atless than half the researcher size of analytical.

Four subdisciplines have more research publications thananalytical over the six years (2008–2013) covered by the report.Physical (at 90% more than analytical) ranks well ahead of allother subdisciplines. Five of the other six subdisciplines have avery similar total publication performance. Theoretical andcomputational is the exception, principally because it wasassessed for only five universities.

Medicinal and biomolecular had the highest research incomefor the years 2011–2013, as well as the number of researchers. Itsrevenue was 86% more than for analytical. The strong revenueposition was not mirrored in the research output. Physical andstructural at 82% above analytical had a strong research outputperformance. The traditional areas of inorganic and organicreceived significantly less research funding than four othersubdisciplines.

The data presented in the 2015 ERA report provide a valuableinsight into the relative strengths of the various chemistrysubdisciplines. Overall, medicinal and biomolecular and physicaland structural are the strongest disciplines in terms of totalnumber of researchers and total research income. Analytical,inorganic, organic and macromolecular and materials all are ofcomparable size. Theoretical and computational is by far thesmallest of all the subdisciplines.

Research capacity of a subdiscipline is closely related to thenumber of researchers. It is useful therefore to examine theperformances relative to this parameter.

Research output and income per FTE researcher –ERA 2015The research output and the research income per FTE researcherare presented in the second graph. The data are normalised to theoverall performance for the chemical sciences average set equal to100. The actual chemical sciences value for the research output


Australian ERA chemistry subdiscipline performances

Number of universities assessed and the average national ratings for the chemical sciences subdisciplines for the 2015 ERA exercise

03 0301 0302 0303 0304 0305 0306 0307All chemical Analytical Inorganic Macromolecular Medicinal and Organic Physical and Theoretical andsciences and materials biomolecular structural computational

Universities 26 16 13 16 12 11 20 5assessed

Average 4.25 4 4.15 4.75 4.08 3.55 4.55 4.6national rating


per FTE is 11.5, while for the research income per FTE the value is$251300. Four of the seven subdisciplines have an outputperformance above the national average for the discipline, i.e.>100. Physical is the highest ranked subdiscipline at 36% abovethe average. Medicinal and biomolecular has the lowest outputperformance at 32% below the average even though it has anabove average research income per researcher. Theoretical andcomputational now has a very competitive publicationperformance at 15% above the average.

Macromolecular and materials is the best performingsubdiscipline for research income per researcher, being 40% abovethe average. Physical and structural at 31% is also well above theaverage. Three subdisciplines – inorganic, organic and theoretical– are around 15% below the discipline average for researchincome. Organic is the only one of these three with an outputperformance below the average.

Performance trend from 2010 to 2015 resultsThe percentage changes from the 2010 exercise to the 2015exercise are presented in the third graph, again for the three mainresearch parameters. Overall, the number of researchers engaged inchemical sciences research increased by 16%, while the researchoutput grew by 28% and the research income by 21%. While theseare encouraging figures, as discussed in the previous article,several other science disciplines have outperformed chemistry.

Medicinal and biomolecular reported the highest growth in FTE

researchers. Theoretical and computational was the most improvedin publication growth and research income. Two areas, organic andphysical and structural, had a decline in the number ofresearchers. Physical and structural, while remaining strong inabsolute terms for the 2015 ERA report, actually declined in totalresearch output and researchers. It also was the field with theleast growth in research income. Interestingly, inorganic receiveda significant increase in research income (64%), evident inincreased research numbers (26%), but not publications (9%) tothe same extent.

The adverse timeline trend for physical and structural should beof concern because of its central importance to chemistry. Overall,it is the weakest subdiscipline in terms of its growth profile.

The ERA assessments provide one valuable measure of theinternational standing of Australian chemical sciences and itssubdisciplines. Universities use these results when makingstrategic investment decisions to support chemical sciencesresearch. The exercise to be held in 2018 will provide furtherinsight into the relative trends between subdisciplines. Overall,the international standing of Australian chemical sciences is high;however, relative to the performance of other Australian fields ofscience, there is need for improvement. This situation wasdiscussed in the previous article (June issue, p. 38).

Professor Emeritus Frank P. Larkins FRACI CChem is at the School of Chemistry,University of Melbourne. Contact him at [email protected] for informationon the performance of individual universities.

AnalyticalMedicinal and biomolecularTheoretical and computationalInorganicOrganicMacromolecular and materialsPhysical and structural

200

160%140%120%100%80%60%40%20%0%

–20%

FTEs

Research output/FTE Research income/FTE

FTEs Output Income

Output Income

150

100100 86 93

42

94

4974

37

89100 100132

186 182

118 108103138

102

157

149%127%

72%

99 9984 86 86

6891

118 125 136115

100

140117

131

100

26% 31%–11% –1% –2%

9% 9%

58%

17% 28%11%

64%78%

21%32%32%39%

16%7% 2% –5%

190

50

0 Chemistry subdiscipline performancesrelative to analytical chemistry – ERA 2015.

Chemistry subdiscipline research output andresearch income per researcher relative tothe average normalised to 100. (2015 ERAoutput data from 2008 to 2013 and theincome data from 2011 to 2013.)

Changes in chemistry subdisciplineperformance from 2010 ERA data set to the2015 data set.

All chemical sciences

Total

Every so often I hear or see something in the news media thatmakes me sit up and ask, ‘Can that be right?’. That was myreaction to a recent breakfast radio report that stated that the15 largest container ships contribute as much air pollution asall the cars in the world. The report went on to discussemissions of sulfur and nitrogen oxides (SOx and NOx) frommarine diesel engines, and how these are influenced by fuelquality.

Sensing a factual disconnect, I delved a bit further, andfound that this was old news, with numerous recurrences of thesame story going back to the original in 2009. However, in thespirit of never letting the facts get in the way of a good story,the reprised stories had not kept abreast of changingcircumstances. The original story was based on a set ofassumptions about fuel quality and the fuel consumption ratesof large and small diesel engines. It assumed that the sulfurconcentration in marine diesel fuel was 4.5%. In 2009, this wasthe maximum concentration allowed by the InternationalMaritime Organisation (IMO). The authors of the original articleapparently assumed this to be the sulfur concentration in allmarine fuels, even though a shipping company executivequoted in the article stated that the average for his fleet was2.5%, and that 4.5% sulfur in fuel was rare. So, unless the15 largest ships only used fuel at the maximum allowable sulfurcontent, the report was flawed from the outset.

In the intervening years, as the story was re-hashed in (atleast) 2013, 2015 and 2017, the IMO has tightened fuelspecifications, so that the maximum allowed sulfur content was3.5% in 2012, with a projected limit of 0.5% in 2020. Also,over this period, cruise ship operators, and maybe othershipping companies, have installed caustic scrubbers on theexhaust systems of their ships. These remove SOx and NOx fromthe exhaust stream, and give a faint plume of stream from theexhaust stack.

These limits are considerably higher than the allowableamounts in automotive diesel fuel (10 ppm in Australia), andthe original article did serve to highlight the disparity.However, by not keeping pace with the latest developments infuel standards, those repeating the story did a disservice to thelay readership.

While it should be no surprise thatmarine diesel engines, operating24 hours a day up to 280 days per year,and with power outputs multiples ofautomotive engines (cars and trucks),produce more emissions, the simpleanalysis used also overlooked the effectof concentration of emissions sources onoverall air quality. The impact of a singleship on the high seas is less than thecombined effect of a million motorvehicles concentrated in a megalopoliswhere millions of people are exposed tothe high concentrations of atmospheric

pollutants. Also, pollutant concentrations determine thepotential for acid rain. However, when ships are groupedtogether (much like car and trucks can be), they can causeappreciable increases in concentrations. This is so on some ofthe major inland waterways around the globe, such as theAmazon and Volga rivers, and the North American Great Lakes.In the latter case, ships contribute to SOx and NOx

concentrations in the airshed of the industrial heartland ofNorth America, where they add to the emissions from motorvehicles and stationary sources.

Despite all this, ships still represent the most efficientmeans of transportation over large distances, with emissionrates per kilometre tonne travelled (for all exhaust gases) wellbelow land-based transport. The development of the shippingcontainer in the 1950s made the movement of materials andgoods more efficient, and was further enhanced by the use ofever larger cargo ships. Low-cost trade has become a realityand, with it, the breaking down of trade barriers such as tariffsand import quotas. Non-tariff trade barriers have also beenattacked and reduced, although in some cases they still existand are relevant and important.

Sometimes, an unintended consequence of free tradeagreements is that technical standards have been relaxed orignored in the process. In Australia in recent years, we haveseen the importation of asbestos-backed floor tiles, lead-basedpaint in children’s toys, building cladding that doesn’t meet fireresistance standards, and faecal contamination in frozenberries. These incidents can be attributed to poor supervision oftechnical trade and quality standards and the lower costs ofimported goods. So, while large efficient marine engines mightbe responsible for atmospheric pollution, they can also beindirect agents facilitating other potential health risks. But,just like the caustic scrubbers on the exhaust stacks, there arecontrol measures, which, if used properly, can deal with riskssuch as these.

environment


Ships ahoy!

Paul Moritz FRACI CChem ([email protected]) isa Principal Contaminated Land Consultant with Douglas Partners,and an EPA-appointed Environmental Auditor in Victoria, New SouthWales and the Northern Territory.

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Are you prepared to collaborate?Mary Turonek, Senior Associate, FB Rice

www.�rice.com.auThe IP Navigators

Collaboration is an essential element of technicalinnovation and successful commercialisation oftechnology. ere are many challenges tocollaboration between the industry and research

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erefore, in order to be ‘collaboration-ready’, researchorganisations need to perform internal due diligence to clearlyarticulate not only the scope of the Background IP but also their legalentitlement to own and use the Background IP.

is raises many questions that are best answered as early aspossible. Most importantly, who has contributed to the BackgroundIP and would they be entitled to co-ownership in their own right?

Under an employment contract, most research staff of universitiesand research organisations are required to automatically assign the IPthey create to their employer. However, no blind assumptions shouldbe made. Do contracts clearly spell out the assignment and/or scopeof ‘normal course of employment’?

Students or visiting researchers are unlikely to be bound in thesame way as research staff. It is important to understand whethertheir participation gives them a claim to ownership of theBackground IP or the IP that may be created during thecollaboration. If this is the case, it would be prudent to negotiate anassignment of their IP as early as possible or prior to them making acontribution.

Do contracts with contractors (e.g. soware developers,consultants) clarify ownership of any IP generated? Are licences fromthird parties required to use the Background IP?

Other important questions to address include: Is there anytechnology or highly sensitive information that needs to be ring-fenced and not distributed regardless of confidentiality agreements inplace? Are there any legal obligations to third parties from pastcollaboration projects? Are there any possible conflicts that should bedisclosed upfront?

e time expended in negotiating IP contracts (typically10 months) is one of the deterrents for collaboration with Australianresearch organisations. Ensuring that your organisation is‘collaboration-ready’ is one step towards becoming an attractivecollaboration partner.

For more information, email [email protected].

As a scientist primarily interested in the chemical and biologicalsciences, I find it hard to go outside and not be reminded ofthe sheer beauty and complexity of the natural world. Studyingand understanding just a small fraction of its chemicalprocesses gives me sheer and humbling joy.

James Kennedy, a chemistry educator in Victoria, shows justhow chemically complex something simple can be in his seriesof ingredients lists for fruits. His ingredients list for a blueberry(bit.ly/2r9chH4) contains around 80 different chemicals. Jamesnotes also that ‘thousands of minority ingredients includingDNA have been omitted for brevity’s sake’.

The family holiday snap shown was taken recently on thewest coast of Tasmania, in the little town of Queenstown. For afun exercise, and hopefully without ruining the magic of thephoto, I am going to describe some of the chemistry pictured.(Beyond, that is, the obvious chemistry between the two peopleon the left.)

CloudsClouds are made up mostly of liquid water and ice, but cancontain other chemicals. They are formed when the water level,temperature and pressure are just right. In Tasmania, we have alarge hydroelectric system, which relies on rainfall. Rainfall, ofcourse, requires the presence of clouds! Research in Australiahas shown that it is possible to use a simple and readily

available chemical to assist in the formation of clouds, andincrease rainfall over a target area. Known as cloud seeding,planes are used to disperse silver iodide, which promotes theformation of ice crystals and water droplets. This has beenshown to be an effective technique in increasing rainfall, andimportantly has been shown to be safe for humans and theenvironment. More information including links to research oncloud seeding can be found through the Hydro Tasmaniawebsite (bit.ly/2qz7Cj3).

Grass, gardens and plants Researchers at Texas A&M AgriLife recently reported that thesmell of freshly mown grass is due to a combination ofchemicals released by the grass as a stress response. The grassis, essentially, yelling for help and activating its protectivemechanisms to help it survive the trauma of being cut open(bit.ly/2sk5S9L). The researchers hope that they can learn moreabout drought tolerance of plants through studying this stressresponse.

The successful tending of a garden can require the tightestof chemical balances. As we well know, some undesirable plantswill grow just about anywhere under the harshest of conditions.Some more ornate, delicate and desirable plants require theright acidity of soil, the right water levels, the right balance ofnutrients, and so on.

August 2017|36 Chemistry in Australia

science for fun

The chemistry of everything

Your advert could be here.For further information about advertising here or on our website, contact:Mary Pappa ◆ 03 9328 2033 ◆ [email protected]

iStockphoto/Jirkab

As biological systems, plants are incredibly complicated, butthe reason they are green is quite simple. Most green plantscontain green pigment molecules known as chlorophylls. Thegreen colour is no accident: it is very much related to thefunction of the plant. Plants are green because they reflectgreen light, which is what you see, but they absorb othercolours. The absorption of blue light by chlorophylls is whatallows them to harness energy from the sun to allow the plantto produce food for itself, and survive.

Car and train enginesSteam engines and typical car engines work by somewhatsimilar processes. Each involves the use of a fuel, which can beburnt, causing a release of energy that is then used to powerthe vehicle. When a fuel burns, it undergoes a combustionreaction. One example of a fuel that can be used to power asteam train is wood. Wood is primarily composed of cellulose,which in turn is composed largely of individual glucosemolecules joined together in long branching chains. While woodis made of a lot of different chemicals that all burn in differentways, the combustion of glucose can be used as a model forunderstanding how combustion leads to energy production.

The overall chemical equation for the combustion of glucoseis:

C6H12O6 + 6O2 → 6CO2 + 6H2Oglucose + 6 (oxygen) → 6 (carbon dioxide) + 6 (water)

Described in words, one molecule of glucose reacts with sixmolecules of oxygen to form six molecules of carbon dioxideand six molecules of water. This reaction is exothermic – itreleases energy.

PeopleTo try to describe every chemical process going on inside aperson would be a near impossible feat. Here I want to describeonly one aspect. There are few activities that humans spend

more time preparing for, planning for and money on than …eating! One of the main reasons we eat is so that we haveenergy. Curiously, one of the main molecules used by our bodiesto get energy from is glucose. Perhaps even more curiously, theoverall chemical equation for the way our bodies get energyfrom glucose is the same as for the combustion of wood. This issomething many of us are familiar with: the concept that webreathe in to get oxygen into our body, and breathe out to ridour bodies of the carbon dioxide that is formed. There is,however, a good reason we don’t eat wood as a source ofenergy. Humans lack the required molecular machinery to breakthe wood down into individual glucose molecules.

Since everything is made up of chemicals, I’m sure there aremany other examples of chemistry to find in the image. I hopeto encourage everyone to marvel in the wonder of our world,and to share this joy with the younger generation. I’ve saidbefore that kids are natural born scientists and investigators –what better way to nurture these traits than to inspire afascination in understanding how things work.

August 2017 | 37Chemistry in Australia

Researchers at Texas A&MAgriLife recently reportedthat the smell of freshlymown grass is due to acombination of chemicalsreleased by the grass as astress response.

Jeremy Just MRACI is a Hobart-based PhD candidate in organicchemistry and a passionate science communicator, specialising inchemistry shows and demonstrations. Jeremy writes these columnsfor members to share with or demonstrate to friends and familywithout formal chemistry knowledge.

Star Carr in North Yorkshire is perhaps the most importantarchaeological site in the UK relating to the Mesolithic periodfrom the end of the last ice age.

Archaeologists have discovered unique organic artefacts atStar Carr that are over 10 000 years old. These include carvedred deer antler headdresses, thought to be part of the earliestshamanic costume, and expanses of worked wood that displaythe earliest evidence of carpentry in Northern Europe.

But recent excavations at Star Carr have produced bone thatwas completely demineralised and wood that was severelycompressed, representing the loss of valuable archaeologicalevidence. The problem was caused by environmental changes inthe waterlogged soil that once preserved the evidence. Andthanks to environmental changes related to things such as landmodification and climate change, other important archaeologyaround the world could be at risk from similar destruction.

Wetlands like Star Carr and other waterlogged environmentscan preserve organic materials that are rarely found elsewhere.This is because the lack of oxygen in the environment preventsbiological decay. This can provide unique evidence for howpeople lived and interacted with the natural environment, from

the remains of prehistoric buildings to delicate ecologicalevidence such as plant and insect remains that tell us what pastenvironments were like.

But wetlands across the globe are increasingly at risk fromenvironmental changes including drainage, land developmentand climate change. Wetland loss can contribute to flooding,drought, coastal erosion and species destruction. But we alsoneed to make sure the effects of this environmental change onthe unique archaeological information found in many wetlandsaren’t overlooked.

The evidence shows that the alarming deterioration ofartefacts at Star Carr was the result of geochemical changes atthe site. But the exact cause and timescale of these changeswas until now unknown, making it hard to make decisions abouthow to mitigate or manage the problem.

In our most recent research, we recreated the environmentof Star Carr in a lab by burying modern and archaeological boneand wood in peat taken from the site for a period of 12 months.We then used a number of chemical analysis techniques tomeasure how much the bone and wood had decayed andcompared it to decay on artefacts excavated from the site itself.

archaeology

Environmental change could be damaging some of theworld’s most precious archaeology

Professor Nicky Milner from the University of York duringexcavations at Star Carr, uncovering Mesolithic timber.University of York/Lorne Campbell (Guzelian)

Alarmingly, we found that within only 12 months thestructure of the bone had completely transformed, visiblyaltering its appearance, This would make it much harder to workout things like its age and what kind of bone it was. We alsofound chemical changes in the wood, although decay wasslower. In comparison, similar material buried in sand or gardencompost for the same time period showed almost no change.

Rapid decayThe main reason for the rapid decay of evidence from Star Carris the increased acidity in the ground caused by a recent dropin water levels. Field drains inserted near the site around theyear 2000 reduced the water table – the level where the groundis permanently saturated – to below the archaeologicalhorizons. This exposed sulfur compounds in the soil to oxygen,producing sulfuric acid. The loss of water in the ground alsocompressed the soil and the wooden artefacts within it, as wellas creating more potential for biological decay.

Our experiments have also shown that the conditions at thesite are causing the loss of organic archaeological material atan incredibly fast rate. This raises serious concerns for thecontinued survival of evidence buried there, and at other siteswith similar conditions.

This decay causes an irreplaceable loss of our culturalheritage. The speed at which we now know it can happen meanswe need to take urgent action when other sites are similarly

threatened. As many wetland archaeological sites are typicallyleft unexcavated, we need to start working out the risk to theevidence they contain. If we don’t improve our understandingand monitoring of wetland conditions – and come up withstrategies to manage them – then we stand to lose some of theworld’s most valuable cultural assets.

Kirsty High is a research fellow and Kirsty Penkman is senior lecturer inchemistry at the University of York. First published at www.theconversation.com.


Our experiments have alsoshown that the conditions atthe site are causing the lossof organic archaeologicalmaterial at an incredibly fastrate. This raises seriousconcerns for the continuedsurvival of evidence buriedthere, and at other sites withsimilar conditions.

Valuable artefacts have been discovered in many wetlands. iStockphoto/Paul_Cooper

After the grape harvest each year, winemakers move their focusfrom the vineyard to the successful completion of fermentationsas well as preparing wine for ageing or bottling. For theviticulturist, management of the vines continues for some timepost-harvest at least until leaf fall or senescence. One of thecritical issues in this post-harvest period is the build-up ofreserves in the vines for the next growing season.

When I first went to the National Wine and Grape IndustryCentre (NWGIC) in Wagga Wagga, I was intrigued to see howlong the leaves remained green after harvest, indicating thatphotosynthesis was occurring. Coming from Melbourne andobserving vine growth in the cooler areas, I was accustomed toleaves dropping within a few weeks after harvest, rather than2–4 months in the warmer areas around Wagga Wagga. Thisdifference in green leaf behaviour is even more apparent in theCôte d’Or region of Burgundy. Here, it is common for the leavesto be brown even at harvest; in some areas, leaf fall may haveoccurred before the grapes are picked. Obviously, there is nophotosynthesis occurring in these Burgundian situations. Allthis becomes significant in managing the crop load for the nextharvest.

When new growth occurs in the following spring, vinereserves are called on to drive this growth. The demand on vinereserves reaches a maximum around the 8–10 leaf stage andthen declines as the growing leaves become sufficiently activefor photosynthesis to meet the vine’s demands. The vinereserves of most importance are carbohydrates and nutrients.Carbohydrates consist of starch as well as glucose, fructose andsucrose (the ‘free’ sugars) while nitrogen and phosphorus arethe major, or macro, nutrients.

After harvest, it becomes part of the viticulturist’s role tomanage the vines to ensure that there are sufficient reserves forthe next season. As a simple rule, it can be assumed that thehigher the grape harvest yield, the greater the need to replenishthe reserves. Thus, higher crop loads can be tolerated in a warmer

region as there is a longer period of active photosynthesis afterharvest while lower crop loads are needed in the cool to coldregions. In some years, monitoring the water status of thevineyard and supplementing with water may be required.Nitrogen fertilisation may also be required post-harvest.

Until recently, decisions were made on experience ofvineyard behaviour. While analyses for carbohydrates andnutrients can be performed, the traditional methods are slowand cumbersome. Starch analysis requires enzymatic hydrolysisof the vine tissue extract followed by glucose determination,while combustion analysis is the approach used for nitrogen.There are three sections of the vine that need to be sampled –root, trunk and cane - as each contributes to the new seasongrowth at different development stages. Once sampled, theplant tissue needs to be dried and then milled to a consistentsize so that the extraction process is uniform.

Dr Jason Smith and Dr Bruno Holzapfel from the NWGIC haveworked extensively on vine reserves. Jason, now in Germany atthe Geisenheim Wine Research Institute, examined thesuitability of attenuated total reflectance Fourier transform IR(ATR-FT-IR) spectroscopy as a replacement technique fortraditional strategies. Vine tissue that Jason had collected inseveral projects from Riesling, Semillon and Shiraz plants fromboth warm and cool regions in Australia as well as Geisenheimwere used. Some 1880 samples were analysed by the starch andnitrogen traditional methods and by ATR-FR-IR spectroscopy.Interpretation of the data sets by chemometrics, performed byDr Leigh Schmidte from the NWGIC, allowed predictive modelsto be developed that validated the ATR-FT-IR approach as aneffective tool for monitoring vine reserves (see Anal. Chim. Acta2012, vol. 732, pp. 16–25). Having access to a procedure forrapid assessment of reserves provides viticulturists with a morerigorous basis for decision-making.

From their studies, Jason and Bruno were able to proposesome general guidelines relating harvest yield to themanagement of carbohydrate reserves. When crop yields are 20–30 or more tonnes per hectare (t/ha), the build-up ofreserves may take 6–8 weeks for proper replenishment, whilewhen yields are less than 10 t/ha, replenishment tends to occurin parallel with berry ripening, provided the canopy is healthy.For yields of 10–20 t/ha, post-harvest reserve managementbecomes increasingly important as the yield increases. Moredetail on this work can be found on the Wine Australia website(bit.ly/2rrWILe (fact sheet) and bit.ly/2rrIc6e (industrypresentation)). A detailed report on vine reserve management(CSU-05-01) is available at bit.ly/2rrIc6e.

All of this assumes that there is adequate water andnutrients and that the vines are disease-free. More tasks for thehard-working viticulturists.

grapevine


iStockphoto/Simon Dannhauer

Geoffrey R. Scollary FRACI CChem ([email protected]) wasthe foundation professor of oenology at Charles Sturt Universityand foundation director of the National Wine and Grape IndustryCentre. He continues his wine research at the University ofMelbourne and Charles Sturt University.

Post-harvest vineyard activity

I have previously written about Alexander Findlay (1874–1966),including his books Chemistry in the service of man andIntroduction to physical chemistry (see June issue, p. 41, andJuly issue, p. 41). Another of Findlay’s books, The phase ruleand its applications (1904), is so prized by chemists that it isavailable online today. It was revised from time to time, latterlywith co-authors for the ninth edition in 1951. While firmlybased in chemical theory, Findlay’s book also has an eye toindustry, with an extensive treatment of iron–carbon alloys, andthe characteristics of steel, with carbon content in the order of1%. The phase diagram, in which cementite, Fe3C, featuresstrongly, is a complex one. Findlay’s book was one of the first ina series published by Longman Green and Co. Included in thebook by way of introduction was a philosophical essay by theseries editor Sir William Ramsay on the differences betweenphysics and chemistry. It rambled on for about 20 pageswithout ever reaching a conclusion.

Not everyone was a great fan of Findlay’s book, however, as Idiscovered when I consulted A.C.D. Rivett’s The phase rule andthe study of heterogeneous equilibria. An introductory study(1923). Rivett’s interest in the phase rule is said to derive fromhis experience in Britain during World War 1 where he was incharge of a factory producing ammonium nitrate. He commentsthat it is based on his lectures at the University of Melbourne,where he eventually succeeded Masson, only to decamp after afew years to the fledgling CSIR. Rivett wrote that Findlay’s book‘covers considerable ground, especially in one- and two-component systems, though the omission of references totypical space diagrams showing the relations between all thevariables in these respective cases make it difficult’ forbeginning students. It was not clear to me whether Rivett wasreferring to a lack of citations – there were hardly any in hisbook – or to the lack of diagrams with the specificcharacteristics. Probably the latter, since his diagrams weremore complex than the 134 figures in Findlay’s text.

As did Findlay, Rivett drew attention to the work of Ostwald,who had included ‘a great deal that is fundamental’ in hisLehrbuch der allgemeinen Chemie (1885). Findlay was a studentof Ostwald’s and included him with Roozeboom and Bancroft asinfluences on his thinking, while retaining Josiah Willard Gibbs(1839–1903) as the father of the phase rule.

While Findlay’s Phase rule was evidently of interest tochemists, it also attracted the attention of the Americanhistorian Henry Brooks Adams (1838–1918). Adams was amember of a political dynasty that started with John Adams(1735–1806), who served two terms as Vice-President to GeorgeWashington before becoming America’s second President (1797–1801). He was succeeded by Thomas Jefferson (1801–9). JohnAdams’ son, John Quincy Adams (1767–1848), was the sixthAmerican President, serving from 1825 to 1829. His son, CharlesFrancis Adams was President Lincoln’s ambassador to Britain,and his grandson was the aforesaid historian.

Henry Adams took a ‘scientific’ view of history and made arather tenuous connection between phases of historicaldevelopment and the phases of matter that were being carefullydefined by 19th-century scientists. It’s not clear to me that heunderstood what the phase rule was all about, but in the earlyyears of the 20th century he would not have been alone inthat. In 1908, he wrote a long essay entitled The rule of phaseapplied to history in which he commented on the work of YaleProfessor Willard Gibbs. ‘(H)is Rule of Phases defies translationinto literary language’, Adams wrote, possibly because ‘(T)hemathematical formulas in which he hid it were with difficultyintelligible to chemists themselves, and are quite unintelligibleto an unmathematical public’.

This was no passing fancy of Adams’. It is clear that he wasfamiliar with Gibb’s memoir on equilibrium of heterogeneoussubstances and ‘on the existent phases of matter’, published inthe 1870s in the Transactions of the Connecticut Academy. Andit is known that he possessed a copy of Findlay’s The phase ruleand its applications. He wrote about ice, water and steam, andunderstood that the phases were in equilibrium. He speculatedabout how rapidly an equilibrium could be established, and thatled him to attempt reconciliation of the evolutionary theory ofhistory and the laws of thermodynamics.

Drawing on the work of other historians, he labelled theyears before 1600 as the Religious Phase that changed, as icedid to water, into the period 1600–1900 that he described asthe Mechanical Phase, and was followed by the Electric Phase.He questioned how long humans could go on developing newphases, and noted that the process of phase-change seemed tobe accelerating and could be described by a ‘law of squares’.

Adams felt that Gibbs got most help from a book called theGrammar of science by Karl Pearson, but since this book waspublished only in 1892 I have my doubts about that assertion.


letter from melbourne

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

Dr Findlay, the phase rule and its admirers

Henry Adams took a‘scientific’ view of history andmade a rather tenuousconnection between phasesof historical development andthe phases of matter that werebeing carefully defined by19th-century scientists.

cryptic chemistry

Across1 Two elements of a lawsuit. (4)4 Absence of colour brought about by

boron deficiency. (5)7 Ceremonial staff 5 Down for self

defence. (4)9 Character creation. (6)10 Rubbish! A bell sound is coming

about. (8)11 Employs tulip size change taking out

fifteen. (8)12 Heat over neon compound. (6)13 Telly Tubbies come over with a

radical . . . (5)15 . . . and three elements. (4)16 Aforementioned four elements. (4)18 Compete with tungsten opinion. (4)20 Red stone composed of three

elements. (4)22 Complete tungsten void. (5)25 Chooks’ levels. (6)26 Boron and phosphorus behind letting

only some frequencies through. (4-4)28 Hamlet on new compound. (8)29 Iridium holds some with a different

arrangement. (6)30 Way with argon plasma sphere. (4)31 Found sooner than expected in

extranuclear lysine studies. (5)32 Even teams may recognise good

television. (4)

Down2 Isolated a component. (5)3 50:50 partner pursues start of

estimated quarterly usage. (7)4 Wind easy. (6)5 Gives a spray for a looser

arrangement. (7)6 Tautomerism displayed by ethyl

acetoacetate, for example, makeslikely doctoral commentarymonopolising centres. (4-4)

7 Tests for fire lighting. (7)8 Can changes in coal be accepted? (9)14 Sodium, for example, is such via tunnel

reaction. (9)17 Ghost occupancy. (8)19 Hydrogen with R1OR2 on tungsten

suggests possibilities. (7)21 Blubber used to exclude air from a

reaction. (7)23 A monosaccharide fed to sheep. (7)24 Object to its 9 Across. (6)27 Hot water cooked meats. (5)

events

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

Fundamentals of Process Safety 28 August 2017 – 1 September 2017, Hamilton, NewZealandwww.icheme.org/shop/events/courses/2017/aus%202017/fundamentals%20of%20process%20safety%20-%20nz.aspx

Energy Cost Reduction – Efficiency and On-Site Generation7 September, Melbourne, Vic.www.icheme.org/sitecore/content/IChemE/icheme_home/Shop/Events/Courses/2017/Aus%202017/energy-cost-reduction

Current Trends in Mass Spectrometry and Chromatography25–27 September 2017, Atlanta, Georgia, USAhttp://massspectra.com

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

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

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

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

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

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

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


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