Volume 72, No. 1, January 2008

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IN NEW ZEALAND ‘ ISSN 0110-5566 Volume 72, No.1, January 2008 ~

metaalaled A Cleaner and Greener New Zealand Thanks to 2,4,5-T, Science, and Silicones Biomedicals from Bone Do We Expect Too Much? Reflection on Chemistry Contentin Higher Education Fighting Food Fraud with Science MALDI-TOF Mass Spectrometry of Cyanobacteria: a Global Approach to the Discovery of Novel Secondary Metabolites The 2007 NobelPrize in Chemistry

2008 International Year of Planet Earth

Published on behalf of the New Zealand Institute of Chemistry in January, April, July and October eachyear.

The New ZealandInstitute of Chemistry Advertising Sales Incorporated Fiona Summerfield 128a Halswell Road PO Box 39-112 Hillmorton Harewood Christchurch CHRISTCHURCH Phone: +64 3 359 7275 Phone: +64 3 980 4809 Mobile: 021 075 4917 Fax: +64 3 359 7248 Email: Email: [email protected] [email protected] Managing Editors and Publishers Disclaimer Fiona Summerfield and Rebecca Hurrell The views and opinions expressed in Chemistry in New PO Box 39-112 Zealand are those of the individual authors and are Harewood not necessarily those of the publisher, the Editorial Christchurch Board or the New ZealandInstitute of Chemistry. Phone: +64 3 980 4809 Whilst the publisher has taken every precaution to Email: [email protected] ensure the total accuracy of material contained in Chemistry in New Zealand, no responsibility for errors Scientific Editor or omissions will be accepted. Professor B. Halton, FRSNZ, Hon, FNZIC School of Chemical and Physical Sciences Copyright 2008 Victoria University The contents of Chemistry in New Zealand are subject PO Box 600 to copyright and must not be reproduced in any Wellington form, wholly or in part, without the permission of the Phone: +64 4 463 5954 Publisher and the Editorial Board. Fax: +64 4 463 5241 Email: brian. [email protected]

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Volume 72, No.1, January 2008 :

Articles and Features

8 A Cleaner and Greener New Zealand Thanksto 2,4,5-T, Science, and Silicones

J A Zabkiewicz 13 Biomedicals from Bone Michael R. Mucalo* and Andrew J. Worth? 18 Do We Expect Too Much? Reflection on Chemistry Content in Higher Education Richard K. Coll 22 Fighting Food Fraud with Science Bea Perks 25 MALDI-TOF Mass Spectrometry of Cyanobacteria: a Global Approach to the Discovery of Novel Secondary Metabolites Jonathan Puddick and Michéle R. Prinsep 29 The 2007 NobelPrize in Chemistry 34 Commenton Climate Change Mythconceptions

Vincent R. Gray 35 Response Doug S. Mackie and Keith A. Hunter 37 New Zealandis Different: Chemical Milestones in New Zealand History

Other Columns

2 NZIC January News 32 Chemistry Behind the News 33 Patent Proze 36 Letter to the Editor 36 Dates of Note 36 ChemScrapes ~ Brendan Burkett Cartoons 37 Book Feature: New Zealandis Different 38 Book Reiew: Handbookof Australasian Edible Oils 39 Conference Calendar 40 Grants and Scholarships

Chemistry in New Zealand January 2008

a 4 New ZealandInstitute of Chemistry ‘S & supporting chemical sciences ‘7 January News

RSNZ Fewllowships Genetargeting allows the production launched in 1977 and the most recent Prof Sally Brooker (Otago Univer- of almost any type of DNA modifi- read-out techniques of today are fur- sity and NZIC Branch Delegate) was cation in the mouse genome,thusal- ther developments of GMR. the sole chemist among the thirteen lowingscientists to establish the roles The prize in chemistry (Oct. 10) elected to Fellowship of the Royal of individual genes in health and dis- was awarded to Gerhard Ertl (Fritz- Society of New Zealand on Nov 7. ease. Gene targeting has already pro- Haber-Institut der Max-Planck-Ge- Congratulations from Council and duced more than 500 different mouse sellschaft, Berlin) for his studies of the Branches. models of humandisorders, including cardiovascular and neuro-degenera- chemicalprocesses on solid surfaces. His groundbreaking studies are in- The 2007 Nobel Prizes tive diseases, diabetes and cancer. dustrially important and help the un- Commencing on October8, the 2007 The physics prize (Oct. 9) went to derstanding of why iron rusts, how prizes were announcedin their usual Albert Fert (Université Paris-Sud, fuel cells function, and how the cata- sequence. A brief synopsis of the sci- France) and Peter Griinberg (Forsc- lysts in our cars work — moredetail is ence awardsis provided below. hungszentrum Jiilich, Germany) for provided elsewhere in this issue. the discovery of Giant Magnetoresis- The physiology medicine prize (Oct. tance. It recognises their work that led The Nobel Peace Prize (Oct. 12) was 8) was awarded jointly to Mario R. to the technology used for data read- shared, in two equal parts, between Capecchi (University of Utah), Sir ing on hard disks. It is thanks to this the Intergovernmental Panel on Martin J. Evans (Cardiff University), them that hard disks have been min- Climate Change (IPCC) and Albert and Oliver Smithies (University of iaturized so radically in recent years, Arnold (Al) Gore Jr for their efforts North Carolina) for their discoveries as illustrated by the sensitive read-out to build up and disseminate greater of principles for introducing specific heads for compact hard disks in lap- knowledge about man-made climate gene modifications in mice bythe use tops and some music players. change, and to lay the foundations of embryonic stem cells. The Laure- for the measures that are needed to ates madea series of ground-break- In 1988 Frenchman Fert and German counteract such change. This award ing discoveries concerning embryon- Griinberg each independently dis- has not been withoutcriticism, nota- ic stem cells and DNA recombination covered totally new physical effect bly by those whoareof the view that in mammals with discoveries that — Giant Magnetoresistance (GMR). CO, levels have had no impact but led to the creation of the immensely The GMR effect was discovered also those whofeelthat the recipients powerful technology known as gene thanks to new techniques developed have donelittle for global peace. targeting in mice. It is now applied during the 1970s to produce very thin to virtually all areas of biomedicine layers of different materials. To work, 2007 New Zealand — from basic research to the develop- GMRneedsstructures consisting of Association of Science ment of new therapies. layers that are only a few atoms thick Awards andforthis reasonit is one of thefirst Genetargeting is often usedto inacti- The Council of NZAS announcedit real applications of nanotechnology. vate single genes. Such gene knock- suite of awards for 2007 during No- The very weak magnetic changes ~e out experiments have elucidated the vemberlast as: that give rise to major differences in roles of numerous genes in embry- electrical resistance ina GMR system onic development, adult physiology, provided the perfect tool for reading Marsden Medal aging and disease. To date, more than data from hard disks when informa- ten thousand mouse genes, ca. 50% The Marsden Medal for outstanding tion registered magnetically has to be of the genes in the mammalian ge- contribution to the cause or profes- converted to electric current. Other nome, have been knocked out. Ongo- sion of science went to Prof Ailsa researchers and engineers subse- ing international efforts should make Goulding, at the University of Otago, quently used the effect to provide the knockout mice for all genes available Dunedin for her sustained leadership read-outheads. Thefirst of these was in the nearfuture. and personal contribution to research

Chemistry in New Zealand January 2087

on bone density, osteoporosis, and A/Prof Eric Ainscough (Manawatu) subscription in the following year the role of obesity and nutrition in for their work in the field of coordi- children’s health. nation chemistry. They have been Branch subsidies to students longstanding collaborators at Massey, Council urges Branches notto subsi- Shorland Medal working in a range of coordination dise travel or conference fees to stu- and organometallic chemistry ar- dents who have less than 6 months The Shorland Medalfor research was eas, most recently on novel ligands membership andare financial (paid- awarded to Dr Robin Mitchell (Hor- derived from phosphazene-derived up members)at the time of any con- tResearch) for making an outstanding scaffolds. sideration for subsidy. personallifetime contribution in using the skills of a chemist to answer Industrial & Applied Chemistry Specialist group an important biological and com- (formerly Nufarm) Professor Jim mercial problem - how pathogenic Johnston (Wellington). Jim has Movesare taking place to set up an bacteria cause harmto plants. Robin madesignificant contributions across environmental green and industrial wasrecipient of the 1978 NZIC East- a wide rangeofindustrial and applied chemistry specialist group. If you in- erfield medal. chemistry areas, most recently using terested in being included, advise the NZIC Office. gold nanoparticles as novel colorants in fashion textiles. Research Medal Clever Kiwis stamps The Research Medal, awarded to a The Denis Hogan Chemical Educa- NZIC now ownsa first day cover with young scientist for outstanding fun- tion Award: Adrian Jull (Manawatu) the ‘clever kiwi’ stamps which in- damental or applied research in the Adrian is a chemistry tutor at Massey cludes the ‘Spreadable Butter’ $1.00 physical, natural, or social sciences and has undertaken significant out- stamp highlighted in the last issue. went to Wellington NZIC Branch reach activities involving high school Secretary A/Prof Kathryn McGrath students. é Chemistry in NZ (Victoria University) for her outstand- It is a pleasure to announcethat Dr Pe- Sponsorship for the prizes for aca- ing research overthe last three years ter Hodder, formerly of the Waikato demic research andindustrial and ap- that spans the disciplines of physical Branchbut now resident consultant plied chemistry has beenlost. Council chemistry and soft-matter physics. in Wellington, has joined the editorial is following up possible new options team asassistant editor. Peter worked but any suggestions for sponsorship as a scientific editor with DSIR prior Science Communicator Award should be directed to the NZIC of- to a university appointment. He has The Science Communicator Award fice. already cut his teeth on the Nobel ar- went to curator of invertebrate zool- ticle and the Branch Newsthat follow ogy at the Canterbury Museum, Dr Council elected to Fellowship in in this issue. SimonPollard. Septemberlast Prof Peter J Derrick (Manawatu) and Dr Tony Woolhouse Council has decided to archive the (Wellington). Peter recently moved Council News Journal from 1936 to provide an eas- from the Warwick (UK) to become Postcodes ily accessible resource for members Massey University’s Head - Institute and a quotation from Datacapis to be Fiona Summerfield, one of the of Fundamental Sciences while Tony considered. Chemistry in New Zealand managers, is an organic chemist with IRL, and has been contracted to update the da- has a longstanding association with NZIC Chemical Education tabase with the new postcodes. These the Wellington Branch. are required from July 2008. It is ex- Trust pected that the costs will be recouped Branchgrants The Chemical Education Trust dis- in cheaper bulk mail rates. Branches that submit a financial tributed $4100 by way of twelve statement and budget before the first grants last October, $705 more than Institute Awards and Council meeting of the year will be in 2006. Twenty applications were Elections paid onehalf of their previous year’s received but only 12 could be funded The annual NZIC prizes ‘have been grant as an interim measure. Thefull with preference given to applications awarded as follows: grants (as recommendedbythe Trea- from schools that had not received surer and approved by Council) will grants in the last 2 years. Most of the Easterfield Medal to Dr Jadranka only be paid out when ail Branch Trust’s income is from interest earned Travas-Sejdic (Auckland Univer- budgets are available. on capital investments, although do- sity) for her work on conducting nations remain an important source. polymers and their applications; she Joining fee The Trustees are most grateful to is also a memberof the University’s those NZIC members who have gen- The joining fee arrangement since PolymerElectronics Research Centre erously supported chemistry teaching Jan. 1 now require new members to (PERC). this way. Members are reminded that pay the full fee up to 31 July of each donations over $5 qualify for tax ex- year. From | Augustto the end of the Chemical Research (formerly Hor- emption. tResearch): Prof Andrew Brodie and year a half fee is payable. All members will then be invoiced for the full ee

Chemistry in New Zealand January 2008

It was disturbing to see many of the Advanced Materials and Nanotech- tense competition pondering over applications made for_very basic nology. Jadranka’s research focuses questions that sometimes had a less equipment suchasburettes, pipettes, on the developmentofbiosensors us- than tenuous link to chemistry. Con- etc., that one would expect a school to ing conducting polymers and quan- testants came from ESR, AgResearch, supply. This clearly demonstrates just tumdots, and on new applications for Crop and Food, Chemistry, Biochem- how poorly equipped many schools conducting polymers. As she is on istry, Management, and the College are andit reflects how scienceis re- Research and Study leave until early of Science. Previous stars at this garded by manyin our community. 2008, Brent Copp (retiring chair) event got done-in by the music ques- will continue until her return. Gor- tions. The results were: 1*, /f takes Andrew Brodie, Convener don Miskelly continues as Secretary/ Alkynes (Alan Downward, Reuben

Treasurer, Gordon Rewcastle retains Jane and Neroli Ayling), 2", The Grant Item School Council delegate, and David Salter Peacocks (Paul Wilson, Sam Ed- $400 pH/mvV/ WanganuiGirls’ continues as Chemical Education wards and Daniel Milligan), and 3" temp meter College equal, The Inhibitorz (Scott Walker, representative. The committee mem- $400 |ourettes Waiheke High bers are Marija Gizdavic-Nikolidis, Hemi Cumming and Leonardo Ne- | School Patricia Shaw, Robert Bennett, and gron) with Nanotrivieomics (Andy

$400 os Katikati College Geoff Beresford. Corrina Thomp- Muscroft-Taylor, Sophie Walker and son (a past-president of the students’ Genevieve Evans).

_ Kaiapoi High Chemistry Club) is the new student $300 burettes School The best team name went to The Im- | representative. portance ofBeing Nernst withIt takes $400 Diji pipettes Mangere College |} The AGM wasfollowed by a very Alkynes a close runner up. An amus- $250 burette Cashmere High ing answer, which wona spotprize in ~ clamps School interesting presentation by Dr Keith Bedford (ESR Ltd.) entitled Chemis- response to the question Which Aus- $400 —— St Mary’s College try, Drugs, and Clandestine Labora- tralian creature could inject a nasty

tories. This talk discussed the evolv- toxin via spurs tucked awayonits $400 oe Tararua College ing nature of the NZ drug scene, and back legs was Most of them with the exception, perhaps, ofsome sheep. the current scientific and legal issues science erage associated with controlofillicit drugs $250 diagrams a High The October meeting was a visit to | in this country. software the Canterbury Innovation Incuba-

$350 safety St Joseph’s Maori Peter Schwerdtfeger (Massey, Auck- tor. A small but enthusiastic group glasses Girls College land) has received $720,000 from the enjoyed a very enlightening session

molecular Bayfield High Marsden Fund for theoretical work during which they heard how the In- $250 models School on chemistry under extreme condi- cubator could help themget a product

molecular way tions. to the market place. Two businesses $300 |models 8 Ranettiket in the Incubator were visited. | College glassware University ofAuckland Double congratulations to Rebecca The Department congratulated Prof Hurrell and Andy Muscroft-Tay- BRANCH NEWS Margaret Brimble (Using molecules Jor on their recent marriage and her from metal enriched mines for new successful application for a position medicines) and Dr Andrew Dingley in the University of Canterbury Liai- Ken Seal — NZIC President in 1972 (Characterizing the molecular and son office. Rebecca, the Canterbury — died in Auckland on October 29", structural mechanismofantimicrobi- Branch Delegate and joint manager 2007. He was 84 years of age. Born al pore-forming toxins) on obtaining of Chemistry in NZ, also maintains in England, he came to NZ in 1952 Marsden grants in the 2007 round. the NZIC website and is an active and had a distinguished career with Chemistry students featured in the member of the Chemical Education Ceramco. Anobituary will appear in Faculty of Science student poster specialist group. Through her position in the Science Outreach office the April issue. competition with Annalisa Durdle and Hannah Kelly (both Forensic she has worked extremely hard in The Branch AGM washeld on Octo- Science) receiving 2" and 3" prizes, promoting chemistry in schools. She ber 18. The new chair is Dr Jadranka respectively, while Mandy Herbst has been instrumental in setting up Travas-Sejdik. She gained her PhD (Wine Science), Lynley Crawford, the Chemteach website. How much from the University of Auckland Tanya Kjallman, and Sandra Baur she will be able to continue these and then worked in industry [Pacific also received commendations. activities in her new role in Liaison Lithium (NZ) Ltd.] before returning remains to be seen. to the University. These have evolved to her appointment as Senior Lectur- University of Canterbury er in Chemistry and Director of the Just when it seemed that the NZIC Polymer Electronics Research Cen- Trivia and Truffles event couldn’t get A welcome barbeque for new staff tre. She is also a Principal Investiga- any better, it did! A record 23 teams members Dr Paul Kruger, Dr Sally tor with the MacDiarmidInstitute for enjoyed an evening of hilarity and Gaw, and Dr Vladimir Golovko was 4

Chemistry in New Zealand January 2087

student, successfully defended his lentjob as mini-symposiumsecretary. world lightweight single scull 1500 This event highlighted the diverse m crownat the recent under 23 World nature of the Branch, with presenta- Championships. tions from Ghislaine Cousins (NZP), Samir Dar Gupta (LASRA), Justin Congratulations to Abby (Wanting) Bendall (Fonterra), Lucy Lesper- Jiao, who was awarded a 2007/8 UC ance (Crop and Food), David Hard- Summer Scholarship. Abby worked ing, Gareth Rowlands, Ashton Par- with Emily Parker and Jim Coxon tridge and Vyacheslav Filichev (IFS, on Modelling the Interaction of Cal- Massey) and Jaspreet Singh (Riddet pastatin with Calpain for the De- Institute, Massey). velopment of Modulators for Trau- matic Brain Injury. Amy Zhang was Grant Bostonhas joined the NZ Pork awarded the HRC scholarship, which Industry Board as Research and Inno- provides one SummerStudentship to vation Manager. a UC student to work in a health related field. Amy will be working with Massey University Emily Parker. The 2007 RSNZ Hatherton Award hosted by the current members ofthe MANAWATU for the best scientific paper by a PhD Inorganic staff. In late October two studentat any NZ university in physi- Visiting Erskine Fellows, Evamarie The Manawatu Branch congratulates cal, earth, and mathematical and in- Hey-Hawkins, and Justin Gooding the Branch Chairman Peter Derrick formation sciences has been awarded and his wife Kat, departed after con- on his election to NZIC Fellowship. to Celia Webby, formerly of Massey tributing a great deal both academi- and now of Oxford University. In cally and socially to the life of the Anumberofmembers ofthe Manawa- 2005, working with Emily Parker, tu Branch were involved in judging Department. Jonathan Morris, pre- Celia published a paper in the Jour- viously an academic in the Depart- entries in the 33" Fonterra Manawatu nal ofMolecular Biology (2005, 354, S & T Fair in August. The Branch ment and now at the University of 927-39) onthe structure and function Adelaide, recently visited. Jono was NZIC prize ($150) was awarded to of an enzyme from the Mycobacte- in town for Sarah Lundy’s PhD ex- Rudi Smith (Palmerston North Boys’ riumtuberculosis. amination and Becs and Andy’s wed- High) for his entry Where there s muck ding. theres brass. The Massey University Recently appointed Head of IFS, Chemistry Prize ($100) was awarded Peter Derrick, has been awarded Recently completing their PhD stud- to David Welman (Palmerston North the Thermo Fisher Scientific Award ies were Janna Nikkel (Andrew Boys’ High) for his entry Taking out by the RSC for his research on both Abell) - The design, synthesis and the caffeine — it’s no tea party. the fundamental and applied aspects biological assay of cysteine protease of mass spectrometry, including ap- specific inhibitor, Sarah Hickford plications to biochemistry and medi- (Murray Munro/John Blunt) - Studies cine. Andrew Brodie was presented in the Chemistry of Marine Natural with a NZ S & T Medalin Wellington Products, and Sarah Lundy (Jona- in December. The award recognizes than Morris) - Synthetic Approach- Andrew’s significant contribution es to the Bicyclic Core of TEO3.1, over an extendedperiod to the promo- Hamigerone and Embellistatin. Sarah tion of science, in particular through is now the Equipment Manager/Post- his far-reachingactivities at the sec- doctoral Fellow for the Biomolecular ondary-tertiary interface. Richard Interaction Centre at Canterbury. Haverkamp has been promoted to Tyler Chen, recently completed his Professor of Nanotechnology. MScdegree (Jim Coxon and Andrew Abell supervisors), and is now a PhD A Massey University Technicians student. He will be working with Jim Award has been given to Gareth and Emily Parker, with Andrew as a Rowlands to study alternative forms co-supervisor-at-a-distance. of chirality in the development of novel organocatalysts. The award Moriah Sandy, a second year doc- David Welman, Massey University will finance a technician salary for toral student at the University of Chemistry Prize winner. 2 years. University postdoctoral fel- California, Santa Barbara, has been lowships have been awarded to Paul The Branch held a mini-sympo- working with Profs John Blunt and Plieger for Metal Salt Extract, and sium on Organic Chemistry in the Murray Munro.Shewill spend three Shane Telfer and Mark Waterland Manawatu, once again sponsored monthshere on fellowship from the for Connecting the Quantum Dots. by Barry Scott from Merck. Serena NSF East Asian Pacific Summer In- Smalley (IFS, Massey) did an excel- stitute program. Storm Uru, a recent Vyacheslav Filichev has obtained 5

Chemistry in New Zealand January 2008

to some Examinationofthe Influence of Con- Marsden fast start funding for his ing pH meters were donated in all text on Curricula Development and project, Synthetie< Probes Yielding of the participating schools. All by Implementation. The genesis ofthis Stable and Selective DNZ Triplexes a great night, thoroughly enjoyed of bookwas Richard’s and Neil’s experi- for Gene Visualisation. Mee-Kyung the students and the large number ences of teaching science in develop- Ahnhas successfully completed her teachers whoalso attended. The quiz by ing countries. Through their interna- PhD underthe supervision of Emily was again generously supported tional contacts they ended up with 30 Parker and is now employed in the UBS,PoppasPizzas, Otago Museum, chapters covering science education Institute of Molecular BioSciences Otago NZIC,and the Chemistry De- Analysis of the sto- with Gill Norris. partment. in 26 countries. ries points to major issues in science curriculum developmentandit seems Chemistry Department OTAGO many resources have been wasted It is with sadness we record the death Henrik Kjaergaard has returned over the years. On a more positive of Otago HON FELLOW Emeritus form his year-long sabbatical with note, the book provides some useful Professor James Roper Robinson on Prof. Jorgensen’s quantum theory suggestions to improvethe process of 28 September 2007, at the age of 93 group in Denmark. Henrik, awarded curriculum development. the years. Prof Robinson was appointed a research professorship from Michéle Prinsep attended the 5" Professor and Head of the Depart- Arhus University research founda- Euroconference on Marine Natural ment of Physiology in Dunedin in tion, is one of four external members Products (Ischia, Italy) and gave a 1961, andretired at the end of 1979 of the newly established Lundbeck talk on her group’s recentalkaloid re- after anillustrious career in renal and Foundation Center for Theoreti- search. She also visited researchers in cell physiology and with a reputa- cal Chemistry headed by Jorgensen. for Singaporeon the wayback. Bill Hen- tion as a superb medicallecturer. He The centre funded a 4-month stay derson is on study leave from Janu- steered the Departmentof Physiology PhD student Anna Garden. Apart ary until September 2008, a welcome through its first major growth phase from research, Anna completed two relief after a six year period as Chair- in the 1960s and early 1970s. His papers in theoretical chemistry and person of the Chemistry Department. contribution to research was recog- now reigns as local expert on coupled He will remain based at Waikato with nised when he was madea Fellow of cluster theory. Henrik gave an in- of shortvisits to Singapore and the UK. the Royal Society of NZ in 1963. He vited talk Atmospheric photolysis as an eloquent sulfuric acid at the 3" Asian Pacific will be remembered A number of students are working on Theoretical and Com- speaker and writer, who facilitated Conference in the Department over the summer. and students putational Chemistry (Beijing). Anna the careers of his staff Rachael Linklater and Nicky Cam- into his home. Garden and Jo Lane attended the and welcomed them eron (Bill Henderson) on chemistry held on Monday | 7 Australian Conference on Vibra- His funeral was of metal sulfide systems, Greer Tan- tional Spectroscopy in Wollongong, October in Dunedin. ner-Dempsey and Aimi Finnegan- presenting an oral paper Estimating Ramanui (Merilyn Manley-Harris) Anotherfantastic evening of Chemis- the OH-stretching linewidths in wa- on detection of honey in imported try Quizzing washeld in late Septem- ter dimers and a poster Fluorosul- medicines and food products, and ber. Some 210 high school students fonic acid and chlorosulfonic acid: the nature of charcoal pigment used from Dunedin, Balclutha, Gore, In- possible candidates for overtone for Ta Moko, respectively. Megan vercargill, and Tuatapere attended. induced photodissociation, respec- Graingeris to set up HPLC input for After five rounds of questions, the tively. Daryl Howard hasspent last the ICPMS, an extremely busy instru- winning teams (in order) were: September in Boulder, Colorado re- mentin the mass spectrometry facil- Phantorium (Logan Park High), We cording vibrational overtone spectra ity. This will permit ion speciation of, are better than you (Kavanagh Col- of SH-containing compounds using for example, arsenic in environmen- lege), and The TM Team(Taieri Col- the FT-IR andcavity ring-down spec- tal samples. Simon Williams will be lege). The winners of the ever-popu- trometer in Prof. Vaida’s laboratory. wool grease samples for a lar Chemical Haiku competition were analysing commercial project and also acting Hey hey ho ho we love bio (James as a teaching assistant for a course Hargest High). Some old, but work- The President’s address from Jan on the operation of the Biacore SPR Wikaira in Octoberwasa fascinating instrument. account of the history of crystallog- Wehave had a numberofinteresting raphy in New Zealand, with the audi- and varied Departmental talks from ence enjoying spotting the infamous visitors recently. Canterbury Erskine faces from their past and present. fellow Eva Hey-Hawkins spoke on Bridging Organometallic and Coor- University of Waikato dination Chemistry, while Neil Ed- University) gave Richard Coll and Neil Taylor (Uni- monds (Auckland a talk on Development of Polymer New England, NSW) have Dr David McMorranpresents the Bunsen versity of Ed- Science Research at Tamaki Campus; BurnerofWisdomto the winners Phanto- now publishedtheir book Science our own Alan Langdontold us about rium (LoganPark High) ucation in Context: An International 6

Chemistry in New Zealand January 2087

Some Chemical and Electrochemical Chemistry Department and School port and reaction of other important Aspects of Water and Waste. Brent of Science and Engineering, Waikato redox active solutes, such as oxygen Copp (Auckland University) gave a University, Hill Laboratories, and and hydrogen sulfide. Greg Olsen talk on Amino Acid-Derived Marine James and Wells (Intellectual Prop- is currently reviewing final equip- Metabolites: Adventures in Biologi- erty Lawyers). ment options for the purchase of a cally Active Alkaloids and Shane Membrane Inlet Mass Spectrometer Telfer (Massey University) told us NIWA (MIMS) simultaneously measuring about Helical Motifs in Coordination the concentrations of majorandtrace and Supramolecular Chemistry. Michael Ahrens’ most challenging dissolved gases, e.g. O,, Ar, N,, CH,, and rewarding new thrill in the last CO,, H,S, over short timescales (<1 ChemQuest 2007,the annual quiz for few months has been without doubt min). Mike Stewart recently attended Year 12 students run by the Chemis- the birth of his first son Gabriel, and a Conference in Faro, Portugal on try Department was held on October the joys (and chores) of fatherhood. Pheromones and Welfare Indicators 17. This was a fun-packed night of Switching back to science, his lat- in Fish and presented some of the chemical questions in the following est research focus has been envi- research currently being undertaken four categories: Periodic Puzzlers, ronmental risk assessment for new at NIWA. While in Europe he also Sensing the Senses, The Wide Worldof and emerging chemicals of concern, visited Dr Mark Viant (University of Chemistry and Demon Demos. A total including surfactants, plastic addi- Birmingham), an expert in Environ- of 52 teams from 18 schools entered tives (flame retardants, plasticizers), mental Metabolomics. this year, with students coming from various biocides and pharmaceuti- all around the greater Waikato region cal and personal care products. He is WELLINGTON to compete for the James and Wells currently collaborating with several trophy, medals, and cash prizes. After colleagues at NIWA and overseas on The Branch congratulates Prof Jim each of the four rounds of questions, detecting these compoundsin envi- Johnston on receiving the Industrial it was Teachers ’ Turn with four teach- ronmental samples. Of particular in- andApplied awardfrom the Institute ers per round competing for a small terest are endocrine disrupting chem- and A/ProfKate McGrath on gaining prize for themselves. It was a most icals, which are bioactive at very low the NZAS Research Medal. enjoyable night for contestants, pre- concentrations. senters and spectators and the follow- The September meeting saw some ing prizes were awarded: I‘, St Paul Bob Wilcock is working on land-wa- 40 members attend the President’s Collegiate, Kool Kids Klub (Craig ter interactions in agricultural land- visit to the Branch. Her lecture New McConnochie, Mare Calderwood, scapes, N,O and CH, emissions from Zealand and New Zealanders’ role Matthew Fisher); 2", The Church waterways and the importance of in advancing single crystal structure College of NZ, Team Levi: (Levi ion-pair formation in lake chemistry analysis was preceded by the presen- Ensing, Ririwai Fox, Tia-may Had- models. Craig Depree has been busy tation of Fellowship certificates to field ); 3", Tauranga Boys College, with FRST proposal writing — re-bid- the eight recently elected members of TBC Fuz (Bryden Church, Jonathon ding the existing antifouling research the Branch. Late September saw the Mitchell, Travis Scott); 4", Rotorua programme. A new research pro- second student function for the year Boys High School, Su/phur Rocks gramme began in October that aims — this time a showing of the movie (Kyle Harford, Nikhil Balakrishnan, to develop novel marine antifouling AnInconvenient Truth. With free ice- Tom Kelly); 5", Fairfield College, materials incorporating photocata- cream prior to the film, a good num- The Eagles (Erica Burns, Erica Pren- lytic TiO, nanoparticles. The FRST ber attended. tice, Nikki Graziotti). For the Teach- project involves researchers from The October meeting was a presen- ers’ Turn, winners were: Lisa Janek IRL Ltd. and James Cook University, tation by Paul Kilmartin (Auckland (Fairfield College) and Leon Rutter- and includes industry partners Altex University) on unlocking the aroma smith (Waihi College). Coatings Ltd. and Resene Paints. Craig has also been digging up streets chemistry of NZ Sauvignon Blanc The quiz was presented by Rich- in conjunction with the Christchurch wine. The large audience was treated ard Coll and Michéle Prinsep, with City Council and Fulton Hogan for a to some fascinating results from the Bill Henderson running the Demon Land Transport NZ project looking chemical, sensory, and viticultural Demos and Lyndsay Main acting as at recycling coal-tar contaminated studies on the fruity and green aro- chief judge. Numerous other people streets. Kay Vopel is studying the mas of one of the country’s popular contributed to the success of the oc- effects of three phosphorus inacti- export wines. casion including staff and students vating agents on the biogeochemis- The November AGM returned in- of the Chemistry Department and try of Rotorua lake sediment, using cumbent Chairman (Richard Tilley), School of Science and Engineering. laboratory microsensor techniques Secretary (Kate McGrath), Treasurer David Mackaskill from James and that enable sub-millimetre resolution. (Suzanne Boniface) and Delegate Wells and Gina Wallace and Leisle The agents are applied to reduce the (Brian Halton) unopposed. Fellow- Noble from Hill Laboratories (the release of phosphorus from the sedi- ship certificates were presented to former two being Waikato gradu- ment into the water column that can Sarah Russell and Tony Woolhouse ates) presented the prizes. The spon- drive phytoplankton blooms. The and the latter then addressed the sors of the quiz, whose contributions research is providing information on are gratefully acknowledged, were the effects of these agents on trans- Continued on page 28... Chemistry in New Zealand January 2008

A Cleaner and Greener New Zealand Thanksto 2,4,5-T, Science and Silicones J A Zabkiewicz Plant Protection Chemistry NZ, PO Box 6282, Rotorua (e-mail: [email protected])

Historical background That new herbicide was glyphosate (3, sold by Monsanto as Roundup”in the early 1980s) but althoughit was quite Those of you old enough to remember NZ being deluged effective against annual broadleaf and grass weeds, when with 2,4,5-T, 1 (one of a series of plant growth hormone applied to the vigorous woody and rhizomatous weeds herbicides that includes 2,4-D, 2) thought it was the en- like gorse, bracken and broom,orperennials like clover, vironmentalists who put a stop to this herbicide. Well, it failed. It was also very expensive, making it economi- not really! It was a combination of a new herbicide and cally and biologically unattractive in the NZ situation. a new spray surfactant (adjuvant) that finally turned the However,it had one huge advantage, it could translocate tables on a productthat hadlittle market competition until very well within plants and kill not just the foliage, but then. And NZ science, with a touch of serendipity, played right down to the roots. a major role in turning a she'll be right approach into a successful technology which has been adaptedin various Plant Biology and Physicochemical ways for a wide range of agrichemical products and crop situations. Interactions It was well known that by adding different oils or surfac- Hill country covered in woody weeds was a huge physi- tants (adjuvants) to the pesticide product you could im- cal and economic problem to the booming forestry sec- provesprayefficacy. The reasonforthis is that the cuticle tor in the 1970s and 1980s, as forests were planted on ina leaf presents a highly lipophilic surface to the external land which had degenerated from pasture to scrub weeds. environment.Thecuticular layer covering plant leaves is Non-chemical methods of weed control - no, it’s not a complex,but in generalconsists of a superficial wax layer new idea - were practiced then, but involved burn-offs (epicuticular wax), then a bilayer cuticular membrane that frequently got out of control andcast a pall of smoke (cuticle layer), the outermost layer (cuticle proper) com- for weekson endin places. Alternatively, huge machinery posedofsoluble (cuticular waxes) and polymerised lipids rumbled up and downthehillsides or rolled huge drums (cutin), and the innermost of polysaccharides which may down them to crush the scrub weeds...so that they could contain high proportions of pectin (Fig. 1). The conun- be burned more safely. Farmers were no better off; they drum is that a lipophilic compound will readily absorb could stock their paddocks with goats which ate every- into the lipophilic cuticle, but will not readily translo- thing in sight, but then they had to have secure fencing as cate in the polar, ionic phloem orsap.' In the case of 1, it took fourto five years to make sureall the woody scrub with an octanol/water (ow) partition ratio of log K,. >3, weeds were controlled - but this was impossible with a it was readily absorbed but poorly translocated.” In con- plantlike bracken fern. So herbicides werethefirst choice, trast, 3 has log Ky = 4,5; it can be readily translocated and with aerial application any terrain could be treated. but poorly absorbed. In the case of gorse not only has the The herbicide 2,4,5-T was used extensively on gorse, spine (leaf) a very thick cuticle covered in wax,’ but also broom, and native scrub weeds. But there was a problem it is covered in hairs (trichomes) that prevent droplets get- (leaving aside the Agent Orange aspects and spray drift ting to the actual leaf surface (Fig. 2). So it was no sur- issues) for, despite a variety of product formulations and prise to discover that only 7% of glyphosate wasactually apparently goodkills of gorse, the plants re-grew within a being absorbed from commercial formulations" andfield few months. This problem was recognised and a research efficacy wasalso low. programmeinvolving the author wasinitiated in 1974 to specifically look at better methods of woody weed control at the former FRI in Rotorua. Over the next few years studies showed that herbicides that acted through the roots were impractical for mature plants, though excellent LoNom urbe at controlling regenerating seedlings. Attention focussed Cetieteit era ecu) on foliar uptake options for the mature plants and radiola- beled herbicides demonstrated large differences in uptake into plant foliage, as well as poor translocation by some, Pepe 5211 B oreSco including 1. In effect it was a good contact herbicide but far from ideal for woody weed control. Something new was needed. Fig. 1. Cross sectional representation of plant cuticle structure. cl ca \-o ch ° Uptake into leaves can occur in two ways, slow diffusion ={ —co,H \—CO0,H_ HO,C-CH,-NH-CHy-PO3H> cl ‘cl through the cuticle or physical flow through stomata (Fig. 1, 2,4,5-T 2,2,4-D 3, glyphosate 3) that exist to absorb CO, for photosynthesis and expel

Chemistry in New Zealand January 2087

complete kill was obtained with one third the rate of the parent product formulation, which itself at full rate could only achieve twothirds mortality.’

The real life benefits of such technology are that glyphosate is used at about one quarter to onethird of the rate per ha that would be needed without smart formulations. A recent survey’ found that ca. 350 tonnes of glyphosate are being used annually. Forestry alone accounts for 144 tonnes of this and had the rates not been reduced, Fig. 2. SEM images ofyoung gorsespine(left, x35) and close this would have exceeded 400 tonnes; national use would up of needle surface (right, x262) showing trichomes(hairs) and have been around 1000 tonnes p.a. Hencein the 20 years dense waxlayer on needle surface. since smart formulations wereintroduced there has been a reduced input of around 5,000 tonnes in forestry and over GooD LIQUID 13,000 tonnes nationally. Prices of glyphosate products J ForMULATION PEPOSTT Vey Rapip have droppedoverthat period butit is clear that national savings to NZ users are more thana billion dollars.

Asusual, the explanation for these beneficial properties came after their discovery. The reason for such a low surface tension of a water solution of the organosilicone CUTICULAR STOMATAL lies in the structure, size, and orientation of the surfactant PENETRATION PENETRATION molecules in the solution. Surfactants have a hydrophilic and lipophilic end in each molecule; the hydrophilic end associates with the water and the lipophile formsa tightly packed arrangement on the surface - essentially a mono- Fig. 3. Representation of xenobiotic uptake through leaf cu- layer surface film. So, in a waterdroplet, the lipophilic sil- ticle. icone moiety coversthe surface thus having the initial interaction with the waxy leaf surface. In the process, some oxygen and water during respiration. Studies had shown* of the surfactant is stripped from the solution and lays a that the geometry andsize of stomata determined whether layer down on the wax, presenting the hydrophilic part liquids having a low enough surface tension could flow for water to associate with and spread over. This process into the sub-stomatal chambers and hence into the leaf is fast, much faster than with conventional organic surfac- mesophyll. Water solutions with a surface tension of 76 tants andthe principles involved have been the subject of mN/m were not able to flow into stomata for obvious manytheoretical studies.'° It accounts for the fact that sur- biological reasons, and neither could Roundup solutions factant concentrations need to be well abovethecritical of 3, so this pathway was unavailable. The advent of a micelle concentration,so that there is excess surfactant to material discovered fortuitously by the author (from an replace the material adsorbed into the cuticle. Evidence assortmentof surfactants discarded by another researcher that treated areas retain some residual surfactant on the in Australia) provided a completely new and novel surfac- surface comes from the fact that if a droplet of wateris tant structure that hadthe ability to bring surface tensions placed in that region, it will spread and give a lower con- down to levels never before achieved with agrichemical tact angle, in contrast to its behaviour on an untreated leaf spray solutions. surface. This again hasbiological implications as chemo- tactic reactions by insects and pathogenscan be disrupted The material was an organosilicone, an oligomeric mix- by surface treatmentof foliage - but that’s anotherstory. ture of trisiloxy polyethoxylate monomethyl ethers depicted by 4 (with n,,, = 7.5) (Scheme 1). Very dilute Another property of organosilicones such as4 is that they solutions of this trisiloxane surfactant, later marketed as are somewhat pH unstable.It is a drawback for long term Silwet L-77”(L-77) or Pulse®, were capable of wetting in-can formulations and accounts for their use only as even Teflon surfaces, and could spread on a leaf surface tank-mix adjuvants. It has a major environmental plus. 50 to 100 times more than other surfactant solutions. So- Although stable at neutral pH for many weekseither in lutions of 4 had surface tensions of 22 mN/m, a value solution or in the presence of solid substrates, 4 can de- well below the theoretical threshold required to infiltrate grade within minutes in low or high pH environments. leaf stomata;’ EtOH and Me,COhavesurface tensions of Extensive studies at Waikato University"! have identified 22.3 and 23.5 mN/m,respectively. Proof that this hap- the degradation pathways. Thepotential sites for cleavage pened was provided by measuring the percentage uptake of the trisiloxane surfactant are illustrated in Scheme 1 of '*C-glyphosate, with different concentrations of4 over and each generates more polar products. The Si-O bondis a period of time. Whereas normal cuticular diffusion is that most easily cleaved within the polymer and leads to a slow process that requires several hours for substantial silanols that are then subject to condensation and analo- amounts of xenobiotic to be taken upinto the leaf,° solu- gous depolymerisation to give a variety of linear and cy- tions with more than 0.3% 4 showed 80%+ uptake within clic silanols and siloxanes. The cyclic derivatives are wa- a few minutes.’ When the combination of Roundup® and ter soluble and knownto be harmless to a range of natural L-77 formulations of 4 was tested on maturegorseplants, organisms.

Chemistry in New Zealand January 2008

Me3Si—O i an area of active study by Plant Protection Chemistry NZ Me—Si—(CH2).—CH2OH Me3Si—O a HOCH.CH,),0H (PPC,,) and othergroups. Anillustration is given by Fig. 4 using confocal laser scanning microscopy (CLSM) and xMe3SiOH c . ar ae fluorescent probes of different lipophilicity. It has been x=10r2 ~~ Mess0 shownthat the uptake and movement (in the presence + Me—Si—(CHg)3- (OCH2CH2);—OMe — linear and cyclic _© Me,si—d = = of a surfactant) through the cuticle proper and into the condensation . qj, ESS Raw 9 prods. (oligo- epidermal cells varies greatly. The mostlipophilic com- meric mix) pound (Fig. 4a) is held completely in the cuticle; one that , Me3si—9 Ma—Si~(CHa)y-(OCH:OHa)H is less lipophilic diffuses evenly into the epidermal cells Me3Si—O (Fig. 4b), while the most hydrophilic compound migrates unstable throughthe epidermal cell walls (Fig. 4c). Scheme1. Potential cleavagesites (a-c) in the abiotic degradationof 4

Oneof the major biological advantages of these organosilicone surfactantsis that they do not show any phytotox- icity to the plant and they can reduce contact phytotoxic- ity with non-herbicidal products. Thusthey are used also with insecticides, fungicides, and plant growth regulators onfield orfruit crops. Their enhanced spreading properties mean that instead ofpesticide residues being deposited in discrete spots, they are spread more evenly over a surface. Such even coverage gives much betterprotection against pests or diseases, but at the same time it can also result in faster degradation of pesticide residues because a. Nile red a muchlarger surface area and a thinnerfilm of pesticide moleculesis involved. This is a very important consideration for food crops.

In subsequent years further work hasled to the developmentof organosilicone blends that combine good spreading but no stomatalinfiltration. Taking advantageoftheir ability to wet andstick to hard to wet surfaces, these new adjuvants are being applied to many horticultural crops where there maybe large differences amongleafandfruit surfaces.'* A further outcomeis that with the correct formulation and application, spray volumes can be reduced. b. Rhodamine 6G This allows for faster crop treatment, better use of expensive machinery and, mostofall the ability to spray under the right conditions and avoid off-site drift. Such concen- trate sprays are retained better, penetrate crop canopies more, andprovidebetter target coverage than do standard spray applications. One such adjuvant product developed by a NZ company has been commercialized globally, so not only are there savings dueto the technology but tan- gible revenuesas well.

Plant Cuticles and Cuticular Uptake c. Fluorescein So whatis the biology and chemistry behind these applications of formulation technology? Fig. 4. Visualisation of movement through a leaf cuticle by fluorescent dyes of different lipophilicity from confocal laser The predominant foliar uptake mechanism is by passive scanning microscopy;all treatments 0.05% dye concentration in diffusion through the cuticle. The relative thickness of the presence of0.2% surfactantafter 24 h into bean leaf. cuticle layer vs the epidermal cell wall varies enormous- ly among species. The cuticle has been shownto have a The diffusion of substances through the cuticle is de- weakacid ion exchange capability and a highaffinity for scribed by Fick’s first law, where the flux is the amount calcium ions,'* as well as containing phenolic constitu- of solute that diffuses through a unit area per unit of time, ents" and reactive epoxy groups.'* This variability illus- Viz.: trates the inhomogeneousnatureofthe cuticle and largely (mass/area) * time. accounts, to date, for the failure to describe comprehen- sively the uptake mechanism of xenobiotics through the It is proportionalto the concentration gradientand the dif- cuticle. fusion coefficient of the xenobiotic.'® Researchers in Ger- The process of xenobiotic uptake throughleaf cuticles is many" have defined the principalfactors affecting uptake rates as solute mobility (which is affected by temperature,

Chemistry in New Zealand January 2087

solute molar volumes, and cuticular wax composition), tortuosity, and driving force. Tortuosity is the length of the diffusion path through the /imiting skinin the cuticle, 100 wherethe limiting skin represents only a proportion of the 10 cuticle thickness, not its entirety, and it is influenced by 1 the size and orientation of the cuticular wax crystals. The 0.4 driving force is affected by the starting and continuing Uptake 0.01 concentration of active ingredient in the solution on the cuticle surface, in the cuticular layers, and in the epider- 0.004 malcell wall. Overall, and in simple terms: 0.0001 0.0001 0.04 1 100 uptake = solute mobility < cuticle tortuosity x driving Initial Dose Applied (nmole mm?) force.

The German studies were performed with isolated cuticles in vitro, using an artificial infinite concentration Fig. 5. Mass uptake of 2 (2,4-D) in the presence of polytrieth- system; spread area wasignored, and onlyplants that had ylene glycol monododecylether (A, ©, 4) and trisiloxane4 (n,,, astomatous upper leaf surfaces were used, mainly from = 7.5) (A, ©, m) into Chenopodium album, Hedera helix, and non-commercial species. Studies by PPC, with intact Stephanotis floribunda, respectively; (---) is maximum uptake plants of many types (using leaf surfaces with or with- representing 100% uptake overthe initial dose range. out stomata) showedthat the influence of droplet spread area was highly significant in vivo.'’ Although two dif- dosages can be usedto interpret interactions with endog- ferent formulations may contain the same concentrations enousplant constituents or structures from a biomolecular of chemicals,ifthe adjuvants are different orat different viewpoint. However, a muchbetter understanding of plant concentrations, thenthe residual droplet spread area will leaf cuticular structures, as well as structure-activity rela- be different. After droplet dry-down, the spray residue tionships with adjuvants, is still required for a successful will be spread over different areas and the mass per unit quantitative model of the uptake of the active ingredient. area will vary.'® These latter studies have shown that this Specifically, there is a need to provide a numerical indica- solution residueorinitial dose (ID) can be related to the tor (tortuosity factor) for plant cuticles that can then be mass uptake of xenobiotics.'* This relationship has been incorporated into models of uptake so as to reflect spe- validated with a wide range of formulations and plants cies or leaf developmental differences. There have been that represent typicalfield rates and formulations.”° Anil- electron microscopic studies of plant cuticles leading to lustration of such a relationship is given in Fig. 5 for 2,4- a classification but the studies are qualitative only. It is D acid 2 in the presence of two quite different adjuvants knownthat cuticle thickness is an inappropriate input as, into three plant species; very similar trends are seen for at times, thin cuticles can prevent uptake more than thick each species. Uptake per unit area at 24 h can be repre- ones; thuscuticular structure is of prime importance. sented by the relationship: As stated above, plant cuticles are complex, with layers Mass Uptake = a[ID]° of epicuticular waxes, embedded cuticular waxes, and a polymeric cutin (or cutan) skeleton. The waxesaresolid where a andb are constants specific to the active on these at ambient temperatures but there are more orless plastic species. regions in both the waxesandthe cutin which have been Total mass uptake can be determined from: termed amorphousorcrystalline. Solid state NUR now provides a measurementof cuticular wax or cuticle matrix Mass Uptake =afID]’x A. (nmole) that is amorphousorcrystalline. Moreover,the proportion of crystalline to amorphous wax could provide a meansof where is the droplet spread area. The mass uptakerela- quantifying the tortuosity factor used in diffusion mecha- tionship has also been used to establish the relative impor- nism equations; this is the current approachusedin a joint tance of species, active ingredient and its concentration, effort between Scion and PPC,, staff. Cuticles isolated and surfactant, to uptake.”! It was found that the concen- from a range of plant species and analysed by "°C solid tration of active ingredient increases in importance with state NMR techniques” show differences in their cross increasinglipophilicity, but that surfactant concentration polarization, magic angle spinning (CPMAS) spectra. is less important as the active ingredientlipophilicity in- The appearance and measurement of the '*C NMRsignals creases. The relationship between the active ingredient account for carbon atomsat different sites of the alkyl concentration and the species is more important for the chains that form the cuticle structures or their cuticular most polar compound, while the interaction of surfactant waxes. For example, fruit cuticles have very similar spec- and species increases in importanceasthelipophilicity of tra and crystalline/amorphous (c/a) ratios. However, the the active ingredient increases. holly cuticle showsa very different spectrum but similar These modelling approaches are markedly simpler than c/a ratios to the fruit cuticles (Fig. 6), while ivy is differ- the original German methods and they can be applied to ent to all of these. It appears that species can be placed any model or operational system andto all plant species. in groups based on their c/a ratios and spectral character, Furthermore, by using a quantitative molecular basis, and this has considerable taxonomic as well as structural significance. Cuticles were previously characterised visu-

Chemistry in New Zealand January 2008

ally by meansoftheir transmission electron microscopy Acknowledgements images and groupedintosix categories.” The species ana- I would like to acknowledge the manystaff of the former For- lysed by CPMAS NMRcanbegroupedbytheirc/a ratios est Research Institute, now Scion, as well as Plant Protection and these groupings coincide very well with the micro- Chemistry NZ (which arose from within the FRI), who have scopic categorisation. been or are associated with various parts of the work spanning three decades. The work has been funded by the FRS&T and Removalofcuticular waxes by solvent extraction caused several overseas and NZ companies. somealterations to spectra and c/a ratios. Measurement of the c/a ratios showed that in each case there was a small References but definite increase in amorphous character. Cuticles 1. McCloskey, W.B. Effect ofsurfactants and adjuvants on post-emer- o were also analysed after soaking 24 h in surfactant so- gence herbicide efficacy — see http://ag.arizona.edu/crop/presenta- tions/2003/mecloskey092403.pdf lutions. As the concentration of surfactant increased, so Zabkiewicz, J. A.; Gaskin, R. E. Proc. 32™ NZ Weed Pest Control the amorphousproportion increased. Thesestudies, while tv preliminary, appear very promising for the characterisa- Conf. 1979, 32, 315-318. tion of isolated cuticles and the interaction with solutions 3. Zabkiewicz, J. A.; Gaskin, R. E. New Phytologist 1978, 81, 367- and surfactants of the polymeric structure and the cuticu- 373. lar waxes. 4. Zabkiewicz, J. A.; Gaskin, R. E.; Balneaves, J. M. In Brit. Crop Prot. Council Monogr. No. 28, 1985, 127-134.

Physiol. 1972, 49, 813-819. Solid state NMR §. SchOnherr, J. Bukovac, M. J. Plant Tomato and PepperFruit Cuticles 6. Stevens, P. J. G.; Zabkiewicz, J. A. Proc. Eur: Weed Res. Soc. Symp. 1988, 145-150; Stevens, P. J. G.; Gaskin, R. E.; Hong, S. O.; Zab- 8 kiewicz,J. A. Adjuvantsfor Agrichemicals CRC Press: Boca Raton, 1992, 385-398. Millions Ds Stevens, P. J. G.; Gaskin, R. E.; Hong, $.0.; Zabkiewiez, J. A. Pes- tic Sci. 1991, 33, 371-382.

8. Balneaves, J. M.; Gaskin, R. E.; Zabkiewicz, J. A. Ann. Appl. Biol. 1993, 122, 531-536. 9. Manktelow, D.; Stevens, P.; Walker, J.; Gurnsey, S. ef al. Project SMF4193 Report, Ministry for the Environment2005.

10. Ananthapadmanabhan, K. P.; Goddard, E. D.; Chandar, P. Colloids andSurfaces, 1990. 44, 281-297. Solid state NMR Holly and Ivy Cuticles 11. Bonnington, L. S. Ph.D Thesis, Waikato University, 2001; Bon- nington, L. S.; Zabkiewicz, J. A.; Henderson, W. Separation and detection In Comprehensive Analytical Chemistry, Knepper, T.P.; Barcelé, D. and de Voogt P. (Eds.), Elsevier Vol. 40, 2003, 627- 653.

12. Gaskin, R. E.; Elliott, G. S.; Munro, J. P. Proc. Brit. Crop Prot. Council (Pests and Diseases) Conf. Brighton, 2000, 687-692; Gas- kin, R. E.; Manktelow, D. W.; Elliott, G. S. NZ Plant Prot.. 2002, 55, 154-158; Gaskin, R. E.; Manktelow, D. W.; Skinner, S. J. NZ Plant Prot.. 2004, 57, 266-270. 200 150 100 50 o ppm 13. Schénherr,J.; Huber, R. Plant Physiol. 1977, 59, 145-150; Hall, G. J.; Hart, C. A.; Jones, C. A. Pest Manag. Sci. 2000, 56, 351-358. Fig. 6. °C CPMASsolid state NMRofisolated cuticles from to- 14. Liakopoulos, G.; Stavrianakou, S.; Karabourniotis, G. Ann. Bot. mato and sweet pepperfruit and holly (/lex paraguanensis) and 2001, 87, 641-648. ivy (Hedera helix) leaves showing similarities and differences among species and sample types. 15. Riederer, M.; Schénherr, J. Arch. Environ. Contam. Toxicol. 1986, 15, 97-105.

Conclusions 16. Price, C. E. The Plant Cuticle, Academic Press: London, 1982, 237- 252: Arising from real-life problem growing on the NZ hill- a sides, whoseresolution has been an operational, environ- 17 Schénherr, J.; Baur, P.; Buchholz, A. 9th IUPAC Congress, RSC: Cambridge 1999, 100-119. mental, and economic success,studies associated with this very practical problem have crossed traditional boundar- 18. Forster, W. A.; Zabkiewicz, J. A.; Riederer, M. Pest. Manage. Sci. ies between biology, chemistry, plant science, and pes- 2004, 60, 1105-1113. ticide efficacy. They involve solution rheology, solution 19. Zabkiewicz, J. A. Crop Prot. 2007, 26, 312-319.

dynamics, liquid-solid phase interactions, plant biology, 20. Forster, W. A.; Zabkiewicz, J. A.; Riederer, M. Pest. Manage. Sci. and plant morphology. Consideration must also be given 2006, 62, 664-672. to the liquid and solid phase structures, both for the spray 21. Forster, W. A.; Zabkiewicz, J. A.; Kimberley, M. O.; Riederer, M. solution and for the composite biological membranesthat Trans. Am. Soc. Agric. Biol. Eng. 2006, 49, 25-31. they interact with at the cellular or nano scale. A genu- 22. Stark, R. E.; Tian, S. Biology of the Plant Cuticle, Blackwell: Ox- ine journey from macro to micro technologies, involving ford, 2006, 126-144. physical, analytical and organic chemistries and using 23. Holloway,P. J. The Plant Cuticle, Academic Press: London fundamental principles whichare being incorporated into 1982, 1-44. practical models.

Chemistry in New Zealand January 2087

Biomedicals from Bone Michael R. Mucalo? and Andrew J. Worth? *Chemistry Department, Waikato University, Private Bag 3105, Hamilton 3240 and Institute of Veterinary, Animal and Biomedical Sciences, Massey University, Private Bag 11222, Palmerston North (email: [email protected])

Introduction device. It serves as a cell transplant vehicle for bringing The realm of biomaterials, under which biomedical ma- about formation of the structural and functional tissue terials can be categorised, has a broad definition base units by the cells that have been transplanted. and recognises materials that are synthesized or naturally sourced. Biomaterials are normally those that come into Bone and its Chemical and Morphological contact with live tissue and physiological fluids. They Characteristics have applications as prostheses to replace lost function Boneis living interdigitated (or interlayered) compos- of joints or to replace bonetissue, for diagnosing medical ite of collagen protein and calcium phosphateplatelets, conditions, as a formoftherapy,or as a storage unit.! The the main mineral phase of which is carbonated calcium diversity and scope of biomaterials science research, and hydroxyapatite. Calcium hydroxyapatite, stoichiometri- especially its application to the improvementof trauma, cally Ca,,(PO,),(OH),, is the hydroxy end group member disease, and congenital defects in the human condition, of the complex apatite family and it has a more complex are makingthis branchofscienceincreasingly dominant chemistry than the related fluorapatite and chlorapatite and topical in many countries. An exciting aspect is that compounds. Whenprepared byprecipitation from aque- suchresearchis interdisciplinary. The varied problems of ous solution, the Ca:P ratio varies from 1.50-1.66 rather the humancondition that biomaterials research addresses than being reproducibly 1.67, the value expected from its occupythe efforts not only of medical doctors whoactas stoichiometry. Structures categorised as being part of the the end users of such technology, but also those of chem- apatite family have had their generic descriptor coined ists, physicists, engineers, and biologists in creating the from the Greek word apato - deceit.* They have the char- technological advances. Chemistry, in particular, plays a acteristic and interesting property of substitutionallability major role in such research,after all it is the foundation in that the cationic and anionic components of the lattice stone on which biomaterials polymer science and bio- structure, e.g. the -PO,, -OH and Ca,,, can be partially medicalscaffold materials are built. replaced with others when in solutions containing ex- changeable ions. Whenlattice substitutions occur in cal- The replacement of any bone due to disease or trauma cium hydroxyapatite, the physical propertiesofthe solids, needsan implant. This implant can fall under one of three ie. their solubility and crystal morphology, can change categories: autograft (fresh, living bone tissue harvested markedly from the state prior to the lattice substitutions. from somewhere else on the patient’s body such as the Biomineralization processes lead to bone deposition in hip), allograft (living bone tissue donated by other indi- the body andthey occurin a complex physiologicalfluid. viduals that is sourced from a bone bank, or xenograft (a The composition of the mineralized apatitic portion of synthetic bone substitute that lacks any living component bone is not stoichiometrically pure but ratherit exists as but which could potentially act as a scaffold to support a carbonated calcium hydroxyapatite doped with various cells, etc. While autografts represent the gold standard of other inorganic elements and/ororganic ions. It was pro- bone implants in terms of minimisation of rejection is- posed in 1958 by Neumanef a/.5 that the mean composi- sues, the pain of bone harvesting and the limitations of tion of bone was [Ca,(H,O),(PO,),][Ca, Mg,;»Na,,,CO,, how much to harvest are disadvantageous. Allografts, citrate, ,]. A more recent report® hasstated that its chemi- alternative bone replacement materials, can have body cal composition can be approximately given by Ca, rejection issues that couple with risks of disease transmis- 8307 (PO,),(HPO, and CO,),, (20H and CO,),,0,, where o sion and paucity of material available for implants. The can equate to a lattice vacancy.Inreality, it is difficult to rationale, therefore, for developmentof xenograft materi- give an exact composition of boneasit varies with species, als is to reduce reliance on autograft and allograft bone. the age of the vertebrate, and the location of bonein the Within the area ofbiomedical materials,the questfor suit- body. Bone also has a specific architecture consisting of able materials that act as osteoconductive xenograft scaf- cortical bone, the harder outer layer of bone, and cancel- folds viz. ones capable of supporting new bone deposition lous bone, which is described as being the softer, spongier and its proliferation, has been an avid subject globally. porous portion residing inside the bone. The cancellous The keennessofinterest in xenograft implantation materi- architecture is created by deposition and resorption pro- als in general has been further accentuated by the recently cesses that occur during bone formation as a result of the emerging area of Tissue Engineering which, according to actions of bone tissue-associated cells such as osteoblasts, Langerand Vacanti* (the pioneering scientists in the field) osteoclasts and osteoblasts.’ The overall porous architec- applies the principles of biology and engineering to the ture of bone that acts as a hardtissue support for the cel- developmentoffunctional substitutes for damagedtissue. lular or parenchymal(living) componentof boneis char- In contrast to conventional xenograft scaffold research, acterised byits interconnected porous channels, known as the scaffold referred to in Tissue Engineeringis effective- the trabecular network,that allow the transport of blood ly a biodegradable (usually polymeric) three dimensional 13 Chemistry in New Zealand January 2008

throughthis living tissue.* cubes of cancellous bone from the condyle portion of the bovine femur bone using a sharp band saw. The condyle Anyhard tissue replacement material for bone must thus is the rounded part of a bone (here, the femoral bone of attempt to replicate the typical bone architecture and be a bovinethat supports its bulk) that fits into the socket of composedpreferably of calcium phosphate materials that another bone to form a joint. The reason bovine condyles are not only biocompatible with the body but also able to are suited to forming xenograft cubeslies in the relatively be remodelled interfacially. This then allows a) new bone- large size of the condyles. There is enough cancellous apatite to be co-deposited with collagen after a process boneina typical (mature) bovine condyle to produce three of dissolution-re-precipitation of the bone-implantinter- to four cubes of materials ca. 25 mm’ each,by cutting." face and, b) new bonetissue to penetrate the implant at Other species of animals commonto NZ agriculture such the bone-implant interface to provide a securely bonded as sheep, deer, or even ostriches have femoral condyles bone-implant interface that effectively lodges the bone which are either too small (sheep and deer) to allow the in its position. The so-termed bioactivity of the bone re- cutting or are overly spongy with a high fat content(os- placement material is important as such materials allow a trich). Bone from other parts of the bovine skeleton, such direct chemical bond (without any so-called intervening as the rib can be processed, but it is more useful for form- fibrous tissue) to occur between natural bone tissue and ing re-precipitated hydroxyapatite powders by acid dis- the implant. Calcium hydroxyapatites have this property. solution processes rather than as xenografts. This contrasts directly with the so-called bioinert (or bio- tolerant) materials represented by e.g. hard ceramics such In cutting the cubes, only frozen femoral condyles from as alumina,zirconia, stainless steel, and titanium. These supermarketabattoirs are used so as to have minimal seal- bond to bonetissue purely through an intervening fibrous ing of the bone pores byfrictional heat-induced collagen- tissue layer of varying thickness which separates natural to-gelatin transformation during cutting. The bone cubes bone tissue from the implant.* Given these needed attri- are then boiled in water (conventional pressure cooker butes for bone tissue replacement, cancellous bovine bone for 6 h and ca. 15 psi) to remove the bulk of the blood arguably is the ideal, almost ready-to-use material. After and fat present in the cubes. Initial work'®"' at Waikato processing (see below), this bone already possesses the involvedpressure cooking of the bones followed by a 16 desired mineral composition and the necessary architec- h soak in NaOH,waterrinse, and microwave heating of ture to allow bone modelling at its interface as well as the bones (in water) to bp (to assist in fat removal). The tissue in-growth. bone cubes were then refluxed in AcOMe, which has a high affinity for fat, and then vigorous shaken or blown Our main focus on producing xenograft bone replace- with compressed air to removeexcessliquidpriorto final ment materials has beento use the plentiful andrelatively drying. Cubesthat contain fat are yellowed in appearance low cost animal bone from ourlarge cattle herds. This (Fig. 1). Deproteination of the defatted cubes was the can be done in NZ because of the strict auditing/tracking next processing step and this was achieved by immers- and MAF/biosecurity procedures that show the country, ing the defatted cubes in simple oxidising agents (NaOCl historically, not to have had any serious, notifiable diseas- or H,O,). This removes the bulk of the collagen protein es afflicting its herds and especially Bovine Spongiform which, wheninterdigitated with carbonated hydroxyapa- Encephalopathy (BSE). It has been allegedly that con- tite, gives the bovine bonea considerable degree of hard- sumption of meat affected with this disease led to human ness. Bonecontaining fat is yellow, defatted boneless so, contraction of the fatal brain-wasting disease known as but that with the protein removed has a whitened chalky variant-Creuztfeldt-Jacob disease (v-CJD) in the UK. The consistency (Fig. 1). The last corresponds to carbonat- continued BSE-free status of NZ (and Australia) allows ed hydroxyapatite with a significant loss in mechanical bone material for biomedical applications to be sourced strength.’* This attribute meansthat it can be shaped for from the country’s mainstream cattle herds rather than the desired implant by using a knife, scissors or a trephine from expensive controlled herds, viz. specially selected (Fig. 1 shows a shaped implant). and certifiably BSE-free, that have to be used overseas for bone-sourced biomedical materials such as Bio-Oss®.®!° From the NZ perspective, this has the potential to produce a cheaper, high value biomedical commodity out of a tra- ditionally low value material currently used for fertiliser or disposedofinto the environment.

Processing Bovine Bone into Xenograft Cubes or Powders The work performed at MIRINZ (NZ Meat Industry Re- searchInstitute) and Waikato’s Chemistry Department in Fig. 1. Bovine cancellous bone specimens. R to L: bovine can- generating xenograft materials and powders from bovine cellous bone cubeprior to reflux with MeOAc showing the yel- bonehas been described previously and the serious reader low colouration due to fat, defatted and deproteinated bovine is directed to the literature.'°" cancellous bone as a bleached and chalky cube, and a shaped piece of defatted and deproteinated bone. Xenografts For the preparation of xenografts, it is necessary to cut 14

Chemistry in New Zealand January 2087

In later research carried out by Mucalo and Foster! and powders for plasma spraying. Here, the powders were continued currently by Laird, Mucalo and Dias," the passed through an Ar plasma under conditions where pressure cooked bone was not subjected to the time con- the re-precipitated hydroxyapatite particles become par- suming solvent-assisted defatting and bleach-assisted de- tially molten and can be impacted ontostainless steel or proteination procedures. Instead it was placed in alumina titanium metal surfaces to form a plasma spray coating crucibles and sintered at 1000 °C in a muffler furnace for (another biomedical type application).'> Such coatings several hours to burn off organic matter and leavethebrit- render metallic surfaces such as titanium or stainless steel tle white mineral shell of the bone intact with its porous more bioactive and give them the ability to bond more architecture (Fig. 2). Under these conditions, the bone strongly to natural bonetissue through the mechanochem- mineral transforms from partially crystalline carbonated ically bonded hydroxyapatite layer; an example of such hydroxyapatite into crystalline hydroxyapatite. a coating is shown in Fig. 3. The heterogeneous and porous nature of the plasma-sprayed hydroxyapatite coating not only improvesthe bioactivity oftraditionally bioinert stainless steel or titanium substrates but mayalso provide a meansoftissue in-growth so improving the bone-coating bondedinterface.

Fig.2. Bovine cancellous boneaftersintering at 1000°C for 3 h.

Powders A variety ofmethodshavebeen used at Waikato to produce powders from bone." In previous studies milled animal bone powderwasproduceddirectly by crushing raw bone from a variety of available animal types, e.g. rib bones, sheep, bovine, corvine bone,efc., in a hydraulic press at Fig. 3. An SEM micrographof plasma sprayed calcium hy- 100 psi and then pressure cooking for 4 h to removetissue droxyapatite coating ona titanium plate. The feedstock powder andfat. After drying the bone chips were ground furtherin for this coating was produced by David Foster by re-precipita- a hammermillto particle sizes <2 mm diam. Further pro- tion froman acid digest of sintered NZ bovine bone. cessing, such as AcOMereflux (to removefurthertraces of fat), NaOHtreatment, or more commonly acid-dissolu- Spectroscopic and Microscopic tion/re-precipitation (using NaOH) wasthen possible. Characterisation of the Xenografts and Powders Derived from Animal Bone Although the acid-dissolution/re-precipitation methods produced powders, the residual fat and protein by-prod- A wide range of spectroscopic, microscopic and other ucts arising from using raw bone asa starting material physical or mechanical testing techniques can be used to produced many problems, even whenanintervening pres- follow the chemical and physical changes that occur in sure cooking step wasused. For example, performing the the bone materials as they are processed for biomedical acid digestions in HNO,led to orange colouration of the purposes. Thus, X-ray diffraction, solid state NMR and resultant hydroxyapatite powdersdueto so-called xantho- IR spectroscopy, atomic absorption spectroscopy (AAS), proteic reactions,'* which arise from interactions of the inductively coupled plasmaoptical emission spectrome- protein residues in collagen with the HNO,. Even HCldi- try (ICP-OES), X-ray photoelectron spectrometry (XPS), gestions (in which xanthoproteic reactions are absent) of scanning electron microscopy/energy dispersive X-ray the milled bone powders led to opaqueness, most likely analysis (SEM/EDXA), differential scanning calorim- due to suspendedcollagen or fat. To remedy this, research etry (DSC) and mechanical testing techniques (aimed at by Mucalo and Foster’? involving cleaner acid digestion/ measuring the bulk modulusandyield stress values of the re-precipitation of already sintered bone pieces was per- bone) have been used in ourstudies to characterise the formed. This minimized problematic bone matrix-associ- bone matrices as a function of processing.!*!2 ated organic impurities by the burn off of these. Cleaner, Generally, IR, solid state magic angle spinning (MAS) white powders were obtained, especially from the HNO, 'C NMR,and (to a lesser extent) XPS showedthat the dilutions, leaving only the washing out of NO,from the main changesduring boiling/defatting/deproteination that powdersafter re-precipitation in the subsequent cleanup led to the xenograft bone were due to the removal offat process. Subsequently, the process developed"! was em- and protein. As mentioned above, the remaining mineral ployedto provide kg-scale re-precipitated hydroxyapatite residue retaining the original porous architecture of the 15

Chemistry in New Zealand January 2008

bone was hydroxycarbonateapatite.'? This was confirmed treatment to give the chalky bone had a deleteriouseffect by an IR spectrum of the crushed bone(Fig. 4) with peaks on the overall mechanical strength of the bovine bones characteristic of carbonate at 1451 and 872 cm"in ad- tested.'’? This is desired because the xenograft material dition to the apatitic phosphate-associated vibrational that results is easily shaped.It is important, however,not modes at 1036, 605 and 564 cm’, respectively. However, to over-process otherwise attempts at shaping can result when the defatting and bleach-assisted deproteination in complete collapse of the xenograft due to extreme brit- are replaced by sintering the boiled bone at 1000°C, the tleness. bone mineral remaining is no longer the partially crystalline carbonated hydroxyapatite apatite; transformation In vivo Study of the Implanted Boiled/ to crystalline calcium hydroxyapatite occurs (Fig. 5), as Defatted/Deproteinated Bovine Bone in a evidenced by weak peaks at ca. 1450 cm’ that indicate Sheep Model the carbonate stems from surface interactions betweenat- mospheric CO, and CaOpresent within the sintered bone. The success and safety of an implant acting as a bone substitute can only be demonstrated properly through a SEM micrographs of boiled/defatted/bleach-deprotein- series of in vitro and subsequently in vivo testing proce- ated bone specimens showedthe successful retention of dures. Jnvitro testing involves subjecting the xenograft to the macroscopic structural detail of porous, cancellous a series of tests that evaluate its biocompatibility/irritation bone along with the needed interconnectedporosity chan- prior to placementin a living organism. One such widely nels for successful integration of the implant in vivo. For used test is the hen’s egg test-chorioallantoic membrane acid-digested/re-precipitated powders derived from bone, (HET-CAM)test. This is described as a biocompatibil- IR spectra show features typical of poorly crystalline cal- ity test intermediate to classical in vitro and in vivo test cium hydroxyapatite; remaining features are usually due protocols.’ The test assesses theirritation potential of a to carbonatessubstituted into the calcium hydroxyapatite particular substance by applyingit directly to the highly lattice structure. Theselatter carbonates can arise by CO, vascularized chorioallantoic membrane of a developing contamination during the alkali-inducedre-precipitation. chicken émbryo that is <10 days old. Under these con- = 4 ditions there is no visibly noticeable embryo, rather a beating heart in the middle of a network of vasculature (Fig. 6) which would develop over time into a full sized chick embryo given the correct incubation conditions. A scoring system! evaluates the potential for tissue irrita- iH | | tion, e.g. haemorrhaging by contact of the material with | = the blood vessels. Other tests that evaluate the material’s sr f} aun Pa | I biocompatibility for physiological environments involve /- 1 ws) the responsesofcells (from specially growncelllines) to ow f 4 contact with the implant materials.'”

4000 ‘3000 ‘000 1000 - Wavenumber (em-1)

Fig. 4. FTIR spectrum (KBrdisk) of ground bovinecancellous bone after subjection to boiling/defatting and deproteination.

Fig. 6. Hen egg chorioallantoic membrane (<10 days old) used to test materials for biocompatibility with living tissues. The Pa os dark imageatright is the embryochick heart. Typicaltest proto- Wavenumber (cm-1) cols note the responseof the vasculature to the materials. Photo courtesy of Dr Kavitha Babu, AgResearch, Ruakura.

Fig, 5. FTIR spectrum (KBrdisk) of ground bovinecancellous The boiling/defatting/deproteination process of bovine boneafter sintering at 1000°C for 3 h.of the calcium hydroxy- bone was presumedsufficient to renderit immunological- apatite from the acid digests. ly inert for in vitro testing. One must notethat fat removal is important because its presence in an implant can make Material strength tests predictably showedthat prolonged it antigenic, viz.cause infection once surgically inserted.'* boiling (6 h) followed by the deproteination hypochlorite However, the existing wide body of clinical knowledge 16

Chemistry in New Zealand January 2087

relating to in vivo bovine-derived materials in living orat Waikato has immediate use as a xenograft material for ganismsarguedfor a surgical protocolfor in vivo implan- veterinary purposes. tation of the bovine bone xenografts. This was developed by Warrick Bruce and Geoffery Horne (Massey Univer- Current and Future Activities sity and Wellington School of Medicine, respectively) Work at Massey University on implantations of the Waika- and approved by the Massey Animal Ethics Council. Sur- to bovine bonein dogs continues while collaboration with geries were carried out at Massey’s Veterinary Teaching Otago is on the development of a sintered bovine bone Hospital and the Wellington School of Medicine, and the material with the strength lost by collagen removal par- Waikato bone cubes were implanted in an ovine femo- tially restored. Biocompatibility testing of these materials ral defect model to evaluate their efficacy as an osteo- using the HET-CAM,as well as separatetrials employing conductive bone graft; the details of this work have been a specific cell line, viz. L929 (to assess whethercells pro- described in the biomedical literature.'? The surgical pro- liferate on these materials) would have been conducted by tocol involved the excising of an autograft bone sample the time this article has gone to press. Eventually, an in- fromthe sheep’s femursoatto create a defectfor the pro- vivo implantation trial in a suitable animal model(likely cessed bovine xenoimplant. The excised autograft bone sheep) will also be considered onthe basis of the initial tissue was placed as a control in a defect created in the biocompatibility testing results. opposite femur of the same test animal. Twelve mature ewes with weights 55-70 kg were used in the study so as Conclusions to avoid the normal growth processes of younger animals It has been shownthat NZ-sourced bovine bone provides and minimize impact upon xenoimplant incorporation. a useful bone replacement material for veterinary applica- The trephine implement removed 8 mm O.D. cylindrical tions and holds strong promise in the future for human cores of the xenoimplant from the (boiled/defatted/depro- applications. Thus value has been added to what was for- teinated) Waikato bone and this was sterilised (y-radia- merly a low value resource in agriculture. Hopefully it tion) prior to implantation. The deposition of new bone will create a new, specialist niche export market for this tissue around the implants was monitored at 15-17, 30-32, country. and 56 daysafter surgery using fluorochromelabel dyes that had been intravenously introduced at certain time pe- Acknowledgements riods after the surgical implantation. The sheep were hu- The work described in this paper could not have been carried manely euthanized ten weeksafter surgery and the distal out without the efforts, supervisory involvement or consultan- femurs harvested. De-muscled bonesections X-rayed and cy services of a numberof people situated at the University of then non-decalcified thin sections embeddedin resin for Waikato, MIRINZ, Massey University, Wellington School of fluorescence microscopy study. Overall, the study sup- Medicine, IRL Ltd, (Auckland), and the Chemnitz Technical ported bovine bone as osteoconductive in the ovine model University,(Germany). Financial assistance from the Waikato used and the fluorescent labelling showed that new bone Medical Research Foundation, the Maurice and Phyllis Paykel Trust and the PGSFis gratefully acknowledged. The plasma material grew overthe implant. Furthermore, the xeno- spraying studies (Germany)were enabled through the generous implant performed similarly or better to the autograft in funding assistance of the Deutscher Akademischer Austausch osteoconductivity. This unexpected observation has been Dienst (DAAD). Theefforts of former Waikato MSc students, ascribed tentatively to the open, porous nature ofthe bo- Glenn Johnson and David Foster, are also acknowledged. vine xenoimplant after trephining. This contrasts to the polishedandsealed surface of the autograft which would References have delayedtissue in-growth. In particular, the study has 1. Bruck, S.D. The International JournalofArtificial Organs 1978, confirmed that boiled/defatted/deproteinated bovine bone 1(2), 63-66. is workable, easily shaped, and compatible to surgical 2. Langer, R.; Vacanti, J.P. Science 1993, 260, 920-925. procedure. 3. Elliott, J.C. Structure and Chemistryofthe Apatites and other Cal- Further surgical work at Massey” implanted boiled/de- cium Orthophosphates, Elsevier Science: B.V. 1994, fatted/deproteinated bovine bone in a defective paw of 4. Aoki, H. Medical Applications of Hydroxyapatite, Ishiyaku Eu- a family’s pet dog. The void in the dog’s paw bone was roAmerica,Inc.: Tokyo, 1994. cleaned out and replaced with a grafting mixture of au- 5. Neuman, W.F.; Neuman, M.W. The Chemical Dynamics of Bone togenous cancellous bone and the Waikato xenoimplant. Mineral, Chicago University Press: 1958. This procedure hasasits ultimate aim not simply reduc- 6. Rey, C. Calcium Phosphates in Biological and Industrial Systems, ing dependence on the quantity of harvested autogenous Kluwer Academic: Boston 1998. bone needed but to use the osteoinductive properties of 7. Simkiss, K. Bone and Biomineralisation, Edward Arnold: London the autogenous bonefor stimulation and propagation of 1975, bone growth and lead to bone growthin the osteoconduc- 8. Hench, L.L.; Wilson, J. An Introduction to Bioceramics, World Sci- tive xenoimplant portionofthe graft. entific: Singapore 1993; Krajewski, A.; Ravaglioli, A. Integrated Biomaterials Science, Kluwer Academic/Plenum Press: New York The dog’s paw was X-rayed post-operatively at 1, 2, 6, 2002. and 10 months and showedoverthis time overall densi- 9. Details on Bio-Oss® can be found at http:/Avww.osteohealth.com fication of bone in the region of the void. The dogitself 10. Johnson, G.S.; Mucalo, M.R.; Lorier M.A. J. Mat. Sci.: Mat. Med. was sound throughoutthis period andisstill believed to 2000, 17, 427-441. be alive todayat time of writing. Thus the bone developed 11. Johnson, G.S.; Mucalo, M.R.; Lorier, M.A.; Gieland, U.; Mucha, H.

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J. Mat. Sci.: Mat. Med. 2000, 11, 725-741. 16. Luepke, N.P.; Kemper, F.H. Food Chem. Toxicol. 1986, 24(6-7), 495-496, 12. Anderson, I.A.; Mucalo, M.R.; Johnson, G.S.; Lorier, M.A. J. Mat. Sci.: Mat. Med. 2000, 11, 743-749. 17. Suzuki, T.; Yamamoto,T.; Toriyama, M.; Nishizawa, K.; Yokoga- wa, Y.; Mucalo, M.R.; Kawamoto, Y.; Nagata, F.; Kameyama, T. 13. Mucalo, M.R.; Foster, D.L. Croatica Chem. Acta 2004, 77(3), 509- J.Biomed. Mat. Res. 1997, 34, 507-517. 517. 18. Frayssinet, P.; Asimus,E.; Autefage, A.; Fages, J.J. Mat. Sci.: Mat. 14. Laird, D.F.; Mucalo, M.; Dias, G. Austral. Soc. Biomat. Conf. Mt Med. 1995, 6, 473-478. Eliza, Melbourne, 2007. 19. Worth, A.; Mucalo, M.; Horne, G.; Bruce, W.; Burbidge, H. Clin. 15. Mucalo, M.R.; Foster, D.L.; Wielage, B.; Steinhaeuser, S.; Mucha, OralImpl. Res. 2005, 16, 379-386. H.; Knighton, D.; Kirby, J. J. Appl. Biomat. Biomech. 2004, 2, 96- 104. 20. Worth, A.J.; Thompson, K.G.; Owen, M.C.; Mucalo, M.R.; Firth, E.C. NZ Vet. J. 2007, 55(3), 143-148.

Do We Expect Too Much? Reflection on Chemistry Contentin Higher Education‘ Richard K. Coll University of Waikato (e-mail: [email protected]) TA publication from the NZIC Chemical Education Special Interest Group

Learning Science a result of the learning processitself.° These studies might Education research in the 1970s, like other related areas, seem curious or odd but, overall, such studies suggested was dominated by quantitative work! during an era for that factors other than the school environment and the which social sciences sought to draw upon the successful teaching processes used were also influential in student scientific approachtypically used in the physical sciences learning. There are now huge bibliographiesof studental- (in particular) to investigate teaching and learning.'* So if ternative conceptions complied, some with several thou- wefelt a cohort of students did not understand some con- sand studies detailed.’ cept, we tried to find out whetheror not a different teach- What is perhaps of more concern is the remarkable te- ing approachcould fix their misconceptions.* But how to nacity ofmany student misconceptions. Students in many do this? Well, drawing ona scientific approach, we would cases seem unwilling to give up their prior beliefs even divide the class or classes up, teach one cohort the same after instruction.*'° Similarly, early research by Osborne way we alwayshad,and the other cohort in our new way, and colleagues'® suggested that even very able students, and evaluate any differences in conceptual understanding i.e. those who passed exams with high marks, did not ac- using, e.g. a standardizedtopic test. Differences would be tually understand fundamentalscientific concepts in ways examinedfor statistical significance of evidence that our we would desire. new approachto teaching had worked. Andthis is the way muchresearch was doneat the time. Control of variables, What might be the overall origins of such problems, and randomized sampling, and so on, were all embedded in what might we do about it? Let me consider this by look- such an approach to educational research. ing at whatI think is a key factor; high, perhaps unrealis- tic, expectations of our students. At about this time, however, key research — someofit NZ-based — suggested teaching and learning was rather Learning Chemistry in Higher Education more complex. Investigation into how students arrive at As mentioned above, considerable concern has been ex- their own viewsofscientific concepts, focused on student pressedin the literature about the high incidence, and re- misconceptions, or alternative conceptions, viz. students’ markable tenacity, of common student misconceptions. views that are at variance with the accepted scientific The vast bulk of this research is concerned with school viewpoint. Perhapsit is not that surprising that students students, but similar issues are reported also for students harbour misconceptions for abstract concepts such as the of advanced chemistry from the higher education sector. kinetic theory, electricity, and force. But some student Some higher education research reports give a real sense views of more common concepts are less easily under- offrustration experienced by teachersorlecturers as they stood and it is likely that they are influenced by other struggle to deal with student misconceptions.""'® While factors such as cultural background. There are some un- there are a numberof conceptsthat studentstraditionally usual examples reported in the literature. For example, find difficult such as aspects of physical chemistry, like one study of misconceptions of Papua-New Guinean stu- thermodynamicsandelectrochemistry," researchers seem dents found some to believe that pregnancy occurs when more concernedat the prevalence of student misconcep- a spirit child enters a woman rather than as a result of tions for even very simple concepts'*"'>'6 For example Her- sexual intercourse.t A Caribbean-based study found that ron'® comments that for his first-year chemistry students somestudents believed that hair would grow more rapidly fewer than 50% ofthe students seemed to comprehend if it was cut during the full moon.’ Other researchers have that it was Clthat was in table salt and not Cl, or that suggested that some student misconceptions mayarise as 18 EEE

Chemistry in New Zealand January 2087

there wasa difference between the two (see p.146). where h, k, and | are the Miller Indices for a givenset of crystal planes, and Ka Ve and z, are the atomic co-ordinatesfor the There is a genefal feeling expressedin the literature that j" atom expressedasfractionsofthe unitcell lengths. such student misconceptions are related to prior learning experiences(orlack thereof!), although some authors sug- Wecanwrite, gest that it may be morerelated to the students’ level of Ae =e t cos 2n(hx, it ky, + Iz) and, cognitive development.'*"’ One key factor I suggest may be the large amountoffactual material that students are Bay = LF sin 2n(hx, ti ky, + Iz). expected to memorise when developing understanding of a complex body of knowledge like chemistry.'*!8 Thusthe total phase and amplitude for the wave becomes,

@ = arctan (B/A)and, A brief review of course material for any one of many chemistry courses shows that we expect students to [Fygl = W(A? + B2). memorise a large amount of material, and often at the same time demandadvanced problem-solving skills. An It is convenient to express the above using complex numbers as, abridged course outline for third-year analytical chemistry I once taughtis given as Fig. 1. F,,hkl = A+iB.

The complex quantity F,,, is knownasthestructure factor. Advanced Analytical Chemistry Since exp(ix) = cos(x) Isotope chemistry. Methods ofdetection, measurement, safe + isin(x), the structure factor can be written as a complex exponential term, handling and application of isotopes to Chemistry, Biology and the Earth Sciences. Stable isotopes. Interfacing of analyt- EF, = “sh exp[27/0], ical instruments with computers. Experimental design. Sta- tistical treatment of data. Quality control. Chromatography. where0 is hx + ky + Iz. Atomic absorption spectroscopy. Mass spectrometry. X-ray diffraction. Electrochemicalanalysis. Assuminginfinitesimally small elements of electron density ratherthan discrete atomic scattering sources, we express Be Fig 1. Topics for advanced analytical chemistry course as an integral rather than a summation thus, High-level understanding of other related disciplines Fy = ! ptxyz) exp2ni0.dv, typically is also presumed, particularly at advanced levels of study. For example, in advanced postgraduate level structural chemistry courses we require advanced math- wherep(xyz)is theelectron density at point xyz. ematical ability and a thorough understanding of many Fourier transformation advancedphysics concepts. yields an expression for p(xyz) in termsofthe structure factor Fa Consider the following extract from a small portion of p(xyz) = x > x F,,, exp(-277/8). one lecture on single-crystal X-ray diffraction delivered Ako to an advancedlevel chemistry class (Fig. 2). From this expression we can calculate an electron density Theinteraction of X-rays with the planes of a crystalline lat- mapforthe entire contentsofthe unitcell andthis will reveal tice is dependent upontheposition of the individual atoms, regionsof high electron density corresponding to atomic po- or morecorrectly elements of electron density, present in or sitions giving the molecularstructure for the material under close to the crystal planes. Assuming discrete(i.e. atomic) study. In principle the Fourier series should be evaluated for scattering sources, the problem becomes one of the super- all values of Ak/ from -cc to +oc. Bravis lattice restrictions position of wavesof different amplitudes and phases. Thus and symmetry constraints do notallow this, however, and the uponinteraction with a given set of crystal planes a wave of resultis small ripples in the calculated electron density map, total amplitude F, has X and Y components, particularly around the heavy atom positions.

X = Yfcosd,and, Y = LS, sin oj Fig. 2. Portion of an advanced level lecture on X-ray crystal- lography. whereJ, is the atomicscattering factorfor the jatom, and 6, is the phaseforj* atom. Even a cursory examination of this brief portion of just The modulusofthe scattered X-ray beam is given by, one lecture clearly shows how much we expect from our students. We expect Fl = Vor +), knowledge and expertise in trigo- nometry, differential and integral calculus, complex number theory, and the phaseis given by the arctangentoftheratio of the Y wave theory, atomic theory, electricity and and X componentsi.e., magnetism, symmetry, andso on. Thislist is by no means exhaustive butit is immediately evident that we assume @ = arctan(Y/X). a remarkable in-depth knowledge of a number of highly abstract concepts. Theperiodic nature of the unit cell restricts the allowed values for dsuch that, There was a widely-held view amongst departmentalstaff 6, = 2n(hx, tky, + Iz) in the institution where I worked whenI taught such topics that this is exactly as it should be. The usualratio- 19

Chemistry in New Zealand January 2008

nale of this is that it is important for us to maintain high Content - Do We Want Depth or Coverage? academic standards in orderto ensure.the integrity and The latter half of the last century was characterised by high reputation of our degree programs. In addition, it is enormousadvancesin science and technologythat result- viewed that such knowledge and skills are important for ed in the demand for a more highly-skilled work-force. students engaging in postgraduate studies or research. This demandhasled to a large increase in students numbers studying science in high school andtertiary insti- If we accept that such expectations are reasonable, the tutions,2°? and to a focus on more applied courses and question remains as to whether we actually achieve the vocationally-oriented degree programs.*! Whilst this is understanding and problem-solving skills we seek with shift may be appropriate, it does present some difficul- ourpresentinstructional strategies? Despite reservations ties. For example, Buntting and co-workers, suggest that occasionally expressed aboutthe students’ abilities, once up to 50% of the intakeoffirst-year science students lack students reachthe final year of the degree program they understanding of key underpinning concepts.” Further almost inevitably graduate. Hence, weare in effect indi- Ss difficulty lies in the enormous numberof applied science cating by virtue of their graduation that, in general, our topics now available, and teaching staff are faced with the students do meet these expectations. A simple illustration difficult task of deciding what topics to include in their suggests that this may notbe the case. courses.

Third-Year Chemistry Student Manylecturers are uneasy about leaving out topics that Understanding of Atomic Structure they see as interesting and relevant to students, and there A representative sample ofthird-year chemistry students at is a tendency to want to include as manytopicsas possi- oneinstitution was briefly surveyed on their understanding ble. However, researchinto learning and instruction sug- of a concept that most of the teaching staff would consider gests that it may be more beneficial to teach a few topics very simple, namely fundamental atomic structure. By in depth, instead of trying to give a superficial coverage comparison with the X-ray analysis of Fig. 2, the concept of a large numberofdifferent topics.’ Moreover, it proof atomic structure as presentedhere is almosttrivial. vides a deeper insight into how students acquire concept- knowledge and reasoning skills as suggested by Eylon The students were asked to sketch an appropriate rep- and Linn.’ resentation for the electronic structure of the hydrogen atom and the carbon atom (Fig.3). It is important to bear The argument here is that students need to develop their in mind that this exercise was carried out with a group own concepts, see how to link new concepts with their of students that had graduated with a BSc at the end of existing concepts, and develop their own strategies for the year this activity was conducted. Furthermore, many higherlevel activities such as problem-solving.”This,it of these students had already been awarded good grades is suggested, is problematic if they are overloaded with for previous chemistry courses, e.g. A (80-85%) and A+ factual material, or encounter too much material at once. (85-90%). Despite this, the incidence of student miscon- There are a numberoffactors that educators need to take ception was high. Only two respondents gave an answer into account during instruction,’? namely content, orga- that could be considered consistent with the currently held nization and presentation of material, the student’s level scientific view. The naiveté of the answers was quite re- of cognitive development, andthe students’ level of prior markable. It seems that most of these students (ca. 70% of knowledge. respondents)still think of atomicstructure in terms of the The instructional strategies suggested by Eylon and Bohr model while some gave answers that weredifficult Linn‘ are based on teaching by a more learner-centered to attribute to any recognisable modelof atomicstructure. or constructivist teaching approach. Interestingly, other Theresults presented here are far from rigorous, but they educators have reported that less content is covered when indicate of a lack of understanding of a fundamental and teaching by a constructivist approach,whichfits in with comparatively simple scientific concept. Since the Bohr reducing our emphasis on content coverage.” modelis not taughtinfirst-year chemistry, it seemslikely that this model of the atom represents prior knowledge Theviewthat teachinginstitutions should teach less mate- that our senior students are bringing to the classroom." rial and instead focus on developing greater learning skills ATOMIC STRUCTURE is gaining increasing attention at tertiary teaching institutions in this country.??*It also has been suggested that the | In the space below, please draw a sketch of what you increasing ease of access to sources of information such understand the to be an appropriate representation for | as the Internet means that fewer educators should place | the electronic structurefor the: emphasis on the mere provision of factual material, and | Hydrogen Atom: greater emphasis on higher-level cognitive skills."

The overall focus for us, as chemistry teachers, should be | to have clear aims and objectives for individual courses | Carbon Atom: and degree programs. In other words, what we needis a clear picture of what knowledge andskills we want our students to possess upon graduation, and what instructional strategies we need to implementin order to achieve Fig. 3. Atomic structure questionnaire for third-year chemistry students. those aims. Research into learning and instruction sug-

Chemistry in New Zealand January 2008

Fighting Food Fraud with Science Bea Perks Deputy Editor, Chemistry World, Royal Society of Chemistry, Thomas Graham House,Science Park, Milton Road, Cambridge CB4 OWF, UK

Text reproduced from Chemistry World, 2007, 4(9), 48-52 by permission of The Royal Society of Chemistry (http://www.rsc.org/chemistryworld/Issues/2007/September/FightingFoodFraudWithScience.asp).

Does your extra virgin olive oil come from a Tuscan tor of the Packaging for Food and ProductProtection Initia- grove? Is your cappuccino made from the finest Ara- tive at Michigan State University, US, estimates the cost to bica beans? Bea Perks meets some of the scientists sub- the global food industry at $49 billion (£25 billion). ‘In the UK,the Food Standards Agency (FSA)estimates the level of jecting our food’s credentials to forensic examination. fraud at 10%, equating to around $7 billion,’ he says. Goneare the daysofreading the word,‘oliveoil’ in a recipe, Distinguishing pure from adulterated cod liver oil would andtrotting downto the pharmacist for a very tiny bottle of certainly take an expert consumer, and even that might be ‘Olive Oil BP’. Today, supermarket shelves heave under the a doddle compared with distinguishing pure from adulter- weight of a bewildering choice ofolive oils - from a fruity ated bee propolis. Bee propolis, for those not familiar with Ornellaia (‘marvellous for salads’) to a light Ligurian (‘ideal the stock oftheir local health food store, is a by-product of for deep-fried zucchini flowers’... yes, really). Andit’s not honeyproduction.It is a wax-like substancethat bees collect just olive oil. There was a time when people bought, simply from buds, and then use as a sort of cement for hive main- ‘beef’ or ‘chicken’. Now youcan choose where yourdesired tenance. Whennotblocking out drafts in beehives, propolis animallived, or whatit ate (mountain reared, corn fed). And is a popular food supplement or ointment ingredient. It is so it continues - where did the cow live that produced the reputedto alleviate a longlist of ailments including inflam- milk used to make the cheese? mation,viral diseases, ulcers, burns- the list goes on. ’Thebig problem’, says food scientist Peter Berry Ottaway, But the genuinearticle is not easy to identify. Propolis can be a consultant at the UK Institute of Food Science and Tech- more orless any colour fromgreen to red, and it is expen- nology,‘is that any high value ingredienthasa risk of being sive - 25 mL ofa solution of unspecified concentration costs adulterated.’ So how are the fakes wheedled out from the about £10 - making it a fraudster’s dream. genuine- free-range, mountain-reared,organic- articles? Bees have even been known to make fraudulent propolis Ottaway’s workisa starkillustration ofthe lengths scientists themselves, sometimes exploiting window putty in place of mustgoto in orderto prove, or disprove, a product’s authen- plant bulbs. Forensic analysis of propolis has shown that the ticity. He oncetravelled to the Arctic Circle in search of cod genuinearticle - not even meddled with by the bees them- and the plankton they eat - to determine if cod livers were selves - contains distinct proportionsofparticular flavonoids the single source ofa particular brand of cod-liveroil. ‘It’s (plant metabolites): a discovery that could help nail genuine very expensive and there’s a huge temptation to cut it with fraudsters, and improvepropolis quality overall by flagging rapeseedoil,’ he explains. up the window putty varieties. The fatty acid profiles for the plankton, cod, and rapeseed weren’t far apart, he recalls. But the picture changed when Technological Revolution he looked atsterols. The sterols foundin the Arctic plankton Fraudsters have capitalised on the variety and popularity of werethe sameasthesterols in the cod, but werenot the same as the sterols in rape seeds. Whenheanalysed the cod liver oil using HPLC he spotted ‘there was something fishy - or not quite so fishy’ going on.

The alarm bells had rung in the first place because the amountofcodliver oil leaving the processing plant was mi- raculously greater than the amountof codliver entering the plant. Theoil turned outto be about 12 or 13 % rapeseedoil, says Ottaway. The Perfect Crime Oneofthe greatest problems facing this branch of criminal investigation - food forensics - is that consumers can’t al- / =" A waystell when they’re being defrauded. The product might Left: The Manufacture ofOil, drawn and engraved by J. Amman taste similar, will probably look similar, will cost about the in the Sixteenth Century (http://upload.wikimedia.org/wikipe- same, and will not necessarily do the consumer any harm dia/commons/8/88/The_Manufacture_of_Oil_drawn_and_en- (apart from financially). For the samereasonit’s difficult to graved_byJ Amman_in_the_Sixteenth_Century.png) and right: say quite how widespread the problem is. John Spink. Direc- Italian olive oil: (http://upload.wikimedia.org/wikipedia/commons/e/e9/Italian_olive_oil_2007.jpg) 22

Chemistry in New Zealand January 2087

health products. Onestudyinstigated A hostofcertification systems,like at the behest of Dutchtradeofficials the PDO enjoyed by buffalo moz- discovered that a third of products zarella, exist to prove the worth of purporting to contain pure aloe vera olive oils - from PDO, to protected (a plant sap used to treat a wide vari- geographical indication (PGI) and ety of medical complaints) had been traditional speciality guaranteed adulterated. The evidence for this (TSG). They are important awards particular study came from what was recognised by the European Union then a new chapterin food forensics: referring to the quality of the olive nuclear magnetic resonance (NMR). oils. ‘Before such awardsare given, regulations imply detailed rules on Aloe vera comprises three main com- the [olive] varieties to use, the geo- ponents: glucose; malic acid; and the graphical area of production, and polysaccharide acemannan, whichis the methodsofoil extraction,’ write composed ofa long chain ofmannose Expensive coffee beans are subj ect to fraud Doveri and colleagues in a report of monomers. On average, each man- their findings (S Doveri et al. J. Agric. Food Chem. 2006, nose monomerring has one acetate group attached to one 54, 9221). ‘As these labels reflect quality products they are of three available positions, explains Germanfood scientist awarded to commandprice premiums.’ Berndt Diehl, who discovered that the NMRprofile ofthese different acetate groups represented an exactfingerprint for PlantPaternity Testing aloe vera. ‘Manipulation ofthis signal is practically impos- Chemicalanalysesperse are notsufficientto sible,’ Dieh! wrotein a report of his findings back in 1998. verify olive oil authenticity, except in cases of adulteration with other veg- Today, NMRisjust one of a long-list of food forensics tech- etable oils, notes Doveri. So DNA markers - unique, short niques you might expect to find in a CSI -style forensics sequences ofDNAthatcan be usedtoidentify olive cultivars lab. - are increasingly being applied to solve provenanceissues.

Fingerprinting Food There is a significant drawback to this, she says, because whole olive fruits are crushed in the milling process. The Earlier this year, Italian researchers reported their findings stone inside each olive fruit is an embryo, and has almost using the polymerase chain reaction (PCR)to study mozza- certainly been fertilised with pollen from anothercultivar. ella. PCR is a molecular biology technique used to replicate “Questions about paternal DNAonthe geneticprofiles need and amplify a small fragment of DNA.Inthis case, it was to be addressed before DNA markers can be used with con- used to detect and quantify rogue cow DNA in mozzarella fidence,’ she notes. labelled as being made frompure water-buffalo milk (R M Lopparelli et al. J. Agric. Food Chem. 2007, 55, 3429). Doveri says her group was the first to compare the DNA inleaves,olives and oil from a singleolive tree. What they Buffalo mozzarella is a highly sought-after Italian product showed was that DNAin a leaf from the olive tree didn’t certified by the European Protected Designation of Origin match DNAin the oil. It’s not an insurmountable problem, (PDO). Mozzarella can be made from cow’s milk, but it she says, becausecertified oils that are grown in specific re- wouldn’t get PDO certification and wouldn’t cost anywhere gions may well havea limited, specific, number of possible near as mucheitherto makeorindeedto buy. This has tempt- pollinators - in which case such analysis might further sup- ed food fraudsters to slip at least some cow’s milk into the mix. port an oil’s authenticity. But future analysis might be safer if restricted to specifically maternal markers - such as those found in Barbara Cardazzo and colleaguesat the University of Padua mitochondrial DNA (whichis only inherited from analysed 64 commercially available ‘buffalo’ mozzarellas the mother). byreal-time PCR,and foundthat mostof the samples were contaminated Black or White? with cow’s milk. The researcherssay that their PCR technique, looking for a cow milk-specific gene, is a Another classic example of an expensive food product vul- marked improvementonthe current control method,isoelec- nerable to fraud is coffee, one of the most important food trofocusing of milk proteins (separating the proteins accord- commodities in world trade, according to Gregory Tuckerat ing to their net charge by passing them through a gel). This the University of Nottingham, UK. The commercial coffee can generate inaccurate results if the cheese has been sub- trade consists almost entirely of Arabica and Robusta cof- jected to high heats, e.g. when the milk is pasteurised. fee varieties, with Arabica considered the highest quality and, naturally, the most expensive. Arabica beans cost two But PCRalso needsto be applied with care, warn researchers in the UK.Silvia Doveri and colleagues at the National In short Institute of Agricultural Botany in Cambridge showedthat + Food fraud is a growin : industry hundredsof the genetic profile of olive oil isn’t necessarily the same as millions of poundsevery yea + Foods that of the olivefruit. It could be a serious problem for any- and supplements inclu q mozzarella and coffee havebee onetryingtotell if their fruity Omellaia extra virgin oliveoil + Avariety of chemical techniques b (about £10 for 500 mL)really did comefromthe 2000 olive rensic scientists, including NMRandge! analysis trees on the Ornellaia estate in Tuscany. to the DNAfingerprinting usedin criminal cases"

Chemistry in New Zealand January 2008

to three times as much as Robusta beans andconstitute more causing those differences...’, says Adrian Charlton, head of than 70% of the world’s coffee production - so ensuring that the NMRfingerprinting team at CSL and a key researcher inferior Robusta beans don’t get into Arabica production in Trace. chain is essential. Ten years ago there was muchless media interest in food Mostcurrent methodsto discriminate between Arabica and authenticity. But nowadays there’s a much more discerning Robusta coffees fall under the analytical/instrumental head- consumer- who makestheir purchases based on whatBrere- ing, says Tucker. Pure varieties are distinguished accord- ton calls “quality attributes’. These might be attributes that ing to profiles of analytes such as sterols, fatty acids, and the consumercares about deeply, but they can’t always iden- total amino acids. Mixtures are characterised using Fourier tify unaided, such as: provenance; production (GM,organic, transforminfrared spectroscopy. The beanscontain different free range); ethical issues (animal welfare, fair trade); and amounts of the two main coffee compounds- chlorogenic sustainability (food miles). acid and caffeine - which have distinctive infrared spectra. Brereton’s team recently developed ananalytical method to DNA-based analysis is new to coffee authentication, but identify corn-fed chicken - chickens that commanda higher Tucker and colleagues say their work on PCR analysis and price asa result of theirrelatively luxurious diet. The method lab-on-a-chip capillary electrophoresis offers a quick and exploits the differences between the biosynthetic pathways straightforward methodsuited to routine coffee analysis. that exist between maize (C4 pathway) and temperate cere- als such as wheatand barley (C3 pathway). C3 and C4plants Tucker’s team used PCR coupled with restriction fragment provide markedly different '°C/'?C ratios when measured us- length polymorphism (RFLP), where amplified DNAis cut ing stable isotope ratio mass spectrometry. Comparison with at specific sites along its sequence - using so-called restric- a databaseofresults from chickens fed differing maize diets tion endonucleases- in order to determine, in this instance, provides an objective means of confirming that a chicken particular coffee varieties. PCR-RFLPis a classic forensic was fed on corn (maize). technique, equally at home in murder cases and paternity testing as it is in food authentication. It is an essential com- The CSL has workedin this area for 20 years: ‘15 years ago ponent of DNAfingerprinting. our main focus was in developing methods to prevent the [European] Commission getting defrauded through aspects Tucker’s method combined PCR-RFLPwith capillary elec- of the Common Agricultural Policy — sugar mountains and trophoresis to separate individual genes and quantify adul- wine lakes andall that — whereas the consumeris the focus teration in green (unroasted) coffee beans. A genetic marker now,’ says Brereton. in chloroplast DNA, which is maternally inherited like mitochondrial DNA, was foundto differentiate Arabica from Working out whether consumers are being taken for a ride Robusta varieties. looks set to focus national andinternational authorities and relevant experts for years to come. The FSA alone currently The Forensic Approach spends approximately £1 million each year on its food au- Mostofthe above methodsare targeted procedures, only ap- thenticity research programme. plicable to one commodity and/or one type of fraud. But a ‘History has taught us that wherever there is a large price pan-European effort is underway to develop more generic difference between two similar products and no objective proceduresfor tracing and verifying food, by scientists with- means of checking is available, fraud can take place,” he in the Trace consortium, a €19 M (£13 M) European Com- stresses. missioninitiative. “The international team of scientists within the project are developingfoodmapping proceduresthat will So you mightthink that a professional food detective would allow provenance claims to be more easily checked,’ says religiously scan the supermarketshelves for reputable labels Paul Brereton from the UK Department for Environment, before buying. ‘No,in terms of food shopping,I tend to be Food and Rural Affairs’ (Defra’s) Central Science Labora- a sceptic,’ says Brereton. ‘I buy based on what tastes good tory in York, the co-ordinator of Trace. They are attempting rather than what’s on the label.’ to link key parameters in food with those foundin the local environment. By studying the climate and geology,the sci- Acknowledgements entists aim to predict what profile of parameters should be Weare gratefull to Mark Peplow (Editor, Chemistry World) expected in a food of given provenance. It is thenrelatively for facilitating reproduction of the text and Martin Howard, easy to checkif the actual profile of the food matches with ESPRESSOWORKZ LTD., Mt Eden, Auckland (www. that predicted. espressoworkz.co.nz) for providing the coffee beansart- Alongside food mapping, Trace is also producing spectro- work. scopic and biological fingerprinting methods that can be Further Reading used to verify food. The increased power of data capture and interpretation techniques developed in recent years al- 1. Trace project: www.trace.eu.org/index.php Central Science Labora- tory: www.csl.gov.uk. lows atypical samples to be rapidly identified. This is ideal for a food verification system as it allows a more forensic 2. FoodStandards Agency: www.food.gov.uk. approach to authenticating food. ‘Rather than us having to 3. Institute of Food Science and Technology: www.ifst.org. know whattypeoffraud is taking place, we can now quickly look for differences between products and identify what is 24

Chemistry in New Zealand January 2087

MALDI-TOF Mass spectrometry of Cyanobacteria: a Global Approachto the Discovery of Novel Secondary Metabolites Jonathan Puddick and Michéle R. Prinsep Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton 3240 (e-mail: [email protected])

Cyanobacteria (blue-green algae) are a group of ancient cused on obtaining quantitative data on the metabolites prokaryotic organismsdating back betweenthree and four present, therefore the potential of these methods as dis- billion years.' They have beenattributed with oxygenat- covery tools is limited. Analysis by high performance ing the earth’s atmosphere? but, since the anthropogenic liquid chromatography (HPLC)is hindered by a lack of euthrophication of lakes, ponds and oceans, they have commercially available standards" so that time is wasted become synonymous with water hygiene issues.’ This is isolating known metabolites. Bioactivity-directed isola- due to the alteration of the nutrient composition of their tion has proved to be very effective in the past8 but again habitat to one which is optimal for growth (or blooms). limits the researcher to detecting molecules possessing a Cyanobacterial blooms may simply cause foul tastes and certain activity. More powerful still is liquid chromatog- odours,* but they can also lead to the production of toxic raphy-mass spectrometry (LC-MS). Here, one can sepa- secondary metabolites poisonous to humans and animals rate the components in a complex mixture and obtain their uponingestion.’ NZ hasyetto suffer a human fatality, but relative molecular masses. This allows one to assess the the deaths of several dogs in Wellington wasattributed to potential novelty of a compoundaccording to both mass homoanatoxin-a 1 (Chart 1) from a Phormidium species.® and elution timepriorto large-scale purification and characterization. Most LC-MSinstruments allow for tandem Althoughtoxins are the most highly publicized cyanobac- MSthat enables structural clues to be deduced and the terial secondary metabolites, a vast array of compounds identity of known moleculesto be confirmed.'’ However, are produced which rangein size, structure, and bioac- separation by HPLC involves costly and time consum- tivity. Terrestrial cyanobacteria have yielded diterpenes ing sample preparation and, due to long run times, high such as the anti-inflammatory tolypodiol 2,’ and the anti- throughput can be cumbersome. Analysis of cyanobacte- microbial comnostins® such as comnostin B 3, in addition rial extracts by matrix assisted laser desorption ioniza- to other unusual metabolites including tolyporphin A 4 (a tion-time of flight (MALDI-TOF) MS can provide com- porphyrin-like compound with multi-drug resistance re- parable data to those from LC-MSbut with far simpler versal properties)’ and the ambiguenes, e.g. ambiguene F sample preparation. 5, whichare antifungal chlorinated alkaloids (Chart 15," MALDI-TOFproducesions from laser irradiation of a Chart 1 sample co-crystallized with a matrix; the laser energy is absorbed and passedto the analyte molecules. This method of ionization predominantly produces singly protonated ions to ca. m/z = 5000,a range which encompassesthe oligopeptides. Thus complex mixtures can be analyzed 1, homoanatoxin-a 2, tolypodiol A from a minute amount ofsample withoutprior separation, andtherelative molecular mass of each component present deduced from the protonated molecularions." Cyano- bacterial extracts are assessed simply from mixing with the matrix, application of the mix to a target, and spectral recording. The advantages described above make MALDI-TOF 4, tolyporphin A 5, ambiguene F screening of cyanobacterial extracts particularly useful in the discovery of novel secondary metabolites. Due to The major class of secondary metabolites produced by the high sensitivity, low sample volumes, and speed of cyanobacteria is that of the oligopeptides, which are syn- analysis, environmental samples can be assessed for the thesised by non-ribosomal peptide synthetases.'' These presence ofnovel compoundspriorto culturing. Evensin- can be dividedinto six families depending ontheir struc- gle cyanobacterial colonies can be analysed by suspend- tural characteristics,'? namely the aeruginosins, the mi- ing them directly in matrix solution.!? Novel compounds croginins, the anabaenopeptins, the cyanopeptolins, the are easily detected using this method by comparing the microcystins, and the microviridins, as exemplified by component masses recorded with those in an appropriate metabolites 6-11 of Chart 2. database. If the mass spectrometer is also equipped for the analysis ofpost source decay (PSD)species,it is then In the past, oligopeptides have been detected via enzyme- analogous to LC-MS with tandem MS,and the presence linked immunosorbentassays, enzymeinhibition assays, of known compoundscan be confirmed from the masses or according to their toxicity.!> These assays have fo- of the fragment ions produced.

Chemistry in New Zealand January 2008

Chart 2 HO,S-O 3 2 4 oo

cl en N. toa HO OH ° OFNNNy ee H NH 6, aeruginosin 98-A

O° eekMe Pak ae x Yo tie °

‘ a H J 9, microcystin-LR Me HN N. Pr 8, microginin HNN 2 4 ou° 4 OH ow’ HN a, 4NH Me

10, microviridin A 11, cyanopeptolin A Pri“ ~N “Me

Since cyanobacterial oligopeptidesare already well char- the German workers, we too have been able to deduce acterized, PSD allows for partial characterization of any mostofthe structure of a new metabolite using MALDI- novel compounds discovered. Often the subclass of oli- TOF MS,namely anabaenopeptin 906, 13. gopeptide present can be deduced by the presence of di- An environmental sample containing cyanobacteria was agnostic fragmentions in the spectrum,e.g. the presence collected from a North Island lake. The MALDI-TOF of a m/z = 135 ion (PhCH,CHOMe”) is characteristic of 2S,3S,85,9S-3-amino-9-methoxy-2,6,8-trimethyl-10- MS(Fig. 1) showed the presence of several known com- poundsas well as an unknown metabolite with m/z = 907. phenyldeca-4£,6E-dienoic acid (Adda, 12), the unique The PSD spectrumofthis m/z = 907 ion is shownasFig. amino acid found in microcystins.'® The low mass daugh- 2 and the loss of 200 Dais clear. This is diagnostic for ter ions indicate the aminoacids present in the molecule, an anabaenopeptin possessing an arginine side-chain. The while those at higher mass can indicate how the amino low mass/chargespeciesindicate the presence of arginine acids are joined together. (Arg; m/z = 70), lysine (Lys; m/z = 70, 84), isoleucine Oligopeptide characterization by MALDI-TOF MS has (Ile; m/z = 86), methylleucine (MeLeu; m/z = 100), and been undertaken successfully in Germany. Using the methylhomotyrosine (MeHTyr; m/z = 107, 164). Thus, approach described above, von Dohren and co-workers five of the six amino acids present in the anabaenopeptins were able to characterize a range of oligopeptides includ- are identified, with the missing mass/charge entity cor- ing aeruginosins, microginins, anabaenopeptins, and cy- relating with that of a phenylalanine (Phe) residue. This anopeptolins, whilst assessing the oligopeptide diversity also matches well with anabaenopeptin G, 7 in thatits of different cyanobacteria. They deduced structures for massis only 2 Dahigherthan the new 13; it corresponds anabaenopeptin G, 7 (Chart 2) and anabaenopeptin 820 to the loss of a hydroxyl group from the tyrosine in posi- from analysis of the PSD fragments.'*'* tion 5, and an additional amino methylation on HTyr in position 3. The anabaenopeptins are cyclic peptides containing six aminoacids. Each contains a D-lysine unit that has an ure- The higher mass fragments provide the sequence of the ido bondto a carbony]thatis linkedto a side-chain amino ring amino acids in 13. Thus, the m/z = 275 fragment acid. The D-lysine also forms a secondary peptide bond shows that the Phe is joined to the MeLeu and the m/z = which encloses the ring. The CO-linked side-chain and 449 fragment showsthat the Phe is also attached to the the ring amino acids vary as does their degree of amino Lys, thus placingit in either position 3 or 6. The m/z = methylation.’ There are 21 published structures of ana- 466 fragment can then be used to show that MeHTyris baenopeptins andthesearelisted in Table 1. The different attached to MeLeuas Pheis already attached to both Lys compoundshavevariedbiologicalactivities including re- and MeLeu. This gives a final sequence of Ile-MeHTyr- laxation of norepinephrine-induced contraction,” protein MeLeu-Phe, and supports the presence of an Ile-MeHTyr phosphataseinhibition, and protease inhibition.*’** Like fragmentat m/z = 305. 26

Chemistry in New Zealand January 2087 Chemistry in New Zealand August 2007

Table I. Amino acid sequence of the known Anabaenopeptinsa

Compound Mr(Da) 1 3 4 5 6 Ref. Anabaenopeptin A 843 Tyr Val HTyr MeAla Phe 20 Anabaenopeptin B 836 Arg Val HTyr MeAla Phe 20 Anabaenopeptin C 808 Lys Val HTyr MeAla Phe 25 Anabaenopeptin D 827 Phe Val HTyr MeAla Phe 25 Anabaenopeptin E 850 Arg Val MeHTyr MeAla Phe 26 Anabaenopeptin F 850 Arg Tle HTyr MeAla Phe 26 Anabaenopeptin G 908 Arg Tle HTyr MeLeu Tyr 18 Anabaenopeptin G* 929 Tyr lle HTyr MeHTyr Tle 23 Anabaenopeptin H 922 Arg Tle HTyr MeTyr lle 23 Anabaenopeptin I 759 Ile Val HTyr MeAla Leu 22 Anabaenopeptin J 793 Tle Val HTyr MeAla Phe 22 Anabaenopeptin T 865 He Val HTyr MeHTyr Tle 24 | Anabaenopeptin KT864 864 HArg lle HTyr MeAla Phe 27 Anabaenopeptin 820 820 Arg Val HPhe MeAla Phe 12 Ferintoic Acid A 866 Trp Val HTyr MeAla Phe 28 Ferintoic Acid B 880 Trp Tle HTyr MeAla Phe 28 Nodulapeptin A 929 lle Met(O,) HPhe MeHTyr Ser(Ac) 29 Nodulapeptin B 913 Tle Met(O) HPhe MeHTyr Ser(Ac) 29 Oscillamide B 868 Arg Met HTyr MeAla Phe 21 Oscillamide C 956 Arg Tle HTyr MeHTyr Phe 21

Oscillamide Y 857 Tyr Tle HTyr MeAla Phe 21

“Numbering for anabaenopeptins amino acids is as for 7 of Chart 2;, D-Lysis omittedasit is always presentin position 2 in the known anabaenopeptins.

Table 2. Fragment ions of anabaenopeptin 906 observed by None of the fragments observed confirm PSD. the order in which the aminoacidsare presentin the ring and whether Ile or Phe is located at position m/z_ Sequence 3. The structure proposed | as 13 has been constructed according to the sequences 70. Arg/Lys-related ion of presently known anabaenopeptins, where Phe is com- 84 Lys-Immonium ion monly seen at position 6 and an aromatic amino acid,

86 Ile-Immoniumion such as HTyr, is always at position 4. This illustrates the limitation 100 MeLeu-Immonium ion in characterizing secondary cyanobacterial metabolites by MALDI-TOF 107 Tyr-side chain MSas,at times, the com- |

plete structure cannot be elucidated and stereochemistry 112 Arg-Immonium ion | can never be deduced. Ultimately, full characterization of 129 Arg-Immoniumion | these novel compounds requires purification and NMR

164 MeHTyr-Immoniumion spectroscopicinvestigations. |

175 Arg + 2H The screening of cyanobacterial extracts 201 CO+Arg for oligopeptides | by MALDI-TOFMSis a very powerful technique that 275 MeLeu+ Phe + H canlead to the discovery of new compounds.It is simple, |

305 Ile + MeHTyr + H quick and inexpensive. Its use requires only a minute amount 449 Arg+CO+Lys + Phe -CO+2H of sample that gives a rapid assessment of the presenceor absence of novel metabolites. 466 MeHTyr + MeLeu + Phe +H

579 Ile ++ MeHTyr + MeLeu + Phe +H Acknowledgements

594 Lys + Phe + MeLeu + MeHTyr + 2H Thecontribution of Susanna Wood (Cawthron Institute, Nelson)

603 Arg + CO +Lys + Phe + MeLeu+H is gratefully acknowledged.

707 Lys + Ile + MeHTyr + MeLeu + Phe +2H References 907 |M+H I. Schopf, W.J.; Packer, B. M. Science 1987, 237, 70-72. |

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_| Chemistry in New Zealand January 2008

4 10 |. Smitka, T. A.; Bonjouklian, R.; Doolin, L.; Jones, N. D.; et al. J. Org.

Chem. 1992, 57, 857-861. Pel ul . Welker, M.; von Dohren, H. FEMS Microbiol. Rev. 2006, 30, 530- 7 563. 12. . Welker, M.; Brunke, M.; Preussel, K.; Lippert, I; von Dohren, H. Microbiol. 2004, 150, 1785-1796. 13, . Xu, L. H.; Lam, P. K. S.; Chen,J. P.; Xu, J. M.; ef al. Chemosphe- re 2000, 41, 53-58; Domingos, P.; Rubim, T. K.; Molica, R. J. Rs Azevedo, S. M. F. O.; Carmichael, W. W. EnvironToxicol. 1999, 14, 31-35. 14 . Mountford, D. O.; Holland, P.; Sprosen, J. Toxicon. 2005, 45, 199- 200. 15, . Jemal, M. Biomed. Chromatogr. 2000, 14, 422-429. 16 . Welker, M.; Fastner, J.; Erhard, M.; von Dohren H. Environ. Toxicol. 2002,17, 367-374 17 . Welker, M.; Marsalek, B.; Sejnohova, L.; von Dohren, H. Peptides 2006, 27, 2090-2103. 18 . Erhard, M.; von Dohren, H.; Jungblut, P. Rapid Commun. Mass Spec- trom. 1999, 13, 337-343. 19. . Erhard, M.; von Dohren, H.; Jungblut, P. Nat. Biotechnol. 1997, 15, 906-909. 3} 20. . Harada, K.; Fujii, K.; Shimada, T.; Suzuki, M.; e¢ al. Tetrahedron Lett. 1995, 36, 1511-1514. 21 . Sano, T.; Usui, T.; Ueda, K.; Osada, H.; Kaya, K. J. Nat. Prod. 2001,

64, 1052-1055. Fig. 2. The MALDI-TOF PSD spectrum of m/z = 907 from 22 . Murakami, M.; Suzuki, S.; Itou, Y.; Kodani, S.; Ishida, K. J. Nat. Prod. 2000, 63, 1280-1282. Fig. 1. 23. Itou, Y.; Suzuki, S.; Ishida, K.; Murakami, M. Bioorg. Med. Chem. Lett. 1999, 9, 1243-1246. 2. Whitton, B. A.; Potts, M. The ecologyof cyanobacteria, their diver- sityin time and space Kluwer: Dordrecht, Netherlands, 2000. 24. Kodani, S.; Suzuki, S.; Ishida, K.; Murakami, M. FEMS Microbiol. Lett, 1999, 178, 343-348. 3. Chorus, L.; Bartram,J. Toxic cyanobacteria in water: a guideto their public health consequences, monitoring and management Spon: Lon- 25. Fujii, K.; Harada, K.; Suzuki, M. Occurrence ofnovelcyclic peptides don, 1999. together with microcystins fromtoxic cyanobacteria, Anabaena species In: Harmful and Toxic Algal Blooms Yasumoto, T.; Oshima, Y.; 4. Jones, G. J.; Korth, W. WaterSci. Technol. 1995, 31, 145-151. Fukuyo, Y. (Eds.) Intergovernmental Oceanographic Commission of 5. Codd, G. A.; Morrison, L. F.; Metcalf, J. S. Toxicol. Appl. Pharmacol. UNESCOParis, 1996, 559-562. 2005, 203, 264-272; Azevedo, S. M.; Carmichael, W. W.; Jochimsen, 26. Shin, H. J.; Matsuda, H.; Murakami, M.; Yamaguchi, K. J. Nat. Prod. E. M.; Rinehart, K. ., etal. Toxicology2002, 181-182, 441-446. 1997, 60, 139-141. 6. Wood, S. A.; Selwood, A. I.; Rueckert, A.; Holland, P.T.; et al. Toxi- 21 . Beresovsky, D.; Hadas, O.; Livne, A.; Sukenik, A.; ef al. Isr. J. Chem. con. 2007, 50, 292-301. 2006, 46, 79-87. 7. Prinsep, M. R.; Thomson, R. A.; West, M. L.; Wylie, B. L. J. Nat. 28. Williams, D. E.; Craig, M.; Holmes, C. F. B; Andersen, R. J. J. Nat. Prod. 1996, 59, 786-788. Prod. 1996, 59, 370-575. 8. Jaki, B.; Orjala,J.; Heilmann,J.; Linden, A.; e¢ al. J. Nat. Prod. 2000, 29, Fujii, K.; Sivonen, K.; Adachi, K.; Noguchi, K.; et al. Tetrahedron 63, 339-343. Lett. 1997, 38, 5525-5528.

9. Prinsep, M. R.; Caplan, F. R.; Moore, R. E.; Patterson, G. M.; Smith, C.D. J. Am. Chem. Soc. 1992, 114, 385-387.

... continuedfrom page 7 + Branch on The Rise and Fall of IRL versity. successfully defended their PhD re- BioPharm:the good, the bad and the searches (The Design and Synthesis Dr Kathryn McGrath attended the ugly - a personal view. of Hybrid Peloruside A-Laulimalide 2007 International Soft Matter Con- Analogues and An Aldol Approach ference (Aachen, Germany) in Oc- Towards the Synthesis of Peloruside Victoria University tober. She gave an oral presentation AandAnalogues Thereof) in the week Recent visitors to the School have Dynamic Processes in Emulsion and of 8 October. Their studies were per- included alumnus Dr Paul Kilmar- a poster Cell Membrane Dynamics formed under the joint supervision of tin (Auckland University) who spoke during Exocytosis in Gonadotrophs Joanne Harvey and Paul Teesdale- on new applications for conducting based on the workof her former MSc Spittle; John Hoberg had supervised polymers, providing an overview of student Pascale Savigny. Shivali prior to his departure. the recent work at the Polymer Elec- Emma Turner and Shivali Gulab tronics Research Centre at the Uni-

Chemistry in New Zealand January 2087

The 2007 NobelPrize in Chemistry

The Chemistry Laureate for 2007 was Gerhard Ertl, an Emeri- tus Professor and retired director of the Max-Planck Fritz Haber Institute in Berlin. The award recognises his successes in providing detailed descriptions of how chemicalreactions take place on surfaces, studies that have laid the foundation of modern surface chemistry. He is awardedthe prize for showing howreliable results can be obtained for such chemicalprocesses.

Ertl, a Germanbybirth, gained his PhD in physical chemistry in 1965 from the Technical University in Munich. In 1986 he suc- ceeded Heinz Gerischeras director of the Departmentof Physical Chemistry ofthe HaberInstitute and was appointedScientific Fel- low. His research focuses on structure and chemicalreactionsat solid surfaces. He has received more than 60 awards for his work, the latest being the NobelPrize.

Introduction to both heterogeneous catalysis and to processes at the Despite the stereotypical image of the chemist holding a air-water interface. test tube in which a numberofchemicals have been mixed After Langmuir, there waslittle progress in the study to produce a new compound, we know that much more of chemical processesat surfaces because two information is needed to understand how a chemical reac- majordiffi- culties had to be overcome.Firstly, tion actually occurs. The branch of chemistry concerned it was, andstill is, notoriously difficult to prepare surfaces of with reactionsonsolid surfaces — surface chemistry - de- controlled composition and morphology. Secondly, mands advanced dust-free laboratories and sophisticated there were few experimental techniques that enabled the direct electronic instrumentation, coupled with advanced meth- moni- toring of molecular events at the odology and great precision. It is neither straightforward surfaces. Instead, the researcher had to rely on measuring the chemical nor cheap! But surface reactions play such a vital role composition in the gas phase outside the surface. in both chemical industry and natural systems that they Inferences can be made about molecular surface events demand to be studied. Knowledgeof surface chemistry from such studies, but the information is uncertain. A can help explain such diverse processes as whyironrusts, transformation of the whole field was triggered by how artificial fertilizers are produced, how the catalyst the emergence of semiconductor technology during the 1950s in a car’s exhaust pipe works, and why chemical reac- and 60s, when methodsfor handling surfaces tions on the surfaces ofice crystals in the stratosphere under high vacuum conditions were developed. Furthermore, are causing the O,layer in the atmosphereto deteriorate. a number of new methods of studying surfaces under high vacuum Knowledge about chemicalreactions on surfaces helpsto conditions emerged. These developmentsled produce renewable fuels more efficiently and create new to the estab- lishment materials for electronics. of surface science, a research discipline that has attracted scientists with backgroundsin condensed matter Surface chemistry:a brief history physics, physical chemistry and chemical engineering. By the end ofthe 1960s a numberofscientists had cometo Chemical processesat surfaces and interfaces have a long realize that useful tools for studying molecular processes history. One half of the 1912 Nobel Prize was awarded at surfaces had becomeavailable. They hoped that these to P. Sabatier for his method ofhydrogenating organic tools would continue to improve so as to enable really compounds in the presence. offinely disintegrated met- detailed chemical studies of reactions at surfaces to be als whereby the progress of organic chemistry has been undertaken. greatly advancedin recentyears. It waslater realized that the crucial molecular eventis the adsorption of H, mol- Precisely because surfaces are so very chemically active, ecules on the metal surface, where they are dissociated it is difficult to keep them clean enough to study a specific into the constituent atoms. Refined, the method remains reaction - oneofthe reasons that precision combined with a standard procedure for hydrogenation of organic mol- a high vacuum system is essential for success. In air, any ecules. Heterogeneouscatalysis was also central to the surface is immediately covered by molecules from the award of the Nobel Prize to Fritz Haber in 1918 for the gases present. Ertl displayed a unique understanding of synthesis ofammonia fiomits elements. Despite technical how to makeuse ofdifferent experimental technologies, improvements, the same basic conceptis used in today’s and he incorporated new technologiesin his palette in or- process. In 1932 Irving Langmuir was awarded the prize der to produce as complete a picture as possible of the re- for discoveries and investigations in surface chemistry, in action underinvestigation. Apart from generating impor- which he made a range of seminal contributions relevant tant knowledge about specific reactions, he constructed, «ho

Chemistry in New Zealand January 2008

above all, a methodology that other researchers have been more precise experiments and more detailed theoretical able to apply to completely different surface reactions. descriptions. Thus, the study of chemical reactionson sur- Initially, Ertl studied the behaviour of H2 on metal surfaces provides one route towards a deeper understanding faces and his studies of fundamental molecular processes of reactions in condensed phases in general. at the gas-solid interface were particularly thorough. Ertl’s contributions to surface chemistry When a small molecule hits a solid surface from a gas Sabatier’s workleft a long-standing question of how H, phasethere are twopossible outcomes. The molecule may is organized on metals like Pd, Pt and Ni. This question simply bounce back or it can be adsorbed. It is the lat- is relevant not only for understanding the hydrogenation ter case that raises the most interesting possibilities. The of organic molecules, but also how hydrogengas is used interaction with the atomsofthe surface can be so strong or produced at metal electrodes in many electrochemical that the moleculedissociatesinto its constituent groups or processes. By combining experimental studies using low atoms. The molecule can also react directly with surface energy electron diffraction (LEED) with measurements groups and changethe chemicalproperties of the surface. of desorption, and also using modeling, Ertl was able to A third possibility is that the adsorbed molecule encoun- provide a quantitative description of how hydrogenis ex- ters another previously adsorbed one andthere is a binary posed onthe metal surfaces.' This was highly relevant to chemicalreaction on the surface. the then current discussion of catalytic mechanisms. Ertl not only gave answers to a numberofthat had been posed Very importantpractical situations exist where these sce- for a long time, but also demonstrated how one could uti- narios are the key chemical events; heterogeneous catal- lize the LEED method in combination with other experi- ysis has been central to the chemical industry for more mental approaches. The most relevant chemical questions than a century. Since 1913, agriculture has been supplied clearly needed more than one method. His approach to with fertilizers rich in nitrogen, produced by the Haber- science is that when new opportunities appearedhe revis- Boschprocessin whichN,gasis converted to NH,using its fundamentalproblemsthat he had analyzed previously. an iron-based catalyst. These days, every car has a cata- Thus, his latest publication on H, adsorption on a metal lyst systemthat converts (toxic) CO and hydrocarbons to surface concerns the vibrational spectrum. CO,in the exhaustgases; the catalyst also adsorbsthe ni- trous gases present reducing their quantity in the vehicle’s The next long-standing and industrially important problem emissions. Currently, large resources are devoted to the that Ertl attacked concerned the molecular mechanism of developmentofefficient fuel cells using H, as a standard the catalytic formation of NH3 in the Haber-Boschpro- vehicle fuel, where surface reactions betweenelectrodes cess (Eq. 1). Ertl’s contribution wasin providing detailed and H,arecritical. Corrosion is caused by chemical reac- knowledge about how this process works. But aboveall, tions at surfaces; it is a major problem in everyday life this study provides an example of systematic methodol- and in sophisticated industrial contexts such as nuclear ogy applied to surface chemistry problems.In this way he powerplants and aircraft. Damage by corrosion may be has established an experimental schoolof thought for the reduced by adjusting the composition of the surface so entire discipline. that it is protected by an oxide layer formedin air. Thin N, + 3H) —» 2NH,..... (Eq. 1) semiconductorlayers are produced by chemical vapor deposition in large quantities in the microelectronics indus- In orderto obtain a suitable thermodynamicdriving force try. Chemical processesat surfaces are, therefore, central for the Haber-Boschprocess (Eq. 1), industrially it is per- not only to a wide rangeofhighly significant practical and formed under high pressure. The commonly usedcatalyst economicapplications of chemistry but also to the basic consists of Fe particles with added KOH on a support of chemical research needed to unravel the details. alumina andsilica. Owing to its economic importance, numerous investigations had been madebythe time Ertl Our theoretical description of chemical reactions concep- initiated his studies in the mid-1970s. Althoughit was un- tually provides the simplest case for the formation of a derstood from kinetic studies that the rate-limiting step molecule in the gas phase where the reacting species is wasthe chemisorption of N,, the underlying mechanism affected only by encounter with its reaction partner. How- and the nature of the reactive species were unclear. Alter- ever, in most practical applications, reactions occur in native mechanisms had been suggested, based on either more complex environments where the reacting species atomic or molecular nitrogen, but it was impossible to are constantly exchanging energy and momentum with discriminate between these on the basis of kinetic data other neighbouring molecules. For example,in a solution, alone. Equipped with the tools of surface science Ertl the environmentis disordered and dynamic and any de- took the opportunity to investigate aspects of the reaction scription typically relies on considering the effect of the in model systems, howeverfar from the realities of the environmentthroughits average properties. The gas-solid Haber-Boschprocess these seemed. interface provides an example of an environmentthat is intermediate between the relative simplicity of the gas Ertl had previously studied H, on metal surfaces andit phase and the molecular complexity of the liquid phase. At wasstraight-forward for him to show that, on the Fe of the surface of a solid an adsorbed molecule can exchange the Haber-Boschprocess, the behavior of N, was qualita- energy and momentum with the surface material, but in tively similar.’ He measured the concentration of nitrogen the most ideal cases this support has long-range order. atoms on the iron surface while simultaneously adding The consequenceis that the interaction between molecule hydrogento the system. He saw that as he added more 17, and support is much more regular, and this allows both the concentrations of N-atoms on the surface diminished.

Chemistry in New Zealand January 2087

Ertl concludedthat nitrogen atoms on the surface disap- comparatively easy to show that the mechanismwasthat pearas they react with hydrogen molecules. This showed of Scheme1. Althoughthis had been suggested previous- that the first step in the Haber-Bosch-reaction takes place ly, Ertl not only confirmedits correctness but also gleaned between hydrogen molecules and nitrogen atoms. If the the energetic details of the individual steps, the later reaction had taken place between molecular hydrogen onesstarting from NH, and monitoring the steps back- and molecularnitrogen, atomic nitrogen would still form wards (which is favoured at low pressures). Adsorption of on the surface, but it would remain unperturbed by the NH,on Fe involvesan energy gain of < 75 kJ/mol, small amountofhydrogen added. enough to ensure complete desorption at typical process conditions (T > 400 °C). According to Scheme1, the ad- In the then current literature, the most controversial is- sorbed NH, can dissociate on the surface. The presence sue was whethernitrogen would dissociate on the surface. of NH, could not be quantified spectroscopically but, The N-N triple bond is one of the strongest known and by co-adsorbing NH, and D,, Ertl was able to infer the dis- it appeared counterintuitive for interaction with the sur- sociation and recombinationrates for the reaction: face to be sufficiently strong to cleave N,into atoms. Ertl showedthat atomic nitrogen was,infact, present on clean NH3.a¢ == NApaa * Haa/Daa iron surfaces,’ and he deduceda detailed structural model NH is present in quantities large enough for observation for the iron-nitrogen structure on the surface. Moreover, using methods like ultraviolet photoelectron spectrosco- it was possible to characterize the kinetics of the nitrogen py, secondary ion mass spectroscopy, and high resolution adsorption in detail.° The formation of atomic nitrogen electron energy loss spectroscopy.* From these measure- occurs with a low activation energy but with a very small ments, it then became possible to formulate the mecha- pre-exponential factor making the process slow. Ertl also nism of Scheme | in energy terms.? discovered that although the activation energy was different for different crystal planes, the reaction proceeds Despite this success, one essential feature of the indus- onall of the three majorcrystal planes, (11 1), (110) and trial process remainedto be explained. Empirically, it had (100). Furthermore, the energy barrier increases with in- been found that the presence of K* ions in the catalyst creasing surface coverage so that the kinetic difference improved the rate of the catalytic cycle. Ertl had found betweenthe crystal planes decreases, that the potassium remained onthe surface of the catalyst under process conditions. Since N,cleavageis rate-limit- Initially it was far from obvious that these model studies ing, the potassium mustinfluencethis reaction step. It was applied to the molecular events in the industrial Haber- then found thatin the presence of potassiumions N,is ad- Boschprocess. To demonstrate the applicability, Ertl and sorbed more readily on the surface and the adsorption en- Thiele’ analyzed the surface composition of a commer- ergy increases by 10-15 kJ/mol; this is attributable to po- cial catalyst using Auger Electron Spectroscopy (AES). tassium donating electrons to neighbouring Fe atoms.!° They found that under ambientconditions the surface had a complex composition but, under the reducing conditions Ertl’s investigations serve as a model ofhow sophisticated of the process,iron and potassium dominateatthe surface. experimental methods canbe usedto study a phenomenon Througha characterization ofadsorption energies, it was of the utmost practical relevance. He began by identify- concludedthatit is only the adsorbed atomic nitrogen that ing the crucial features of the reaction in the industrial remains on the surface when the reaction chamberis emp- context, demonstrated the relevance of model studies, and tied after a catalytic cycle at high pressures. By using AES then identified a numberof elementary steps that became to analyze how surface nitrogen coverage varied with H, the targets of focused studies. The steps were character- pressure during the reaction, the high-pressure data were ized from structural, energetic, and kinetic points of view shown consistent with those for model measurements at using state-of-the-art methodology that involved the use low pressures. Furthermore, there was consistency be- of manydifferent techniques with highly sophisticated tween the observed rates of the elementary processes equipment. For each questionthereis, at any given point and the macroscopically measured kinetics. These stud- in time, an optimal method.It is clear that, throughouthis ies, bridging whatis called the pressure ap, were crucial careerErtl’s ambition has been to use that method. in gaining acceptance of the surface science approach to Ertl not only clarified the molecular catalysis by a community struggling with the realities of events of the Haber- Boschprocess, but he also industrial processes involving heterogeneous catalysis. demonstrated whatit takes to unravel Scheme 1 mechanisms of catalytic processes in general. This has had a lasting influence onthefield of heteroge- Hy = 2a neous catalysis.

In the Haber-Bosch process,the observed macroscopicki- Ny +Hag == NHgg netics of NH, productionarerelated to the kinetics of the NHqg+ Hag = NH2aa individual steps of the reaction observed underidealized conditions. For some heterogeneously catalyzed Npad + Hag == NH3,4a reactions it had been foundearlier that the macroscopic kinetics in- NH3,aa == NH3 dicated an oscillatory rate, a clear sign of non-linear dynamic behaviour. Challenged Having identified that the dissociation of N, into atoms by such observations, Ertl also made anin-depth study of another was slow, and having demonstrated that the model syS- classical catalytic reaction - the oxidation of CO by O, on tems wererelevantfor to the Haber-Boschprocess,it was Pt. This reactionis

Chemistry in New Zealand January 2008

importantto the catalytic converter in a car’s exhaust sys- attributed to his meticulous precision combined with an tem. The crucial questions What is the mechanism behind outstanding capacity to refine problems. He painstakingly the non-linearkinetics? and What other phenomena can and systematically searched for the best experimental be inferred in addition to the kinetic oscillations? led to techniques to investigate each separate question. this reactionillustrating a range of phenomenatypical of non-linear kinetic reactions. Ertl showedthat the rates of His methodology sets a standard for how chemical pro- different steps in the reaction vary over time. Somesteps cesses on surfaces can be studied and elucidated. oscillate between different rates, and the reaction pro- References ceeds differently depending on the coverageofthe plati- numsurface. Sometimesthesevariations lead to a chaotic 1. Conrad, H.; Ertl, G.; Latta, E.E. Surface Sci. 1974, 41, 435; Christ- mann,K.; Schober, O.; Ertl, G.; Neumann, M. J. Chem. Phys.1974, course of events so that the reaction is not reversible and, 60, 4528; Christmann K.; Ertl, G.; Pignet, T. Surface Sci. 1976, as a consequence, becomes much more difficult to study 54, 365; Christmann, K.; Behm, R. J.; Ertl, G.; Van Hove, M.A.; than the Haber-Boschprocess. Weinberg, W. H. J. Chem. Phys. 1979, 70, 4168. Badescu, S.C.; Salo, P.; Ala-Nissila, T.; Ying, S. C.; et al. Phys. nv A series of imaginative studies" led Ertl to the microscop- Rey, Lett. 2002, 88, 136101; Badescu, S.C.; Jacobi, K.; Wang, Y.; ic causes of the observed non-linear behaviour. Again, he Bediirftig, K.; et al. Phys. Rev. B 2003, 68, 205401. demonstrated how the full spectrum of surface physics/ 3. Bozso, F.; Ertl, G.; Grunze, M.; Weiss, M. Appl. Surface Sci.1977, chemistry methods can be combined to yield a compre- 7, 103. hensive understanding of important and complexcatalytic 4. Bozso, F.; Ertl, G.; Grunze., M. J. Catalysis 1977, 49, 18; Ertl, G.; processes. High pressurein situ methods, FTIR,and X-ray Huber, M.; Lee, S.B.; Paal, Z.; Weiss, M. Appl. Surface Sci. 1981, diffraction gave information on the state of the catalystit- 8, 373. self. These methods are generally much less precise than 5. Imbihl, R.; Behm,R.J.; Ertl, G.; Moritz, W. Surface Sci. 1982, 123, high vacuum techniques, but they gave invaluable cor- 129. roborating information and helpedclose the pressure gap. 6 Ertl, G.; Lee, S.B.; Weiss, M. Surface Sci, 1982, 114, 515. In the study of sensitive oscillatory reactions on surfaces, 7. Ertl, G.; Thiele, N. Appl. Surface Sci. 1979, 3, 99. the energy input must be controlled and minimized, and this is an added constraint. Thus,the use ofAES,although 8. Weiss, M.; Ertl, G.; Nitschke, F. Appl. Surface Sci. 1979, 2, 614; Drechsler, M.; Hoinkes, H.; Kaarmann, H.; Wilsch, H.; Ertl, G. powerful for the Haber-Boschstudies, is not feasible. In- Appl. Surface Sci.1979, 3, 217. stead, low energy methods such as LEED were employed to directly monitor structural changes, and photoemission 9. Ertl, G. J. Vae. Sci. Tech. 1983, Al, 1247. electron microscopy (PEEM) to monitor the local work 10 Ertl, G.; Weiss, M.; Lee, S.B. Chem. Phys. Lett. 1979, 60, 391. function with high spatial resolution. These studies en- 11 Behm, R.J.; Thiel, P.A.; Norton, P.R.; Ertl, G. J. Chem. Phys. 1983, abled Ertl to demonstrate that his methodology applies 78, 7437; Cox, M.P.; Ertl, G.; Imbihl, R. Phys. Rev. Lett. 1985, 54, not only to systems wherethe kinetics are dominated by a 1725; Imbihl, R.; Cox, M.P.; Ertl, G.; Mueller, H.; Brenig, W. J. single rate-limiting step, as for the Haber-Boschprocess, Chem. Phys. 1985, 83, 1578; Imbihl, R.; Cox, M.P.; Ertl, G..J. Chem. Phys. 1986, 84, 3519; Eiswirth, M.; Moller, P.; Wetzl, K.; Imbihl, but also to systems where non-linear dynamicsprevail. R.; Ertl, G. J. Chem. Phys. 1989, 90, 510; Jakubith, S.; Rotermund, H.H.; Engel, W.; von Oertzen, A.; Ertl, G. Phys. Rev. Lett. 1990, 65, Ertl’s lasting contribution to the 3013; Kim, M.; Bertram, M.; Pollmann, M.; von Oertzen, A.; ef al. Science 2001, 292, 1357; Beta, C.; Moula, M.G.; Mikhailov, A.S.; understanding of surface chemistry Rotermund, H.H.; Ertl, G. Phys. Rev. Lett. 2004, 93, 188302. The 2007 Laureate, Gerhard Ertl, was one of thefirst to understand the potential of the new technology and he Compiled by Brian Halton and Peter Hodderfrom materialfree- laid the methodological foundations for an entire field ly available from the Nobel Foundation. Further details may be of research. The great reliability of Ertl’s results can be obtained from: http://nobelprize.org

Chemistry Behind the News Drugs and Toys

Twochildren being admitted to hospital caused a popular ate (GHB). GHBis abused as recreational drug.It is children’s toy to be pulled from shop shelves. They be- also foundnaturally in the brain whereit is thought to be cameill from swallowing beadsthat werepart of the toy. a neuromodulator. GHB also seems to affect dopamine levels in the brain. Thetoyis a craft kit made up of multicoloured beads that when sprayed with water, stick to each other so they can 1,4-butanediol is mostly used in the manufacture of poly- be used to makepictures andother items. urethanes suchas surface coatings, foam and adhesives.

1,5-pentanediolis used in the toys’ manufacture, butit ap- The chemical that was meant to be used in manufac- peared this had beensubstituted with 1,4-butanediol. ture was pentamethylene glycol or 1.5-pentanediol (OHCH,(CH,),CH,OH).It is a water miscible liquid that In the liver, 1,4-butanediol (C,H, ,O,) is broken down by is used as a hydraulic fluid as well as in the manufacture alcohol deyhydrogenase and aldehyde dehydrogenase of polyester and polyurethaneresins. into metabolic products including gamma-hydroxybutyr- 32

Chemistry in New Zealand January 2087

Significant Changes To The US Patent System By Blair Hesp and Jarrod Ward

STOP PRESS: The USPTO rule changes discussed below were intended to comeinto force on 1 November 2007. However, they are now the subject ofan 11"hour interim injunction against the USPTOgranted in a US District Court on 31 October 2007. Although the newrules are not currentlyin force, the intention ofthe USPTOis to applythese rules retrospectively to any application under examination if, and when,the injunctionislifted, Therefore, new applicants should be awareof the following issues when planning a US patentstrategy.

The US is the homeofthe world’s largest economy, and Continuation Applications manyinventors consider the grant of a US patent to be a It is commonpractice in the US, especially in the phar- significant milestone on the road to protecting and com- maceuticalfield,to file “continuation applications” before mercialising an invention. Consequently, the large num- a parent application is granted. These applications have ber of patent applications filed by applicants from the the same invention description and priority date US, andother countries, has created a heavy examination as the parent application, but different claims. For example, a workloadfor the United States Patent and Trademark Of- continuation application may be directed to a preferred fice (USPTO). In response, the USPTO has attempted to embodimentofan invention which was described, but not introduce several new rules in order to accelerate patent claimed, in examination. the original application. In a further attempt Numberof Claims to reduce the number of applications awaiting examination, the USPTO has attempted to re- Firstly, the USPTO prefers new inventions to be encom- strict the number of continuation applicationsfiled from passed within a single, succinct patent application com- any parent application, or family of applications, to no prising a maximumof25 claims. If this limit is exceeded, more than two. However,this limit would notinclude ap- the USPTO would then require the applicant to restrict plications which have been divided out from a parent ap- the number of claims during examination, or to justify plication in responseto a unity of invention objection(i.e. the numberofclaims in an “examination support docu- whenan application is deemedto be directed to more than ment”. oneinvention).

In addition, the USPTO has proposedfurtherrule changes The USPTObelievesthat these rule changes will reduce in an attempt to stop applicants circumventing the new examination times, while promoting innovation and im- claim limit by filing several applications directed to dif- proving patent quality. While it is yet to be seen how ferent embodiments of the same general invention. In effective these measures will be if, and when, they are particular, the USPTOwill seek details of any related US implemented,it is clear that any US patent applicant must application if the related application has a commoninven- now operate with a heightened level of caution. In partic- tor, acommonowner,and wasfiled within two months of ular, contingenciesforall of the above-mentioned factors the new application. should be incorporated into any USpatent strategy. Furthermore,if the disclosure of a new application is sub- A reminder: if you have any queries regarding patents, stantially the same as any other US patent application or or indeed any form of intellectual property, please direct granted US patent, then the USPTO will reject the new them to: application on the presumption that the claims of each application are not distinct. However, this presumption Patent Proze would be able to be rebutted by demonstrating that the Baldwins claims of the new application are patentably distinct when PO Box 852, Wellington comparedto the claims ofthe earlier application. Email: [email protected]

Blair Hesp and Jarrod Ward of Baldwins specialise in chemistry and biotechnology patents. Blair joined Baldwins in 2006, and has a PhD in pharmacology from the University of Otago as well as a NZDipBus with a management focus. Jarrod joined Bald- wins in 2007, and has submitted a PhD thesis in chemistry to the University ofAuckland. Blair and Jarrod are currently studying towards law degrees andregistration as patent attorneys.

Chemistry in New Zealand January 2008

Commenton Climate Change Mythconceptions Vincent R. Gray 75 Silverstream Rd, Crofton Downs, Wellington (e-mail: [email protected])

The article by D. S. Mackie and K. A. Hunterin the last issue to estimate, and easily can exceed the supposed g/obal warming of this Journal' revived the traditional game of AuntSally as a ofthe past century. meansofscientific discussion. The authors assembled what they The samples are grossly unrepresentative of the earth’s surface claimed to represent as Common Arguments supposedly made - itis like judging the results of an election from polling only one by Climate Change Deniers. No actual denier was identified, suburb ofonecity. The sites chosen are mainly near towns and andthe replies did not display a very deep knowledge of Climate subject to urban heating. Science. Some of those Common Arguments are correct what- ever the authors maysay. Attempts to correct for some of these errors have shown that there has been no global warming in the USA or China for the Common Argument 5: Temperature measurements by satel- past 100 years. Many better kept local long-term records confirm lite and radiosondeballoons show nosignificant warming this, including those for Christchurch from 1900to the present. There wasnosignificant warming shownby both of these mea- Comparisons of proxy temperature data from the past with the surements from 1979 to 1997 and from 2001 to 2007 whenboth recent human-influenced surface record merely emphasize the periods experiencedlarge greenhousegasincreases. This author recentinfluence of urbanheating. has refuted completely the claim that new datasets have been developed that do not showsuch discrepancies (between surface 2. Atmospheric carbon dioxide concentrationis not well-mixed and loweratmosphere records) quoted from the web-published but variable CSSPReport. It might be remarkedthat the latter period, 2001- Measurementof [CO,] in the atmosphere is manipulated by the 2007, also showsnosignificant warming in the surface record IPCC inan attemptto concealits variability. Some 90,000 previ- either. ous measurements* have been suppressed and unwantedfigures are not published by the proponents. The reasonforthis is that Common Argument 6: Computer models of the climate are the formula for calculating radiative effect of the gas is logarith- worthless mic,so it gives a higher figure when applied to constant [CO,] No computer modelhasever been validatedas this needsa rigor- than for a variable sample. - ous processto be carried out by computer engineers and requires successful future prediction. The IPCC knowthis is true since 3. Levels ofuncertainty they only claim that the models are projections. The IPCC uses Uncertainty levels for climate quantities are often unknown and, the gutfeeling ofself-styled experts as a substitute for validation. even whenthese are supplied, they are questionable. Much of Their levels of likelihood with their spurious probabilities have the Mackie-Hunterarticle uses line graphs of highly uncertain no scientific basis. No model has ever been shownto be success- quantities to make a numberofpoints. The uncertainty levels of fulin future prediction. these plots and oftheir Table | are not even mentioned. The obvious example is the fact that the g/obe has not been The question as to whether ancient atmospheric [CO,], measured warming for the past eight years, however you measureit. This with huge uncertainty in only oneplace, increased beforeorafter proves without any doubt that the models are worthless. a rise in temperatureis the subject of much controversy andthis cannotbe decided from such uncertain data. Arguments not Answered Conclusion I. The data andproceduresusedto provide evidencefor global warming arescientifically and mathematically unsound Scientists do not go in for consensus, but for facts and evidence. The Mean Annual Global Temperature Record, whichfigures I would encourage the readers to make up their own minds, not so largely in IPCC thinking, has been obtained without using just by trying to find theflaws in only oneside of the argument, any actual measured average temperature from any place on as a game of AuntSally, but by an impartial assessmentofall the earth’s surface. So in order to provide a long sequence for the evidence. their record, these authors were stuck with continual use of the References procedure adopted bythefirst meteorological stations in 1850. This involves a once daily measurement from a maximum and 1. Mackie, D.S.; Hunter, K, A. Chem. in NZ 2007, 71, 72-78 minimumtemperature thermometer. The mean ofthese two is 2. Gray, V R. Energy Environ. 2006, 17, 707-714. taken to be a daily average, but, as anystatistician will tell you, this is not true. The bias (usually positive) is variable, impossible 3. Beck, E-G. Energy Environ. 2007, 18, 239-281. New Wayto Test Sulfur AgResearchhas developed a new sulfursoil test. poorly.

Dr Gordon Rajendram developedthetest as part of a PhD proj- Currently there are twosoil tests that measure easily extractable ect. The new test makesscientific analysis easier and gives farm- organic sulfur and sulfate-S (SO,). These tests are measured on ers accurate information to decide how much sulfur fertiliser twodifferent instruments and then easily extractable organic sul- their soil needs. fur is calculated using a difference technique. Sulfur is very important for good plant growth becauseit is used Thenewtest is easier to measure using a single instrument and in the production of amino acids that make up plantproteins. gives morereliable results. Hill Laboratories is carrying out the A sulfur deficiency gives plants yellow leaves and they grow newtest. 34 Chemistry in New Zealand January 2087

Response Doug S. Mackiéand Keith A. Hunter

Departmentof Chemistry, University of Otago, PO Box 56, Dunedin (e-mail: [email protected])

Wheninformedthat a scientific objection had been madeto our It is very sad to see that Gray revertsto the classic conspiracy article and asked ifwe wished to respond we werenaturally keen theory concerning suppression of evidence by the IPCC. It is lu- to engage in meaningful debate and wearegrateful to the editor dicrousto suggestthat the many hundredsofrespectable climate for this opportunity. However, having now read the criticisms, scientists around the world involved with IPCC would stoop to wefeel they are so lackingin clarity and substancethat it would this, and muchless crediblethat such a conspiracy couldactually be uncharitable to respondin detail. Instead, we have confined be organized and keptsecretfrom all but a few. Gray references ourselves to a few observationsofpoints that puzzled us and will to the work of E.G Beck, also published in Energy and Envi- doubtless puzzle readers. ronment. This article presents a graph summarizing historical CO, measurements (not The common arguments we cite came from list entitled Zen considered reliable by IPCC scientists) whichpurports Jacts about global warming THEY don't want youto know.' For to show,inferalia, that the concentration of co, several monthsa link to these Zenfacts appearedatthe top ofthe in the atmosphere changedfrom 310 ppm in 1936 to 472 ppmin 1943, and then back downto mustreadlist at the website of the New Zealand Climate Science 320 ppmin 1950. This represents a net change,in both Coalition (NZCSC) — a group of which Gray is a founding and directions of ~5.1 x 10'® g C per year, approximately 15 times the fossil fuel current member. After we pointed out someerrorsin this list of emissions for 2004 (7.4 x 10'S g C). The global arguments to NZCSC,thelist wasaltered in accordance withthe carbon cycle simply doesnot, and indeed suggestions of the NZCSCscience advisor — in our view giving cannot, worklike this. To believe that it can, showsa willful dis- regard for the basic thelist a stamp ofapproval (and demonstrable input) by NZCSC. principles of chemistry, physics and biology, and we doubt that the debate will be furthered by reference to The NZCSC amendments were cosmetic and in no wayaltered a such egregiously flawed work. the substance ofthe claims. Wewill be glad to provide copies ofthe list and relevant correspondenceshould anyone wantthis Weconclude by stating what is obviousto us as scientists. Hu- from us. We will also be glad to provide copiesofpress releases manactivities such as agriculture, deforestation, and fossil fuel and populararticles written by NZCSC members that were, until combustion have seriously disturbed the atmospheric inven- recently, hosted by their website but which were removed only tories of greenhouse gases,particularly CO,, over the last 250 days after we beganto critically examine them— as was the link years. Atmospheric CO,is intimately linked to the regulation of to the /0factslist. the Earth’s climate, and this has been so for millions of years. Gray makesreference to articles he has produced for Energy Therefore, we should be worried about the future. The almost unilateral action of world governments and Environment and we must confess that we have notread his to address this problem has not been undertaken oeuvre there. Energy and Environmentis a journalnotlisted by lightly, and has come about because of an enormous bodyofscientific evidence and opinion. Thompson-ISI and cannot, therefore, be assessed in termsofits To suggest thatthelatter is nothing but quality. It is interesting, however,that only critics of mainstream a falsehood borne out of conspiracy belongs only in Alice in Wonderland. climate science seem to publishin it, which speaks volumesfor its reputation amongst the majority of climate scientists. The References commentary by Environmental Science and Technology about Energy and Environmentis especially informative. 1. See: http:/Avww.numberwatch.co.uk/ten_facts_about_global_warm- ing.htm Weare puzzled that Gray can assert that ground temperature 2. See: http://pubs.acs.org/subscribe/journals/esthag-w/2005/aug/policy/ measurements are invariably biased and cannotberelied upon, pt_skeptics.html . but only a few lines later usesprecisely the sametype of data for The websites were checked Christchurch to showthat no global warming has occurred. at the time of going to press (October 18, 2007). Finding Answers in Food DrLai Yeap Foofrom In- Cranberries are one of the top ten selling botanicals in the dustrial Research Limited USAtoday but indigenous North Americansalso used them in Wellington received an medicinally. award from the cranberry Researchis continuing to be donein the area of growers’ co-operative, cranberries —_ andurinary tract infections. In April 2007,the positive Ocean Spray for his con- results of a pilot study on concentrated cranberry extract preventing tribution to international recurrent urinary tract infections in women waspublished molecular nutrition and in the journal, Phytomedicine. food science. Dr Laihasalso developedan anti-inflammatory He found what mechanism wasresponsible for the cranber- product from passionfruit skins that can lower blood pressure for patients ries’ ability to inhibit urinary tract infections. Since his re- suffering from hypertension. search the cranberry product business has grown 150%. In the future he is hoping to further develop a grapefruit skin Cranberries are one of only three species of fruit native to woundhealing product. North America and New Zealand is now growing its own cranberries on the West Coast of the South Island. 35

Chemistry in New Zealand January 2008

Letter to the Editor Re: Climate change mythconceptions (This Journal, tinue over next century (minimum). 2007, 71, 72-78) 8. Climate events will become moreerratic and severe. Further to this article and those global processes that re- Keystuff is political: sult in temperature change and [CO,] in the atmosphere —what I call the mechanisms involved. I think the issue 9. There is no global consensus on action. of global temperature increase is unquestioned. What is 10. Global consensusis unlikely in foreseeable future. at issue is the way the [CO,] is increasing and I suggest 11. Effective restriction of CO, is likely 10 to 15 years that the following policy brief summarises the issues key away. to any discussion. 12. There will be large costs geographically, socially, and There are two crucialfacts of science: economically. Global conclusion: 1. Humanactivity has increased and intensified global CO, production. 13. Global warmingis the perfect hammerneededto forge 2. Global systems adjust slowly to excess CO, and hu- global social/political consensus. If so, costs are worth manactivity has eroded someof the absorption capac- it in relation to long term social/political benefits to ity. humanity, and the loss of life and costs likely to be muchless than manyofthe other alternatives for forg- Otherscientific issues: ing the consensus. 3. Baseline for CO, data is with no human activity; this New Zealand conclusion: is notrealistic. 4. Global systemswill adapt to increased CO,, butit will 14. NZis not able to lead global consensus withoutseri- take centuries. ous adverse impact and economicrisk. 5. Humanity will adapt to global systems and produce 15. NZ needs take prudent steps manageable within cur- less CO,, but overall levels will be higher than the current economic circumstances. rent baseline being used whichis in absence of human 16. NZ forward planning needs bring to account the im- | activity. plications of this policy brief. 6. CO, will increase as ppm in atmosphere over next 50 17. NZ should be fastfollower. years (minimum). Graham R.Little (gr/@xtra.co.nz) 7. Global temperature/climate change will increase/con-

Dates of Note

This year marks the 100" anniversary of the a-particle 150 years ago, on March 30,thefirst US patent for a com- scattering experiment devised by Ernest Rutherford with bination lead pencil and eraser was issued to Hyman L. Hans Geiger and E. Marsdenthatled to the discovery of Lipman (No. 19,783) while on 6 April 1938, Roy J. Plan- the atomic nucleusin 1911. kett discovered Teflon at DuPont.

February | is the 35" anniversary of Hewlett-Packard’s introduction of the hand-held calculator. The HP 35 re- tailed for $US395. On February 29, 1936, Nature carried Niels Bohr’s Neu- ChemScrapes tron capture and nuclear constitution often referred to as the bow!ofballs explanation for the effect of bombarding particles on a nucleus (Nature, 1936, 137, 344-348). | mee]

March 2 is the 125" anniversary of the birth of Walter Norman Haworth, recognised for his projection formu- lae, while the 5" marks the 200" anniversary of the birth of Petrus Jocobus Kipp, inventorof the apparatus for hy- «| drogensulfide generation namedafter him. Some 340 years ago (March 10, 1668) German-Dutch | chemist Johann Rudolf Glauber, the German father of chemistry, died. He prepared HCI from NaCl and H,SO, I'm telling you, you're NUTS...... they'll never buyit! and pointed out the virtues of the residue, Na,SO,- sal Brendan Burkett mirabile, better known as Glauber’s salt. 36

Chemistry in New Zealand January 2087

New Zealandis Different: Chemical Milestones in New Zealand History ~=

This NZIC publication, edited by the late Denis Hogan and funding. Essayists Earle, Davey and Wright benefited from Sir Bryce Williamson was published by Clerestoy Press, (Christ- Ernest Marsden (Head, DSIR)establishing the Defence Scien- church) in 1999. It was subsequently distributed free to every tific Corps by gaining research overseas experience via a doc- secondary school in NZ through funding from the Stout Trust toral degree before returning to NZ. and is now out of print. Council is keen to gauge interest in a possible reprint. If you are interested in purchasing a copy Eachessayis appropriately referenced and contains enoughin- please e-mail us at: [email protected] The decision to formation to whetthe appetite. Abstruse technical detail is mini- reprint will be madein conjunction with the publishers and will mal andlimitedto informationboxes that can be omitted on first depend upon a numberoffactors. reading. The essays stand alone but have common themes and cross-linkages. Walker [known to manyreaders as theaffable Council is also convinced that there are numberofstories akin vegetable gardener on the (earlier) Maggie Barry show] gives to those in this volumethatarestill to be brought to the atten- an erudite accountof the impact of rye-grass and clover-based tion of people with aninterest in things chemical andalsoto the pastures on the economy,and the importance of superphosphate generalpublic. To this end New Zealand is Different Vol. 2 is as fertilizer. Superphosphate production,the first major chemi- being considered. If you have ideas of suitable stories, know cal process industry, had handling difficulties with the raw ma- of potential authors for a suggested essay, or are prepared to terials as described by Higgins. write an essay yourself please e-mail the NZIC office: NZIC. [email protected] Wrighttraces 50 years ofresearch carried out on climate controlled We reprint below an abridged facial eczema. Clare relates andedited version ofthe 2000 re- bush-sickness/North Island soil view (Kennedy, M. This Journal, New Tealandis Different cobalt deficiency to effects in 2000, 64, 15-16). grazing animals. The solution to this problem more than paid for a The NZIC is to be congratulated all the agricultural research up in commissioning this splendid to that time. Letham’s account chemical history. It contains ele- fel nenal(e:1) . of cytokinins and their influence ments ofsocial history and politi- Milestones in on plant developmenttypifies the cal and commercial skullduggery, ability of NZ scientists to carry twists and turnstypicalofthe best New Zealand out high-quality research under detective stories, all interwoven History poor conditions with limited re- with true-life tales about some of sources. Clinton describes work NZs outstanding chemists - and on developing atomic absorp- written in a style that can easily tion spectroscopy so necessary in be understood bythe lay as well these studies. as the scientific reader. For the 26 essays in New Zealandis Differ- The Wright, Clare and Letham es- ent are written by people who not saysare fascinatingtales ofdetec- only understand their research ey tion. So too is Walker’s account (and wereoften at the centre of Prat) of what caused NZ wool cargoes the work they describe) but who cor to ignite spontaneously during know how to communicate that een ACLS} shipping. It provides an example work with greatclarity andflair. of good chemistry underpinning an importantindustry. Fenbytells The opening essay points out how NZ developmentsof cyani- those NZs chemical problems, originating as they do from the dation led to resurgencein the gold industry; while Kennerley country’s unique geology and geographyare unlike most. Poli- shows how chemistry made important contributionsto the sci- ticians and administrators, dubious of home-grown expertise, ence of concrete-making. Davey describes the chemists and demanded reassurance from overseas experts who too often biochemists of the MIRNZefforts to establish why Canterbury come,give advice, take their fee and depart. The NZ chemists lamb was tough whenit reached the UK; Robertson introduces and chemicalengineers have beenleft to discover and solve the us to the cheese making system developed by the NZDRI real problems. that has mechanized the makingofworld cheeses; Foster et al., trace the rise andfall of the NZ ceramic industry. In the early days, most NZ research was done in Government institutions like the DSIR. Hogan traces the evolution of such Difficulties in chemistry commercialization are evidenced in institutions from the days of the Colonial Museum throughto Leary’s essay on the work of DSIR Chemistry Division and Ian the creation of the CRIs in 1991. Since then, and perhaps be- Miller’s story of seaweed industry and, also in Cambie’s NZ cause of the market-driven forces, it has becomefashionable plant natural products account. Stonyer gives a tragi-comedy to disparage the achievements of the DSIR. He suggestsit is on attempts to make terpineol economically from by-product too soontotell whether the new system will produce bettersci- turpentine; one couldn’t help but wonder what might have hap- ence for NZ. However, one doubts whether the achievements pened had TVL and AC Nottingham combinedforces. The suc- recorded herein would be possible underthe present system of cess of small-scale fish-liver oil production during wartime for 37

Chemistry in New Zealand January 2008

the nation’s infants is described by Mattingley. dustrial success in establishing a pulp and paper industry based on Pinus radiata, is told by former NZFP chemist and manag- Since 1964, the growth of chemical and allied industries has ing director, Mackney. been large by world standards and industrial chemists and chemical engineers provide essays dealing with many of these. Whata collection of plots and authors. Appearing in the cast, A chemical engineering viewpoint on the lactose industry by from time to time, are politicians like Ward, Seddon,Sullivan, Woodis particularly interesting as is Earle’s model for univer- Douglas, Birch, and Muldoon.Toooften, they showed a lack of sity-industry collaboration through NZ Pharmaceuticals. confidencein the ability and ingenuity of NZ scientists and engineers, and blind faith in the overseas expert. One way to help Collaboration led to NZs dominance in the understanding and this change wouldbe to make NewZealandis Different compul- utilization of geothermal power - Ellis shows how. The DSIR sory reading for every MP, and Government Department Head zeolite team underParkeris largely responsible for NZs success so that Government’s wish to add value to NZ exports might in the conversion of natural gas to petrol by the untried Mobil moreeasily be achieved. Finally, readers of Chemistry in New process. Marshall and Wylde describe steel-making from NZ Zealand will find it a snip at $30. iron sandsasa classic case-study. Similarly, the solar salt industry at Lake Grassmereis told by Pollard. Lastly, NZs great in- Abridged by the Editor

Book Review: Handbookof Australasian Edible Oils Editor: Charmian O’Connor. Managing Editor: Laurence Eyres ISBN 978-0-473-12283-6, 297 pages

With widespread commentanddiscussion in the media on food a majoritem in our diet, is not covered in this bookasit so fa- related health matters such as obesity, low density lipoproteins miliar to*most people, but comparisonsof its composition and ys. high density lipoproteins, saturated fats vs. unsaturated fats, properties with products made from other animaland vegetable trans-fatty acids vs. cis-fatty acids, omega-3 fatty acids, ‘nat- fats and oils are given. ural’ and modified fats and oils, etc. this publication from the Oils & Fats Specialist Group of the New Zealand Institute of Those interested or concerned aboutthe pros and cons of what Chemistry is very timely. It contains 14 chapters written by 25 they should and should not eat will find authoritative informa- people with expertise in their particularfields. Listing thetitles tion on which to makedecisions. of the chapters is the best wayto illustrate this and convey the Reading this book reminded me of what I experienced as an material covered: “academic chemist”on receivingarticles for Chemical Process- 1. Methods ofanalysis — a brief introduction; 2. Avocado oil es in New Zealand: how eachindustry has its own jargon, much and other nicheculinary oils in NZ; 3. The development of the of which is familiar to lay people, but the meaning of which is NZextra virgin olive oil industry; 4. Setting quality standards not always obvious to someoneoutside that industry, be they a for Australasian olive oils; 5. Marine oils in Australasia; 6. A chemist, technologist, cook etc. So I wasso pleased to find that survey of omega-3-fatty acids in common NZ seafood; 7. Ma- familiar terms used in chapters 12 and 13, covering the process- rine oil production for nutraceutical use; 8. Lipids and cancer; ing of raw materials to produce the range of edible products 9. Nutracceuticaloils derived from plants; 10, Fat in the diet of wefind on supermarket shelves, were clearly explained as they children; 11. International evidence supporting addition ofplant wereintroduced. There were occasions where| felt a brief glos- sterols and stanols to functional foods; 12. Processing oils and sary ofsome terms would havebeen usefulto readers with lim- fats in NZ; 13. Theedible oil industry in Australia; 14. Deep- ited chemical knowledge,especially on the numbering used in frying mediums in NZ. unsaturated fatty acids. Howevera recent previous publication of the same group, A New Zealand Lipid Manual, also edited A twelve page Table of Contents listing the headings of every by Charmian O’Connor, and subtitled Readings and introduc- section in each chapter adequately also fulfils the role of an in- tion to the science, technology, analysis and nutrition ofoils and dex, and allows a readerto quickly find a topic of interest. Ab- fats, 136 pages,is available (from Ruth Eyres — see below) and breviations (e.g. PUFA) are widely used through out the book, providesa basic introductiontothisfield. but an excellent alphabeticallist priorto the first chapter allows the readerto find the meaning easily. Every chapter has an ex- Thetitle Handbookis apt as it will serve as a comprehensive tensivelist of referencesto the primary literature. reference book for those working and researching in the food and health industries. Howeverit is not just a reference book. This book will be invaluable to a wide range of people, both Individual chapters are easy to read and cover manytopics that professional and lay. In view of the public interest in many of should interest consumers. the topics I would hopeall public libraries purchase a copy. Health and food journalists, political spokespersons on health The Oil and Fats Group should be congratulated in producing and food should certainly have ready accesstoit. It will be inthis invaluable sourceofinformationofinterest to a broad range valuable for students in the areas of food technology, health and of people. medicine. The composition and properties ofall the different Thecost including GST andpostage is $80 and the book can be fats and oils used in making products for a wide range of food ordered by post (Ruth Eyres, PO Box 25-499,St Heliers, Auck- manufacturers, and ofthe finished products these manufactur- land), by fax (09 528-7032) or e-mail [email protected] ers produce and wefind in our supermarkets, are given clearly in manytables throughout the book. The manufacture of butter, Reviewed by John Packer 38 Chemistry in New Zealand January 2087

Conference Calendar

26" Australian Colloid & Surface Science Student Confer- Brisbane, Australia, 15-19 June 2008 ence, Warrnambool, Victoria, Australia, 4-8 February 2008 Further details available at the website: www.whec2008. Further details available at the website: http://home.ipri- com/ mus.com.au/jaymez/stucon2008/index.html Dalton Discussion 11: The Renaissance of Main Group Fifth International Meeting on Photodynamics, Havana, Chemistry, Berkeley, California, United States, 23-25 June Cuba, 4-8 February 2008 2008. New Zealand Trace Elements Group Conference 2008, Uni- Further details available at the website: www.rsc.org/Con- versity of Waikato, Hamilton, New Zealand, 13-15 February ferencesAndEvents/RSCConferences/DD11/index.asp 2008 Further details available at the website: www. tracenz.org Ill International Conference on Colloid Chemistry and Phys- icochemical mechanics, Moscow, Russia, 24-28 June 2008 ICAM2008,International Conference on Advanced Materi- Further details at the website: www.icc2008.ru/en/ als, Kottayam, India, 18-21 February 2008 Furtherdetails available at the website: www.materialschem. Gordon Research Conference on PolymerPhysics, Newport, org/ United States, 29 June - 4 July 2008, Furtherdetails available at the website: www.grc.org/ International Symposium on Biothermodynamics, Frank- furt, Germany 21-22 February 2008 Drug Discovery & Development, Couran CoveIsland Resort, Further details available at the website: http://events. Queensland, Australia, 13-17 July 2008 dechema.de/Biothermodynamics_2008 Further details available at the website: www. 3datthecove. org/ ICONN 2008, 2008 International Conference on Nanosci- ence and Nanotechnology, Melbourne, Australia, 25-29 BOSSXI, 11" Belgian Organic Synthesis Symposium, Ghent, February 2008 Belgium, 13-18 July 2008, Further details available at the website: www.ausnano.net/ Further details available at the website: www.boss11.org iconn2008/ 19" IUPAC Conference on Physical Organic Chemistry, San- Heterocyclic and Heteroatom Chemistry Conference, tiago de Compostela, Spain 13-18 July 2008 Heavier heterocycles and heteroatom chemistry, Cancun, Further details available at the website: www.icpoc2008. Mexico, 25-29 February 2008 org/ Further details available at the website: www.zingconfer- ences.com/ XXII IUPAC Symposium on Photochemistry, Goteborg, Swe- den 28 July - 1 August 2008 Pittcon 2008 Conference and Expo; 59* Pittsburgh Confer- Further details available at the website: http://photosci- ence on Analytical Chemistry and Applied Spectroscopy, ence. la.asu.edu/Goteborg2008/ New Orleans, Louisiana, USA 1-7 March 2008 Further details available at the website: www. pittcon.org/ 5th SETAC World Congress, The Society of Environmental Toxicology and Chemistry, Sydney, Australia, 3-7 August Chem. 05, Green and Sustainable Chemistry for Developing 2008 Countries, Cairo, Egypt, 3-6 March 2008 Further details available at the website: www.setac2008. Further details available at the website: http://chem05. com/ cu.edu.eg/ XX" International Symposium on Medicinal Chemistry, Vi- ASCC Conference 2008, Annual conference of the Austra- enna,Austria, 31 August - 4 September 2008 lian Society of Cosmetic Chemists, Gold Coast, Queensland, Further details available at the website: www. ismc2008. org Australia, 6-9 March 2008,

Organic Process Research and development, the origi- PSA2008, Particulate Systems Analysis 2008, Stratford nal process chemistry conference, Dublin, Ireland, 11-14 Upon Avon, United Kingdom, 2-4 September 2008 March 2008 Further details available at the website: www.psa2008. co.uk/ 10th YoungScientists conference on Chemistry, Rostock, Germany, 27-29 March 2008 Praha 2008, The 20*International Conferenceon High Res- Further details are available at the website: www.jcf-frue- olution Molecular Spectroscopy, 2-6 September 2008 hjahrssymposium.de/2008/ Further details available at the website: www.chem.uni-wup- pertal.de/conference/ WFC10, 10" World Filtration Congress, Leipzig, Germany, 14-18 April 2008, 23" European Colloquium on Heterocyclic Chemistry, Ant- Further details available at the website: www.wfc10.com/ werp, Belgium, 9-13 September 2008. Further details available at the website: www.echc08.org/ ICC2008, International Catalysis Conference, Tehran, Iran, 28-30 April 2008 RACI Organic 08, Wrest Point, Hobart, Tasmania, Australia, Further details at the website: http://icc2008.sbu.ac.ir/ 7-12 December 2008 Further details available at the website: www.organic08. WHEC 2008, 17% World Hydrogen Energy Conference, org/

39 Chemistry in New Zealand January 2008

Grants and Scholarships

International Conference Fund and research, usually in New Zealand. It is usually for three years and provides up to $20,000 peryear. Closing date for This fund is provided by the Minister of Research, Science and Technology and administered by the Royal Society of applications is 1 March 2008. New Zealand. It is funding to assist organizations and in- For further details, criteria and an application form see the stitutions to host major international conferences in New website: WwW. NZVCC.ac.NZ Zealand. There is no closing date for applications. Meat & Wool New Zealand Postgraduate Scholar- For further information see the website: www.rsnz.org/ funding/int_conf/ ships These scholarships are for high achieving students to help Conference Assistance Programme complete a postgraduate qualification that will support the This programmeprovides assistance for bidding to host an sustainable development of the meat and woolindustry in international conference in New Zealand. This can include New Zealand. Successful Masters applicants receivea sti- discounted airfares to travel to present bid, help to write pend up to $30,000 in total, while successful doctoral ap- bid documents and accompanying marketing material as plicants will receive $25,000 per year for up to three years. well as other assistance. Applications close 14 March 2008. For further details see the website: www.conventionsnz. For further details and criteria see the website: www.me- com/cap.aspx atandwoolnz.com

Technology in Industry Fellowships Bank of New Zealand Scholarships These fellowships enable completion of R & D projects in These scholarships are available to Masters, PhD or post- companies. Fundingprovides a stipend of up to $25,000 de- graduate diploma students. The scholarship is $4000 for one pendingon the levelof postgraduate study, $5,000 host fee year. Closing date for applications is 1 April 2008. to tertiary institute and $1,000 accommodation and travel Forfurtherdetails, criteria and an application form see the allowance website: www.bnz.co.nz For furtherdetails, criteria and an application form see the New Zealand Science and Technology Postdoctoral website: www. frst. govt.nz/Fellowships/Tif.cfm Fellowship Scheme Growth Services Fund These fellowships are for those with a doctoral degree. This fund is intended to assist new initiatives that will have Funding is $58,000 per annum for up to three years and up a significant impacton a business that will lead to substan- to $29,000 per annum for research related costs. Closing tial and sustained growth. Co-funding of up to 50% is of- datefor applications is 3 April 2008. fered. For further details see the website: www. frst. govt.nz/fel- Forfurther details see the website: www.nzte. govt.nz/sec- lowships/PostDocs.cfm tion/ 11964. aspx#acc Maori Education Trust Professions Scholarship Royal Society of New Zealand Travel Grants This scholarship is available to Maori students undertaking This provides for $1,000 to assist students, undertaking research at post-graduate level in a profession where very full-time PhD study in science, to attend their first over- few Maori are represented. It is valued at $5000. Closing seas scientific conference (excluding any conferences they date for applications, April 2008. have been toin Australia). Closing date for applications is For further details, criteria and an application form see the 1 March 2008. website: www. maorieducation.org.nz/sch/post_grad.html For furtherdetails and an application form see the website: www. rsnz.org/awards/travel/ Horticulture New Zealand Scholarship This scholarship is for postgraduate students with a special LB WoodTravelling Scholarship interest in the fruit or vegetable industry. The scholarship is This scholarship is to supplement postgraduate study in for one year and up to $10,000. Applications close 10 March Britain. It is for not more than three years and has an an- 2008. nualvalue of $3000. Closing date for applications is 1 March For further details, criteria and an application form see the 2008. : website: www.hortnz.co.nz/communications/pdfs/Schol- For further details, criteria and an application form see the Brochure.pdf website: www.nzvcc.ac.nz New Zealand Postgraduate Study Abroad Award Shirtcliffe Fellowship This award is available to postgraduate students enrolled This fellowship is to assist graduate students of outstanding in either Doctoral or Master’s degree programmesat a New ability and character to continue their studies. The Fellow- Zealand institution, whose research would benefit from up ship is for up to three years at a value of $5,000 per year. to six months of study or research overseas. The value of Closing date for applications is 1 March 2008. the award is up to $10,000 depending on the proposed project. Closing date for application is 1 May 2008. For furtherdetails, criteria and an application form see the website: www.nzvcc.ac.nz For further details see the website: www.newzealandedu- cated.com/int/en/institutions_courses/scholarships/out- William Georgetti Scholarship going/new_zealand_postgraduate_study_abroad_award This scholarship is to help encourage postgraduate study 40

New Zealand Trace Elements Group Conference 2008 TOpicCswill include:

Trace elements in the environment, agriculture and horticulture: from natural geochemical processes to modern anthropogenic impacts. i icc(@emalototleM iMateameteraar i essential, non-essential, from intakes % and biochemistry to epidemiology. Analytical techniques for measuring trace elements: from ensuring analytical accuracy and precision to state-of-the-art instruments. Web: www.tracenz.org

Venue: - = - : is Pe WEL Energy Trust fiPal ls ~ Academy of Performing Arts | a ‘i University of Waikato | Hamilton, New Zealand Bolt ated aoe 7 i | piraccenz Pl m3 ie)ee : . = Diary dates: eae Feb2ee

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