Inside

Volume 79, No.3, July 2015

Articles and Features

128 Electrospray ionisation – a simple prelude to the understanding of other mass spectrometry techniques William Henderson 132 Carbon sequestration chemistry John McDonald-Wharry 137 The chemistry and metallurgy of beryllium Onyekachi Raymond, Lakshika Perera, Penelope J. Brothers, William Henderson, Paul G. Plieger 144 Heroes and plots in chemistry storytelling Peter Hodder 149 Metals: ancient and modern Robert H. Bennett 157 Some unremembered chemists: Henry Edward Armstrong, FRS (1848-1937) Brian Halton

Other Columns

120 Comment from the President 154 Correspondence 120 From the Editor 155 Patent Proze 121 July News 161 Dates of Note 136 Corrigendum Inside back Conference calendar

119 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 News Comment from the President. New Zealand Institute of Chemistry This issue I’d like to draw longer was there a stream of bright young technicians supporting chemical sciences your attention to the growing and learning in our labs and project teams and need to sustain and grow feeding through to our oil, paint, milk, food and other man- July News our technical and science ufacturing industries. More recently, this qualification has technician workforce been reviewed and is to be again replaced by the New Zea- in the face of changing land Diploma in Applied Science beyond December 2016. NZIC News Resigned posed for the centenary celebration tertiary education struc- photo. The day ended with cocktails David Bibby, former Dean of Science Auckland Branch: Mr Malcolm tures, the changing needs Is the current process delivering skilled science technicians and canapés and a self-guided tour of at Victoria University of Wellington, Smith, Mr Thilliar Varnakulasing- of employers and a future to meet our needs as scientists and science employers, and the Museums' WWI exhibition. was appointed a Companion of the ham, Mr Amir Ali, Mr Lindsay Main. President/Editor where demand for these in the wider industrial community? Does it meet the stu- Order of New Zealand (CNZM) in the On the Saturday, a day of lectures skills is certain to grow. dents’ needs in terms of gaining suitable experience and Manawatu Branch: Mr Christopher skills to springboard to a career? Does this meet New Zea- Queen's Birthday Honours. aimed at a more general audience Having worked within the Rowse. government science sys- land’s anticipated demand for technicians in terms of the was presented to a near full lecture tem since 1979, I’ve seen relevance of training and in the quality and quantity of stu- Membership Wellington Branch: Dr Barry Dent, theatre, including a lively talk by Pro- big changes in the way dents being trained? So many questions. Dr David Bull, Dr Hilary Hamnett, Dr fessor Gordon Miskelly about the his- that we as a nation have managed the training and quali- New Members 2014-2015 (MNZIC) David Herman. tory of the school and the “academic The Royal Society of New Zealand is considering forming lineage” of alumni. fications for science technicians. I recall that every year an expert advice panel to look at the future science tech- Auckland Branch: Dr Robyn Somer- throughout the 1980s at DSIR Chemistry we took on a clus- Canterbury Branch: Dr William (Bill) nician workforce. Wearing both my NZIC and RSNZ hats, ville (ESR); Dr Ivanhoe Leung, A/Prof The whizz bang chemistry display was ter of bright new high school students enrolled for NZCS or Swallow, Miss Anne Wignall. I would welcome your feedback and comments with re- Christian Hartinger (University of a highlight of the day that saw the NZCE qualifications. The students worked within assigned spect to what extent there are perceived to be problems Auckland). Overseas: Dr Campbell Page. children in the audience mesmerised research teams, learning the essentials of laboratory skills and what those problems are. This would certainly assist development while undertaking course work most days at Waikato Branch: Dr Anatoly Chemy- by exploding balloons and frothy, the Royal Society to decide how high a priority to give to Deceased the local polytech. It wasn’t a perfect system, but it placed shev (Ruakura Research Centre); Dr fizzy and bubbly lab experiments. this issue and help in framing the future work programme. Tours of the glassblowing laborato- young people into laboratories and enabled them to work We in the chemistry profession can only benefit through Andrew P Vogt (Scion). Auckland Branch: Mr Birger Nord- alongside scientists and engineers. For many it was a direct mark. ries proved very popular, as did the improved structures and processes that lead to enhanced Manawatu Branch: Dr Catherine tours of the newly renovated chem- path to a career outside DSIR in industry - an important quality and quantity of trained science technicians. We as Whitby, Dr Andrew Sutherland- Wellington Branch: Dr Anthony istry laboratories. conduit to get sharp young people trained and into our a nation need to get it right. manufacturing sector. For some, the career path stayed Smith, Dr Patrick Edwards, Mr Nigel Woolhouse. Two days of celebrations concluded within DSIR and its successors. For a few, there was a desire Finally, as we went to press, we learnt that Distinguished Kerr (Massey University); Dr Maurice Otago Branch: Mr Rex Malthus. with the exclusive gala dinner held to take on more rigorous study within a university course Professor Margaret Brimble of the University of Auck- Judd (IPC Tertiary Institute); MrAllan in the University marquee on the Old structure. Many of us know current and former colleagues land has received a global award for being an outstanding Dodge (Moed Consulting). Government House lawn. who took one of these paths, and the value that this cre- achiever in her field. She was named as one of this year's Auckland Canterbury Branch: Mrs Lesley Park- ated for them, for their employers and for our economy. Distinguished Women in Chemistry or Chemical Engineer- Congratulations to Distinguished ing by the International Union of Pure and Applied Chemis- er (Westmount School); Mr Scott The University of Auckland The much respected NZCS/NZCE education pathway didn’t Franklin (Christ’s College); Ms Miri- Professor Margaret Brimble being try. Margaret has been a Fellow of our Institute since 1999 The School of Chemical Sciences cen- last. The NZ Qualifications Authority, established in 1989, am Bugler (Linwood High School). named as one of this year’s Distin- and is the first New Zealander to be named for this biennial tenary was celebrated with two days guished Women in Chemistry or initiated changes in the structure, function and funding of award. Our very best congratulations. Otago Branch: Dr Anna Garden (Uni- of events to showcase the wealth of Chemical Engineering. The biennial polytechs and heralded a new technical education path, Ian Brown versity of Otago). talent that resides within the School awards, which honour prominent with the introduction of a National Diploma in Science in Callaghan Innovation and a look back at a rich history of women chemists from around the 1997. The mechanism for training students in situ within NZIC President 2015 the government agencies and other bodies dried up. No Overseas: Dr Erin Leitao (Bristol, UK). transformation, from humble begin- world, were handed out by the Inter- nings in an old courthouse in the national Union of Pure and Applied Student members 1800s, to a diverse School thriving Chemistry. For more details, follow From the Editor Auckland Branch: Winnie Cao, Yu Li across campuses at six different loca- the NZ Herald link: www.nzherald. (University of Auckland). tions. co.nz/technology/news/article. Following on from the reader than resized within a document. cfm?c_id=5&objectid=11451801 survey results reported in the Manawatu Branch: Ewan Fisher, Owing to the special anniversary, October 2014 issue, you may I have also been contacting people directly to solicit con- Josh Blazek (Massey University). the annual Research Showcase was Distinguished Professor Margaret have noticed some changes tributions which I hope will be reflected in more articles held at the Auckland Museum where Brimble, was also awarded a 2015 that have been made to our from chemists in industry and those in schools/education Wellington Branch: Benjamin the school’s PhD students presented Vice-Chancellor’s Commercialisation journal this year in response to as well as other disciplines. There have been a number of McVey, Emma Wrigglesworth, Tai- their research. Matthew Calvert was Medal at the University Research Ex- suggestions for improvements. high profile scientists who have visited various institutions tusi Taufa, Victoria Woolner, Sophie awarded first place for his 15-minute cellence Awards in May. Our publisher, Rebecca Hurrell, throughout the country over the past few months but un- Geyrhofer (Victoria University). oral presentation, A biomimetic syn- has updated the fonts to give fortunately it has not been possible to extract articles from thesis and structural revision of Yure- Dr Christy Wang was awarded one of the articles a fresher look and them. Once again I would encourage you to get in touch if Canterbury Branch: Vivek Poonthiyl, mamine, winning the $500 Thermo- the five Vice-Chancellor’s prizes for some regular features now have a new format. A change you have any ideas for a special feature to appear in our Jean-Batiste Lena, Nic Bason, Ben- Fisher prize. The day was also marked the best doctoral theses at the Uni- of printer has also improved the overall appearance of the journal from a distinguished visitor you are hosting. The jamin Wilson, Lance Buckett, Shane by three-minute talks and poster pre- versity of Auckland in 2014. Christy journal. One consequence of the latter change is that pho- reader survey highlighted the fact that members would ap- Verma, Alexandra McNeill (Univer- sentations from PhD students. was also awarded the Briggs prize tographs and images must be of sufficiently high resolution preciate some more variety in content so let’s try to make sity of Canterbury). from the School for the best PhD dis- to ensure they are good quality once printed. Please bear that happen. After the keynote address from Pro- sertation in 2014. Congratulations to this in mind when contributing your articles or news – it Otago Branch: Hannah Davidson fessor Robert H Grubbs followed by Christy, and her supervisor, Dr Jona- Cath Nicholson is preferable to send the original images separately rather (University of Otago). Professor Russell Egdell, the School thon Sperry, for mentoring Christy to 120 121 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

tors of the compound TH-4000, Dr arrive in the next couple of months. win. Auckland was the other finalist, Florence Houdouin - an intern stu- Adam Patterson and Dr Jeff Smaill, John Robertson is taking six months coming off a semi-final where they dent from France. Florence gradu- senior academics from the Auckland of sabbatical leave. He will be work- demolished Otago 300-120. There ated from the Institute of Technol- Cancer Society Research Centre and ing on terrestrial drone technol- was only five points in it going into ogy in chemistry (IUT) and also went the Maurice Wilkins Centre, have ogy and spending a month in North the final segment but they put the on to obtain a Bachelor degree in collaborated with a NASDAQ-listed -Western Australia flying drones with foot down and pulled away to win chemistry. Florence is currently in her American biotechnology company, an Aboriginal group mapping their 210-155, taking home the trophy. It second year of a Master’s degree in Threshold Pharmaceuticals (TP), to traditional lands. Mark Duxbury is was an amazing experience for them, organic chemistry at the University of advance the compound to this stage. undertaking mangrove elemental competing against a number of won- Maine in Le Mans, France. Florence TH-4000 is described by Threshold as analysis (which involves getting up derful teams, and if any other chem- has recently joined Peter Steel’s re- a molecular-targeted, hypoxia-acti- to his knees in mud collecting man- istry students ever get the chance to search group as part of her Master’s vated irreversible epidermal growth grove leaf samples, then measuring take part, seize the opportunity with degree. Her research will focus on factor receptor (EGFR) tyrosine ki- nitrogen isotopes in the leaves). John both hands. the synthesis of heterocyclic sulfox- nase inhibitor (TKI) that may over- Milligan has gone to a 0.6 position, ides and sulfones for use as ligands come resistance to therapy from con- where he looks after the Founda- If anyone wants to see the show, the in metallosupramolecular chemis- PhD students who gave 15 minute talks at the Research Showcase, together with the ventional EGFR-TKI compounds. “We tion Chemistry students. Heather most recent episodes are on SkyGo try. Outside of chemistry, Florence Dean of Science, Prof John Hosking (left) and Head of School, Prof Kevin Smith (4th from are grateful for the funding support Aspeling, formerly a teacher at Ho- for free (you have to make an account enjoys mainly dance, and hiking from nd the let). The winner was Matthew Calvert (2 from right). from the Ministry of Business Inno- wick College, has been appointed as to view them, but you don’t have to time to time. Florence is eager to dis- vation and Employment, the Health a Chemistry Teaching Assistant for be a Sky subscriber). cover more of New Zealand’s nature. Research Council of New Zealand and If anyone knows of good places to go both the Foundation and First Year Visitors the Maurice Wilkins Centre over the courses. around Christchurch then she would years,” said Drs Patterson and Smaill. We have welcomed a number of visi- love to hear from them. Canterbury tors recently: Aoife Noonan - a stu- In September 2014, TP licensed ex- dent from Utrecht University in the Leyla Bustamante – working in the clusive worldwide rights to a clinical The annual NZIC BBQ for 2nd, 3rd and Netherlands. Aoife is in her second department with Emily Parker as a development programme based on 4th year university and polytech stu- year of an MSc in drug innovation Research Associate. Leyla completed TH-4000 from Auckland UniServices, dents as well as postgraduates and and is doing a research internship at her first degree at the Universidad Na- the technology transfer company NZIC members was held on 12 March Canterbury, with Antony Fairbanks’ cional in Bogotá, Colombia. Following of the University of Auckland. “We at the University of Canterbury Staff group. Aoife is originally from Ireland a two-year spell researching molecu- are delighted to join forces with our Club and was well attended by hun- and completed her BSc in the chemis- lar markers of drug resistant malaria friends and experts in the field of tu- gry hoards. try of pharmaceutical compounds at at the International Centre for Train- mour hypoxia and hypoxia-activated University College Cork before mov- ing and Medical Research (CIDEIM) in prodrug technology at the University University of Canterbury ing to the Netherlands. In her spare Cali, Colombia, she moved to Spain to of Auckland, and look forward to our time Aoife loves to travel and is look- undertake a PhD at the Universidad PhD student Anna Farquhar (Dow- collaborative efforts in the develop- ing forward to seeing New Zealand Complutense in Madrid, investigating Members of the School of Chemical Sciences pose for the centenary celebration photo. nard group) had a very successful ment of TH-4000 as a potential new while she is here. changes in the expression of the oxi- therapy that has potential to over- week at the Advanced Materials & dative cascade genes in malaria para- come the limitations of currently Nanotechnology (AMN7) conference Natacha Massenet - a visiting intern sites following chloroquine exposure. available EGFR-TKI therapies,” said Dr in Nelson, 8-12 February (www.mac- student from New Caledonia. Nata- Postdoctoral positions led her to the Pearce of Threshold Pharmaceuticals. diarmid.ac.nz/event/amn-7/). She cha joined Ian Shaw’s Human Toxi- United Kingdom where she first stud- won the best poster prize and a prize cology Research Group as part of her ied mechanisms of action and resis- Auckland University of Technology for the best dancing. Former Down- Master’s degree in ecotoxicology. tance to antimalarials, before joining ard PhD student, Dave Garrett, won For Natacha’s research project she the Wellcome Trust Sanger Institute The Auckland University of Technol- the prize for the best beard. Shane will be studying the mechanisms of as a Scientific Manager for the ma- ogy has recently appointed two Pro- Telfer (Massey University), a former estrogenicity of the ubiquitous envi- laria programme. At the Sander In- fessors of Chemistry in the School of member of the Hartshorn group, was ronmental pollutant, dibutylphtalate stitute, Leyla provided operational Applied Sciences. Nicola Brasch and an excellent Conference Chair. (DBP) and assessing its risk to human management to the laboratories to Allan Blackman both obtained their health. support the delivery of their planned PhD degrees under the supervision of In June of last year Steward Alexan- goals and also undertook research Dave Buckingham and Charles Clark. der was part of the UC team for a Before coming to New Zealand Na- focused on the study of protein-pro- Nicola’s interests centre around the new series of University Challenge, tacha was studying for her Master’s tein interactions to understand how chemistry of vitamin B , while Allan’s along with Gerald Pfiefer, Rachel 12 degree at the Université de Lorraine, the malaria parasites invade human SCS Centenary Research Showcase Committee members with the Head of School and research focusses on the synthesis Harris, Daniel Redmond and Liam northern France. She graduated with erythrocytes, which resulted in the Vice-Chancellor. From left to right: Prof Kevin Smith (HoS), Dr Tilo Soehnel, Dr Viji and reactivity of complexes con- Boardman. The programme has two diplomas: a DUT (university un- Sarojini, Mr Tasdeeq Mohammed, Dr Peter Swedlund, Mrs Anoma Ratnayake, Dr Ivanho identification of a receptor that is es- taining multidentate amine ligands. been televised on Prime at the un- dergraduate degree) in biology en- Leung, Dr Jianyong Jin (Committee Chair) and Prof Stuart McCutcheon (Vice-Chancellor). sential for erythrocyte invasion and The school is currently renovating a fortunate time of 11.30am on - Sat gineering from Université de Stras- has a clear vaccine potential. Leyla large chemistry research laboratory, urday. Despite a shortage of science such a high level of achievement. search, two University of Auckland bourg (2012) and a Bachelor’s degree recently moved to New Zealand, fol- and has recently taken delivery of questions, Stewart gave his share of medical oncology researchers along in environmental biology with a major lowing her kiwi husband who took a Congratulations to all the students a glove box, a Cary100 UV-Vis spec- answers, ranging from T. S. Eliot, to with their dedicated teams have in environmental health and chemis- position as a research scientist within who graduated at the autumn gradu- trometer, a stopped-flow instrument chlorophyll, to The Proclaimers. The developed a new anti-cancer com- try (Université de Lorraine, 2013). In the Protein Science and Engineering ation ceremony earlier in May. and a microwave plasma instrument. team secured a place in the semi- pound that will advance to human her spare time Natacha would love to Team of Callaghan Innovation. Leyla A Bruker 400 MHz NMR and a laser finals against the favourites – Victo- Phase II clinical trials. The co-inven- explore the South Island. enjoys cycling, travelling and cooking, After a decade of discovery and re- flash photolysis instrument are set to ria - and came away with a narrow 122 123 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 and is looking forward to doing some copy and this morphed into a interest laide University, Metal nanoparticles Jameson group PhD student Casey Matthew Clarkson has joined the de- Recently submitted theses in the de- kind of extreme sport, as she is given in studying the fundamental proper- and clusters. Davies has been awarded both a partment to undertake postdoctoral partment include: to believe all New Zealanders do. ties of gas phase metal clusters, both Freemasons' Postgraduate Scholar- research using metal isotope systems PhD: experimentally and computationally. otago ship and also a Brooker United Travel to investigate the de-oxygenation Maryne Dubois, a student from Paris, This has subsequently led to the ex- award. Concluding their PhD studies of the oceans during warm 'super Megan Grainger: Kinetics of conver- has recently joined Antony Fairbanks’ ploration of metal clusters in photo- Professor Larry Overman (Univer- in the Brooker group, Matthias Fell- greenhouse' climates occurring 90 sion of dihydroxyacetone to methyl- group as part of her Master’s degree catalytic systems. Greg is also actively sity of California, Irvine) was in New ner successfully defended his PhD million years ago, as part of a Mars- glyoxal in honey (supervisors Merilyn in molecular chemistry majoring involved in developing innovative Zealand in March to give the 2015 thesis in May and Antonia Seidel re- den-funded project led by Claudine Manley-Harris, Jo Lane and Emeritus in organic chemistry. Maryne com- teaching approaches to improve lear- Ferrier Lecture. He visited the Univer- cently presented a research seminar Stirling. Matthew’s PhD work at Professor Richard J. Field (University pleted her undergraduate studies in ing outcomes, as exemplified by his sity of Otago to meet with staff and about Kinetic studies of lactoperoxi- the University of Edinburgh, linking of Montana, Missoula, USA). biomedical science and during that presented an excellent seminar, co- dase. ocean acidification to widespread university, state and national teach- John McDonald-Wharry: Carbonisa- period she completed two intern- sponsored by the NZIC, titled Linking mass extinction 252 million years ing awards. When not inundated tion of harakeke (Phormium tenax) ships in biology and pharmacology. chiral rings at stereocenters. In March, Daniel Killeen presented ago, has been published in Science with administrative duties, he likes to biomass for potential application as During her study Maryne was most his PhD research Carrots, beer and (2015, 348, 229–232). travel (with his family – for pleasure), composite reinforcement (supervi- interested in chemistry and so did a University of Otago, Department of mānuka: quantitation and localisa- eat and imbibe local produce, and sors Merilyn Manley-Harris and Kim specialisation in chemistry in the last Chemistry tion of bioactive natural products by tries to balance gastronomic excesses waikato Pickering). year of her degree. In her spare time with exercise. spectroscopic methods co-supervised Maryne enjoys sports and dancing. The Polymer and Supramolecular by Nigel Perry and Keith Gordon. University of Waikato MSc: Maryne would like to go on to do a Group (Moratti and Hanton) wel- Daniel then successfully defended Manawatu PhD in chemistry incorporating phar- comed Eleonore Mathis as a proj- his thesis, which was placed on the Professor Doug Macfarlane, the RSC Daniel Bernstein: Development of a macology. ect student from France here for six Division of Sciences Exceptional The- Australasian Lecturer from Monash method for trace analysis of dioctyl Massey University, Institute of Fun- weeks. Sophie Mills recently gradu- damental Sciences sis List. He has published four pa- University, Australia, recently visited sodium sulfosuccinate by liquid chro- Nicole Behme joined Owen Curnow's ated from the group with a well- pers from his thesis work including a and gave a very well attended lecture matography mass spectrometry and group as a research intern as part of Dr Vyacheslav V. Filichev in collabo- deserved MSc with distinction. The study in New Phytoligist which used on Ionic liquids for sustainable chem- its application to samples from the her Master’s degree in synthesising ration with Dr Gillian E. Norris has group’s work was highlighted on Our Raman microscopy to demonstrate istry: applications in the chemical-, MV Rena incident (supervisor Meri- ionic liquids. Nicole is from Germany been awarded a Cancer Society grant changing world (Radio New Zealand that mānuka sequesters herbicidal materials-, electro- and bio-sciences. lyn Manley-Harris). and completed research for Tech- for a project devoted to helicases, National, 26 March) which gave an β-triketones in leaf oil glands. Daniel nische Universitat Chemnitz where G4-DNA and drug design ($160,568 account of recent “experiments” in We welcomed Blair Munro as a new Alicia Lloyd: Analysis of amino acids has accepted a position with Plant & in manuka honey (supervisor Merilyn she examined the self-assembly of over two years). dropping our gels from a helicopter Food Research in Nelson, where he first-year tutor in chemistry and fare- Janus particles. In addition, Nicole to show how tough they are. Stephen welled Pat Gread who retired recently Manley-Harris). Dr James M. Withers, who success- will be performing research relating was a scientific assistant involved in Moratti returned from Morocco after 26 years of service as a techni- Steven Salmon: An estimation of the fully finished his PhD under supervi- to marine natural products. synthesis dyes and solvatchromatic where he presented the group’s work cian in the department. Pat was in concentration of atmospheric nitrous sion of Dr. Filichev and Associate Pro- th measurements with ionic liquids. on supramolecular gels at the 13 In- Jeremy Rooney is a recipient of a Cal- charge of the first-year laboratory oxide containing complexes (supervi- fessor Shane Telfer, has been offered When she’s not studying Nicole likes ternational Conference on Polymers laghan Fellowship to undertake PhD when she started at Waikato, but for sor Jo Lane). hiking, biking, painting and travel. a postdoc position in the laboratory and Advanced Materials. research in the Gordon group. Jere- many years was in charge of the sec- of Dr Glenn Burley in the Depart- my will be working with NZ Steel and ond- and third-year organic and inor- Alice Wang: Elucidating the modes of Amelia Albrett is working in the De- ment of Pure and Applied Chemistry The exhibition The world of Joseph is co-supervised by Steve Moratti. ganic laboratories. Her experience and action of the antitumour New Zea- partment as our new instrument at University of Strathclyde, UK. Ja- W. Mellor (1869-1938) chemist, ce- Jonathan Barnsley has been selected dedication to that role was absolutely land marine natural product ptero- support person. Amelia completed mie will start working on the design ramicist, & cartoonist ran 17 De- as a finalist for the AMP Ignite Pitch invaluable. She was the “go to” person cellin A (supervisor Michèle Prinsep). cember 2014 – 5 March 2015 at the her PhD in chemistry in 2009 at the and preparation of modified DNA Your PhD competition. He will pres- for any problems in the lab and many Megan Wyllie: Applications of - hy De Beer Gallery, University of Otago University of Auckland with Penny nanostructures, DNA-binding mol- ent how dye-sensitised solar cells students, demonstrators and staff droxymethylphosphines (supervisor Central Library. Notable items on Brothers, working on the synthesis ecules and new surface immobilisa- work and why solar energy is an in- have benefitted from her wisdom and Bill Henderson). of novel boron porphyrin deriva- tion chemistries in July 2015. display included a manuscript ‘text- teresting realm of research. Geoffrey experience in these lab classes. Out- tives. Following this, she has been a book’ notebook compiled by Mellor side of these classes, Pat was always Dr Gareth J. Rowlands welcomed Smith is speaking at the upcoming In- BSc (Hons): Postdoctoral Fellow at the University in 1888-1890, testimonials from Pro- ternational Conference on Advanced a very willing helper in other areas. As Leonie McKenzie who joined the Richard Brunton: The extraction, of Otago in Christchurch with Tony fessor James Gow Black and George Vibrational Spectroscopy in Vienna the technician in charge of the Micro- Massey synthetic chemists for her quantification and characterisation Kettle and Christine Winterbourn in M. Thomson, and Mellor’s chemistry about his work titled Imaging the ToF mass spectrometer, she has been PhD and Lise Deuilhe as a French in- of kavalactones from Piper methysti- the Centre for Free Radical Research. publications including his Compre- desolate microscopic landscape of invaluable to many research proj- tern for four months. cum (Kava) (supervisor Merilyn Man- This research was concerned with hensive treatise on inorganic and cheese using Raman microscopy that ects, training students and running theoretical chemistry (1922-1937). ley-Harris). investigating the role of white blood The Institute of Fundamental Sci- was conducted in conjunction with samples, including those for chemical Co-curator Lyall Hanton opened the cells, free radicals and antioxidants ence welcomed several international Fonterra. Keith Gordon is an invited services. Pat could always be relied Geoffrey Tait: Natural products exhibition and presented a public in health and disease. Amelia enjoys guest speakers to the campus. These speaker at the meeting andGreg Huff upon to assist capably with school from Malaysian fungi (supervisor Mi- lecture on the life Mellor in Febru- travelling, dancing and spending time speakers and their talks were: Pro- who is also attending the conference visits, university open days and after chèle Prinsep). with family. ary. An online version of the exhibi- was a recipient of a travel scholar- hours publicity events such as Chem- fessor Joshua J. Pak from Idaho State Hayden Thomas: Synthesis & char- tion is available at:www.otago.ac.nz/ ship. quest. Pat’s talents extend well be- Gregory Metha has arrived as an University, I-III Bimetallic complexes: acterisation of mercury and rhodium library/exhibitions/mellor/ yond chemistry. She is an enthusiastic Erskine Fellow. Greg is currently the molecular precursors for chalcogen- NHC complexes containing polyfluo- Congratulations to Chris and Megan cyclist, walker and bridge player, and Head of Chemistry at the University of ide semiconductors; Associate Profes- Bill Hawkins was invited to speak at roaryl substituents (supervisor Gra- Larsen on the birth of their baby an excellent cake baker and decorator, Adelaide where he started as an ARC sor Ketul Popat from Colorado State SynthCon3, a biennial conference fo- ham Saunders). University, Micro/Nano-engineering daughter Mia, and to Alvie Lo and baking cakes for staff morning teas Research Fellow in 1997, transferring cused on synthetic chemistry in Aus- Tye on the birth of their second child, of material surfaces for tissue engi- and for grandson Aidan’s birthday par- New students include Huma Saeed into academia in 2003. His research tralia, held in the Yarra Valley in April daughter Aeress. Mothers and chil- neering and regenerative medicine; ties. We wish Pat all the very best in who is doing an environmental interests were initially focussed on 2015. dren are doing well; fathers are both and Professor Greg Metha from Ade- her well-deserved retirement. chemistry PhD with Adam Hartland gas phase molecular (laser) spectros- writing-up. 124 125 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 and Michael Mucalo on lakes and range of public engagement activities source where she developed her describing the topological and graph phosphorus, Hayden Thomas who related to environmental science. expertise in the use of synchrotron theoretical properties of fullerenes, is undertaking a PhD with Graham Her research now focuses on com- techniques. She has been a member and then pointed out the many un- Saunders on synthesis and reactions munication activities by scientists. of the powder diffraction and small solved and interesting mathematical of metal complexes of fluoroaryl- angle X-ray scattering proposal ad- (and chemical) problems open in this substituted N-heterocycle carbenes, Dr Alexander Maxwell of Victoria’s visory committees at the Australian field. A few examples he discussed in- Hannah Lowry who is undertaking a History Department provided the Synchrotron, and represented New cluded i) how to generate all possible Masters project with Michael Mucalo April seminar and gave a fascinating Zealand synchrotron users on the non-isomorphic graphs for a fixed on controlled release delivery of bio- and illuminating discourse From al- user advisory committee. Her current vertex count, ii) whether fullerenes actives/nutrients of relevance to the chemy to Moseley: a history of the role is to provide synchrotron advice are Hamiltonian (Barnette’s conjec- agritech sector, Jacob Shrubsall who elements. He began by pointing out and expertise to the NZ science com- ture) and what is the number of dis- is undertaking a Masters project with that elemental theories of matter munity. tinct Hamiltonian cycles, iii) the Paul- Michèle Prinsep on bioactive natu- have a long history and illustrated the ing bond order and the number of ral products from marine bryozoans, four-element theory from ancient Victoria University – SCPS perfect matchings and iv) the search Lewis Dean who is carrying out his times to the beginning of modern his- for suitable topological indices to find tory. He then pointed out that Marie- The 2014 Ferrier lecture was deliv- Honours project with Michèle Prin- ered by Professor Larry Overman the most stable fullerene structure Anne and Antoine Lavoisier together 9 sep on peptides from nudibranchs (Chemistry Department, University out of the many (N ) possibilities, or and their bryozoan prey and Con- first provided the beginnings of our how to pack fullerene cages in 3D current understanding of elements of California-Irvine) on March 3. He nor Haisley-Bossard who is carrying visited the Ferrier Institute and gave space (Hilbert problem). His research out his Honours project with Merilyn in the late eighteenth century. Dur- group in Albany is now developing a a research lecture the previous after- Prof Kate McGrath and Lia van den Kirkhof Manley-Harris studying the nectar of ing the nineteenth century, various general-purpose program (Program discoveries enabled Mendeleev to noon and then delivered the more Dactylanthus taylorii. general named lecture in the evening Fullerene) that creates 2D graphs and an Associate Professor at Richmond. over the past few years and provided devise his periodic system. Then the accurate 3D structures for any fuller- Although it was a select audience, he a summary of his areas of operation. great discoveries of quantum me- in Rutherford House on the VUW WELLington ene isomer through various different gave a fascinating lecture. Dr Gregory chanics enabled scientists to con- Pipitea campus. The Overman group Among the students who graduated has developed an amazing ability to graph-theoretical methods and algo- F. Metha (Department of Chemistry, W.E. (Bunt) Dasent, a longstanding struct a complete table of elements in May was Pauline Calloch, super- design and synthesise new molecules rithms, and subsequently performs a University of Adelaide) gave a semi- member of the Branch, former VUW in the early twentieth century culmi- vised jointly by Dr Ian Brown of Cal- for molecular level investigations in topological analysis. nar entitled Combining theory and senior lecturer in Chemistry, Bursar nating in Moseley’s completion and laghan Innovation and Professor many areas of science. The research experiment to understand the pho- and eventually its Pro-Vice-Chancel- prediction of the missing long-lived Associate Professor James D. Crowley Ken MacKenzie (VUW). Dr Calloch’s centres on the invention of new tocatalytic potential of metal clusters lor died on July 11. elements. (Otago University) visited and gave research was on New reaction paths transformations and strategies in on titaniaand met with relevant staff an excellent well attended seminar members. His June 5 seminar cov- for advanced SiAlON/TiN compos- The first meeting of 2015 was the May saw Dr Bridget Ingham of Cal- organic synthesis, and the total syn- entitled Functional (supramolecular) ered the background to the knowl- ites. Lia van den Kerkhof, one of the March meeting addressed by Dr laghan Innovation speak on Shining thesis of complex organic molecules molecular architectures and ma- edge that gold nanoparticles of less staunch student representatives on Rhian Salmon (Victoria University of synchrotron light on materials sci- having promising biological proper- chines: It’s as easy as 1,2,3 ‘click’ in than 2 nm in size are catalytically ac- the 2014 Branch Committee, gradu- Wellington) on Adventures and op- ence. She discussed the nature of ties. The named lecture was entitled: late March. The cycloaddition of an tive. He went on to show that strong ated with her MSc degree from joint portunities made possible by study- synchrotron facilities - large X-ray Natural products synthesis: insights organic azide with a terminal alkyne evidence is emerging showing that supervision by Justin Hodgkiss, Kate ing chemistry in which she described light sources, producing intensely into chemical reactivity and inspi- catalysed by Cu(I) readily provides very small gold clusters, comprising McGrath and John Spencer. Her the opportunities available after focused beams six or more orders of ration for new antitumor agents in 1,4-disubstriuted 1,2,3-triazoles (1) only a dozen or so gold atoms, are re- work encompassed the synthesis of taking a science degree because we magnitude brighter than laboratory which Larry described two of his re- and it is this reaction that has led the sponsible for most of the activity of anthracene-based liquid crystals as want to make a difference. This could instruments. The increased flux thus cent natural products total synthesis Crowley group to much success in catalysts prepared by crude methods, photon up-converters for solar cells. be as true in medicine, new tech- available offers better signal to noise projects, one that led to new strate- area of functionalised molecular - ar even though such small clusters con- nologies, psychology and physics as ratios and reduced measurement gies for coupling complex molecular Others who have completed their chitectures. stitute <1% of the total gold content environmental sciences such as con- time, to the point where perform- fragments and another to a new class PhD degrees recently include Mat- on the surface. He then went on to servation biology or climate change ing real-time studies is possible. The of preclinical epigenetic antitumor thias Herzog (Jim Johnston), Teresa discuss his current studies explor- research. But what aspects of our X-ray wavelength is also tuneable, agents. His more ‘hard core’ Monday Vaughan and Melanie Nelson (both ing the potential of a range of metal science really do make a difference? allowing element-specific informa- lecture at Gracefield covered aspects John Spencer). Ben McVey and Lucy clusters such as Au , Au , Au Pd, Ru , Is it the doing, or the understanding? tion to be obtained. She went on to of the epipolythiodiketopiperazine 8 9 6 3 Gloag have left Victoria University to Ru and AuRu , that are ligand stabi- Is it the results or the communication give an introduction to synchrotron (ETP) alkaloids. These are described The lecture concentrated on the 4 3 complete their PhD studies with Pro- lised and experimentally confirmed of those results? She took us on a radiation and illustrate how it can be as highly complex natural products metallo-macrocycles and cages gen- fessor Richard Tilley now at the Uni- to have precisely defined metal cores journey through different aspects of used by way of case studies, including with potent anticancer activity; glio- erated this way and diverged to versity of New South Wales. for use as co-catalysts in photo-cata- her career – from a BSc in chemistry in situ electrochemical corrosion ex- toxin and sporidesmin are examples. discuss their potential use as anti- lytic processes involving various TiO On 8 June, Ken McKenzie hosted and PhD in atmospheric chemistry – periments, nanoparticle formation, bacterial, anti-cancer and drug de- 2 Professor Peter Schwerdtfeger, 2014 substrates. a visit by Professor Ivar Reimanis to becoming an Antarctic research amorphous metal carbide fuel cell livery agents. Dr Kelling Donald (De- Rutherford Medallist (Centre for (Metallurgy and Materials Depart- scientist and climate science com- electrode materials, structural tran- partment of Chemistry, University of Dr Ben Clark, a former VUW chem- Theoretical Chemistry and Physics, ment, Colorado School of Mines). He municator. She took a critical look sitions in polymers, and the mimick- Richmond, Virginia) visited at the end istry honours graduate (with Peter Massey University, Auckland) visited works on the development of energy at how (or indeed if) we can make a ing of calcium-binding to protein mi- of March and gave a seminar entitled: Northcote) visited, met with col- the School on March 6 and gave his conversion devices and transparent difference with our science, and how celles in milk. Bridget is now a senior The ionic switch - chemical bonding leagues and gave a lecture that sum- lecture: The topology of fullerenes. armour from waste materials and chemistry in particular influenced researcher at Callaghan Innovation. and relativistic effects in binary metal marised some of his work entitled: He pointed out that fullerenes are gave a seminar entitled: A taste of her life and career. Rhian is a senior She gained her physics PhD at VUW dihalides. He gained his PhD at the Assorted natural products – metabo- three-connected cubic planar graphs ceramics research at Colorado School lecturer in the Science in Context and undertook postdoctoral studies University of The West Indies, had lomics, chemotaxonomy, and drug consisting of pentagons and hexa- of Mines, which highlighted the me- group at Victoria University and has at Imperial College (London) and the postdoctoral experience at Cornell discovery. This knitted together his gons only. He outlined the great chanical behaviour of an unusual ce- designed and co-ordinated a wide Stanford Synchrotron Radiation Light and Darmsadt T.U., and is currently doctoral and postdoctoral studies progress over the last two decades ramic. 126 127 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

Electrospray ionisation — a simple prelude to the understanding of other mass spectrometry techniques William Henderson Article Chemistry, School of Science, University of Waikato, Private Bag 3105, Hamilton 3240 (email: [email protected]) Keywords: mass spectrometry, electrospray ionisation, review, applications C

Introduction tected. This technique is ideal for analysis of non-polar Mass spectrometry (MS) is a powerful analytical tech- but volatile substances such as hydrocarbons, and as Fig. 1. A schematic diagram of an electrospray capillary, showing the nique used in the characterisation of a wide range of an illustrative example, University of Waikato research- ionisation process chemical and biochemical substances. The technique is ers have used electron ionisation mass spectrometry to extensively used in research, across a wide range of dis- provide analytical data on oils recovered from the 2011 which is held at a high voltage (hence, the electro part of ciplines. One of the main strengths of mass spectrometry Rena marine disaster.3 Because electron ionisation typi- the word electrospray). The effect of this is that the drop- is that miniscule amounts of sample are typically needed, cally requires the compound to be volatile (and therefore lets which are formed are enriched in positive ions (if the of low molecular weight, and uncharged) it finds most in the order of micrograms or less. While the study of capillary is positive), or negative ions (if the capillary is B spectroscopic techniques has been a part of qualifica- use in the analysis of small organic molecules. It cannot negative). These droplets are then evaporated using tions such as the International Baccalaureate Diploma be used to directly analyse polar, involatile substances more nitrogen gas, which has the effect of converting the A for some time,1 a new Achievement Standard on Spec- such as sugars or proteins, which typically degrade rather original analyte solution into the gas phase (effectively, it † troscopy has been introduced relatively recently into the than volatilising when heated. Until the advent of elec- has nowhere else to go!). Solubility in a suitable solvent, New Zealand Chemistry Curriculum, which includes the trospray ionisation, many types of chemical substances rather than volatility, becomes the most important factor technique of electron ionisation (EI) mass spectrometry.2 were effectively inaccessible to MS analysis. in determining the likely success of the technique in gen- This article aims to provide, for those perhaps encoun- erating ions that can be subsequently detected. D Electron ionisation is also rather ‘harsh’, the mass spec- tering mass spectrometry for the very first time, a short trometry equivalent of using a sledgehammer to crack discussion on electrospray ionisation mass spectrometry How does it work in practice? Imagine the electrospray Fig. 2. A typical modern electrospray ionisation mass spectrometer open a walnut; it works, but what is formed can some- process applied to the analysis of a solution of sodium (Bruker MicrOTOF); the sample is introduced via a syringe and a syringe as an alternative introduction to this important analytical pump (A) to the instrument’s spray chamber (B). The ion detector in * times pay little resemblance to the original nut. The con- chloride in water. Of course, when sodium chloride is technique. this instrument is a time-of-flight detector (C), which accurately deter- sequence of this is that the molecular ion – the original + - dissolved in water, Na (aq) and Cl (aq) ions are formed; mines the time for ions of differing m/z to travel the length of a long Mass spectrometry starting molecule which has ionised by losing a single spraying this solution through a positively-charged cap- tube under vacuum. Data collection and processing is controlled by a electron – is typically of low intensity, or in some cases + PC (D) In essence, mass spectrometry separates gas phase ions illary produces droplets that have an excess of Na (aq) unobservable. This is because the high energy of the + according to their mass-to-charge ratios (m/z), which is ions. Evaporation of these droplets forms Na (g) ions electron ionisation process imparts excess energy to the which can then be analysed. If the capillary is negatively- simply the mass of an ion m divided by its charge z. There ions formed, causing their fragmentation. This results in Non-polar organic molecules such as alkanes cannot be are two main processes involved in mass spectrometry charged, the resulting droplets are enriched in negative- analysed by ESI directly because they cannot be proton- the formation of various fragment ions. Although this can ly-charged chloride ions, so the electrospray technique – ion generation, and ion detection – and this article will provide a lot of very useful structural information, to the ated; electron ionisation MS remains the technique of focus on the former, of which electrospray ionisation is can be used to study both the cations and/or the anions choice for these substances. mass spectrometry beginner it can be somewhat daunt- of salts very easily. As stated earlier, lack of volatility is but one example. Electrospray ionisation is conceptually ing to be faced with an array of peaks. Furthermore, if it simple, and its beauty lies in the simple and easily inter- not an issue – large cations such as cetylpyridinium (as Obtaining isotope information is molecular weight information which is desired, a weak its chloride salt, used as an antibacterial agent in mouth- preted spectra which are often obtained. The technique or unobservable molecular ion can complicate matters. Many elements exist as a single stable isotope, but other can also be used to illustrate the concept of isotopes. wash) can be analysed very easily, and produces the mass elements can exist as two or more isotopes.6 Electrospray Electrospray ionisation provides a useful and simple al- spectrum shown in Fig. 3. ternative in many cases. ionisation mass spectrometry can be used to demon- Ionisation techniques Applications of electrospray ionisation mass spectrom- strate isotopic composition very easily – indeed the pow- An ionisation technique is the physical process by which Electrospray ionisation etry are not restricted to salts; neutral compounds can er of mass spectrometry was realised in the very early a sample of the substance being investigated – the ana- Today, electrospray ionisation (ESI) mass spectrometry is also be characterised, providing that a charge can be at- days of the technique around 100 years ago, when J.J. lyte – is converted into gas phase ions. Depending on the one of the most important analytical techniques used by tached to the molecule in solution. In practice this means Thomson showed that neon existed as two isotopes hav- chemical and physical nature of the sample, the choice chemists, biochemists and materials scientists; its impor- that the molecule should contain an atom which has at ing atomic masses 20 and 22, in the ratio of 10:1, consis- of an appropriate ionisation technique is absolutely cru- tance was recognised by the co-award of the 2002 Nobel least one lone pair of electrons, for example most (but tent with the average atomic mass of neon being 20.2. cial; an ionisation technique might work beautifully for Prize in Chemistry to John Fenn, the inventor of the tech- not all) of the common functionalised organic molecules Since then, mass spectrometry has been extensively de- one type of substance, but be completely useless for an- nique.4 (alcohols, ketones, esters, amines, amides, carbohy- veloped as a way of providing isotopic information, in ap- other. A good example of this is electron ionisation (EI). drates, proteins...). Protonation of the analyte molecule plications that range from the nuclear industry (the first In this technique, a sample of the substance is heated Fig. 1 shows a schematic diagram of an electrospray cap- can commonly occur [from the small concentration of separation of uranium-235 for an atomic bomb was de- under vacuum, causing some of the substance to vola- illary, and a typical modern mass spectrometer is shown H+(aq) ions which arise from the self-dissociation of wa- termined by mass spectrometry), to archaeological and tilise. The volatilised substance is then bombarded with in Fig. 2. Electrospray ionisation is conceptually quite - geological dating techniques. ter through H O → H+(aq) + OH (aq)], but other cations high energy electrons; these cause the neutral gas-phase 2 simple, and involves forming a very fine spray of drop- such as Na+ (and K+) can also form adducts5 water stored molecules to become positively-charged ions by loss of The power of the technique in providing isotope informa- lets of an analyte solution, using an inert nebulising gas in glass bottles will invariably contain sufficiently high an electron, and the resulting ions are separated and de- tion is best illustrated by an example. Consider the analy- (typically nitrogen); this is the spray part of electrospray. concentrations of dissolved sodium ions from the glass. The solution is sprayed from a fine metal capillary tube, sis of an aqueous solution of silver nitrate. The ESI pro- A neutral analyte molecule M will therefore typically give cess simply transfers Ag+(aq) ions to the gas phase, and * This article was originally written for the general readership of + ChemEd NZ, but with the demise of this publication, is now published in † Substances such as sugars can, however, be converted into more vola- a protonated ion [M + H] , and/or a sodium adduct [M + removes their associated water molecules, giving ‘bare’ + Chemistry in New Zealand as a gentle introduction to mass spectrom- tile derivatives by suitably modifying them, typically by converting polar Na] , and it is normally a very simple process to deter- Ag+(g) ions. Two peaks are observed, corresponding to etry (especially electrospray ionisation) for those unfamiliar with the –OH groups into less polar groups such as –OSiMe , by reaction with a 3 mine the molecular mass of M from the observed ions. the two isotopes of silver (107Ag, 51.8% and 109Ag, 48.2%) technique. suitable derivatisation reagent. 128 129 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 as shown in Fig. 4. 304.18 sis. The material is not a pure substance, but instead ex- - - BrO3 BrO3 ists as a range of chain lengths, with an average of 33 A second example illustrates the ESI MS analysis of the 10 CH(CH3)CH2O repeat units in the polymer chain. The ESI salts KClO3 (potassium chlorate), KBrO3 (potassium bro- mass spectrum of Jeffamine® D-2000 is shown in Fig. 7. - mate) and KIO3 (potassium iodate). The EO3 ions are The spectrum shows two main groups of peaks; the set easily observed in the negative-ion mass spectrum. As t y centred around m/z 1700 are due to the monoproton- - - BrO n s i Cl 2 an approximation we will assume that oxygen exists as N ated ions [M + H]+, where M represents an individual 16 7 e i n t s y a single stable isotope, O. The mass spectrum of a mix- i n t e polymer molecule. The separation between adjacent - - -

ture of the three ions ClO + BrO + IO (Fig. 5) shows all a t i v 3 3 3 peaks is 59 mass units, corresponding to the mass of a - three ions at their expected m/z values, but the appear- BrO -CH(CH3)CH2O- repeat unit, and the mass of an individual R e l ance of the peaks is different for each one. This is due R e l a t i v polymer molecule can easily be obtained, as the mass of to the different elemental isotopic composition of the the ion minus 1 (for the mass of the added proton). The - three halogens chlorine, bromine and iodine. For IO3 , a second set of peaks centred around m/z 1054 is due to single peak is seen, because iodine exists as a single iso- the doubly protonated ions [M + 2H]2+. It is easily seen Br- tope (127I), and a single peak at the expected m/z (127 that adjacent peaks in this set are more closely spaced 60 80 100 120 140 160 60 80 100 120 140 m/z - m/z + 3x16 = 175) is seen (charge z =1). However, for BrO3 together (by 29.5 m/z units, i.e. half of 59). For these two approximately equal intensity peaks are seen, at m/z 200 300 400 500 m/z ions the smaller m/z values arise because the charge z on (a) (b) 127 and 129, which are a consequence of the presence Fig. 3. Positive ion electrospray ionisation mass spectrum of cetylpyri- these ions is now 2. Fig. 6. Negative-ion electrospray mass spectrum of a solution of KBrO 79 81 dinium chloride (structure shown as inset) 3 of two isotopes of bromine ( Br, 50.7% and Br, 49.3%). at capillary exit voltages of (a) 70 V (non-fragmenting conditions) and - - - For ClO3 , two peaks are also seen at m/z 83 and m/z 85, Applications of ESI MS in inorganic (b) 180 V (fragmenting conditions) showing the formation of BrO , BrO 107 + 109 + 2 but the intensities are now in a 3:1 ratio because of the Ag Ag and Br- fragment ions; in each ion the distinctive isotope pattern from (m/z 108.94) chemistry 35 (m/z 106.94) 79Br and 81Br isotopes is observed two chlorine isotopes in unequal proportions ( Cl, 75.8% Although perhaps not immediately obvious, many inor- and 37Cl, 24.2%). ganic substances have features in common with biologi- [M + H]+ Fragmentation cal molecules such as proteins. For example, inorganic y

t salts, and many coordination compounds are water sol-

Inspection of any electron ionisation mass spectrum will s i n uble, ionic, and involatile compounds that decompose e typically show a plethora of fragment ions, which can t

(rather than volatilise) on strong heating. Not surprising- y t i n NH provide substantial structural information. Ions generat- H2N 2 ly, ESI MS can often be usefully applied to the characteri- s i n O t i v e ed by electrospray ionisation can also be fragmented, to e t x

l a sation of many inorganic compounds, providing of course n CH3 CH3 different extents, at will, by causing them to collide with i

R e the substance is soluble in some suitable solvent, and can

residual nitrogen gas molecules from the ionisation pro- t i v e

generate ions (if not already charged). Figs. 5 and 6 (vide a 8 l cess. The effect of this can be seen on the negative-ion supra) have already demonstrated the ability of ESI MS to e electrospray mass spectra of BrO - in Fig. 6. Under low R 3 analyse simple salts, and the reader is refereed to more [M + 2H]2+ fragmentation conditions (Fig. 6a) the parent ion is ob- comprehensive texts for a full discussion of this topic.11 served, but under more fragmenting conditions (Fig. 6b) ions formed by loss of oxygen atoms are seen, giving se- Conclusions quentially BrO - (bromite), BrO- (hypobromite) and finally 102 104 106 108 110 112 m/z 2 Electrospray ionisation mass spectrometry (ESI MS) is a - Br (bromide). Unlike electron ionisation, ESI inherently Fig. 4. Positive-ion electrospray mass spectrum of a solution of AgNO3 showing the two isotopes of silver through the ions 107Ag+ and 109Ag+ powerful analytical technique, which can be applied to produces relatively ‘intact’ ions, which can be subjected almost any compound, providing it is soluble in a suit- to fragmentation if this is desired. - IO - able solvent, and providing it is either charged, or can 500 1000 1500 2000 2500 - BrO3 3 m/z ClO3 Applications of ESI MS to the analysis of become charged by a suitable, gentle, solution-based Fig. 7. Positive-ion electrospray mass spectrum of a solution of Jeffam- process (protonation, addition of alkali metal cations ineÒ D-2000 showing the sets of monoprotonated [M + H]+ and dipro- polymers and biomolecules 2+ Ò such as Na+, and others). ESI MS has revolutionised the tonated [M + 2H] ions, and the structure of Jeffamine D-2000 Given that there is no requirement for an analyte to be

t y characterisation of many types of substances that were volatile in order to be analysed by electrospray ionisation i derstanding of spectroscopic data in chemistry, December 2012, previously relatively inaccessible to mass spectrometry available at http://www.nzqa.govt.nz/qualifications-standards/ mass spectrometry, it is not surprising that the very earli- t e n s techniques, in particular polymers, bio-molecules such qualifications/ncea/ (accessed 10/03/2015). est studies on the technique demonstrated its success- as proteins, as well as involatile inorganic compounds. 3. See: http://sci.waikato.ac.nz/research/projects-and-case-studies/ ful use in obtaining mass spectra of large, involatile and The beauty of the technique lies in its gentle ionisation rena-research (accessed 10/03/2015). a t i v e n sometimes heat-sensitive molecules such as polymers l (which causes minimum fragmentation), and the simplic- 4. See: http://www.nobelprize.org/nobel_prizes/chemistry/laure- R e and proteins. This is important because it allows the mo- ity of the spectra which are often obtained. However, as ates/2002/illpres/mass.html (accessed 10/03/2015). lecular weight (or in the case of a polymer, the molecular with any analytical technique, it has its limitations, and weight distribution arising from individual polymer mol- 5. Sodium and potassium ions are invariably present in low concen- electron ionisation mass spectrometry – the technique trations when solvents such as water and alcohols are stored in ecules having different chain lengths) to be measured. which has been chosen to represent mass spectrometry glass bottles (glass contains considerable amounts of sodium ions). Again, the behaviour can be illustrated by an example, in the Chemistry curriculum – retains an important role 6. Information on the isotopic composition of the elements can be in this case the polyether-amine Jeffamine® D-2000. for the analysis of volatile, and in particular, non-polar obtained from books, for example Aylward and Findlay’s SI Chemi- Polyether-amines find widespread technological applica- 60 80 100 120 140 160 180 m/z organic molecules. cal Data, A. Blackman and L. Gahan, John Wiley & Sons, 7th edi- tions, including the formation of polymers, and as a fuel Fig. 5. Negative-ion electrospray mass spectrum of a solution contain- tion 2013 (or earlier editions). Alternatively, reputable online data 9 ing a mixture of KClO , KBrO and KIO showing the different appear- sources such as from the Royal Society of Chemistry (http://www. additive, for example Techron®. Jeffamine® D-2000 has 3 3 3 ance of the ClO -, BrO - and IO - ions arising from the elemental isotopic References and notes rsc.org/periodic-table) and tools such as the University of Shef- the structure shown in Fig. 7; it is based on the CH(CH ) 3 3 3 3 compositions of chlorine, bromine and iodine 1. See for example: Brown, C.; Ford, M.; Standard Level Chemistry de- field’s Chemputer (http://winter.group.shef.ac.uk/chemputer/iso- CH2O repeat unit, with NH2 groups at each end of the veloped specifically for the IB Diploma, Pearson Education, Harlow, topes.html) provide easily-accessed data. chain. These amine groups are basic and provide a site Essex, 2008. for protonation in electrospray mass spectrometry analy- 2. Achievement Standard AS91388 Chemistry 3.2: Demonstrate un- Continued on page 136 130 131 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

timated to quickly return around half this carbon back complete combustion of the non-char pyrolysis prod- Carbon sequestration chemistry 1b to the atmosphere as CO2 due to respiration. Large ucts is approximated in equation 6. Combined with the John McDonald-Wharry amounts of carbon go into building polymers such as cel- photosynthesis chemistry which formed the wood in the lulose and lignin to be used in structures such as leaves first place, a simplified equation for the net conversion School of Science, University of Waikato (email: [email protected])

Article and wood (Eq. 4) which allows living biomass to store a of carbon dioxide into char is represented in equation 7. Keywords: carbon sequestration, carbon dioxide, photosynthesis, carbonisation, carbonation, charcoal considerable amount of carbon (estimated at around 560 Well-carbonised chars often contain more than 80% car- gigatonnes of carbon). However, ecosystems can release bon by weight when dry, making them one of the more The amount of carbon dioxide in the earth’s atmosphere limestone and sand (equation 3).3 almost as much carbon as they remove from the atmo- concentrated forms of carbon sequestration. has increased by approximately 40% between 1850 and sphere on an annual basis since much of the biomass will 5CaCO + 2SiO → 3CaO.SiO + 2CaO.SiO + 5CO (Eq. 3) 1b, 7 (Wood) C H O + 1.2O → (char) CH O + 2015. The cause of this increase is largely attributed to 3 2 2 2 2 eventually be eaten, burnt or decomposed. 1.96 3.33 1.16 2 0.18 0.06 0.96CO + 1.573H O (Eq. 6) the industrial-scale combustion of coal, petroleum and 2 2 1 Capture or collection of carbon dioxide CO + 0.85H O → (wood) CH O + 1.13O (Eq. 4) natural gas. Cement production, deforestation and 2 2 1.70 0.59 2 CO + 0.09 H O → (char) CH O + 1.015 O (7) As the carbon dioxide concentration in flue gas from 2 2 0.18 0.06 2 other land-use changes are also regarded as making sig- Planting forests and letting arable land revert to wood- industrial facilities such as thermal power stations are nificant contribution to this massive transfer of carbon land is known to cause an accumulation of carbon in There is also scope to sequester carbon in construction around 350 times higher than the atmosphere it makes to the atmosphere. Reducing additional emissions of car- living tree biomass, as well as leaf litter and soil - car materials which contain biomass-derived chars. Like soil sense where practical to collect/capture carbon dioxide bon dioxide in an effort to reduce risk of global warm- bon, with the majority of carbon accumulated in above conditioner applications, the use of charred and- car at these emission sources.4 ing and ocean acidification has been widely discussed for ground biomass.8 If protected from decomposition, bio- bonised biomass in construction is also an ancient prac- many decades. Even if global carbon dioxide emissions tice with the Roman engineer Vitruvius recommending The two main approaches to collecting carbon dioxide mass can sequester carbon by keeping it out of the at- are drastically reduced during the course of this century, the use of charred wooden stakes and charcoal especially from the atmosphere are direct air capture (DAC) and mosphere for longer periods of time. A number of ap- hundreds of gigatonnes (1 gigatonne is 1,000,000,000 proaches have been proposed based on collecting and in the construction of foundations owing to their resis- 12 biological photosynthesis. DAC proposals usually involve 14 tonnes or 10 kg) of excess carbon may need to be ac- storing biomass for carbon sequestration including the tance to decay. Evidence of the use of chars in ancient large devices to scrub carbon dioxide from the atmo- 15 tively removed from the atmosphere and then stored or 7a Chinese and Japanese construction is also reported. sphere using alkaline solutions or amine resins with a sinking of crop residues into the anoxic deep ocean and sequestered for a long period of time. Practices which 1b,4a increased wood harvest with the burial of logs in aban- Recently, char-plaster and char-concrete composites regeneration cycle, which are currently considered 16 can result in net transfer of carbon from the atmosphere 7b have been developed at the Ithaki institute. At the both expensive and having large energy requirements.5 doned mines. into solid materials or geological/marine reservoirs are University of Waikato, char-resin composites have been The biological photosynthesis approach instead involves referred to by a number of terms including “carbon se- under research and development since 2010, with the growing trees, crops, or algae which are naturally solar Carbon sequestration in chars and questration”, “carbon dioxide removal” (CDR) and “nega- latest formulations having over 80% of the carbon con- powered. Most of the proposed approaches to seques- carbonised biomass tive emissions technologies” (NETs).1 Such practices are tent sourced from recent photosynthesis with scope to ter carbon dioxide as carbonates discussed later in this Heating wood and other biomass material and convert- sometimes given the more controversial labels of “geo- sequester over a kilogram of carbon per litre of mate- article have been initially targeted towards the high con- ing them into carbon-rich chars is a very old practice with engineering”, “climate engineering” or “climate inter- rial. Early char-resin composite research appears to have centration industrial emission point sources, though in the resulting chars often used as charcoal for fuels and vention” depending on the definition being used and been focused toward dental implants and the last few principle could use carbon dioxide recovered from the smelting metals. Another old practice, that of adding often the intentions of those proposing (or carrying out) years have seen a large increase in papers featuring vari- atmosphere by DAC proposals. chars to cultivated soils as a soil conditioner, has recently 1a ous types of composite materials containing charred/car- practices which could sequester carbon. This article will seen a considerable revival of interest in using these so- bonised biomass.17 briefly cover the industrial production of carbon dioxide Carbon sequestration through geological called biochars to both sequester carbon and improve and the major approaches that have been proposed for storage of carbon dioxide soil fertility.9 carbon sequestration. The proposed approaches will be Carbon sequestration in carbonates In the case of geological storage, the plan is to store car- grouped according to the chemical form of the stored The pyrolysis and carbonisation of biomass is complicat- Many proposed approaches to carbon sequestration in- bon by pumping compressed carbon dioxide into under- carbon (carbon dioxide, cellulosic biomass, chars, car- ed with complex mix of reactions taking place as the bio- volve the formation of magnesium carbonates and/or ground reservoirs. Geological formations such as deplet- bonates, and bicarbonates). mass is heated. Equation 5 is based on the approximate calcium carbonates using carbon dioxide as a feedstock ed oils wells and deep saline aquifers are the commonly stoichiometric equation for cellulose pyrolysis at 400 °C (sourced either from the atmosphere or directly from proposed reservoirs. In some situations the carbon diox- The industrial production of carbon dioxide proposed by Klason et al. in 1909 and shows the forma- emission sources). Carbonate formation takes place ide is expected to react with brines of minerals to form The combustion of coal, petroleum and natural gas are tion of char along with a mixture of pyrolysis tars.10 when some metal silicates, metal oxides or metal hy- solid carbonates otherwise it is hoped that impermeable regarded as making the largest contribution to increasing droxides react with carbon dioxide. These reactions are rock layers will hold the carbon dioxide underground. (Cellulose) C H O → (char) CH O + exothermic and occur naturally during the weathering of atmospheric CO2 levels over the last few centuries. The 1.6 2.67 1.33 0.60 0.13 Geological storage is often proposed as part of carbon 1b,18 combustion of coals is represented in a generalised way (tars) C0.40H0.33O0.10 + 0.13CO2 + 0.07CO + 0.77H2O (Eq. 5) some minerals. Calcium silicate and carbon dioxide capture and storage (CCS) proposals where carbon di- in equation 1 (based on a middle of the range bituminous forming calcium carbonate and silica is shown in Reac- oxide is to be scrubbed from the flue gas from thermal Most biomass contains other polymers such as lignin coal while ignoring the ash and sulfur components2). tion 8.18 power stations, compressed and then injected into geo- and hemicellulose which adds complexity to the char- The combustion of the major component of natural gas 1b,4a ring reaction . The resulting char is also often carbonised logical formations. (Wollastonite) CaSiO + CO → CaCO + SiO (Eq. 8) (methane) is represented in equation 2. Complete com- further at temperatures well above 400 °C, resulting in 3 2 3 2 bustion reactions for the various hydrocarbons in petro- One type of proposal gaining prominence is bioenergy further enrichment in carbon with the preferential re- Because silicate weathering reactions are regarded as leum would fall between the coal and methane examples with CCS, where the thermal power station is burning moval of hydrogen and oxygen. Chars produced at higher slow at lower temperatures and atmospheric concentra- with lighter hydrocarbon producing more water relative biomass. As the carbon in biomass was relatively recently carbonisation temperatures are generally considered tions of carbon dioxide, research effort has been devoted to carbon dioxide. removed from the atmosphere by photosynthesis, stor- more stable and resistant to decay than those produced to accelerating this carbonisation process by carrying out ing the post-combustion carbon dioxide underground at lower temperatures.9b,11 (Coal) CH O + 1.13O → CO + 0.33H O (Eq. 1) the reaction using elevated temperatures, higher carbon 0.66 0.07 2 2 2 should in principle be able to reduce atmospheric carbon dioxide pressures and catalysts.18-19 Olivine and serpen- 4a,6 In many cases, the tars, oils, carbon monoxide and hy- CH + 2O → CO + 2H O (Eq. 2) dioxide concentrations. tine are magnesium silicate minerals commonly proposed 4 2 2 2 drogen formed during biomass pyrolysis are combusted to be mined for carbon sequestration reactants. Equa- to supply heat or electricity, although there is consider- Other industrial processes also add large quantities of Carbon sequestration in cellulosic biomass tion 9 represents the net reaction commonly proposed able interest collecting some these products for uses carbon dioxide to the atmosphere, chief among these Globally, photosynthesis by organisms such as plants is for olivine and carbon dioxide reacting to form magne- such as liquid fuels.9a, 12 A stoichiometric equation which are ones which involve calcination of calcium carbonates estimated to remove around 120 gigatonnes of carbon sium carbonate (magnesite) and silica.1b, 18-19 In a patent approximates the preparation of a char carbonised at such as the manufacture of Portland cement clinker from from the atmosphere each year. However, plants are es- concerning silicate-to-carbonate processes for carbon ~700 °C from a pine wood precursor13 and assuming the 132 133 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 sequestration, Blencoe et al. used sodium hydroxide to of sequestering carbon, rapidly re-carbonising a large The case of mineral carbonation converting the mineral quires less mass of material per tonne of carbon seques- form metal (calcium, magnesium or iron) hydroxides and proportion of the cement and reducing the net amount olivine into magnesium carbonate provides an example tered when compared to the use of carbonates. However, then regenerate the sodium hydroxide at the end of the of carbon dioxide released during cement manufacture.25 of the massive material requirements for carbon seques- such sequestration is reliant on biological photosynthesis process as the metal carbonates are precipitated from an tration proposals in general. Pure magnesium carbonate and at the scale of gigatonnes such carbon sequestra- aqueous solution. The use of resulting carbonates as ma- Carbon sequestration in dissolved is just over 14% carbon by mass, therefore it would take tion activity would consume a few percent of total net terials for road construction, amendment of acidic soils bicarbonates approximately 7 gigatonnes of magnesium carbonate to primary production of the entire planet’s ecosystems. and cement-like products has also been proposed.19 Instead of storing sequestered carbon in solid carbonate store 1 gigatonne of carbon. Based on its density,27 this For biochar, the extremely ambitious estimates for the minerals, a number of proposals aim to store the car- quantity of magnesium carbonate would take up at least amount of carbon that could be sequestered globally (Olivine) 0.5Mg SiO + CO → MgCO + 0.5SiO (Eq. 9) 12a 2 4 2 3 2 bon as bicarbonate anions dissolved in water. A source 2260 million cubic metres and this volume is hypotheti- range between 3.25 and 9.5 gigatonnes of carbon per The Calera Corporation also proposed a means of captur- of magnesium, calcium or other metal is required and cally represented as a cube in Fig. 1. In practice, quan- year by the end of the century9a,12a with lower estimates ing carbon dioxide from industrial sources and convert- a number of factors in the water chemistry can affect tities of material involved would be considerably larger, of 0.6-1 gigatonnes per year considered more credible. ing it into carbonate minerals for carbon sequestration the bicarbonate formation.4b,26 Due to the difference in since rocks containing olivine are not purely magnesium Wood harvest and storage proposals have reported that and construction materials.20 Equations 10 and 11 are charge between the bicarbonate and carbonate ions, minerals and silica is also formed in the carbonation re- a rough theoretical potential of 10±5 gigatonnes of car- the reported overall reactions for Calera processes which bicarbonate ions could theoretically sequester twice as actions mixed with the carbonates. Unreacted olivine bon could be sequestered per year, although these es- proceed through bicarbonate and carbonate ions formed much carbon per atom of calcium or magnesium when will often be present if the olivine is not ground finely timates were reduced to 1-3 gigatonnes per year once by reactions with the hydroxide ions. These reactions compared to carbonate ions based on stoichiometry. This enough for it to completely react, which could increase large land areas were removed from the calculations to require a supply of calcium and/or magnesium cations is shown in equation 14 from a proposal which involves the amount of material required. Calcium carbonate is account for existing uses, biodiversity/ecosystem pro- along with a source of alkalinity which appears to be con- the accelerated weathering of olivine-containing rock by only 12% carbon by mass, meaning that a greater volume tection and food production.7b In the proposal for sink- sumed in the overall process.21 Alkalinity was proposed grinding it into a fine powder before spreading it on land, and mass of material would be needed to sequester a ing crop residues into the deep ocean, it was estimated to be sourced through electrolysis of sodium chloride large river systems or the ocean, although in practice it is given amount of carbon as calcium carbonate. Calcium that ~0.6 gigatonnes of carbon per year could potentially to produce sodium hydroxide and HCl. The magnesium unlikely to reach this theoretical maximum.26a and magnesium silicates are abundant minerals so in be sunk into the ocean as part of such a sequestration and calcium were at one stage proposed to be sourced principle there is more than enough mineral feedstocks method.7a (Olivine) Mg SiO + 4CO + 4H O→ 2Mg2+ +4HCO - from brines (either natural or residue from seawater de- 2 4 2 2 3 to potentially sequester many thousands of gigatonnes 21 + H SiO (Eq. 14) 18 Energy requirements and economics have not been cov- salinisation) or fly ash. The high costs associated with 4 4 worth of carbon emissions as carbonates. The feasibil- ity is more a question of handling and processing materi- ered in this article. Currently these estimates of energy electrochemistry in the Calera process were reported Another proposal, often called “ocean liming”,4a involves als at these massive scales. Portland cement production requirements and cost vary greatly in the literature, even to have led to the founder of Calera Corporation leaving the addition of calcium oxide into the upper ocean where is one of the few industrial processes conducted at the within the same type of proposed process. This reflects and starting a new company (Blue Planet) with the same it is expected to dissolve, react with carbon dioxide and scale of a few gigatonnes per year3,20 and current produc- the fact that many proposals are often still based large- goal of sequestering carbon in carbonate construction then store the carbon as bicarbonate ions. Equation 15 tion is estimated to exceed 3.4 gigatonnes per year.4a The ly on back-of-the-envelope type calculations at larger materials made using seawater, while claiming to have is the net reaction proposed by Kheshgi with the minor global cement industry is an important example of the scales. overcome the limitations of the Calera processes using species not listed said to account for the discrepancy in reality of what is involved in mining, processing, handling an osmotic process rather than electrolysis to supply the hydrogen stoichiometry.26b Since the calcium oxide of Conclusions 22 and utilisation of materials on the scale of gigatonnes. alkalinity. equation 15 will likely be produced from calcium carbon- Carbon sequestration potential of carbonate and bicar- This article has provided a brief overview of the build- 2+ - ate which releases carbon dioxide, this will in effect re- Ca + CO + 2OH → CaCO + H O (Eq. 10) bonate-based proposals are often estimated at between up of carbon dioxide levels in the atmosphere and the 2 3 2 duce the net carbon dioxide sequestered by ~56% (with- 0.5 and 2.7 gigatonnes of carbon per year.4a,26a Although it chemistry behind a number of proposals to actively re- Mg2+ + CO + 2OH- → MgCO + H O (Eq. 11) out including extra emissions if coal or gas are used to 2 3 2 is theoretically possible that they could be implemented duce these levels by carbon sequestration. The various supply energy to the calcination kilns). This ocean liming at far larger scales, it is difficult to assess the plausibility approaches have different requirements in terms of re- Metal oxides found in slags, cement manufacturing waste approach is often combined in proposals with collection of activities at a scale much larger than contemporary ce- agents and the storage of the carbon in different chemi- and fly ash from coal burning can be reacted with CO2 to and geological storage of the carbon dioxide emission ment manufacture. cal forms. Implementation of any of these potential car- form carbonate minerals. If the metal oxide reactants are 4a,26b from the calcination kilns. bon sequestration proposals at the scale of gigatonnes formed originally from carbonates, then equation 12 and 2+ - Sequestering carbon in wood (~ 50% carbon by dry mass) will involve massive quantities of materials and will re- equation 13 will overall only be replacing (to some ex- CaO + 1.79CO2 + 0.79H2O + …→ Ca +1.62HCO3 + 0.17 2- or well-carbonised chars (>80% carbon by dry mass) re- quire an immense, concerted effort. tent) the carbon dioxide released when the original car- CO3 + … (Eq. 15) bonates were calcinated. Precipitated calcium carbonate formed in equation 13 (although going through a slaked A proposal intended to avoid the need for calcium car- lime, calcium hydroxide step) is reported to be produced bonate calcination was put forth by Rau and Calderia. It industrially at several million tonnes per year to be used involves the reaction of carbon dioxide in flue gas with in the paper industry23. a wet bed or slurry of calcium carbonate. The reaction involves the formation of carbonic acid when the carbon dioxide and water react, with the net reaction shown as MgO + CO2 → MgCO3 (Eq. 12) equation 16.4b The bicarbonate solution is then proposed CaO + CO2 → CaCO3 (Eq. 13) to be dumped in the ocean.

In a similar carbonation process, some calcium species in (Limestone, calcite) CaCO + CO + H O→ Ca2+ + 2HCO - cement will react with carbon dioxide to form carbonates. 3 2 2 3 (Eq. 16) These cementitious carbonation reactions have been es- timated to recover ~8% of the carbon dioxide released Questions of scale and feasibility during the calcination of limestone as part of the cement With global carbon dioxide emissions from human acti- manufacturing process over the lifetime of a building. vity estimated to total around 10 gigatonnes of carbon The grinding of demolition concrete and exposing it to per year,5 important questions arise concerning whether air for 30 years has also been estimated to increase this carbon sequestration proposals are feasible on a scale re-carbonation up to 57%.24 Curing concrete using carbon sufficient to make a significant difference to the carbon dioxide instead of water has also been proposed as a way Fig. 1. The minimum volume of magnesium carbonate required to sequester a gigatonne of carbon (or 3667 million tonnes of CO2). The Great dioxide concentration in the atmosphere. pyramid of Giza and the world largest skyscraper (Burj Khalifa) depicted at the same scale. 134 135 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 Article References 15. Zwerger, K., Wood and Wood Joints : Building traditions of Europe, Japan and China. 2nd ed.; Birkhaeuser Basel, 2012. The chemistry and metallurgy of beryllium 1. (a) Vaughan, N. E.; Lenton, T. M. Climatic Change 2011, 109, 745- 790; (b) Lal, R., Carbon sequestration. Philos. Trans. R. Soc. B-Biol. 16. Schmidt, H. The use of biochar as building material; see: www. Onyekachi Raymond,1 Lakshika C. Perera,2 Penelope J. Brothers,2 William Henderson,1 Paul G. Sci. 2008, 363, 815-830. biochar-journal.org/en/ct/3 (accessed 15/05/2014). Plieger3,* 2. Zheng, T.; Xing, W.; Dahn, J. R. Carbon 1996, 34, 1501-1507. 17. McDonald-Wharry, J.; Manley-Harris, M.; Pickering, K., Carbona- 1 2 ceous materials from the pyrolysis of biomass: Chemistry, prop- Chemistry, School of Science, University of Waikato, Private Bag 3105, Hamilton, School of Chemical 3. Phair, J. W. Green Chem. 2006, 8, 763-780. erties and some potential applications. In Advanced Biofuels Re- Sciences, University of Auckland, Auckland, 3Chemistry, Institute of Fundamental Science, Massey 4. (a) Caldecott, B.; Lomax, G.; Workman, M. Stranded carbon assets search Network Science Symposium, Rotorua, 2014. University, Palmerston North (email: [email protected] ) and negative emissions technologies: Working paper; Smith School 18. Lackner, K. S.; Wendt, C. H.; Butt, D. P.; Joyce Jr, E. L.; Sharp, D. H. of Enterprise and the Environment, University of Oxford: Oxford, Keywords: beryllium, ligands, chronic beryllium disease, coordination chemistry Energy 1995, 20, 1153-1170. UK, 2015; (b) Rau, G. H.; Caldeira, K.Energy Conversion and Man- agement 1999, 40, 1803-1813. 19. Blencoe, J. G.; Palmer, D. A.; Anovitz, L. M.; Beard, J. S. Carbon- Introduction ation of metal silicates for long-term CO sequestration US Pat. 5. Cusack, D. F.; Axsen, J.; Shwom, R.; Hartzell-Nichols, L.; White, S.; 2 8,114,374 B2, 2012. Beryllium (Be), the first of the group 2 alkali-earth ele- Mackey, K. R. M. Frontiers Ecology Env. 2014, 12, 280-287. 20. Monteiro, P. J. M.; Clodic, L.; Battocchio, F.; Kanitpanyacharoen, W.; ments, is a silver-gray metal possessing an unmatched 6. Read, P. Climatic Change 2008, 87, 305-320. Chae, S. R.; Ha, J.; Wenk, H.-R. Cem. Concr. Comp. 2013, 40, 14-20. combination of physical and mechanical properties, 7. (a) Strand, S.; Benford, G.Environ. Sci. Technol. 2009, 43, 1000- which are vital for a variety of applications that offer tre- 21. Scientific synthesis of Calera carbon sequestration and carbona- 1007; (b) Zeng, N.; King, A. W.; Zaitchik, B.; Wullschleger, S. D.; ceous by-product applications; Donald Bren School of Environ- mendous benefits to society. It is the lightest workable Gregg, J.; Wang, S.; Kirk-Davidoff, D. Climatic Change 2013, 118, mental Science and Management, University of California, Santa 245-257. metal, only two-thirds the weight of aluminium, yet it has Barbara, 2011. six times the stiffness of steel, making it an ideal mate- 8. Powlson, D. S.; Whitmore, A. P.; Goulding, K. W. T. Eur. J. Soil Sci. 22. (a) Blue Planet Ltd. http://www.blueplanet-ltd.com/ (accessed rial for stiffness-dependent and weight-limited applica- 2011, 62, 42-55. 23/04/2015); (b) Sweet, B. A bold attempt to make cement produc- tions. The chart in Fig. 1 illustrates how much beryllium 9. (a) Lehmann, J.; Gaunt, J.; Rondon, M. Mitig. Adapt. Strateg. Glob. tion a carbon sink. See: http://spectrum.ieee.org/energywise/en- outclasses other engineering materials with respect to Chang. 2006, 11, 395-419; (b) Crombie, K.; Mašek, O.; Sohi, S. P.; ergy/environment/a-bold-attempt-to-make-cement-production-a- Brownsort, P.; Cross, A. GCB Bioenergy 2013, 5, 122-131; (c) Jeffery, carbon-sink (accessed 23/04/2015). thermal conductivity and dimensional stability (ability of S.; Verheijen, F. G. A.; van der Velde, M.; Bastos, A. C. Agri. Ecosys. a material to retain its uniformity under stress measured 23. Zevenhoven, R.; Eloneva, S.; Teir, S. Catalysis Today 2006, 115, 73- Environ. 2011, 144, 175-187. 79. as the Young’s modulus to density ratio). These unique 10. Antal, M. J.; Grønli, M. Ind. Eng. Chem. Res. 2003, 42 (8), 1619- properties of beryllium translate into performance en- 24. Dodoo, A.; Gustavsson, L.; Sathre, R. Resources, Conservation and 1640. hancement in the end product, for instance the James Recycling 2009, 53, 276-286. 11. Singh, B. P.; Cowie, A. L.; Smernik, R. J. Environ. Sci. Technol. 2012, Webb Space Telescope (JWST: see Fig. 2). The next gen- 25. Monkman, S.; Yixin, S. Can. J. Civil Eng. 2010, 37, 302-310. 46, 11770-11778. eration James Webb Space Telescope, scheduled tobe 26. (a) Köhler, P.; Hartmann, J.; Wolf-Gladrow, D. A.; Schellnhuber, H.-J. 12. (a) Lee, J. W.; Hawkins, B.; Day, D. M.; Reicosky, D. C. Energy Envi- launched in 2018 as NASA’s replacement for the Hubble Proc. Natl. Acad. Sci. USA 2010, 107, 20228-20233; (b) Kheshgi, H. ron. Sci. 2010, 3, 1695-1705; (b) Hammond, J.; Shackley, S.; Sohi, S.; telescope, will utilise a 6.5 meter wide beryllium mirror S. Energy 1995, 20, 915-922. Brownsort, P. Energy Policy 2011, 39, 2646-2655. to reveal images of distant galaxies 200 times beyond 27. Aylward, G.; Findlay, T., SI Chemical Data. 5th edn., Wiley, 2002. .Bridges, R. Design and characterisaton of an ‘open source” pyroly- what has ever been sighted .13 ser for biochar production. Massey University, Palmerston North, 2013. Unfortunately, beryllium is also problematic. It is brittle, 14. Vitruvius, Des Architectura. In The ten books of Architecture, Har- hard to machine, expensive and extremely toxic. It is a suspected human carcinogen, an initiator of chronic be- vard University Press Cambridge, 1914. Fig. 1. Some properties of beryllium and beryllium oxide as ryllium disease (CBD) and is regarded as the most toxic compared with alternatives (thermal conductivities used with non-radioactive element in the periodic table. Surprising- permission from American Beryllia Inc.) Continued from page 131 ly, this has not deterred its production and usage, making 7. Oxygen actually has trace amounts of 17O (0.038% abundance) 10. Huntsman Corporation Technical Bulletin Jeffamine D-2000 it imperative to gain a better understanding of this ele- and 18O (0.205% abundance). amine; see :http://www.huntsman.com/portal/page/por- ment. This review surveys aspects of beryllium metallur- tal/performance_products/Media%20Library/global/files/ gy within a New Zealand context, including applications 8. The ions are accelerated by means of a potential difference; the jeffamine_d_2000_us.pdf (accessed 10/03/2015). higher the accelerating potential, the greater the acceleration of and toxicity. The coordination chemistry of beryllium is the ions, producing higher energy impacts resulting in more exten- 11. Henderson, W.; McIndoe, J. S. Mass Spectrometry of Inorganic, also discussed with an emphasis on the trends amongst sive fragmentation. Coordination and Organometallic Compounds – Tools-Techniques- ligands that exhibit strong interactions with beryllium as Tips, John Wiley & Sons, 2005. 9. See for example: http://www.caltex.com/nz/techron-tech/faq/; well as research activities within our group to identify http://en.wikipedia.org/wiki/Techron (accessed 10/03/2015). suitable chelators for beryllium.

Sources and production Corrigendum Beryllium is the 44th most abundant element and occurs The article published in Chemistry in New Zealand vol 79, no. 1, Jan 2015, pp36-41 authored by Grant J. McIntosh naturally in the earth’s crust, fossil fuels, air, and water. It et al. erroneously referred to alumina as an adsorbate in the title and elsewhere in the text. Alumina is in fact the is also found in trace quantities in foods although it has adsorbent. no known biological function in the human body. Beryl- lium was discovered in 1724 by Vauquelin, and later iso- lated independently by Bussy and Wöhler in 1828. Origi- nally, it was named glucinium (Gl) after its sweet tasting oxide but in 1957, IUPAC adopted its present name. Commercial outlets for beryllium began in the 1920s, but its usage has increased over the years and its annual Fig. 2. The James Webb Space Telescope scheduled to be demand is estimated to approach 500 tonnes by 2018.1 launched in 2018 will utilise a 6.5 m (21 ft) wide beryllium mir- Mining of beryllium is only viable from a few of its miner- ror to reveal images 200 times beyond what has ever been sight- ed. (Picture credit: NASA; used with permission) als including beryl (Be3Al2Si6O18, 5 % by weight beryllium) 136 137 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

2 2 and bertrandite [Be4(OH)2Si2O7, 15% by weight beryllium] It is has a high neutron scattering cross section and is ap- However, appropriate disposal via the segregation of state electron configuration is 1s 2s and the loss of the in the United States, China, Kazakhstan, Mozambique, plied as a neutron moderator, reflector, and blast shields. these components is recommended considering the im- 2s2 electrons leads to its only stable ion Be2+. The small Brazil, Australia and Madagascar. Beryl also occurs natu- In construction of nuclear fusion reactors, beryllium is minent increase of beryllium in electronic waste. Expo- beryllium cation (31 pm) has a charge to size ratio (Z/r) of rally in New Zealand in pegmatite on the West Coast and a superior material for the lining of interior walls as it sure to beryllium can also result from the combustion of 6.45, which is comparable to the Al3+ cation (6.0) hence Hawks Crag Breccia in the Buller Gorge.2 However, over erodes more slowly and retains less of the plasma while fossil fuels, especially coal which can contain significant these two elements illustrate the typical periodic table two-thirds of the world’s beryllium is produced by the US the inclusion of beryllium oxide in fuels for nuclear fis- amounts of beryllium. The main concern for beryllium diagonal relationship observed among the main group el- while the rest comes from China, Kazakhstan and Rus- sion can speed up cooling, thereby offering significant exposure involves occupational related activities with be- ements. Indeed, the chemistry of beryllium shows more sia. To extract beryllium, its minerals are first crushed and improvements to safety and efficiency of nuclear power ryllium components. The occupational exposure limit for similarities to aluminium rather than its heavier alkali leached with acid to produce a beryllium salt solution plants. beryllium in New Zealand is 2 µg m-3 for an 8 hour time- earth metal congeners such as magnesium and calcium. from which the metal hydroxide is precipitated. Since the weighted average but it remains unclear if this limit actu- For instance both elements exhibit a tendency to form beryl crystals are more resistant to acid attack, it must Toxicity ally excludes the development of CBD. No CBD case has strong covalent bonds, and form strongly solvated cat- first be melted at a high temperature. The stability of Although beryllium possesses highly attractive proper- been documented in New Zealand but a single beryllium ions that are acidic and prone to hydrolysis. They also these minerals and their low beryllium content require ties and a variety of applications, it is also necessary to sensitisation case was reported among aircraft mainte- dissolve in non-oxidising acids or alkalis with the libera- expensive extraction techniques, making beryllium an consider its toxicity and the hazards involved with the nance staff in Air New Zealand.6,7 The company thereaf- tion of hydrogen. This striking similarity between the expensive metal. The resultant hydroxide is further pro- continual production and usage of the metal, its oxide ter set up a copper beryllium project in 2006, sampling two metals resulted in beryllium being overlooked as a cessed into beryllium’s three most useful forms namely and alloys. Beryllium is extremely toxic, both as a carcin- work areas to identify and manage potential health risks constituent of beryl until 1724. In fact even after beryl- the pure metal, beryllium oxide, and its alloys with met- ogen and as an initiator of acute and chronic beryllium to its workers involved in beryllium work areas. Note- lium’s discovery, scientists presumed beryllium to have als such as copper, nickel and aluminium. disease (CBD).3-5 Although beryllium is considered a car- worthy in their findings was the uncharted occupational an oxidation state of +3 and placed it above aluminium in cinogen, its carcinogenicity has only been established in hazards associated with beryllium-related operations in group 13 of the periodic table. However, aluminium still Properties and uses animals while carcinogenicity in humans is still a subject New Zealand. exhibits some differences from beryllium. Aluminium is a Beryllium is vital and indispensable in many of its appli- of debate with recent studies questioning beryllium cy- larger sized cation, therefore it prefers an octahedral ge- cations. An understanding of the relevance of beryllium totoxicity.3 Nevertheless, exposure to beryllium fumes or The chemistry of beryllium ometry and is effectively complexed by EDTA while beryl- is best illustrated in its regard as a critical and strategic dust particles by inhalation and possibly dermal contact Beryllium is an s-block element with a relative atomic lium maintains a four-coordinate tetrahedral geometry metal in the US and Europe. This is to highlight the im- in certain individuals (1-15%) can lead to beryllium sen- mass of u = 9.01218307(8) and an atomic number of z = and shows poor binding with EDTA. pact its shortage or substitution could have on the econ- sitisation and further progress into CBD. Chronic beryl- 4. Its only naturally occurring isotope is 9Be making it the omy, national security and defence. Interestingly, while lium disease (CBD) is a debilitating granulomatous lung only element having an even atomic number with one Interaction with simple inorganic ligands the usage of beryllium in certain applications has been disorder resulting from an uncontrolled cell-mediated stable isotope. Beryllium has a density of 1.84 g cm-3 and Generally, only a few inorganic ligands can compete with discontinued for safety reasons, new and crucial appli- immune response marked by the proliferation of the is one of the lightest metals, second only to lithium, yet it the hydroxyl ligand for a binding site with beryllium be- cations have emerged leading to its continuous demand CD4+ T cells.4 The dissolution, speciation and exact mech- has one of the highest melting points (1287 °C) amongst cause in aqueous solution the 2+ Be ion is strongly sol- and production. anism by which beryllium particles trigger CBD is not the light metals. vated. It also exhibits complex pH- and concentration-de- clearly understood. Current molecular understanding of pendent aqueous speciation. In very acidic solution (pH The application of beryllium in aerospace and military the disease proposes that inhaled beryllium is detected In comparison with its periodic table neighbours the < 3.5), without any ligand present, beryllium exists as the equipment has been the most extensive. It is found in coordination chemistry of beryllium has been relatively 2+ by antigen-presenting cells which trigger the body’s im- tetra-hydrated ion [Be(H2O)4] . The high charge density missiles, sensors, jet fighters, helicopters, landing gear, mune system into producing blood cells that engulf the understudied due to its toxicity and a strong tendency of the Be2+ cation polarises the water molecules caus- heat shielding and brakes for military and commercial particles forming granulomas that eventually harden the towards hydrolysis. Solution techniques such as poten- ing the negative end of their dipole to align toward itself aircrafts. Components made from beryllium are essential lungs causing respiratory abnormalities.4 The onset of tiometry and NMR are often utilised in the investigation while the protons are strongly repelled such that they are 2+ in spacecraft or military equipment because of its high CBD can be delayed for over 20 years after exposure and of the coordination chemistry of the Be cation and its easily transferred, leaving the hydroxyl ion OH- in contact 9 strength which can sustain various structures without there is no strong correlation between levels of exposure interaction with ligands. Be NMR has a narrow range of with the beryllium ion. Subsequent increases in pH or adding weight or losing strength from vibrations, there- and CBD development, suggesting that a change in the chemical shifts and suffers line broadening as a result of concentration yield several polynuclear hydroxo cluster by ensuring safety, precision and reliability in the end beryllium speciation could be culpable. Interestingly, the quadrupolar beryllium nucleus (S = 3/2) and aqueous species in varying degrees of abundance (Fig. 3). The tri- product. The high infra-red reflectivity of beryllium also there is a genetic correlation to the disease as research beryllium sulfate is used as the reference peak. Compu- mer is the predominant hydroxo species and it exists as a makes it an ideal optical material for military, navigation evidences suggest that the risk of CBD is increased by the tational techniques are also invaluable and by the -cor cyclic six-membered ring structure with the four-coordi- and communication satellites, for instance, in the James presence a specific gene- the HLA-DPB1.5 Based on this, a relation of experimental and theoretical NMR chemical nation of the beryllium ion preserved by water molecules. 2+ Webb Telescope and Galileo Navigation Satellite System. beryllium lymphocyte proliferation test (BLPT) has been shifts, coordination to the Be cation can be identified NMR and potentiometric measurements9,10 have char- developed for routine use in diagnosis and workplace without isolating the resulting complex. This safe method acterised the [Be(H O) ]2+, [Be (OH)]3+, and [Be (OH) ]3+ Besides aerospace and military applications, beryllium 2 4 2 3 3 screening to predict susceptibility towards the disease. for beryllium investigation has been pioneered by an au- species while crystal structures of the picrate salt [Be (µ- components have gained prominence in telecommunica- 8 3 Another interesting correlation with CBD is that it is asso- thor in our group. Further research in our group utilises OH) (H O) ](picrate) ·6H O have confirmed the stability tions, consumer and automobile electronics which now 3 2 6 3 2 ciated only with the processed forms of beryllium, such electrospray ionisation mass spectrometry (ESI-MS) as a account for 45% of beryllium usage. The exceptional as beryllium metal and the oxide. Beryl and other ores solution technique for the cross validation of beryllium thermal conductivity and electrical insulation of beryl- of beryllium do not trigger a similar immune response speciation. ESI-MS could be the technique of choice for lium ceramics makes it an excellent heat sink for elec- possibly due to the lack of bioavailability of beryllium the investigation of beryllium speciation in solutions, tronic devices to support miniaturisation and the design from these ore as they are insoluble in aqueous solution. being able to transfer pre-existing solution species into of compact components. Furthermore, alloys contain- It has also been observed that there is no beryllium oxo the gas phase where they are analysed by the mass spec- ing beryllium in various proportions exhibits highly en- cluster (Be-O-Be) in the beryl structure (Be Al Si O ), but trometer. Importantly, this technique is sensitive, requir- hanced properties utilised for air bag sensors, electrical 3 2 6 18 rather silicon oxide units bridge beryllium and aluminium ing only miniscule amounts of sample in solution thereby relays in automobiles, non-spark tools for oil and gas atoms.4 minimising any exposure to beryllium dust and allowing exploration, fatigue resistant springs and housing for un- rich information on beryllium speciation to be gained dersea cables. In comparison with other metals, beryl- Beryllium in New Zealand from a study utilising only tiny quantities of beryllium lium is very transparent to X-rays due to its low atomic compounds. number and is applied in X-ray windows for medical and Beryllium is neither mined nor processed in New Zea- Fig. 3. Beryllium hydroxo species distribution diagram in acidic scientific equipment. land and although beryllium components are found in The coordination chemistry of beryllium is largely - gov electronic devices and other consumer products, they solutions. Tetra-coordination of beryllium is maintained by aqua erned by its small size and high charge density. Its ground ligands removed for clarity (adapted from reference 10 with Beryllium also possesses interesting nuclear properties. are well encased and offer no hazard to general users. permission from the Royal Society of Chemistry) 138 139 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 and cyclic nature of the trimeric species (Fig. 3).11 The (Eq. 2) the strongest bidentate ligand for beryllium, forms a six- equilibrium is further complicated by other minor spe- (Eq. 3) membered chelate ring. 4+ 4+ cies in solution of which the [Be5(OH)6] and [Be6(OH)8] 10 Chelate species offer the best fit for speciation data. Between Beryllium halides of the structure BeX2 (X = F, Cl, Br, I) are not easily formed in the presence of water and often lead ring Dicarboxylate Diketonate Dihydroxy pH 5.5-12.0, insoluble beryllium hydroxide Be(OH)2 pre- to different hydrolysis products. In most cases, in order to size cipitates. In solutions of higher alkalinity (pH > 12), this Fig. 5. 2:1 Be-citric acid complex (a) and similar ligands (2-hy- overcome this, harsh conditions of high temperatures and amphoteric Be(OH)2 precipitate begins to dissolve, giving droxyisophthalic acid (b) and 2, 3-dihydroxybenzoic acid (c)), - liquid ammonia are employed to form the halides by way possessing polynuclear binding pocket for beryllium via a car- rise firstly to [Be(OH)3] and then, at even higher alkalinity, 2- of thermal decomposition. The dihydrogen phosphate boxylate and a bridging hydroxyl group the tetrahydroxoberyllate dianion [Be(OH)4] is formed. Five This occurs in the 9Be NMR spectrum as a narrow peak at ion H PO - is also known to replace water and results in 2 4 Tropolonate 12 2+ Oxalate (4.08) 2 ppm. IR spectroscopy also proved the existence of this the complexes [Be2(OH)(H2PO4)] and Be3(OH)3(H2PO4)3. (8.40) Tiron (13.50) hydrogen bonded proton that can easily be displaced by species with a characteristic IR band in the range of 700- NMR results further suggest the existence of another the similarly small but tetrahedral Be2+ cation.25 These li- -1 13 12 complex with the formula [Be O(H PO ) ]2- containing gands also possess high pKa values and Fig. 6 shows some 750 cm . Several M[Be(OH)4] salts have been isolated 3 2 4 6 ­ where M = Ca, Sr or Ba but a later attempt to resynthe- a ‘beryllium acetate’ type structure (see next section) examples. This concept was further explored in identify- sise the Ca[Be(OH) ] complex (at pH 13.5-14) resulted in where three beryllium ions are bound to a central oxy- Six ing the tri-dentate ligand 2,6-bis(2-hydroxyphenyl)pyri- 4 Acetylacetonate Malonate (5.91) Chromotropic the isolation of a crystal whose structural investigation gen atom with three phosphate units bridging the metals (12.36) dine (BHPP) (Fig. 6b) as a fluorescent Be indicator for cel- showed that it contained the hydroxoberyllate trianion, and the tetrahedral arrangement of the beryllium is com- acid (16.34) lular studies as it is able to detect and solubilise beryllium [Be (OH) ]3-, instead of the expected [Be(OH) ]2- as previ- pleted by terminal phosphate ligands.17 in phosphate media under physiological conditions.27 X- 2 7 4 Fig. 4. Formation constant (log k) of beryllium complex among 14 3- ray crystal structure of the Be(BHPP) complex revealed ously assumed. The [Be2(OH)7] anion was found to be analogous ligands of 5 and 6 membered chelate rings (Log k val- associated with two calcium cations and a Z-shaped hy- Interaction with organic ligands ues from reference 13) that the metal is coordinated in a tetrahedral geometry droxide hydrate anion [HO-H-OH]- which resulted in the Recent research efforts have focused on beryllium spe- by the pyridine nitrogen and the two oxygen donors of 14 The interactions of the beryllium ion with hydroxycarbox- the phenolic groups while the fourth coordination site is Ca2[Be2(OH)7](HOHOH)(H2O)2 complex. The presence ciation by ligands of interest with the objective of iden- 2- 18-21 ylate ligands have been extensively investigated because taken up by a water molecule. This understanding of be- of yet another hydroxoberyllate anion [Be4(OH)10] was tifying suitable sequestering agents as well as to ob- further identified by Schmidbaur et al. as crystals ob- tain a clearer picture of the “mystic beryllium species” they exhibit significant binding with beryllium and can ryllium’s interaction with ligands possessing suitable sites tained from aqueous sodium beryllate solutions at high guilty of triggering an uncontrolled immune response in serve as models for ligands of biological interest. In fact, of strong hydrogen bonding offers new insight into the 4,22-25 the aromatic hydroxycarboxylate aurin tricarboxylate binding of beryllium to proteins and other biomolecules pH (13.2) result in the hydrated species Na2[Be4(OH)10] beryllium sensitisation and CBD. Beryllium is highly (H O) .15 The tetraberylliumdecahydroxide dianion spe- oxophilic and a hard Lewis acid; therefore, it binds prefer- (aluminon) was earlier developed for chelation therapy in relevant for the biomolecular understanding of how be- 2 5 13 cies was found to have a highly symmetrical adamantane entially to hard donor atoms such as oxygen in carboxyl- beryllium poisoning. In a remarkable contrast, aliphatic ryllium triggers CBD.24 structure where four beryllium atoms occupy the ver- ates, hydroxyl and phosphate groups as well as nitrogen hydroxycarboxylates generally show a weaker interaction tices of a regular tetrahedron with a terminal hydroxyl donors but to a lesser extent. Three themes have been with beryllium with the exception of citric acid. Citric acid group at each metal centre while the remaining six bridg- central in studies of the interaction of beryllium with or- is an excellent ligand for beryllium capable of solubilising ing hydroxyl groups completed the tetra coordination to ganic ligands, namely functional groups, chelate ring size beryllium at molar concentrations across the entire pH 23 beryllium atoms.15 The energetics for the existence of the and ligand geometry. range. It binds beryllium in a polynuclear fashion with 2- a metal to ligand ratio of 2:1 (Fig. 5a). To further under- [Be4(OH)10] anion can be explained by the condensation 2- - The significance of the chelate effect in beryllium’s inter- stand the strong binding of citric acid with beryllium, six of the species [Be(OH)4] with the extrusion of OH an- Fig. 6. Ligands possessing strongly bonded hydrogen sites suit- ions (Eq 1). action with ligands is highlighted by the fact that biden- other aliphatic hydroxylcarboxylic acids have been stud- able for beryllium binding: (a) 10-hydrobenzo(h)quinolone-7-sul- tate dicarboxylate ligands have increased binding to be- ied, each chosen to highlight the relevance of the hydrox- fonate (HBQS), (b) 2,6-bis(2-hydroxyphenyl)pyridine (BHPP), (c) ryllium compared to the monocarboxylate ligands, while yl or carboxylate functionality toward a strong beryllium 2-(2-hydroxyphenyl) pyridine dicarboxylate ligands possessing rigid structures that chelation. Competition experiments have shown that An alternative geometry for beryllium binding which (Eq. 1) prevent chelation show poor binding with the beryllium the significant binding of beryllium to citric acid could forms the central theme of research in our group involves ion.12 Acetate, a typical monocarboxylate ligand, forms be attributed to the formation of a five- and- six-mem tetra-dentate ligands which potentially encapsulate the The fluoride ion similarly exhibits high affinity for berylli- a polynuclear beryllium complex species Be O(O CCH ) bered ring Be-O-Be motif via a bridging hydroxyl group.23 4 2 3 6 Be2+ cation (Fig. 7). This is illustrated in the binding of um and was found to be the only inorganic ligand to form where six acetates act as bridging ligands for four beryl- In agreement with this, two aromatic analogues, 2-hy- (2- nitrilotripropionic acid to beryllium (Fig. 7a). Nitrilotri- all four substitution products with water, [Be(H O) F ] 16 2 4-n n lium atoms. In contrast to this, the dicarboxylate ligands droxyisophthalic acid (Fig. 5b) and 2,3-dihydroxybenzoic n)+ 16 propionic acid binds beryllium through the central amine where n = 1-4. Based on equilibrium measurements, reveal beryllium species of the types [Be(H O) L], [BeL ]2- acid (Fig. 5c), which offer a similar polynuclear binding 2 2 2 and the three carboxylate groups which wrap round it was found that the fluoride ion effectively competes and [Be (OH) (L) ]3-.16 The trimeric hydroxo/dicarboxylate pocket for beryllium via a carboxylate and a bridging hy- 3 3 3 the Be2+ cation creating six-membered chelate rings with the hydroxo ligand up to pH 8, at which point 3- species [Be (OH) (L) ] was further crystallised, highlight- droxyl group, revealed an even stronger interaction with 28 Be(OH) precipitates and species such as [BeF (H O) ] and 3 3 3 with appropriate tetrahedral geometry. Ligands such 2 2 2 2 ing the stability of the hydroxo trimer and the competing beryllium as well as excellent selectivity in the presence - as phthalocyanine (Fig. 7b), although tetradentate, do [BeF (H O)] exist in solution at a pH ranging from 0.5-8 in 22 3 2 hydrolytic tendency in the presence of other ligands in of other metal ions. This development is of particular 19 not provide a tetrahedral arrangement of donor atoms varying concentrations. The F NMR spectra of these be- aqueous solution.17 Further support for enhanced inter- interest considering the abundance of similar functional- however, a chiral binapthyldiimine- Be(II) complex (Fig. ryllium species give rise to signals of 1:1:1:1 quartet split- action and stability of beryllium with ligands that form ities in the major histocompatibility complex (MHC) class ting due to coupling to the 9Be nuclei.12 In the 9Be NMR 7c) analysed in solution by Plieger et al. have revealed a suitable chelate rings can be shown by a survey of for- II receptor gene implicated for the genetic susceptibility 2+ spectrum, a mixture of species containing [BeF(H O) ]+, tetrahedral coordination with the Be cation suggesting 2 3 mation constants (logk values) among analogous ligands in CBD cases. 2+ [BeF (H O) ] and [BeF (H O)]- can be distinguished as sep- that selective uptake of Be could possibly be attained 2 2 2 3 2 of varying chelated ring size (Fig. 4). Ligands that form arate signals from an overall multiplet of a 1:1 doublet, a However, other ligands lacking the characteristic poly- by incorporating mixed N/O donor atoms as in polyami- six-membered rings with beryllium are the most stable 13,19 1:2:1 triplet and a 1:3:3:1 quartet. The observation of the nuclear binding pocket of citric acid have equally been nocarboxylic acids. Potentiometry and NMR spectros- for the binding of beryllium since they offer the most 28 19 copy have further supported the selectivity of a mixed quartet in F NMR suggests that the fluoride anions are compatibility for a tetrahedral geometry with the small observed to bind beryllium strongly (Fig. 6). An example N/O donor ligand and the ligands nitrilotripropionic acid attached to a single beryllium and that they do not form sized Be2+ cation. Consequently, malonate which forms is 10-hydroxybenzo[h]quinoline-7-sulfonate (HBQS) (Fig. bridges between two beryllium atoms while the relative 6a) which binds beryllium extremely well and is now part and nitriloaceticdipropionic acid revealed selective up- a six-membered ring binds beryllium more strongly than 2+ 2+ 26 take of Be in the presence of Mg . However, the flex- intensity of the signals shows that some of the hydrated oxalate which forms a five-membered ring, while suc- of a commercial beryllium detection system. This has BeF species undergo ligand dissociation and redistribu- led to the proposition that the beryllium cation actually ibility afforded by the alkyl arms used for encapsulation 2 cinic and maleic acids which form seven-membered che- 12 cannot effectively preclude the ligand binding to larger tion in solution (Eq 2, 3). late rings also reveal weaker binding. Chromotropic acid, interacts strongly and is bonded by ligands possessing a metal cations.21 Therefore, nitrilotripropionic acid-type 140 141 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 ligands have further been investigated in a study which ring sizes of these ligands are shown in Fig. 9. The supe- to unravelling the mystery of the uncontrolled immune 16. Alderighi, L.; Gans, P.; Stefeno, M.; Vacca, A. Aqueous Solution incorporated the rigidity of aromatic groups to enhance rior interaction of the PO moiety with beryllium is again system’s response to beryllium particles. Chemistry of Beryllium. In Advances in Inorganic Chemistry; Sykes 20,21 A. G.; Cowley, A. Academic Press: Califorornia, USA, 2000; 50, 109- selectivity (Fig. 8). Full encapsulation of the beryllium revealed in the stronger interaction of methylenediphos- 197. Acknowledgements cation by these ligands was validated by correlating -ex phonate over phosphonoacetate. Both ligands differ only 17. Li, Y.; Liu, Y.; Bu, W.; Lu, D.; Wu, Y.; Wang, Y. Chem. Mater. 2000, 12, perimental and theoretical Be NMR chemical shifts, while in a second donor site. Methylenediphosphonate pos- We appreciate financial support from the Marsden Fund 2672-2675. the synthetic variation of the chelate ring size and the sesses two phosphonate groups while the phosphono- (contract MAU1204) of the New Zealand Government, 18. Ciavatta, L.; Iuliano, M.; Port, R.; Innocenti, P.; Vacca, A.Polyhedron, donor atom in one of the encapsulation arms (Fig. 8) acetate coordinates via a phosphonate and carboxylate administered by the Royal Society of New Zealand. 2000, 19, 1043-1048. reiterated beryllium’s binding preferences. Significantly, group. The stronger binding of methylenediphosphonate 19. Plieger, P. G., John K. D., Burrell, A. K., Polyhedron, 2007, 26, 472- this study revealed that the combination of unfavourable and phosphonoacetate over phosphonopropionate is References 478. features in ligands such as weakly coordinating donors presumably due to the latter forming a seven membered 1. Merchant Research & Consulting Ltd. Beryllium: 2015 World Mar- 20. Shaffer, K. J.; Davidson, R. J., Burrell, A. K., McCleskey T. M., Plieger, 30 ket Review and Forecast; see: http://mcgroup.co.uk/researches/ P. G. Inorg. Chem., 2013, 52, 3969-3975. and five-membered chelate rings results in weaker bind- chelate ring. Accordingly, all the bidentate ligands in Fig. beryllium (accessed 17th April 2015) ing with the Be2+ cation. For instance, the calculated 9Be 9 containing phosphonate groups exhibit superior bind- 21. Shaffer, K. J. Toward Selective Small Cation Chelation. PhD Thesis, 2. Christie, T.; Brathwaite, B. Mineral Commodity Report 19-Beryl- Massey Universtiy, Palmerston North, 2010. NMR chemical shifts for the beryllium complexes with ing with beryllium compared to the monodentate meth- lium, Gallium, Lithium, Magnesium, Uranium and Zirconium, 2008. 22. Keizer, T. S.; Sauer N. N., McCleskey, T. M. J. Am. Chem. Soc., 2004, see: http://www.nzpam.govt.nz/cms/investors/our-resource-po- ligands shown in Fig. 8a and 8b did not correlate well ylphosphonate. This is relevant since metal complexes 126, 9484-9485. tential/minerals/minerals-commodity-reports/beryllium.pdf (ac- with the experimental shifts, suggesting that they might of nucleotides containing the phosphate groups such as 23. Sauer N. N., McCleskey, T. M. J. Inorg. Biochem., 2005, 99, 1174- 2+ cessed 17th April 2015) not be able to fully encapsulate the Be cation like the adenosine 5-monophosphate, -diphosphate (ADP) and 1181. 3. Strupp, C. Ann. Occup. Hyg., 2011, 55, 43-56. ligands in Figs. 8c-f, which offer either a strongly -coor –triphosphate (ATP) play a fundamental role in biologi- 24. McCleskey, T. M.; Ehler, D. S.; Keizer, T. S.; Asthagiri, D. N., Pratt, L. 4. Scott, B.L.; McCleskey, T. M.; Chaudhary, A.; Hong-Geller, E.; Gnana- dinating oxygen donor or an unstrained six-membered cal processes. Potentiometric titrations31 have revealed R.; Michalczyk, R.; Scott, B. L.Angew. Chem., 2007, 119, 2723-2725. karan, S. Chem. Commun., 2008, 25, 2837-2847. McCleskey, T. M.; Scot, B. L. J. Occup. Environ. Hyg., 2009, 6, 751- chelate ring .20,21 higher stability constants for the [Be(ATP)]2- species (log 25. .Richeldi, L.; Sorrentno, R.; Saltini, C. Science, 1993, 262, 242-244 .5 k = 6.52) compared with the corresponding [Mg(ATP)]2- 757. 6. Gregory, A. Thinking Outside the Cube. In Safeguard Magazine; 26. Matsumiya, H.; Hoshino H.; Yotsuyanagi, T. Analyst, 2001, 126, species (log k = 4.10) and beryllium is also known to in- Thomson Reuters: New Zealand, 2009, 116, 39. 32 2082-2086. hibit alkaline phosphatase and DNA replication. Using 7. Young, J.; Ward, M. Copper Beryllium Alloys – the Value of Occu- 27. Diyabalanage, H. V.; Ganguly, K.; Ehler, D. S., Collis, G. E.; Scott, B. L.; a competitive fluorimetric approach, it was further ob- pational Hygiene Principles When Investigating an Occupational Chaudhary, A., Burrell A. K., McCleskey, T. M., Angew. Chem., 2008, Health Issue within Aircraft Maintenance Operations? see: http:// served that the decrease in the number of phosphate 120, 7442-7444. www.ohsig.org.nz/uploads/images/documents/library/OSIGH%20 groups from ATP to ADP resulted in a remarkable de- 28. Chinea, E.; Dominguez, S.; Mederos, A.; Brito, F.; Arrieta, J. M.; San- 2+ Copper%20Beryllium%20Alloys.pdf (accessed 17th April 2015) Fig. 7. Tetradentate coordination of beryllium to (a) phthalo- crease in binding affinity confirming that the Be cation chez A.; Germain, G. Inorg. Chem., 1995, 34, 1579-1587. 8. Plieger, P. G.; John, K. D.; Keizer, T. S.; McCleskey, T. M.; Burrell, A. K.; cyanine (b) nitrilotripropionic acid (c) chiral binaphthyldiimine 33 is chelated by adjacent phosphate groups in ATP. Fer- Martin, R. L. J. Am. Chem. Soc., 2004, 126, 14651-14658. 29. Alderighi, L.; Vacca, A.; Cecconi, F.; Midollini, S.; Chinea, E.; Domin- ligand ritin is also another phosphate binding biomolecule. It guez, S.; Valle, A.; Dakternieks D.; Duthie, A.; Inorg. Chim. Acta, 9. Akitt, J.; Duncan, R. H. J. Chem. Soc., Faraday Trans. 1, 1980, 76, 1999, 285, 39-48. is an iron storage protein that reveals significant binding 2212-2220. 30. Valle, A.; Chinea, E.; Domı́nguez, S.; Mederos, A.; Midollini S.; Vac- with beryllium and is likely to provide binding sites that 10. Bruno, J. J. Chem. Soc., Dalton Trans., 1987, 10, 2431-2437. 4,33 ca, A. Polyhedron, 1999, 18, 3253-3256. allow beryllium to pass through cellular systems. 11. Cecconi, F.; Ghilardi, C. A.; Midollini, S., Orlandini, A.; Mederos, A.; 31. Alderighi, L.; Dominguez, S.; Gans, P.; Midollini, S.; Sabatini, A.; Inorg. Chem., 1998, 37, 146-148. Vacca, A.; J. Coord. Chem., 2009, 62, 14-22. 12. Schmidbaur, H. Coord. Chem. Rev., 2001, 215, 223-242. 32. Mederos, A.; Domínguez, S.; Chinea, E.; Brito F.; Cecconi, F. J. Co- 13. Wong, C. Y.; Woollins, J. D. Coord. Chem. Rev., 1994, 130, 243-273. ord. Chem., 2001, 53, 191-222. 14. Schmidt, M.; A. Schier, J. Riede and H. Schmidbaur, Inorg. Chem., 33. Zheng, Y.; Lin, L.; Hang, W.; Yan, X.; Marrone, B. L. Talanta, 2011, 85, 1998, 37, 3452-3453. 638-643. 15. Schmidbaur, H.; Schmidt, M.; Schier, A.; Riede, J.; Tamm T.; Pyykkö, P. J. Am. Chem. Soc., 1998, 120, 2967-2968.

Fig. 9. Malonate and ligands with the phosphonate functionality

Conclusions Beryllium is a very useful speciality metal and is indis- pensable in several of its applications. However, its us- age should be limited considering its toxicity and strict Fig. 8. Nitrilotripropionic acid-type ligands for the full encapsu- lation of beryllium industrial and government controls should be adminis- tered to reduce future potential exposure of beryllium in Another functional group relevant for beryllium binding New Zealand workplaces. Substitutes for beryllium metal is the phosphonate group but fewer studies have inves- and alloys include titanium and pyrolytic graphite, while tigated the solution chemistry of beryllium phosphonate beryllium oxide can be replaced by aluminium nitride. complexes despite the fact that phosphonate ligands Unfortunately, these substitutes often result in a notable (PO moiety) form stronger complexes than carboxylate/ reduction in the performance of the end product and this hydroxyl ligands (CO moiety). For instance, methylphos- has led to a sustained usage of beryllium. It is important, phonate, a monodentate ligand, forms a stronger com- therefore, to identify selective and tight binding ligands plex than the malonate ligand while methylenediphos- with suitable functional groups and arrangement of do- phonate, which offers a similar six-member chelate ring nor atoms for applications in the area of beryllium detec- as malonate, reveals a much stronger interaction with tion, remediation and chelation therapy. Research in our beryllium.29 Using potentiometric and multinuclear NMR group is building a greater understanding of the coordi- methods, the interaction of beryllium with some phos- nation chemistry of the Be2+ cation for the development phonate ligands have been ordered as malonate

142 143 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

Heroes and plots in chemistry storytelling either the chemical processes themselves or the people nature”.18 From such a statement it can be inferred that involved. the process of discovery of at least these chemical ele- Peter Hodder ments did not run smoothly; Scerri’s narratives show that 12 The typology of storytelling in Table 1 suggests that the scientific endeavours are disrupted either by person- Victoria Business School, Victoria University of Wellington and HodderBalog Social and Scientific most stories comprise five stages: the call, the dream,

Article ality issues affecting the heroes or by external influences, Research, Wellington (email: [email protected]) 13 frustration, ordeal, and resolution. Such an analysis of in particular war and politics. As a result, rather than all Keywords: storytelling, plots, heroes, chemical processes, chemical elements fiction has inevitably attracted criticism, one critic- not being ‘quests’, some of the seven tales have character- ing that “Booker’s framework ends up less a source of istics of other types of plot, as shown in Table 2 and de- enlightenment than a straitjacket, leaving whole areas of In recent years there has been an explosion in the publica- tailed below. literature and storytelling fundamentally either inexpli- tion of ‘popular’ books written about various disciplines, cable, or reduced to an uninteresting ‘essence’”.14 How- As told by Screrri, the discovery of francium by Margue- including scientific ones. While some of these have been ever a number of contemporary novelists find merit in rite Perey has the hallmarks of a ‘rags to riches’ story. collaborative efforts – as for example the book Are An- the approach.15 Perey was initially a technician in Curie’s laboratory in gels OK?,1 where discussions with scientists provided a 1929, working on concentrating actinium. The ‘call’ and feedstock for creative writers to exploit, others such as On the basis of this reductionist approach to stories, ‘initial success’ stages related to her observation that the The Elegant Universe of Albert Einstein are a compilation many stories in New Zealand is Different and other simi- half-life of the decay of actinium could not be attributed of science tales,2 possibly motivated by discussions with lar compilations seem likely to take the form of a ‘quest’, to actinium’s daughter isotopes alone, but to actinium creative writers, but not unduly influenced by them. In in which a group of scientists undertake a research jour- itself. She deduced that actinium decayed to another ele- the preface to As Far as We Know: Conversations About ney with a successful outcome, albeit with setbacks and ment – element-87. There is not much of a ‘central cri- Science, Life and the Universe,3 Professor Sir Paul Cal- failures along with the way (see Table 1), although one sis’ in this instance; rather than everything going wrong, laghan opined, “… it is the responsibility of science to tell essay in New Zealand is Different is considered by its au- Perey was simply cautious in announcing her discovery. its own story, and to communicate as widely and clearly 16 Fig. 1. The combined holdings in 2010 of ‘popular’ science books thor to represent a ‘tragi-comedy’. With respect to the fourth stage – ‘independence and as possible why the scientific view enriches human un- in the libraries of Auckland University of Technology, University the final ordeal’ – Perey had kept her two mentors inde- derstanding. The last decade has seen a steady stream of Waikato, Victoria University of Wellington and University of In the preface to Eric Scerri’s book A Tale of Seven pendently advised of her success, but the mentors could of science communication literature through books of re- Otago, by the decade in which the books were published. There Elements,17Oliver Sacks notes that Scerri’s storytelling is a clear post-Second World War ‘spike’ before a minimum in not agree which of them should share the credit for the markable quality aimed at a general audience.” The time “allows us to see chemistry, and science generally, as an the 1980s followed by a more recent revival in publication of discovery, so, as Scerri puts it, Perey was “permitted to trend of publication of such books is demonstrated in Fig. essentially historical enterprise – a human adventure this type of book. (The plot can only be indicative because it keep the discovery to herself”. The final stage – ‘comple- 1, but it is interesting that fewer than 5% of the topics takes no account of book purchasing policies of the libraries or that shows the best, and sometimes the worst, of human in the Conversations between Callaghan and broadcaster any culling of books since acquisition). Kim Hall were chemistry related. 4 Table 1. Summary of stages of Booker’s seven basic plots* Such books are of a type that can be considered to “… re- Type of plot Stages state the triumphal status of science in contemporary so- ciety… These accounts allow us to see the prevalence of The Monster 1, The Call (or An- 2, Initial success (or 3, Confrontation 4, Final Ordeal Miraculous Escape a scientific world view, an ‘ideology’ – scientism – that is ticipation) Dream) (Frustration) (Nightmare) (and Death of a commonly shared perspective on the world around us. Monster) The public are presented with and assimilate a range of Rags to Riches 1, Initial wretched- 2, Out into the 3, Central crisis – 4, Independence 5, Completion and resources in constructing their understanding of science, ness and ‘call’ to world – initial suc- “everything goes and final ordeal fulfilment and given the composition of much of this material, it is activity cess wrong” unsurprising that we see a societal understanding of sci- The Quest 1, The Call: rectifica- 2, Journey across 3, Arrival and frus- 4, The Final Ordeals 5, After a ‘last thrill- ence that reflects aspects of popular science accounts.”5 tion of intolerable hostile terrain tration – a last series of ing escape from oppression requires with monsters and tests death’, the kingdom The NZ Institute of Chemistry has been involved with sev- a journey temptations to or life-transforming eral compilations of chemistry ‘stories’. The editor of one overcome† treasure is won of these books indicated, as befits its title Chemical– Pro- Voyage and 1, Anticipation and 2, Initial fascina- 3, Frustration stage, 4, Nightmare; 5, Thrilling escape cesses in New Zealand,6 that “we have tried to keep the Return ‘fall into another tion, which may with intruding shadow‡ dominates and return emphasis on chemical processes occurring in New Zea- world exhilarate because shadow and threatens Fig. 2. “Life is Chemistry” image used on the cover and title of unfamiliarity survival land”, while admitting that “the level of chemistry varies page of Chemical Processes in New Zealand (reference 6). No from article to article, and a lot of non-chemical descrip- people feature in the image. Comedy 1, A ‘little world’ in which people 2, Worsening confusion and dark- 3, Previously unrecognized things ‡ tive material is included”. The cover and title page of this are confused, frustrated and shut ness; a nightmarish tangle come to light, changing percep- off from one another tions and dispersing shadows, book include a graphic with the theme “Life is Chemistry” In the 1999 book, New Zealand is Different, the cover ‘little world’ becomes happy (Fig. 2), and yet a striking feature of the compilation is blurb notes that the essays Tragedy 1, Anticipation; 2, Dream stage: 3, Although initially 4, Nightmare – mat- 5, Destruction or the minimal reference to the scientists actually involved “… are a testament to the dedication and skill of New hero incomplete, hero becomes com- imperceptible, frus- ters out of hero’s death of hero, by in either the development or the application of the pro- Zealand chemists and engineers as well as to the effec- hoping for unfilled mitted to a course tration sets in, with control, there is an forces hero has cesses described. Providing anonymity to scientists was tiveness of government research establishments. More gratification, nut of action in which dark acts performed increase of fear and roused, or a final perhaps more understandable in the Institute’s pollution importantly, this volume conveys something of the hu- finds a focus for things initially go and threats from despair act of violence report in the 1970s,7 being closer in time to the publica- action improbably well shadowy figures‡ man activity behind the achievements, since most of tion of Silent Spring, perhaps the first book to demonise Rebirth 1, Hero influenced 2, All seems well, 3, Threat returns 4, Continuation 5, A miraculous the authors were personally involved in the events they 8 by ‘shadow of dark the threat appar- forcefully of threat to its redemption science. In an earlier book published in 1940, which was 11 described”. ‡ presumably targeted at a general audience, Chemistry power’ ently receding perception of the 9 dark power being in the Development of New Zealand Industry, and rath- Indeed, each essay is prefaced by biographical details triumphant er later in A History of Chemistry Division (published in and a photograph of its author. There is a certain ‘heroic’ 1981),10 the chemists undertaking the research described *See Reference 12 character to all the stories told, in which the ‘heroes’ are †Quests always have more than one hero, to ensure that mistakes can be shared and the hero survives are specifically identified. ‡Shadow or darkness may be physical or psychological 144 145 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

Table 2. Mapping of Scerri’s seven elements to Booker’s seven basic plots properties and the priority of its detection. In a sense, of the same approach can be applied to non-fiction, as 25 Scerri’s seven elements then, for the hafnium ‘side’ the story is a comedy, while described below for Brian Halton’s autobiography. Type of plot Proactinium Hafnium Rhenium Technetium Francium Astatine Promethium for the celtium ‘side’, it might be considered a tragedy. The Monster The chapter on rhenium could be considered a combi- Rags to Riches l nation of a quest in respect of the actual discovery of The Quest l ¢ the element, and a tragedy in respect of the activities of Voyage and Return Japanese scientists to rehabilitate an earlier claim by Ma- Comedy l l l sataka Ogawa of the discovery of an element he thought Tragedy ¢ ¢ l l was element 43, but which others subsequently inferred Rebirth was probably rhenium. Scerri’s description of the “ardu- l Dominant type ously long extraction” by which the rhenium discoverers ¢ Subordinate type Walter Noddack, Ida Tacke (later Ida Noddack) and Otto Berg “obtained just one gram of rhenium after processing tion and fulfilment’ – is amply demonstrated by Perey Three of the stories – those for hafnium, astatine and about 660 kg of the ore molybdenite” may be considered being invited by the International Union of Pure and Ap- promethium – fit the stages for comedy. Each opens in the nature of a quest. However, in Scerri’s narrative plied Chemistry to suggest a name for her discovered with a ‘little world’ of protagonists separated from each this quest pales by comparison with the tragedy revealed Fig. 3. ‘Emotional valence’ versus narrative time compiled by element (she chose ‘francium’ to honour her homeland other, with worsening confusion, and ultimately resolved Matthew Jockers for James Joyce’s Portrait of the Artist as a by the ‘frustration’ of the Japanese in attempting to rep- and to recognise the contribution of French scientists to through changed perceptions of reality. Young Man (http://motherboard.vice.com/read/computers- licate Ogawa’s work, the ‘nightmare’ of their reinterpre- radiochemistry), by her being invited to submit research find-that-there-are-six-plots). tation of spectroscopic and X-ray data, and Scerri’s ulti- for a doctorate (despite having no undergraduate de- Scerri’s introduction to his story of the discovery of pro- mate destruction of the claim by drawing attention to the Brian Halton’s career, as revealed by his annual research gree), and by her being appointed to a chair in nuclear methium sets it up as a comedy, referring to two sides of implausibility of cultural excuses made by the claimants. publication record is probably typical of many scientists: chemistry at the University of Strasbourg. a priority debate, both of which “appealed to X-ray data and Moseley’s law”, yet “… neither side was correct. In a dominance of peer-reviewed papers, interspersed with Scerri’s story of technetium is to some extent bound up Although other researchers are mentioned, Scerri’s story their own way each side was working in complete delu- chapters, books, and edited books, and with contribu- with that of rhenium. Walter and Ida Noddack’s claim for of the discovery of protactinium focuses on “[Lisa] Meit- sion, since element 61 [promethium] is highly radioac- tions to professional – rather than scholarly – journals element 43 was never formally retracted, even though ner and [Otto] Hahn’s path to protactinium”, in essence tive and unstable, does not occur naturally on Earth and comprising a greater proportion of annual outputs as his the claim is unjustified “for the simple reason that the a ‘quest’. The good progress that Meitner makes during could only be isolated in minute quantities by artificial career draws to a close (Fig. 4). discovery of this element had to await its artificial syn- the First World War is described by Scerri as providing means when such methods became sufficiently devel- thesis following the discovery of nuclear fission” (Scerri, “increasing confirmation that she was succeeding in find- oped in the 1940s” (Scerri, reference 17, p.176). In fact, reference 17, p. 124), something only achieved much ing the mother substance of actinium”. The ‘frustration’ the actual discovery in 1949 was not a deliberate attempt later than the Noddacks’ work. The actual discovery by stage comprises the other potential claims to discovery, at synthesis, but came about as a result of interpretation Emilio Segrè is said by Scerri (reference 17, p. 132) to be even though they were relatively easily discounted, prin- of an unexplained peak on an elution curve from ion ex- serendipitous, leaving him, as the storyteller, to focus on cipally because the alleged discoveries were of short-lived change chromatography of isotopes. This is the classic the tragedy of the unsuccessful rehabilitation of the Nod- isotopes. The story could have ended in 1918 with the end to a comedy, with a “coming to light of things not docks’ claim. discovery of protactinium, but Scerri chose to continue previously recognised [by which] perceptions are dra- Meitner and Hahn’s ‘quest’ by including their continued matically changed” (see Booker, reference 12, p. 128). Scerri admits to his stories being “revealing of the often work on uranium through which they discovered nuclear frail humanity of the scientists involved or perhaps of the A similar little world of people closed off from each other fission. Doing so introduces the ‘ordeal’ of Meitner be- scientific method as a whole and the pressures it places sets the scene for the discovery of astatine. Confusion ing an Austrian Jew at the time of the Second World War, on scientists”, and that they are “dominated by national- reigns through the 1940s, made worse by the isolation of with Hahn, although publicly opposed to Nazi policies, istic drives” which sometimes “comes from the scientists some of the protagonists from each other during World bowing to their pressure and asking Meitner to resign themselves while in other cases it is supporters of these War 2. By the end of the chapter one group appears to her research post in Berlin. Meitner and her nephew then scientists or perhaps even the press in the countries in- have succeeded (although the accolade of discovery may recognise the prospect of uranium fission to barium, later volved that fuel the nationalism” (Scerri, reference 17, Fig. 4. Distribution of selected types of publication over Brian yet be shared20) in part because an influential contribu- Halton’s career in chemistry (compiled from reference 25, Ap- cited by a science historian thus: “Sixty years old and of- p. xxxii). In essence, he has woven his narrative around tion to Nature21 clarified the rules for naming rights of pendix 2). ficially retired, Meitner had explained one of the great- some facts and around his and others’ interpretations of est discoveries of the century”.19 Meitner may not have elements, thereby changing previously held perceptions. those facts to create stories that are his own. The peaks in such a distribution would be expected to received a Nobel prize, and Hahn’s claim “that physics An element of atomic weight 180 was predicted by Dmi- correspond with times of a greater sense of career ful- had actually hampered the discovery of nuclear fission In a similar way, Primo Levi’s autobiographical use of se- tri Mendeleev as a homologue of zirconium, but there filment, but their precise cause is difficult to determine. and that it had been a triumph for chemistry alone”, in an lected chemical elements in The Periodic Table – Il Siste- was prolonged confusion as to whether the new element Peaks and troughs are also apparent in a plot of ‘senti- obvious slur to Meitner’s contribution (Scerri, reference ma Periodico22 can be interpreted in terms of the relative was a transition element (provisionally named hafnium) ment’ versus time (Fig. 5), where ‘sentiment’ is - deter 17, p. 79) could be inferred to make this story a tragedy, emphasis of his life, his work as a chemist and his devel- or a rare earth element (provisionally named celtium). mined from the difference between the number of times but it is countered by an affirmation of the quest’s success opment as a writer. As the book progresses the relative Theoretical physics evidence suggested the former was selected ‘positive’ words are mentioned and the number in the final paragraph in a section of the chapter entitled emphasis ‘swings’ between each of these aspects.23 Such correct, while initial X-ray data appeared to favour the of times selected ‘negative’ words are mentioned on “But Why No Nobel Prize for Meitner”: variation resembles that found by Matthew Jockers in his latter. The scientific differences of opinion were further each page of Halton’s autobiography. Often-repeated plots of ‘emotional valence’ versus ‘narrative time’ for complicated by nationalistic fervour, leading to “one words deemed ‘positive’ for an academic scientist such “But by what is perhaps a nice touch of irony, an element Irish fiction, including that for James Joyce’s Portrait of of the most bitter and acrimonious priority disputes in as Halton were: ‘research’, ‘teaching’, ‘conference’ and that had been provisionally called hahnium was eventu- the Artist as a Young Man (see Fig. 3).24 Of his method for twentieth century science” (see Scerri, reference 17, p. the name of his wife (Margaret). On reading the autobi- ally named meitnerium, albeit several years after Meit- determining ‘emotional valence’, Jockers notes that the 91). In Scerri’s narrative, the hafnium supporters won the ography, the most negative influences were those related ner’s death in 1968. Hahn had effectively been deprived process involves two major components: “a controlled day, perhaps in part because the celtium supporters un- to Halton’s being unwell: ‘health’, ‘heart’ and ‘hospital’. of having an element named after him. Too little too late vocabulary of positive and negative sentiment markers successfully tried to change the rules in respect of the These measures are also compiled for each chapter of perhaps, but quite significantly the suggestion came …. and a machine model that [he] trained to identify and relative importance of determination of the element’s the book (Table 3). from a German…” (Scerri, ref. 17, p. 79). score passages as positive or negative.” A simple version

146 147 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 Article Table 3. Sentiment by chapter of Brian Halton’s autobiography Metals: ancient and modern Sentiment* Robert H. Bennett Chapter in From Coronation Street to Consummate Aggregate Pages Positive Negative Chemist sentiment† Consulting Chemist, 1/96A Verbena Road, Birkdale, Auckland (email: [email protected]) A B C D E F G Keywords: metals, metallic alloys, compounds with metallic conduction The Early Years – Lancashire and London 1-9 1 0.11 University Years - Southampton 10-20 9 1 1 2 0.64 Florida in the Mid-1960s 21-31 6 6 1.09 Robert Bennett attended crystal structure and on the temperature and pressure. school in Christchurch and One famous example is the behaviour of tin at low tem- A New life, a New Place, and an Emerging Career 32-58 32 14 3 24 1 1 2.63 studied chemistry at the peratures (“Tin pest”).5 Articles made of tin have been A Young Family, a Career, and Momentum 59-76 15 3 8 8 3 2 4 1.39 University of Canterbury, observed to crumble into dust when kept at low tem- Chemistry and Service 77-93 8 4 5 4 1.24 graduating with an MSc in peratures for long periods, e.g. church organ pipes in 1984. From 1985-2000 he mediaeval Europe.5 The transition temperature is 13.2 °C From Recognition to Retirement 94-128 47 21 8 8 4 8 15 1.63 worked at LabPlus, Auck- for pure tin. This is supposed to have affected Captain RF The Joys of Emeritus Professor – What Better Role? 129-139 27 14 1 2 1 3.55 land Hospital, mainly with Scott's 1912 expedition in the Antarctic when leaks de- *Positive ‘sentiments’: A, Research; B, Teaching; C, Conferences; D, Margaret (Brian Halton’s wife); Negative ‘sentiments’: E, Health; F, Heart; G, Hospital hormone radioimmunoas- veloped in soldered kerosene tins and Napoleon's troops

†The aggregate sentiment for each chapter is (NA + NB + NC + ND – NE – NF – NG)/NP, where NA is the number of times sentimentA is mentioned; N B, says. From 2003-2014 he during the Russian Campaign when tin uniform buttons 5 the number of times sentiment B is mentioned, etc.; and NP is the number of pages in the chapter was an industrial chemist crumbled. Both examples are disputed. The low temper- with Ashland New Zea- ature form (α-Sn) is a grey powder, has the same crystal land Ltd (now Solenis NZ structure as silicon and diamond and is a semiconductor. Table 3 shows the hallmarks of ‘the quest’ type of story: Acknowledgements building to initial success (a high value of aggregate senti- Ltd). Following a company The band gap of α-Sn is quite small (0.08 eV) and it seems I am grateful to Eric Scerri for providing a review copy of restructuring, he is now free to pursue other interests, possible that under high pressures the band gap of α-Sn ment – 2.63 – in the fourth chapter), followed by darker A Tale of Seven Elements, which has been a cornerstone times (reaching the nadir with a value of the aggregate which include electronics, food science and the history would be zero or negative. α-Sn has a lower density (5.77 in the development of this paper, and to Brian Halton of chemistry. g/ml) than β-Sn (7.31 g/ml), so would not be stable at sentiment of 1.24 in the sixth chapter), with all coming for his agreement – albeit with some skepticism – for his right at the end (with the highest value of aggregate high pressures, but the transition might be slow. Germa- autobiography From Coronation Street to Consummate Introduction nium has a high pressure form (β-Ge) which has the same sentiment – 3.55). The stages of an idealised story are Chemist to be used in a more quantitative way than he Lavoisier's 18th century table of elements was based on structure as β-Sn and should be metallic. Indium has a less clear from Fig. 5, indicating that even with the same would have ever imagined. facts, a different story could have been told, and with a the distinction between Sb, Au, As, Bi, Co, Cu, Sn, Fe, Mn, tetragonal crystal structure like tin, and it may be that different emphasis a story here classified as a quest could Notes and references Hg, Mo, Ni, Au, Pt, Pb, W, Zn and the non-metals S, P, non-metallic crystals of In could also be made with a less 1 dense crystal structure. be a tragedy, or a tragedy could be a comedy. Storytelling 1. Callaghan, P.; Manhire, B. Are Angels OK? – The Parallel Universe of C, Cl, F, B. Earlier than this, alchemists generally distin- New Zealand Writers and Scientists, Victoria University Press: Wel- guished metals, which they connected with the seven is unashamedly an art, and if (as is often said) art imitates The calculations concerning copernicium being a semi- 26 lington, 2006. wandering stars of antiquity (Fe/Mars, Cu/Venus, Ag/ life, then storytelling also imitates life, of which the con- conductor rather than a metal6 are likely to remain theo- duct of science is a component (Fig. 6). 2. Barnes, T. et al. The Elegant Universe of Albert Einstein, Awa Press: Moon, Au/Sun, Hg/Mercury, Sn/Jupiter, Pb/Saturn), from Wellington, 2007. non metals (C, S) and semi-metals (As, Sb), which were retical for some time to come. Assuming that the band not so connected. Mercury seemed to be different, but gap is also a function of cluster size, as many physical 3. Callaghan, P.; Hill, K. As Far As We Know: Conversations about Sci- properties are for Hg, it would seem to require several ence, Life and the Universe, Penguin: Auckland, 2007. was still associated with silver and the other metals, e.g. “quicksilver” or “hydrargyrum (Hg)”. Alchemists generally hundred copernicium atoms at least to be prepared, and 4. Hodder, P. Showing Science: A History of Presenting Science to the assembled in the same crystal. Public in New Zealand, HodderBalog: Wellington, 2011, p. 158. viewed mercury as the metallic principle, e.g. Paracelsus' “three primes” – his other two being sulfur and salt.2,3 5. Ericksen, M. Science, Culture and Society: Understanding Science in Effect of high pressures the Twenty-first Century, Polity Press: Cambridge, UK, 2005. There are many properties of metals listed in old chem- It may be that most elements will have metallic forms 6. Packer, J.E.; Robertson, J.; Wansbrough, H. Chemical Processes in istry books, such as being shiny, malleable, ductile, con- at extremely high pressures. Arsenic has a high pressure New Zealand, NZ Institute of Chemistry: Auckland, 1998. ducting heat and electricity well, etc. These are mostly a form with a simple cubic structure which is metallic.7 7. Environment and Industry: A Pollution Report by New Zealand Sci- consequence of having reasonably free electrons – elec- Sulfur is metallic at high pressures >100 GPa.7 Iodine is entists. NZ Institute of Chemistry: Christchurch, 1974. trons which are not bound to one atom, or a few atoms, metallic at pressures of 16-18 GPa and greater.7 Argon, 8. Carson, S. Silent Spring, Fawcett Publications: Greenwich (Con- but are free to move throughout the crystal, or put an- krypton and xenon have been calculated to be metallic at necticut), c.1962. other way, they contain electron bands which are par- pressures > 132 GPa.8 Possibly astatine will show metal- Fig. 5. Sentiment analysis of Brian Halton’s autobiography. From the number of times the positive sentiments (research, teach- 9. Chemistry in the Development of New Zealand Industry – A review tially filled. lic properties if enough of it can be made to study. Apart ing, conferences, Margaret (Brian Halton’s wife)) less the num- of the Influence of the Chemist in the first Hundred Years of New from the old speculation about metallic hydrogen,9 there ber of times the negative sentiments (health, heart, hospital) Zealand’s History, New Zealand Section, Institute of Chemistry of One property of metals that is useful for distinguishing has also been some speculation that ammonium might Great Britain and NZ Institute of Chemistry: Christchurch, 1940. feature on each page, five-page moving averages of the aggre- them from other substances is that they conduct electric- 10 This publication is reproduced as the final chapter in reference 6. be metallic at very high pressures. gated sentiments are calculated and plotted against the page ity less well hot than cold. Semiconductors and ionic con- number. 10. Hughson, W.G.M.; Ellis, A.J. A History of Chemistry Division, NZ De- ductors are usually better conductors hot than cold. For Apart from the approximately 90 metallic elements, partment of Scientific and Industrial Research: Wellington, 1981. example, the lodestone, magnetite (Fe3O4) is a low band- there are many more metallic alloys and metallic com- 11. Hogan, D.; Williamson, B. New Zealand is Different – Chemical gap (0.1 eV) semiconductor, not a metallic conductor. Its pounds. Milestones in New Zealand History. Clerestory Press: Christchurch, electrical resistance (100-1000 Ω cm) is close to the me- 1999. tallic range, but decreases with temperature. Below 120 Metallic alloys 12. Booker, C. The Seven Basic Plots – Why We Tell Stories, Continuum: K, it changes structure and becomes an insulator .4 Some alloys, e.g. brass, have been known since ancient London, 2004. times. Brass was known before zinc was isolated, at least 13. Unsurprisingly, other typologies have been suggested. A simpler Metals on the edge Fig. 6. Inter-relationship between art, storytelling, science and in Europe. As a material, it has retained its separate iden- life. The central oval is “art imitating life” – or “life imitating Whether an element is metallic or not depends on the tity, being listed in many tables of physical properties. art” (see ref. 26) Continued on page 153 148 149 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

The properties of brass are quite different from those of Whether different metal atoms readily substitute for and niobium(II) oxide, NbO, are also metallic conductors, is formed with solvated metal cations and solvated elec- a linear combination of copper and zinc properties, as each other and form alloys or not depends mainly on the as are CrO2 and MoO2. There are other oxides which may trons. The dilute solutions have the electrical properties shown in Table 1. atomic radius, but also on the crystal structures, the va- be metallic conductors when non-stoichiometric, e.g. expected from electrolytes. If more metal is added, a 17 lency of the metals (a metal with low valency is more like- ~SnO2, ~EuO, ~In2O3, etc. bronze phase is formed (for lithium, above a mole frac- Table 1. Properties of copper, zinc and brass ly to dissolve in a metal with high valency than vice ver- tion of 0.1) which conducts electricity very well, in the 14 VO is a metallic conductor at room temperature and 30a sa) and their electronegativities (Hume-Rothery rules ). 2 range of metallic conductors. Solutions of this type are 18 Copper α-Brass Zinc About ±15% difference in atomic radius is about the limit. changes to a semiconductor/insulator at 340 K. A num- known for other solvents such as amines and ethers,30b ber of these oxides are superconductors at low tempera- % Cu 100 70 0 For instance, iron (metallic radius 126 pm) forms substi- but are less stable. tutional alloys with other elements with an atomic radius tures. % Zn 0 30 100 of between 105 pm and 145 pm. The preparation of potassium by electrolysis of molten The perovskites CaVO 19 and SrVO 20 are also metallic 3 3 KOH or KCl is more difficult than the corresponding prep- Crystal structure fcc fcc hcp 21, 22 Most non-metallic elements can also form metallic alloys conductors. arations of sodium, because potassium is distinctly solu- with metals. For example, antimony is usually considered ble in molten KOH or KCl. Rubidium metal is more soluble Melting point ºC 1083 900 420 The high temperature superconductors discovered at most a semi-metal, but it forms many metallic alloys. in molten rubidium salts than potassium is in its molten Density (kg/m3) 8.9 8.5 7.1 in the late 1980s are also mixed oxides, e.g. “BSCO”: Sb alloys (such as type metal) often expand on freezing salts, and caesium is completely miscible with molten Bi Sr Ca Cu O (n=1, 2, 3) and “YBCO”: YBa Cu O . Electrode potential which is useful for good quality impressions when casting 2 2 n-1 n 2n+4+x 2 3 7-x caesium halides. These solutions appear to be metallic 0.34 -0.35 -0.76 (V) type. This expansion on freezing is also seen with indium solutions with free electrons, similar to the liquid ammo- The tungsten bronzes - Mx WO3 (0alloy,11,12 which can- another relativistic effect? lic. This may have given support to the mercury-sulfur- formed. not be made by heating, as it is unstable above 350 °C. salt 3-element alchemical theory, as the properties of Similarly, iron amalgam, which cannot be made directly, Metallic compounds Tetramethylammonium amalgam and other 'onium sulfides are quite variable and can be adjusted by vary- can be made by electrolysing a ferrous sulfate solution Oxides amalgams have been reported.34,35 There has been a pat- ing the proportion of sulfur. However, most of the shiny, using an iron anode and a mercury cathode.13a It is also ent granted for hydrazinium amalgam.36 Vanadium (II) oxide, VO, was mistaken for the element metallic looking sulfides are low or medium band-gap possible to make iron amalgam by reducing ferrous sul- itself by Berzelius in 1831.16 It is a metallic conductor, 17 13b semiconductors. The lanthanide dihydrides are also metallic conductors, fate solution with sodium amalgam. so this should not be surprising. Titanium(II) oxide, TiO, 37 3+ with delocalised electrons : Ln (H¯)2 (e¯). Some but not Table 2. Hume-Rothery limits for mercury and properties of selected elements which do and do not form mercury amalgams Sulfides of the main group elements are semiconductors all of the lanthanide dihalides are metallic conductors 37: or insulators. Transition metal sulfides and lanthanide 3+ Ln (X¯)2 (e¯). Lanthanum also forms a metallic mono- Atomic radius (metallic) and actinide sulfides can be semiconductors, insulators iodide LaI with a NiAs structure 38 : La3+ (I¯) (e¯) . Element Electronegativity Valency* 2 (pm) 15 or metals. Anisotropy of metallic properties Mercury 151 2 2 CoS and CuS are metallic conductors.25 CeS is a metal- 2 2 Most metals and alloys crystallise in cubic crystal struc- Hume-Rothery limits for lic conductor, as is ThS.26 The higher sulfides of thorium 128-174 1.6-2.4 ≤ 2 tures, so the physical properties are the same in three mercury (Th S , ThS , etc.) are semiconductors.27 2 3 2 dimensions. It is a similar case for metals that crystallise Elements which readily form amalgams: Some interesting semiconducting metal sulfides include in hexagonal crystals. There should be slight differences Sodium 186 0.93 1 between the properties in the x, y, z directions and on the FeS2, iron pyrite or fool's gold; PbS, galena, which is dark diagonals. Metals that crystallise in orthorhombic crys- Potassium 227 0.82 1 and shiny; bornite, Cu5FeS4 (red-brown fresh and irides- tals (Ga) or tetragonal crystals (In, Sn) should show some Copper 128 1.9 2 cent purplish blue when exposed to air) and CuS, covel- lite. These, and many others, were used for making cats more directionality of electric conductivity and other Silver 144 1.93 1 whisker detectors (Schottky barrier diodes) and Perikon properties. Gold 144 2.54 3 detectors 28 (p-n hetero-junction diodes) in the early days The metal oxide conductors BSCO and YBCO have crys- of radio. The first three are semiconductors and may be Calcium 197 1 2 tal structures with elongated unit cells and they should n-type or p-type depending on their impurities, defects Aluminium 143 1.61 3 show marked anisotropy as normal metallic conductors. and stoichiometry. CuS is automatically p-type because 20 When using them for making electrical wires, great care Tin 145 1.96 4 of its structure (Cu+) (S−)(S 2−) and is a very good electrical 3 2 needs to be taken to have the crystals lining up at the Elements which do not readily form amalgams: conductor. CuS is sometimes listed in reference books as boundaries, otherwise the wire will not exhibit supercon- a “p-type metal”. It was used for the first field effect tran- Iron 126 1.83 3 ductivity. sistors (FETs) constructed in the late 1920s.29 Platinum 139 2.28 4 ? Antimony and grey arsenic have layer structures and Tungsten 139 2.36 6 Other compounds with metallic conduction should conduct electricity better in the plane of the lay- Tantalum 146 1.5 5 When lithium, sodium, calcium or a number of other ers. This is well-known for graphite (which has the elec- metals are dissolved in liquid ammonia, a blue solution * It is not clear in what sense Hume-Rothery used the term “valency”. It has been taken here to mean maximum common oxidation state. trical properties of a semiconductor rather than a metal). 150 151 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

It could also be possible for a crystal to show metal- Paracelsus. In “A Book about Minerals”, Paracelsus (as translated 1963, 15, 1191-1193] 33. Reedy, J.H. J. Chem. Educ. 1929, 6(10), 1767. doi: 10.1021/e31 lic properties in one or two directions and non-metallic by Waite) defined a metal as “that which fire can subdue, and out MA d006p1767. This is a demonstration of the transport of am- of which the artisan can make some instrument.” He also stated 28. Pickard, G.W. US Pat. 1,118,228 (Nov 24, 1914). A zincite-bornite monium through mercury. Ammonia and ammonium salts are not properties in the others. This could be useful for making that mercury is not a metal; that the association of planets and combination was often used in “Perikon” detectors developed by soluble in mercury, so this is reasonably convincing. electronic devices. metals was false, and that there were other metals such as “zinc” Greenleaf W. Pickard about 1909, which consist of a crystal of n- (non malleable metal, probably Zn) and “cobalt” (black, no me- type zincite (ZnO) in contact with a crystal of p-type bornite, i.e. in 34 (a) Hoch, C.; Simon, A. Z. Anorg. Allg. Chem. 2006, 632(14), 2288- The elements in the p-group near Ga, In and Sn would be tallic sparkle: ?NiAs, ?CoAs, ?Bi) and one or two others. He also modern terminology a p-n hetero-junction diode. These were less 2294. doi:10.1002/zaac.200600163; (b) Littlehailes, J.D.; Wood- expects that others will be discovered in the future: “I think it very sensitive than the galena cat's whisker detector, but were much hall, B.J. Discuss. Faraday Soc. 1968, 45, 187-192. a good place to look for this sort of behaviour. The ele- more mechanically stable. ments in this zone of the periodic table are close to the likely that a large number [of metals] still remain [to be discov- 35. Littlehailes, J.D.; Woodhall, B.J. US Patent 3534078A (October 13, ered].”... and in another paragraph...Only the principal ones [met- 29. Lilienfeld, J.E. US Pat. 1,745,175 (Jan 28, 1930). FETs eventually 1970). border between metals and non-metals, and they can als] are known, which are more ready and convenient for use, such became commercially available in the 1960s, using silicon as the crystallise in crystals of less than cubic symmetry. as gold, silver, iron, copper, tin, lead. The rest are pretty completely semiconductor material. Later, gallium arsenide-based FETs be- 36. Whitney, W.B. US Patent 3,301,773 (Jan 31, 1967). neglected, and nobody cares about their properties — neither the came available. 37. Atwood, D.A. (Ed.) The Rare Earth Elements: Fundamentals and The alchemical quest, or the philosopher's smith nor the ironworker, the tinman, brazier, or goldsmith. Nev- Applications, John Wiley & Sons (eBook), 19 February 2013. ertheless, these metals are for other operators, not yet born.” 30 (a) Zurek, E.; Edwards, P.P.; Hoffmann, R. Angew. Chem. Int. Ed. stone 2009, 48, 8198-8232. doi: 10.1002/anie.200900373; (b) Dainton, ISBN: 9781118632635. 4. Blaney, L. Magnetite (Fe O ): Properties, Syn- One objective of the alchemists was to find the “philoso- 3 4 F.S.; Wiles, D.M.; Wright, A.N. J. Polymer Sci. 1960, 45(145), 111- 38. Ryazanov, M.; Kienle, L.; Simon, A.; Mattausch, H. Inorg. Chem. thesis, and Applications, 2007, 15, Paper 5. pher's stone”, a means of converting base metals to gold. 118. 2006, 45(5), 2068–2074. doi: 10.1021/ic051834r. ISSN: 0020- See: http://preserve.lehigh.edu/cas-lehighreview-vol-15/5 (ac- 1669. The modern industrial equivalent of the philosopher's cessed June 2015). 31. Bredig, M.A. Mixtures of Metals with Molten Salts. ORNL Report stone is the corrosion inhibitor, which turns iron (or an- 3391, 1969; see: http://moltensalt.org/references/static/down- 5. See: http://en.wikipedia.org/wiki/Tin_pest (accessed June 2015). loads/pdf/ORNL-3391.pdf other base metal) into a noble metal, resisting corrosion. The physical properties of metals are not entirely fixed: 6. Gaston, N.; Schwerdtfeger, P. Angew. Chem. Int. Ed. 2007, 46, 32. (a) Seebeck, T.J. Ann. Chim. 1808, 66, 191; (b) Berzelius, J.J.; Pon- 1663–1666. doi:10.1002/anie.200604262 they are capable of considerable variation, depending on tin, M.M. Gilbert's Annalen 1810, 36, 260. The research of See- beck and Berzelius and others into ammonium amalgam seems to crystal size, impurities, defects, internal stress, surface 7. Tonkov, E. Yu. High Pressure Phase Transitions – A Handbook (Vol. 1), Gordon and Breach Science Publishers: Philadelphia, 1992. be an early example of a research goldrush, precipitated by Davy's treatment, etc. This is also true to some extent of chemi- ISBN: 2-88124-761-X (v.1) preparation of sodium and potassium. A later example was the cal properties – for instance, many metals become more research into high-temperature superconductors in the 1990s. easily corroded when stressed, an effect often seen with 8. Boehler, R.; Ross, M.; Sõderlind, P.; Boeker, D.B. High Pressure Melting Curves of Argon, Krypton and Xenon; see: http://ftp.esrf. stainless steel. eu/pub/UserReports/18682_A.pdf (accessed June 2015). When meals are electroplated, the internal stress in the 9. Wigner, E.; Huntington, H.B. J. Chem. Phys. 1935, 3, 764. metal is often very high, and this varies depending on the doi:10.1063/1.1749590 Continued from page 148 plating bath conditions (electrodes, temperature, chemi- 10. Bernal, M.J.M.; Massey, H.S.W. Monthly Notices Royal Astron. Soc. example is the three-stage story proposed by Foster-Harris, W. The 22. Levi, P. The Periodic Table, Penguin: Melbourne, 2010. [Translated cal form, concentration and presence of additives). The 1954, 114, 172. Basic Patterns of Plots, University of Oklahoma Press, 1959. from the Italian Il Sistema Periodico by Raymond Rosenthal] chemical resistance of electroplated metals does differ 11. Parkinson, N. J. Electrodepositors Tech. Soc. 1951, 27, 129-151. 14. Bradley, C. “The Seven Basic Plots by Christopher Booker”, Workers 23. Hodder, P. Chemistry in New Zealand 2013, 77 (2), 48-51, especially depending on the type of plating bath used, and stress 12. Møller, P.; Rasmussen, J.P.; Köhler, S.; Nielsen, L.P. NASF Surface Liberty; see: http://www.workersliberty.org/node/5432 (accessed fig. 5. January 2015). may be part of the explanation. Some alloys have un- Technol. White Papers Dec 2013, 78(3), 15-24. 24. “A novel method for detecting plot”; see: http://www.matthew- expected properties e.g. electroplated tin-nickel, which 13. (a) Stiles, H..Astrophysical Journal 1909, 30, 48; (b) Mørup, S.; Lin- 15. The cover of The Seven Basic Plots carries 11 affirmations, including jockers.net/2014/06/05/a-novel-method-for-detecting-plot/(ac- looks like silver, and is relatively unreactive compared deroth, S.; Jacobsen, J.; Holmblad, M. Hyperfine Interactions1992 , one from English author, essayist and playwright Fay Weldon, who cessed June 2015). asserts that the work “at last provides a comprehensive answer to 12 69, 489-492. with either tin or nickel. the age-old riddle of whether there are only a small number of 25. Halton, B. From Coronation Street to Consummate Chemist, Brian 14. Badeschia, H.K.D.H. http://www.msm.cam.ac.uk/phase- ‘basic stories’ in the world”. Halton: Wellington, 2011. References and notes trans/2004/titanium/hume.rothery.html (accessed June 2015). 16. Stonyer, C.L.H. “Terpinol from turpentine: a tragi-comedy”, in Ho- 26. “The concept of art’s imitation of life and vice versa is one that has 1. Lavoisier, A-L. Traité Élémentaire de Chimie, présenté dans un 15. See: https://www.webelements.com/atom_sizes.html (accessed gan, D.; Williamson, B., New Zealand is Different – Chemical Mile- been explored, debated and discussed for millennia…The concept ordre nouveau, et d'après des découvertes modernes, Cuchet, June 2015). stones in New Zealand History, pp. 179-187. Actually, the events was first encountered in Ancient Greece by the great philosophers Libraire: Paris, 1st ed. 1789. http://gallica.bnf.fr/ark:/12148/ in this particular story, described as a “sad tale” by its author, are Plato and Aristotle. The Aristotelian mimesis was the most promi- btv1b8615746s/f15.image.r=.langEN (accessed June 2015). 16. (a) Roscoe, H.E. Phil. Trans. Roy. Soc. 1868, 158, 1-27; (b) Berzelius, more akin to tragedy than comedy (see Table 1). nent of these theories; Aristotle (384-322 BC) stated that human The table of elements appears on page 192. There is an English J.J. Poggendorff's Ann. Phys. Chem., 1831, xxii, 1. beings are creatures of imitation and as such, have a natural urge translation available online; see: http://www.gutenberg.org/eb- 17. Scerri, E. A Tale of Seven Elements, Oxford University Press: Oxford, to create art that represents and reflects reality and the world 17. Tsuda, N. (Ed.) Electronic Conduction in Oxides, Springer, 2nd ed. ooks/30775 (accessed June 2015). Lavoisier did not distinguish 2013. around them. Two thousand years later, the notorious writer and 2000. ISBN: 3-540-66956-6 between metals and semi-metals, As and Sb appearing in the me- poet Oscar Wilde challenged Aristotle’s theory and argued that art 18. Sacks, O. “Preface”, in Scerri, E., A Tale of Seven Elements, pp. ix-x. tallic section. He also noted (p195) that he had omitted the “fixed 18. Biermann, S.; Poteryaev, A.I.; Georges, A.; Lichtenstein, A.I. Phys. did not, in reality, imitate art and that it was life that imitated art, alkalies” potash and soda from his table, as they were evidently Rev. Lett. 2005, 94, 026404. 19. McGrayne, S. Nobel Prize Women in Science, John Henry Press: a philosophy that informs the belief that it is through art that we compound substances, and as yet he was unaware what elements Washington, 2002. derive the aesthetic principles by which we perceive life.” From they were composed of. Ca,Mg,Ba,Al,Si are included in a sepa- 19. Chamberland, B. L.; Danielson, P. S. J. Solid State Chem. 1971, 3, https://urbantimes.co/2014/05/laure-hatchuel-becke/ (accessed rate section. These elements had not been prepared at 1789, and 243. 20. Thornton, B.F.; Burdette, S.C. Bull. Hist. Chem. 2010, 35, 86-96. January 2015). Lavoisier avoided theorising too far ahead of experimental data. In 20. Rey, M. J.; Dehaudt, P.; Joubert, J. C.; Lambert-Andron, B.; Cyrot, 21. Paneth, F. Nature 1947, 159, 8-10. his preface, Lavoisier is critical of the old chemical theories which M.; Cyrot-Lackmann, F. J. Solid State Chem. 1990, 86, 101. were not experimentally based, or chemists rejecting observa- tions because they do not fit in with theory. 21. Onoda, M.; Ohta H.; Nagasawa H. Solid State Comm. 1991, 79(4), 281-285. 2. von Hohenheim, P.A.T.B. (alias Paracelsus), Opus Paramirum (1531); see: http://www.paracelsus.uzh.ch/texts/paracelsus_ 22. Falcon H.; Alonso, J.A.; Casais, M.T.; Martinez-Lope, M.J.; Sanchez- medical.html (accessed June 2015). Version in modern type, from Benitez J.; J. Solid State Chem. 2004, 177, 3099. the J. Huser edition of 1589-1591: Johannes Huser (Ed.), Conrad Waldkirch, Basel, 1589-1591 volume I; see: http://daten.digitale- 23. Wöhler, F. Ann. Phys. (Berlin) 1824, 2, 350. sammlungen.de/%7Edb/0002/bsb00022502/image_6 (accessed 24. Dickens, P.G.; Whittingham, M.S. Quart. Rev. Chem. Soc. 1968, 22, 3/06/2015). 30-44. 3. von Hohenheim, P.A.T.B. (alias Paracelsus); Waite, A.E. (Ed. & 25. Mosselmans, J.F.W et al. Phys. Chem. Min. 1995, 22, 311-317. Transl.), The Hermetic and alchemical writings of Aureolus Phil- lipus Theophrastus Bombast of Hohenheim, called Paracelsus the 26. Tetenbaum, M. J. Appl. Phys. 1964, 35, 2468. Great, Eliot, London, 1894; See: https://archive.org/stream/her- 27. Samsonov, G.V.; Dubrovskaya, G.N. Atomnaya Énergiya 1963, meticandalch00paragoog/hermeticandalch00paragoog_djvu.txt 15(5), 428-430. [English translation: Soviet Atomic Energy, Nov (accessed June 2015). The mercury-sulfur idea is much older than 152 153 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 Patent Proze Correspondence Patent Searching Tim Stirrup In Peter Hodder's article in the April issue ofChemistry in in Fig.2 of this response, would really constitute an en- Baldwins Intellectual Property, PO Box 5999, Wellesley St, Auckland, www.baldwins.co.nz NZ, p107-109, there seem to be a couple of errors with hancement of the bathing experience. (email: [email protected]) the conductivity units. In Table 1 and elsewhere, con- ductivities are given as ranging from 750 to 7500 mS/cm, Picture this scenario: you are a researcher and you invent searching but has the downside that the classifications but this is much too high. The units should probably read a new process for the extraction of gold from seawater. could be incorrect, or obscure to the non-specialist. microSiemens per centimetre. You’re pretty excited to say the least. You take great care to avoid public disclosure, engage a patent attorney to draft Scope of the search In Table 5 (Editor: Fig. 5), most of the increasing conduc- and file a provisional patent application and set up a com- The databases queried in a patentability search will in- Correspondence tivity at pH<3 could be attributed to the hydrogen ions pany to commercialise the process. You obtain some fund- clude patent databases and may also include academic themselves. The equivalent conductivity of hydrogen ing from friends and family and refine the process over the publication databases and general web searches. Some ions in water is much more than that of other ions, and a next twelve months. You file a Patent Cooperation Treaty useful patent search databases include the following: conductivity of about 400 microSiemens/cm at pH 3, or (PCT) application funded by Angel investors. You engage 4000 at pH 2 is to be expected. project partners to help with commercialisation – a busi- • PatentScope – developed by the World Intellectual Property Office (WIPO). Enables full-text searching The electrical conductivity of water probably isn't very ness development consultant, a chemical engineer, an ac- of PCT applications as well as patent collections from relevant to the bathing experience, as it isn't sensed by countant. The PCT application is examined by an interna- a number of countries (USA, European Patent Office, the skin (as far as I know). The density and osmotic pres- tional examiner and the examiner says that your invention Canada, China among others). sure might be more interesting. is neither novel nor inventive based on the disclosure of document D1. You look at document D1. It discloses the Robert Bennett Fig. 1. “A Labour supporter stares in amazement at Prime Min- • Espacenet – developed by the European Patent Office ister Helen Clark, apparently enjoying the extreme heat of a exact same method that you invented. You check the In- (EPO), this database provides full-text searching of pat- Author’s Response: Rotorua hot pool. The Prime Minister languishes in boiling mud tellectual Property Office of New Zealand (IPONZ) patents ent documents from multiple collections in multiple and is surrounded by clouds of steam. She shouts at him that database. A patent was granted five years ago which cov- The correspondent is correct in respect of the conduc- compared with the last six months this is nothing. She refers to languages. tivity units – they should indeed be microSiemens cm-1, ers the exact same process that you believed you invent- the heat generated in the House over election overspending and • United States Patent and Trademark Office (USPTO) i.e. mS cm-1, as shown in the Thousand Springs database, the saga of Taito Philip Field in particular.” ed. You realise that not only is your invention not novel, Patent Databases – The USPTO was the first patent from which the data were derived, rather than mS cm-1. but if you carry out your process, you will be infringing the Credit: DANGER! Boiling hot pool, Rotorua Council. "Compared existing NZ patent. office to launch an online patent database (back in to the last six months, this is nothing..." 28 October, 2006. Scott, 1994). However, it suffers from usability issues and only In respect of the correspondent’s comments on Fig. 5 of Thomas, 1947- :[Digital cartoons published from 2003 onward the article, the clarification is helpful. The near-surface in the Dominion Post]. Ref: DCDL-0002575. Alexander Turnbull While somewhat uncommon, this scenario does demon- searches US issued patents (PatFT) or published US pat- oxidation processes yield waters of low pH which are Library, Wellington, New Zealand; see: http://natlib.govt.nz/ strate the importance of considering the patentability of ent applications (AppFT). records/22761857. your invention and whether you havefreedom to operate, highly conducting for the reason the correspondent cites. • The Lens – Open source search and patent analytics i.e. will you infringe someone else’s patent rights. covering multiple collections. The conductivity of these waters is a proxy for the com- bination of chloride ions, bicarbonate ions, sulfate ions, Patentability search • Google Patents – easy to use, but somewhat limited in etc., which balneologists claimed, not always convinc- The most fundamental patentability criterion is whether scope, search options and analytics. ingly, to contribute to the waters’ therapeutic properties, the invention is novel, i.e. has the invention been disclosed For particular inventions, specialist databases may also be and presumably thereby to the bathing experience. How- publicly anywhere in the world before the filing date of the searched. For example to determine the novelty of com- ever, Table 1 of the article shows a poor correlation of vis- patent application? A novelty search involves assessing pounds, chemical formulae databases may be searched, itor rating with conductivity, much lower than with pH or the invention and searching for documents which disclose e.g. UniChem, ChemSpider, Reaxys, SciFinder, PubChem. turbidity, for example, so the correspondent’s assertion the invention (referred to as prior art documents). A pat- To determine the novelty of gene or protein sequences, that “electrical conductivity probably isn’t very relevant entability search is somewhat wider in that it also consid- sequence databases may be searched, e.g. Genbank, EM- to the bathing experience” is confirmed by the data. The ers other patentability criteria. For example whether your BL-EBI, Swissprot, PIR. In addition to the search providers density of the geothermal water is related to its chemi- invention is inventive, i.e. non-obvious. above, there are also a number of proprietary databases cal composition, and the osmotic pressure is a function that provide access and advanced search/analytics/report- of the concentration of the solute. Both parameters are The first step in a novelty search is for the searcher to inti- ing on a commercial basis. thus related to the water’s conductivity, so, even had mately understand the invention and its context. For this the data been available, the correlation between density reason it is preferable that a specialist in the particular Following initial review of the search results, the searcher or osmotic pressure and the bathing experience, might technology field carries out the search. Once the searcher will typically refine the search and search again in an it- Fig. 2. “Interior view of a therapy room in the Government understands the technology, the invention’s context in not, in fact, be any more ‘interesting’ than those already Sanatorium, Rotorua, New Zealand. The view shows one man erative process. Refinements may include amending key- shown in Table 1, and its associated figures. on a raised bed under a shower while another man adminis- that area and the objectives of the search, they can for- words/classifications, or searching by a particular compa- ters a massage. Two hoses on the floor are spraying both with mulate a search strategy. One part of this is choosing ap- ny or inventor of interest. I remain rather surprised that there was not a better cor- water. A caption states that the therapy in progress is an `AIX propriate keywords (including common synonyms) which relation between water temperature and visitor rating massage douch.' Photographed by an unknown photographer in describe the invention. Those keywords are then used to about 1926. Interpretation and analysis (Table 1), but of course, other factors may contribute to query online databases. For some keyword combinations Once a manageable number of search results has been ob- visitors’ willingness to ‘take the waters’ (Fig. 1 of this re- Credit: Aix massage douche, Sanatorium, Rotorua, New Zea- a large number of search hits are returned. tained, the next step is to review and analyse those docu- sponse). land. Railways album 2. Ref: PA1-f-051-26-3. Alexander Turnbull Library, Wellington, New Zealand; see: http://natlib.govt.nz/ Since it is unpractical to trawl through thousands of docu- ments to see if the invention is novel. This involves carrying Finally, the correspondent’s reference to osmotic pres- records/22830728. ments, patent search databases typically allow you to filter out a detailed review of the prior art document to see if it sure caused me to wonder whether subjecting the skin by technology classification. The most common classifica- discloses all of the features of the invention. Going back – a semi-permeable membrane – to relatively high-pres- tion system is the International Patent Classification (IPC). to the example of extraction of gold from seawater, does sure geothermal waters, as in the ‘Aix douche’ shown Searching using classifications enables more focussed the prior art document disclose each step of the extrac- tion process? And does it disclose each parameter of each 154 155 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 Feature S eries step? Essentially, if the document discloses all features of bers of search results. On the other hand, title/abstract Some unremembered chemists the invention then the invention lacks novelty. searches are more focussed but can miss documents with undescriptive titles or terms in the abstract. FTO search- A series of articles that explores the lives and work of selected chemists who have made a significant contribution to One common issue that arises during novelty searching is ing can be refined by searching for particular companies the advancement of the discipline, the profession and well-being of mankind, yet who are little remembered. the use of different terms to describe a similar concept. or individuals known to be active in the tech area being This can mean that the keyword combinations do not find considered. relevant documents. Other issues include where only part Henry Edward Armstrong, FRS (1848-1937) of a step is disclosed (although the other part may be in- If relevant documents are found in the FTO search, the Brian Halton herent in how the step is described), or where a slightly patent claims should be analysed in detail. It is the claims different process step is disclosed yet the same result is that define the exact scope of monopoly of the patent School of Chemical & Physical Sciences, Victoria University, PO Box 600, Wellington 6140 achieved. and therefore what a party must do to infringe the patent. (email: [email protected]) Claim interpretation and infringement analysis requires a Absence of evidence ≠ evidence of absence good understanding of the patent law and practice of the Henry Edward Armstrong After 18 months of study, Frankland took Henry Armstrong Novelty searching is an essential part of the patent pro- country in question and should only be undertaken by an was born on May 6, 1848 into his private laboratory as his personal assistant and it cess and we recommend that all new inventors familiarise experienced patent attorney. in Lewisham, then a part was there that Henry began his first research. Frankland themselves with the prior art. An appreciation of the prior of Kent but now South-East had been appointed as one of three to a Royal Commission art helps the inventor and patent attorney to understand A major limitation of FTO searches is that they only pro- London.1 He was the first tasked with enquiry into the pollution of England’s rivers the context of the invention and the scope of protection vide accurate information on granted patents. In most of seven children to Rich- and waterways.3 Armstrong’s task was to devise ways of that the applicant might ultimately be able to obtain. It can countries the specification of a pending patent application ard and Mary (née Biddle) estimating the organic impurities in sewage and of sewage also avoid wasting time and money on pursuing patent ap- is not even published until 18 months after the date the Armstrong. His parents had matter in drinking water. For this Armstrong and Frankland plications for inventions that are later found to lack novel- application is first filed. These unpublished applications eloped and married before established a successful combustion method in vacuum ty. However, be aware that the old adage applies: absence will not be uncovered by an FTO search. Pending patent they were 21 years of age that led to Frankland’s analysis of the British water sup- of evidence is not evidence of absence. In other words, fail- applications may be in the patent pipeline for a number of in 1847 and Henry is cited ply. Not surprisingly, after about one year, Armstrong left ure to find an invention after a quick google search does years and their ultimate scope of protection (and the as- as a ‘seven-months child’.2 to study for his PhD. Kolbe, in Leipzig, had been mentor not guarantee novelty and that a patent will be granted. sociated infringement risk) only becomes known close to The Armstrong family saw to Frankland and it was to him that Frankland sent Hen- Although searching relevant databases with carefully for- the patent being granted. Henry’s parents remain in ry. There, in October 1867, Henry was introduced to the Lewisham for the rest of sulfonic acids and the interest enkindled in Henry by this mulated keywords is to be encouraged, it is quite common Freedom to operate searching is a risk management strat- their lives, while Henry lived there for his entire life, except class of compounds remained with him throughout his for inventors to search and find nothing when a profes- egy that should be employed before entering a new mar- when overseas.1,2 The mid-nineteenth century had Lew- life. In fact,2 the day that Henry arrived was spent nitrat- sional searcher would find relevant prior art. ket. Even where no infringement risk is found, targeted isham as a country village beginning to provide homes for ing 4-hydroxyphenylsulfonate (1). He spent the next five FTO searching can provide valuable market intelligence on It is important to understand that there is no such thing as London businessmen who liked the country air. Although semesters studying under Kolbe, the begin- an exhaustive patent search. For example a prior art docu- technology trends and emerging key players. the Armstrong home was always there, they moved hous- ning of his lifelong study of aromatic com- HO SO3H ment published in a different language or in an obscure es as Richard’s fortunes rose and fell from his position as pounds. The master’s, ‘Try it, Try it’ had a The bottom line 1 journal will rarely be found by an English-language search. a commission agent and importer of Mark Lane in the city lasting impact on Henry, who gained his PhD Although a high quality novelty search will give a good idea The most important fact to consider about patent search- of London. Thus, Richard Armstrong was a businessman in 1869 for a thesis the essence of which was published in of the prior art relevant to an invention, there is always the ing is that one can never be certain that every relevant with sufficient income to support his wife and increasing the Proceedings of the Royal Society that year.4 Armstrong risk of a prior art document surfacing to torpedo your pat- patent has been located. Therefore, a balance needs to be number of children in fair comfort. Sadly, only four of the returned to London in 1870 taking up residence back in his ent rights in the future. Searching simply reduces that risk. struck between the thoroughness of a search and the cost seven children survived childhood. parents’ home, though in another house on Belmont Hill. For this reason, a novelty search with a favourable opinion involved. For novelty searching, where this balance lies of- There, living next door but one in her parents’ home, he on patentability is a valuable tool to show to investors to ten depends on the value of obtaining patent rights and Henry’s home in Lewisham was on Avenue Road, a street met Frances Louise Lavers, who he subsequently married reduce their perceived investment risk. the consequences of uncovering relevant prior art down that now has disappeared and is replaced by what is the on August 30, 1877. the line. For FTO searching factors to consider include the main entrance to The Lewisham Centre. After attending a Freedom to operate (FTO) searching total value of the project, and the consequences of having number of small schools, Henry moved to Colfe’s Gram- On his return to London, Henry gained a position as as- This involves answering the question: Do I risk infringing to remove the product/service from the market (or negoti- mar School on Lewisham Hill bordering on Greenwich, to sistant to Dr Matthesson at St. Bartholomew’s Hospital, another party’s patent rights if I make, use or sell my prod- ate with the patentee). In both cases it is advisable to con- which he walked from home. It remains one of the old- teaching chemistry to the medical students. He held this uct in a particular country? The key difference from pat- duct searching early on to avoid setbacks later. est established schools in London. He left there at age 16 post for 12 years until Matthesson died. Then, in 1871, years with ‘no particular interest, but observant and an ex- he gained another part-time appointment as Professor entability searching is that an FTO search is restricted to If you have any queries regarding intellectual property examining existing patent rights in a particular country. In perimentalist’ and was thought to be ‘delicate’.1 Because of Chemistry at the London Institution where he taught related matters (including patents, trademarks, copyright of this, he spent the following winter in Gibraltar with his classes from 6-8 pm on ‘analytical chemistry and methods contrast, a patentability search looks at the entire body of or licensing), please contact: [email protected] human knowledge published before the filing date. There- uncle, likely on the recommendation of his grandfather of original investigation’.1,2 The salary for this was low (£50 Baldwins Intellectual Property, PO Box 5999, Wellesley who had been Governor of the Convict Prison there. He re- pa) but he had a private laboratory though no allowance fore FTO searching generally provides a more definitive Street, Auckland. www.baldwins.com answer because the body of knowledge being searched is turned to Lewisham in the spring of 1865 and ‘just slid into for it or the necessary supplies! The lab, little more than limited. chemistry’ as his father let him attend the Royal School of a coal-hole, was close to the lecture theatre and it was 1 Tim Stirrup of Baldwins Intellec- Chemistry (RSC) on Oxford Street. That was for the sum- there that Henry Armstrong began his extensive studies of A typical FTO search strategy involves understanding the tual Property in Auckland spe- mer term of 1865 just before the noted August Wilhelm the constituents of coal-tar. The rather unpleasant odours technology in question and identifying all features that cialises in chemistry and biotech- von Hofmann returned to Berlin and Henry was taught by from the higher boiling fractions had a lasting impact on may present an infringement risk. The relevant Patent Of- nology patents. Tim obtained his Edward Frankland.3 Chemistry was the only subject avail- the pupils and teachers using the lecture room. The in- fice database is then searched using selected keywords. PhD in molecular biology from able at the RSC and so Armstrong took other courses at the come from his two posts was insufficient to maintain a Some Patent Office databases allow full-text searching of the University of Southhampton in the UK in 2007. He qualified affiliated Royal School of Mines given by Tyndall, Huxley professional scientist, let alone the prospects of house and 2 patent documents. Others, e.g. the Intellectual Property as a registered New Zealand and and Ramsay. Keeble also tells us that Henry attended the family. Thus, Henry supplemented his income by writing, Office of New Zealand (IPONZ) only allow searching of Australian patent attorney in operating theatre of St. Bartholomew’s Hospital regularly examining, abstracting (for the Chemical Society Journal) the title and abstract of the patent. Full-text searching al- 2011. on Saturdays, a factor in his subsequent career. and as a professional witness in legal chemical technol- lows deeper analysis but can provide unmanageable num- ogy cases. It was from the exposure to examination and 156 157 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 cross-examination protocols and the need for precision in aminations of sulfonation and other reactions, delineat- that gained attention and it has an element of satisfaction mixtures of pure hydrogen and pure oxygen would not be speaking, which, when coupled with Kolbe’s incisive style, ed the nature of the ring and the orientation of substitu- associated with it. Armstrong found that the Kekulé for- explosive, and that atmospheric corrosion (rusting) would made Armstrong the unpleasant critic that he described tion, results that were of immense value to the dyestuffs mula for benzene did not provide him with an adequate be impossible even in the presence of air and water if an himself to be.1,2 The various part-time occupations re- industries.1 The difficulties experienced in separating mental picture of the molecule free from the ambiguity of electrolyte were absent. sulted in Armstrong regarding himself as a ‘free-lance and mixtures of sulfonic acids led Armstrong and Wynne to formal p–bond character. In 1887, he suggested that the iconoclast’.1 use chlorosulfonic (chlorosulfuric) acid as their sulfonat- molecule was better represented by a ‘centric’ representa- The educational impact of Henry Edward Armstrong was ing agent for naphthalene; they obtained a single prod- tion as had been proposed6 by Lothar Meyer in 1872. Here especially significant to chemistry in the last 20 years of th Armstrong’s life work began in 1879, some 16 months af- uct, naphthalene-1-sulfonic acid (2; Scheme 1). When 1 Armstrong suggested that the fourth valency of each car- the 19 century and laid the foundation for teaching in the th ter his marriage. At age 31, he was appointed by the City was treated with slightly in excess of two molar equiva- bon atom was directed towards the centre of the molecule first half of the 20 century. Henry concluded early in his and Guilds (of London Institute for the Advancement of lents of chlorosulfonic acid, diacid 3 was obtained and resulting in increased centric density. The six central affini- career that the deficiencies in the knowledge of the av- Technical Education) with William Edward Aryton, a physi- identified as the 1,-5-derivative. ties were assumed to neutralise each other without imply- erage boy coming into advanced classes were a result of cist and electrical engineer, to organise classes in chemis- ing any cross-linking within the ring. Remember that the bad elementary education. He was convinced that higher try and physics. The appointments stemmed from lengthy electron was neither named nor discovered until the 1890s education in technical subjects could only succeed from discussions after the 1851 Exhibition and a definite 1876 and Armstrong’s ‘affinity’ was, in essence, the electron. a sound educational basis. Thus, in 1884 he proposed decision to explore Technical Education by the City Livery The centric form was independently proposed by Baeyer teaching the general science of daily life at school by hav- Companies of London. It led to the establishment of the in 1892 as the Armstrong-Baeyer centric formula and it ing students perform simple practical experiments. This City and Guilds Institute in 1878 and Henry’s appointment. In order to complete this series of studies accurately, Arm- was extended satisfyingly by Armstrong to the annulated formulated his heuristic approach to teaching – learn The classes by Armstrong and Ayrton in Cowper Street, strong chose to settle a series of reference compounds derivatives, naphthalene, anthracene and 9,10-anthraqui- from doing, not simply from a static dogmatic collection Finsbury, were, in essence, a trial to see how their subjects and, in so doing, he prepared and characterised all ten the- none as shown in Chart 2. Henry essentially invented the of facts – a revolutionary concept at the time. Henry led could best be taught. The fact is they became so popular oretically possible dichloronaphthalenes (Chart 1), elimi- concept of delocalisation when he said that any one atom his students through experiment to self-discovery. He was 5 that a separate specially adapted building was needed. The nating two that had been proposed incorrectly. The study has an influence on other atoms not contiguous to it in the quoted as saying: “If the Almighty were in the one hand Finsbury Technical College was created as the first institu- was experimentally demanding, requiring high experimen- ring.7 These late 1880 ideas were so close to the modern to offer me Truth and in the other the Search after Truth, tion of its kind in the city. However, the focus of the City tal accuracy. Many of the compounds were confirmed by theory of chemistry that it is surprising he never drew the I would humbly but firmly choose the Search after Truth”. and Guilds was the establishment of the Central Institution synthesising them from different starting compounds of appropriate conclusions once the electron was known.7 He was among the first to base instruction and writing in (later the Central Technical College) and the expertise of known configuration, a masterpiece of synthetic and ana- chemistry upon Mendeleev’s periodic table and, early on, Armstrong and Ayrton was utilised to the full in realising lytical accuracy from the late 19th century. The studies led he emphasised that molecules must have spatial configu- this. The pair went on a tour of laboratories in Germany to explanations for the speeds (rates) of certain reactions rations that determine crystal structures. during the autumn of 1881, each to study the nature of that included the industrially important diazotisations. By those for his subject. It was from these times that Arm- the end of 1895, Armstrong and Wynne had prepared and From 1887 Armstrong served on two important education strong’s lifelong interest and impact on the teaching of characterised all 14 of the trichloronaphthalenes, four of Another important aspect of Armstrong’s legacy is his in- committees - that of the British Association charged with chemistry is dated. which melt over the narrow 90-92 oC range. Each was syn- clusion of crystallography in teaching. He instilled into his reporting on teaching methods, the other on the teach- 9 thesised in a quantity of between 35 g and 50 g. All of his students the need to think not just in one but in three- ing of chemistry. The reports were influential in bringing Following the Armstrong-Ayrton report to the City and work on the naphthalenes was geared to establishing the dimensions. He took crystal properties to the chemist and about the changes that Armstrong saw as vital for science Guilds, changes were made to the Central Institute, and factors that govern substitution in the nucleus. showed that it did not belong solely in the realm of the (and chemistry) but it took many years before the rec- then the Central Institution for more advanced study (in mineralogist. His own classes at the Central Technical Col- ommendations had any real effect. Nevertheless, it was Exhibition Road, South Kensington) was opened by the lege were the first to impart the ideas and subsequently he Armstrong who had the foresight to see what was needed Prince of Wales in 1884. Henry Armstrong was appointed arranged for courses on crystallography to be taught from and it is he to whom science education is much indebted. as inaugural Professor of Chemistry and, after some per- 1886. His publications invariably include a detailed de- Henry fought the conservative spirit that pervaded much suasion, William Edward Aryton the inaugural Professor scription of the crystals of each new compound reported. of society all of his life. That his views were still not fully of Physics. There were two other professors, namely W.C. accepted, even after his death, is nicely illustrated1 by a Unwin (Engineering) and O. Henrici (Mathematics). Henry Armstrong made significant contributions to the dyestuffs 1940 letter from Plymouth school teacher A.G. Lowndes Armstrong remained at the Central until it became a part industry as has already been alluded to. He also instigated in Nature. Lowndes states:10 “As pointed out by the Edi- of the Imperial College of Science and Technology in 1911. the quinone theory of colour, which became a guiding tors of NATURE a large majority of the boys complete their By then, 27 years later, Armstrong was 63 years old and principle to the industry.8 Although his experimental work ‘formal’ education at the School Certificate stage and for required to retire upon the closure. He was given the title in this area was minimal, he proposed that “the unsaturat- this ‘formal’ education practical work is unnecessary. Had I of Emeritus and the use of a private laboratory; all his stu- ed hydrocarbons are not only more reactive than the par- my own way, ..… I would make every boy in a public school dents had left by 1914. affins but the beginnings of colour are manifest in them if learn Latin until he were either fifteen or had passed the Armstrong was just as interested in the benzene series of examination be made in the regions above and below the School Certificate. Two good science lectures weekly with Armstrong’s work falls into three categories, the chemical compounds and, although much of the nature of substitu- visible spectrum” and that “the quinonoid origin of visible demonstrations are all that are required”! research that started at the London Institution, his inter- tion had been established by the time he was able to con- colour appeared so general that if a coloured compound est in and impact on chemical education, and his other tribute, his study of the sulfonation of aniline and its de- was not quinonoid its formula was suspect”. More impor- At the Central Institution in South Kensington, Henry lec- activities almost always related to chemistry. It was from rivatives had impact as it established that meta-directing tantly, he claimed that “ultimately colour would be traced tured only to the first-year students espousing the view Armstrong’s chemical researches that his name was rec- groups have no ortho/para-directing influence and actu- to that peculiar condition represented conventionally by a that the ground-work was the most important, a feature ognised far beyond England. His studies, the most sub- ally inhibit it. By way of example, Armstrong and his stu- double bond, the atoms being regarded as altogether sub- common in Commonwealth Universities until the- lat th stantial covering the chemistry of naphthalene, started in dents showed that when amines are converted into salts ordinate”. All this before the electron was known or conju- ter part of the 20 century. His lectures covered much the mid-1870s and provided some 60 short papers, mostly their o/p effect is negated and that, in strong fuming sul- gation recognised! ground and were filled with demonstrations that almost published in the Proceedings of the Chemical Society. At furic acid, metanilic acid (3-aminobenzenesulfonic acid) is always worked. For the senior levels he led discussions its inception, little was known about naphthalene, its de- obtained. With Miss Evans, he showed that N.N-dimethyl- Other inspirational insights from Armstrong can be given rather than held formal lectures (the modern tutorial!). th rivatives or its chemistry, and industrialists in the dyestuffs aniline affords the p-sulfonic acid with chlorosulfonic acid, by way of snippets from his 19 century writings that pre- Armstrong was a Governor of St. Dunstan’s College in Cat- industry were only just beginning to see the potential of but the m-acid is formed only with increasing difficulty date chemical discovery of the facts. Thus, he believed ford, neighbouring on to Lewisham, and Christ’s Hospital, its compounds. Conceived when Henry was intimately in- and then only when fuming sulfuric acid is the sulfonating that in water, HCl interacted with the solvent in the same a co-educational school established in 1552 for the orphan volved in establishing technical education for students in agent. However, it is Armstrong’s concepts of the benzene way as did ammonia, that all chemical change was electri- children of poor Londoners in the old Grey Friars buildings industry, the very extensive and analytically detailed - ex nucleus and his extension to the benzo-fused derivatives cal in nature (a forethought to reaction mechanism?), that on Newgate Street in the City. To this latter school he gave 158 159 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015 D ates of Note great service, especially after its removal to West Horsham Armstrong was awarded a Hon. LLD from St. Andrews, Dates of Note in Sussex in 1902 when he designed and equipped its labo- Hon. DSc degrees from Melbourne and Madrid, the Davy ratories. It was the best school for science teaching in Eng- medal of the Royal Society, the Messel medal of the So- land. Henry also set up workshops for manual training and ciety of Chemical Industry, the Albert medal (see above), July 8 1955 saw the opening of the Geneva Conference on revolutionised art training. Armstrong was deputy chair- and the Horace Brown medal of the Society of Brewing. He 21 Henri-Victor Regnault, the French chemist and physi- the Peaceful Uses of Atomic Energy - known as the man of Christ’s education committee for 14 years from served the Chemical Society for many years ruling it with cist noted for his work on the properties of gases, was atoms for peace conference. 1926 and its Chairman until 1937. There can be no doubt ‘an iron rod’1 as Secretary from 1875-1893 and serving as born in 1810. This day in 2000 an international col- 10 Henry Gwyn-Jeffreys Mosely, the English physicist that significant changes did take place in the 50+ years af- President from then until 1895. Following this tenure, he laboration of scientists at the Department of Energy's who experimentally demonstrated that the ma- ter Armstrong began his educational campaign. That they took the role of Vice-President until his death save for two Fermi National Accelerator Laboratory announced jor properties of an element are determined by the happened at all are in very great measure due to him. short breaks. He was, in essence, a member of the Council direct evidence for the subatomic particle, the tau atomic number and not by the atomic weight, died almost continuously from 1873 until 1937. neutrino, the third kind of neutrino known to particle 100 years ago. Henry Armstrong also had much interest in agriculture that physicists. likely started with his upbringing in rural Lewisham. This Upon marriage to Frances Lavers in 1877, Armstrong pur- 11 Erwin Chargaff, the Austrian-American biochemist impacted on his chemistry with his major contributions to chased his own home in Lewisham – one that his father 25 Rosalind Franklin, the English crystallographer who who studied the nucleic acids chromatographically terpene and camphor research that date from 1878 and had previously owned! The contributed to the discovery of the molecular struc- and enunciated two rules that helped determine the involved the isolation of the D- and L-forms of sobrerol (4), couple had seven children, ture of DNA, was born this day in 1920, the day that double helix, was born in 1905. which he named after Ascanio Sobrero, its 1851 discov- four boys of whom indus- Herbert Calhoun Reed, the American chemist noted erer. He became associated with the Rothamstead Experi- trial chemist Edward Frank- internationally as an analytical and consulting chem- 12 James Batcheller Sumner, the American biochemist mental Station in Harpenden, Hertfordshire. land Armstrong (1878- ist to the leather industry and allied trades, died in who was the first to crystallise an enzyme to show that He served as the Chemical Society representa- 1945) was the eldest, and 1940. enzymes were proteins and shared (with Northrop tive of the Lawes Agricultural Trust Committee three daughters. In 1882 and Stanley) the 1946 Nobel Prize for Chemistry, died 26 1895 saw the day that Pierre Curie married Marie from its establishment in 1889 until shortly be- the family moved to Gran- in 1955. fore his death in 1937. It was his efforts that ville Park in the same town Sklodowska (Curie) in Sceaux, France. It was the fol- persuaded the Indian Government to set up a and that was their perma- lowing year that she decided to investigate Henri Bec- 13 John Ulric Nef, the Swiss-American chemist whose research institute for the cultivation of indigo nent home. Their youngest querel's discovery of radioactivity in uranium for her studies demonstrated that carbon can have a valence in 1915. His strong support of the British Dyestuffs industry daughter Nora never mar- doctoral thesis. of two, e.g. in a quinone, as well as four, died this day extended to his personal proffering of its wares. He wore ried but looked after her 100 years ago. 27 Bertram Borden Boltwood, the American chemist brightly dyed waistcoats at formal evening functions. One parents until their deaths, and physicist whose work on the radioactive decay of such piece of clothing, a Caledon Jade Green, has been de- Frances in 1935 and Henry 15 Constantin Fahlberg, the Russian chemist who dis- H.E. Armstrong in later life uranium and thorium was important in the develop- covered saccharin, died in 1910. scribed as the most becoming, but another of indigo-blue some two years later on July from ref. 2; source unknown ment of the theory of isotopes, was born in1880. with thioindigo-red (Chart 3) facings was the most striking. 13, 1937. 18 Friedrich Strohmeyer, the German chemist who dis- Both are Vat Dyes that had to be reduced to make them 29 Heinz L. Fraenkel-Conrat, the German-American bio- References and Notes covered the element cadmium in 1817, died in 1835. inert and water soluble prior to the dyeing process, then chemist who first showed that reproduction of a virus oxidised to regenerate the original colour. 1. Rodd, E.H. Obituary - Henry Edward Armstrong, J. Chem. Soc. 1940, 19 Johan Gottlieb Gahn, the Swedish mineralogist and 1418-1439. is controlled by genetic information within its RNA crystallographer who improved smelting methods 2. Kibble, F.W. Henry Edward Armstrong, Obituary Notices of Fellows of core, was born in 1910. the Royal Society 1941, 3(9), 229–226 (doi:10.1098/rsbm.1941.0001, and by-product usage, discovered manganese and se- accessed 5 November 2014). 31 Friedrich Wöhler, the German chemist who co-dis- lenium, and assisted Carl Wilhelm Scheele, was born 3. Halton, B., Some Unremembered Chemists: Sir Edward Frankland, covered vanadium but is best known for his 1828 syn- in 1745. This was the day in 1765 that Axel Fredrik Chem. in NZ, 2013, 77, 92-96 thesis of urea from ammonium cyanate to create an Cronstedt, the Swedish chemist and metallurgist who 4. Armstrong, H.E. Proc. Royal Soc. (UK) 1869, 18, 502-513. organic compound from an inorganic one, was born first isolated nickel, died in1765, and that Lothar 5. Armstrong, H.E.; Wynne, W.P., Proc. Chem. Soc. 1890, 6, 77-88. in 1800. Meyer, the German chemist who discovered the Peri- 6. Meyer, L. Die Moderen Theorien der Chemie der Chemie, Verlag von odic Law independently of Dmitry Mendeleyev and at Maruschke und Berendt, 2nd edn. 1872. August about the same time, was born in 1830. Henry Armstrong was a strong supporter of the Royal So- 7. Rzepa, H. Chemistry with a Twist, www.ch.imperial.ac.uk/rzepa/ 1 Georg von Hevesy, the Hungarian-Danish-Swedish 11 ciety of Arts. The first meeting that he presided at was in blog/?paged=24 (accessed 21 November 2014). chemist awarded the 1943 Nobel Prize for his iso- 20 Paul Ehrlich, the German medical scientist whose 1883 and he occupied the chair seven times. He provided 8. Armstrong, H.E. Proc. Chem. Soc. 1888, 4(49), 27-34. topic tracer techniques, was born in 1885, the day pioneering work in chemotherapy included the dis- lectures on Problems of food and our economic policy in 9. Brock, W.H. (ed.), H.E. Armstrong and the teaching of Science 1880- that Otto Warburg, the a German biochemist who covery of Salvarsan (arsphenamine), died this day 100 1919, and two courses of Juvenile Lectures entitled: How 1930, CUP, Cambridge, 1973. was awarded the 1931 Nobel Prize for Physiology or years ago. chemists work (1889) and Alice in Wonderland at the 10. Lowndes, A.G. Practical Science in Schools, Letter to the Editor, Na- Medicine for his research on cellular respiration, died ture 1940, 146 (No.3691), 133. 23 Sir Henry Tizard, the English chemist whose work on breakfast table (1926). He was awarded the Society’s silver in 1970. medal for a lecture on the indigo situation in India and its 11. The Late Professor H. E. Armstrong, FRS, J. Royal Soc. Arts 1937, aircraft fuels ultimately led to the octane rating sys- Albert Medal for his discoveries in chemistry and his ser- 85(4421), 903-904. 3 Guillaume François Rouelle, the French apothecary tem, was born in 1885. vices to education. 12. Armstrong, H.E. On the Teaching of Natural Science as a Part of the and chemist who first proposed the modern defini- Ordinary School Course, and on the method of Teaching Chemistry 25 Sir Hans Adolf Krebs, the German-born British bio- tion of salts and distinguished acid, basic and neutral in the Introductory Course in Science Classes, Schools, and Colleges: chemist who received (with Lipmann) the 1953 Nobel Much of what Henry Edward Armstrong foresaw has come Address for the Proceedings of the International Conference on Edu- salts, died in 1770. true and many of his beliefs of what should be studied cation, London 1884; Armstrong, H.E. Introduction to the Study of Prize for Physiology or Medicine for discovering in liv- formed the basis of much late 20th century research. Sev- Organic Chemistry: The Chemistry of Carbon and its Compounds, 6 Joseph-Achille Le Bel, the French chemist who pre- ing organisms the series of chemical reactions known eral remain current areas of intense activity and include London: Longmans, Green, and Co. 1874 (4th edn. 1884); Armstrong, sented a theory on the relationship between mole- as the tricarboxylic acid cycle (or the citric acid cycle) H.E. The Teaching of Scientific Method and Other Papers on Educa- better known as the Krebs cycle, was born in 1900. dyes and dying (now nano-particle involvement), agricul- tion, New York: Macmillan and Company, Ltd. 1903; Armstrong, H.E. cules and how they absorb or reflect light, and pre- tural chemistry, diet and nutrition, and collaborations and dicted that optical activity is due to an asymmetric The First Epistle of Henry the Chemist to the Uesanians, J. Chem. 26 Hedley Marston was the Australian biochemist who joint interdisciplinary publication. In many respects, Henry Educ. 1925, 2, 731-736; Armstrong, H.E. Art and Principles of Chem- carbon atom bound to four different groups, died in researched the role of cobalt and other trace ele- Armstrong was a man before his time. His educational istry, London: Ernest Benn Ltd., 1927. 1930. ments in animal and plant nutrition. He is remem- writings are listed for completion.12 160 161 Chemistry in New Zealand July 2015 Chemistry in New Zealand July 2015

bered for announcing at the 1935 ANZAS meeting ric acid, arsenic, carbon monoxide, and other indus- gist who assisted his older brother Juan José in exper- German physicist who discovered the presence of he- Conferences that a wasting malady of sheep in certain coastal trial poisons, died in 1970 aged 101. iments to separate tungsten from its wolframite ore lium in the Earth's atmosphere, died the same day in regions was corrected by giving cobalt salt supple- two years after Scheele had discovered it, was born 1940, 75 years ago. ments. He was born in 1900. It is the day that Johann 23 Clifford G. Shull, the American physicist who shared in 1755. It was the day that Heinrich Caro, the Ger- Friedrich Miescher, the Swiss biochemist and biolo- the 1994 Nobel Prize for Physics (with Brockhouse) man chemist who invented new industrial chemical 15 Konrad Bloch, the German-born American biochem- gist who studied cell metabolism and discovered the and developed the neutron diffraction process, was processes that enabled the German company BASF to ist who shared the 1964 Nobel Prize for Physiology or nucleic acids, died in 1895. born 100 years ago. become the leading manufacturer, died in 1910. Medicine (with Lynen) for their discoveries concern- ing the natural synthesis of cholesterol and of fatty 27 Gallium was discovered by P.E. Lecoq de Boisbaudran 24 Severo Ochoa, the Spanish-American biochemist and 12 Sir Arthur Harden, the English biochemist who shared acids, died in 2000. This is also the day that Herbert in 1845. recipient of the 1959 Nobel laureate for his discovery (with Euler-Chelpin) the 1929 Nobel Prize for Chemis- Henry Dow, the noted industrialist and pioneer in US of an enzyme in bacteria that enabled him to synthe- try for work on the fermentation of sugar and the en- chemical industry, died in 1930. 28 1845 saw the first issue of Scientific American pub- sise ribonucleic acid (RNA), was born in 1905. Georg- zyme action involved that set biochemistry as a sepa- lished. es Claude, the French chemist, engineer and inven- rate discipline, was born in 1865, 150 years ago. Paul 17 William Cookworthy, the English chemist who pio- tor who invented the neon light, was born in 1870, Hermann Müller, the Swiss chemist who received the neered the manufacture of porcelain in Britain, died 30 Sir Joseph John Thomson, the English physicist who while Hans Geiger of Geiger counter fame died that 1948 Nobel Prize for Physiology or Medicine for dis- in 1780. This day in 1855 saw the Bessemer steel pro- discovered the electron, died in 1940, 75 years ago. day in 1945. Hermann Hellriegel, the German chem- covering the potent toxic effects on insects of DDT, cess patented. ist who discovered the fixation of nitrogen by certain September died this day 50 years ago. Franz-Joseph Müller von 18 In 1955 the discovery of the sub-atomic particle, the legumes, also died on this day, but in 1895. Reichenstein, the Austrian mineralogist and mining 5 Frederick George Donnan, the British chemist whose negative or antiproton, was reported at UC-Berkeley. engineer who discovered tellurium in 1782, was born research contributed to the development of colloid 25 William Cumming Rose, the American biochemist on July 1, 1740 and died on this day in 1825. chemistry and who is remembered for his investiga- who determined the role of amino acids in nutri- 19 Sir Charles Wheatstone, the English physicist who tion of the Donnan Effect (1911) that advanced the tion, showed which were essential and calculated the popularised the Wheatstone bridge, died on October 14 Friedrich Wilhelm Georg Kohlrausch, the German 19, 1875. understanding of the living cell, was born in 1870. minimum daily requirement for each of them, died in physicist who investigated the properties of electro- 1985. lytes, was born in 1840, while Heinrich Kayser, the 6 Phoebus Levene, the Russian-American chemist who found that the carbohydrate present in nucleic acid 28 Paul-Urich Villard, the French physicist and chemist from yeast is the pentose sugar ribose, died in 1940, who identified gamma rays, was born in 1860, the day 75 years ago. Louis Pasteur died in 1895. Conference Calendar 29 Peter Dennis Mitchell, the British chemist and 1978 7 Rodney Porter, the British biochemist who (with Edel- 2015 Society of Environmental Toxicology laborative nature of chemistry as a multidisciplinary sci- man) was awarded the 1972 Nobel Prize in Physiology Nobel Laureate in Chemistry who clarified how ADP and Chemistry (SETAC) Australasia Confer- ence and the opportunities to network with Pan-Pacific or Medicine for discoveries concerning the chemical is converted into the energy-carrying ATP, was born in research groups at the Pacifichem meetings. structure of antibodies, died 30 years ago. 1920. ence The conferences has eleven topic areas: The Rutherford Hotel, Trafalgar Square, Nelson, 8 Hermann Staudinger, the German who received the 30 Sir Robert Abbott Hadfield, the English metallur- New Zealand Core areas: analytical, inorganic, macromolecular, or- 1953 Nobel Prize for Chemistry for discovering of the gist who developed manganese steel died in 1940, ganic, physical, theoretical and computational structure of polymers as long-chain molecules and 75 years ago, as did Charles Richter, of Richter scale 25-28 August 2015 Multidisciplinary or cross-disciplinary areas: agrochem- coined the term macromolecule, died 50 years ago, as fame, in 1985. Abstract submissions close 8 May 2015 istry, environmental, and geochemistry, biological and did Willard Frank Libby, the American chemist who materials and nanoscience: devised carbon-14 (or radiocarbon) dating, the same October The conference will provide a great opportunity to show- day in 1980. case your latest research results and discuss with col- Chemistry solutions to global challenges: chemistry of 2 Robert Runnels Williams, the American chemist and leagues from other SETAC regions. The ambitious theme clean energy conversion, storage, and production, bench first to synthesise thiamine (vitamin B ), died in 1965. to bedside: chemistry of health care and connecting 9 Paul J. Flory, the American polymer chemist and re- 1 is 'System Approach to Environmental Management' and recognises the continuity of environmental processes in chemistry to society cipient of the Nobel Prize for Chemistry in 1974 for his 3 On this day in 1805, the first US pharmacopoeia was synthetic and natural macromolecules studies, died space and time, a concept that can enable us to better prepared. manage the environment and develop more sustainable www.pacifichem.org in 1985. solutions. Both novice and experienced presenters are Chemistry, Chemical engineering and Chemi- 4 Michael Smith, the Lancastrian born Canadian bio- encouraged to submit an abstract for either an oral or 10 John Kidd, the English chemist and physician who ob- chemist who won (with Mullis) the 1993 Nobel Prize poster presentation. The social programme, as with all cal Process (CCECP 2016) tained and named naphthalene in 1819, was born in for Chemistry for his development of a technique SETAC conferences, will provides plenty of opportunities Hotel Fort Canning, 11 Canning Walk Singapore 1775. called oligonucleotide-based site-directed mutagen- for delegates to network with colleagues with various expertise. 18-19 January 2016 11 This day in 1940 saw the first demonstration of re- esis, died in 2000. mote computing by teletype. To maximise the value of your travel to New Zealand, the Full paper submission by 13 July 2015 6 1790 saw Jacob Schweppe show his process for mak- conference organisers have coordinated with Ecobiore- 16 Gordon Gould, the American physicist who coined ing artificial mineral water. finery 2015, which will be held in Rotorua from 30 August The conference aims to foster and conduct collabora- – 4 September. tive interdisciplinary research in state-of-the-art meth- the word laser from the initial letters of Light Ampli- 7 1970 saw BP make the first big oil find in the British odologies and technologies within Chemistry, Chemical fication by Stimulated Emission of Radiation, died 10 sector of the North Sea and the day that Niels Bohr, www.setac2015.org.nz Engineering and Chemical Process. The meeting aims to years ago today. the Danish physicist and first to apply the quantum attract participants with different backgrounds, to foster theory to the problem of atomic and molecular struc- Pacifichem 2015 cross-pollination between different research fields, and 19 John Kenneth Harold Inglis, Professor of Chemistry at to expose and discuss innovative theories, frameworks, ture, was born in 1885. Honolulu, Hawaii, USA the University of Otago, died on this day in 1935. methodologies, tools, and applications. 22 Alice Hamilton, the American known for providing 8 Henry-Louis Le Chatelier, best known for the prin- 15-20 December 2015 http://chemistry-conf.org/index.html safer working conditions by investigating mines, mills, ciple named after him, was born in 1850. The theme of Pacifichem 2015 is Chemical Networking: Building Bridges Across the Pacific, emphasizing the col- and smelters, concentrating on lead, aniline dyes, pic- 11 Fausto D'Elhuyar, the Spanish chemist and mineralo-

162 163