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The 23rd RACI Organic Division Conference, ORGANIC-08, was held at Wrest Point, Hobart, Tasmania, from 7 to 12 December 2008. More than 270 delegates attended to celebrate the breadth and share the excitement of organic chemistry. The conference program included eight plenary lectures, the Birch Medal lecture by Associate Professor Michael Sherburn (ANU), and invited and other oral presentations by researchers and postgraduate students. Topics covered exemplified the diversity of our discipline, and included natural products chemistry and synthesis, new synthetic methods and catalysis, bioorganic and medicinal chemistry, physical and mechanistic chemistry, and supramolecular chemistry and nanotechnology. The papers published in this special issue of Aust. J. Chem. include review articles from three of the plenary lectures at ORGANIC-08. Professor Ian Paterson (Cambridge, UK) reports on ‘Recent Advances in the Total Synthesis of Polyketide Natural Products as PromisingAnticancerAgents’,[1] while Professor Chris Moody (Nottingham, UK) describes a unique class of natural products, the benzothiazole alkaloids, in his review entitled, ‘Naturally Occurring Nitrogen–Sulfur Compounds. The Benzothiazole Alkaloids’.[2] A review in the supramolecular chemistry–nanotechnology area is provided by Professor Jean-Francois Nierengarten (Strasbourg, France) on ‘Synthesis and Properties of Fullerene-Rich Dendrimers’.[3] Professor Yasuyuki Kita, Ritsumeikan University, Japan, also a plenary speaker, reports on the unique chemistry of hypervalent iodine compounds in a Rapid Communication entitled ‘Organoiodine-Catalyzed Oxidative Spirocyclization of Phenols using Peracetic Acid as Green and Economic Terminal Oxidant’.[4] Plenary lecturer, Professor Stephen Hashmi (Heidelberg, Germany) communicates more of his fascinating gold catalyzed chemistry in a full paper entitled ‘Gold Catalysis: Chemoselective Indolin Synthesis in the Presence of Acrylate Units’.[5] Articles by some of the invited speakers highlight the different themes of the conference and include the synthesis of bioactive

The traditional Gaussian basis sets used in modern quantum chemistry lack an electron-nuclear cusp, and hence struggle to accurately describe core electron properties. A recently introduced novel type of basis set, mixed ramp-Gaussians, introduce a new primitive function called a ramp function which addresses this issue. This paper introduces three new mixed ramp-Gaussian basis sets - STO-R, STO-RG and STO-R2G, made from a linear combination of ramp and Gaussian primitive functions - which are derived from the single-core-zeta Slater basis sets for the elements Li to Ne. This derivation is done in an analogous fashion to the famous STO-$n$G basis sets. The STO-RG basis functions are found to outperform the STO-3G basis functions and STO-R2G outperforms STO-6G, both in terms of wavefunction fit and other key quantities such as the one-electron energy and the electron-nuclear cusp. The second part of this paper performs preparatory investigations into how standard all-Gaussian basis sets can be converted to ramp-Gaussian basis sets through modifying the core basis functions. Using a test case of the 6-31G basis set for carbon, we determined that the second Gaussian primitive is less important when fitting a ramp-Gaussian core basis function directly to an all-Gaussian core basis function than when fitting to a Slater basis function. Further, we identified the basis sets that are single-core-zeta and thus should be most straightforward to convert to mixed ramp-Gaussian basis sets in the future., Peer reviewed, 13 pages, 7 figures, 11 tables. Australian Journal of Chemistry (2020, available online)

This is the first paper in a sequential pair devoted to the enzyme mutarotase (aldose 1-epimerase; EC 5.1.3.3). Here, the broader context of the physiological role of mutarotase, among those enzymes considered to be part of ‘metabolic structure’, is reviewed. We also summarise the current knowledge about the molecular mechanism and substrate specificity of the enzyme, which is considered in the context of the binding of fluorinated glucose analogues to the enzyme’s active site. This was done as a prelude to our experimental studies of the anomerisation of fluorinated sugars by mutarotase that are described in the following paper.

Accurate prediction of the separation conditions for a set of target analytes with no retention data available is fundamental for routine analytical assays but remains a very challenging task. In this paper, a quality by design (QbD) optimisation workflow capable of discovering the optimal chromatographic conditions for separation of new compounds in hydrophilic-interaction liquid chromatography (HILIC) is introduced. This workflow features the application of quantitative structure−retention relationship (QSRR) methodology in conjunction with design of experiments (DoE) principles and was used to carry out a two-level full factorial DoE optimisation for a mixture of pharmaceutical analytes on zwitterionic, amide, amine, and bare silica HILIC stationary phases, with mobile phases containing varying acetonitrile content, mobile phase pH, and salt concentration. A dual-filtering approach that considers both retention time (tR) and structural similarity was used to identify the optimal set of analytes to train the QSRR in order to maximise prediction accuracy. Highly predictive retention models (average R2 of 0.98) were obtained and statistical analysis of the prediction performance of the QSRR models demonstrated their ability to predict the retention times of new compounds based solely on their molecular structures, with root-mean-square errors of prediction in the range 7.6–11.0 %. Further, the obtained retention data for pharmaceutical test compounds were used to compute their separation selectivity, which was used as input into a DoE optimiser in order to select the optimal separation conditions. Experimental separations performed under the chosen optimal working conditions showed good agreement with the theoretical predictions. To the best of our knowledge, this is the first study of a QbD optimisation workflow assisted with dual-filtering-based retention modelling to facilitate the method development process in HILIC.

On 14–16 January 2013, the 3rd Molecular Materials Meeting (M3) @ Singapore was successfully held at Biopolis, a biomedical hub of Singapore hosting key research institutes of A*STAR and research and development laboratories of multinational corporations.With the theme of ‘Frontiers inMaterials Science, Chemistry and Physics’, the conference featured six thematic sessions, namely NewCatalysts and Catalytic Science, Soft Materials for Cosmetic and Health Care, Electrochemical Energy Conversion, Storage Materials and Technology, Materials for Advanced Sensors and Transducers, Lanthanidedoped Luminescence Nanomaterials, and Interface Engineering for Devices. The 3-day conference enabled lively discussions geared at cross-discipline collaborations in molecular materials (Fig. 1). This year, the M3 @ Singapore follows the past practice to publish a commemorative edition in the Australian Journal of Chemistry on selected papers presented at the conference. In the first issue [Aust. J. Chem. 2011, 64 (9)], the volume covered diverse topics that reflected the contemporary interests in the broad field of molecular materials, e.g. from temperature-driven molecular self-organisation to atom-transfer radical polymerisation based functional amphiphilic polymers synthesis, from dye-sensitised solar cells to nanoparticle-catalysed water-splitting, from metal-organic frameworks to aggregation-induced emission bioimaging, etc. The second edition [Aust. J. Chem. 2012, 65 (9)] is however relatively focussed. It featured mainly on contributions in research of nanoparticles and organic energy materials. The nanoparticle papers typified the harness of nanotechnology to enable new applications, e.g. using electro-responsive core-shell nanoparticles for rheology tuning, carbon nanotube-basedmaterials as catalysts in fuel cells, using chitosan-functionalised Au/Pd alloy nanoparticles/nanoclusters for catalysis of aerobic oxidative homocoupling reactions, and CdTe based hybrid fibres enabled low-voltage-driven electroluminescence devices, etc; papers on organic semiconductor research focussed on the structure–property relationship that leads to design and synthesis of high performance molecular materials, e.g. heterocyclic dyes for efficient dye-sensitised solar cells, phenyl-1Hpyrrole end-capped thiophenes for organic field-effect transistors, and pyridine incorporated dihexylquaterthiophene as blue emitter in organic light emitting diode applications. In this commemorative edition, seven papers are selected as highlights of the meeting. Bai et al. (Institute of Materials Research and Engineering, Singapore) introduced a new dinuclear Cu(II) complex (Fig. 2) with 1,2,3-triazoles of a chelatebridging mode. Using rare azole-bridged ferromagnetically coupled dinuclear Cu(II) complexes as examples, the paper demonstrates the potential of using heterocyclic triazoles to support magnetically active dinuclear Cu(II) complexes. The finding marks a step closer to the establishment of magnetostructural relationship and understanding of magnetic exchange

It is true to say that Sir John and Lady Rita Cornforth need no introduction to those familiar with chemistry, and particularly with Australian chemistry, where they occupy a unique position in our chemical heritage. We know they studied together at the University of Sydney, before they travelled to England in 1939.We know they enjoyed a unique partnership for 70 years. We knowmany honours were bestowed upon them, particularly to Sir John – whommost of us know simply as ‘Kappa’ (Fig. 1). However, perhaps what we don’t know sowell is what Kappa thought about their chemistry. Luckily, for Kappa’s 75th birthday, Bernard Golding inspired Kappa, and many of his colleagues and friends, to write about the Cornforth publications and these were duly published as ‘Selected Research Papers with Commentaries’. Some of these papers and commentaries I share with you now.

This issue of the Australian Journal of Chemistry is a tribute to the life and work of Professor Richard Francis Langler who died on 3 February 2014 in Bedford, Nova Scotia. Rick was a dedicated and inspirational teacher, and a rigorous researcher and steadfast mentor, especially for undergraduate researchers at Mount Allison University. He was one of those rare professors who had an enormous impact on his students, scientifically and pedagogically driven by the most sincere passion for organic chemistry (Fig. 1.) Rick has published an impressive 129 papers over his academic career (35 in Aust. J. Chem.) and contributed to textbooks. Rick’s attention to scientific detail was complemented with his thorough, direct nature and dry sense of humour, and reflected in his ability to ask the pointed and important questions at any scientific gathering. Rick was born in Sarnia, Ontario in 1945. In 1957, he received his honours degree in chemistry from Dalhousie University. He obtained his Master’s degree in chemistry from the University of NewBrunswick, working in the area of aminoheterocycles and bisnorquassin derivatives. In 1975, he received his doctorate from Dalhousie University, studying a new dithiochelate and the synthetic consequences of the sulfohaloform reaction. Rick spent time as a visiting lecturer at the University of Toronto before undertaking post-doctorate research at Dalhousie University. Rick was an Assistant Professor at Mount Allison University and Saint Mary’s University, and, after tenure and Associate Professorship at the Florida Institute of Technology, he returned to Mount Allison for the remainder of his career. Rick spentmore than 30 years (especially 7–12 pmon Friday nights) training undergraduate students in research areas ranging from organosulfur chemistry tomolecular orbital theory and often resulting in first authorship on several papers before graduating. Rick last published in this Journal on implementing perturbational expressions for the development of a novel set of approaches to embedding. Papers for this issue have been contributed bymany of Rick’s former students, colleagues, and friends from all over the world. As a tribute to Rick, this issue covers research in various areas of organic and organometallic synthesis and structure determination as well as computation and catalysis (inorganic and enzyme). Rick’s former student, Christopher Graves from AlbrightCollege, alongwith his researchgroup, including several undergraduate researchers, synthesised and characterised several aluminum-amidate complexes and further demonstrated that the complexes were pre-catalysts for both theMPV reduction of carbonyls and the Oppenauer oxidation of alcohols. Rick’s former undergraduate research student, Stephanie MacQuarrie (Cape Breton University) and colleagues, including three undergraduate research students, report on the stabilisation and improved catalysis of the enzyme phenylalanine ammonium lyase. Diane A. Dickie (University of New Mexico), another former student inspired by Rick’s teaching and high standards, along with her colleagues describe their synthesis and characterisation of zwitterionic CS2 adducts of bis(dialkylphosphino) amines. Catalytic asymmetric C–C formation implementing terminal alkyl-metal nucleophiles in tandem hydrometallation– isomerisation is reported by Stephen Fletcher and his research students from the University of Oxford. Stephen obtained his undergraduate honours degree working in Rick’s research laboratory developing potent antifungal disulfides. Stacey Wetmore, a former student and colleague of Rick’s, along with her research team present an article characterising and analysing the interactions between the side chains of Ser and Cys and DNA or protein p–rings in nature. Paul Hayes is another former undergraduate student inspired by Rick to follow an academic path and pursue scientific research. Along with his co-workers from the University of Lethbridge, Paul describes the synthesis and characterisation of several sterically hindered bis(phosphinimine) dibenzofuran ligands followed by zinc metalation. It is appropriate that long-time colleagues of Rick’s, Steve Westcott, Christopher Vogels, Andreas Decken, and Felix Baerlocher, in addition to several undergraduate researchers, conclude this memorial issue with an article on the synthesis, characterisation, and antifungal activity of eight new fluoroand methoxysubstituted benzodiazaborines.

This issue of Aust. J. Chem. is dedicated to Desmond Joseph Brown, formerly of the JohnCurtin School ofMedical Research, ANU, whom we always referred to as ‘Des’. An honorary member of the RACI and an eminent organic chemist who influenced the careers of many chemists, Des was a graduate of the University of Sydney and was awarded Ph.D. and D.Sc. degrees by the University of London. His detailed obituary has been published in Chemistry in Australia, July 2014, pp. 28–29. Des’s career (1942–1985) in academic organic chemical research was almost entirely in the field of heterocyclic chemistry, with emphasis in medicinal chemistry. His interest in these fields began during a year of study in Professor Adrien Albert’s ChemotherapyUnit at the University of Sydney. He thenwent to Imperial College, University of London, where he carried out research on heterocyclic analgesics for his Ph.D. degree under the supervision of Dr A. H. Cook and Professor Ian Heilbron. This was followed by a year at University College, University of London, working on pyrimidine and pteridine research. He was then appointed to the Department of Medical Chemistry in the John Curtin School of Medical Research (JCSMR) at the newly establishedAustralianNational University (ANU), where Adrien Albert had the foundation Chair. He assisted Professor Albert in the design of the building in Canberra, which was completed in 1956, and in establishing the department. Des was Professor Albert’s right-hand man until Professor Albert’s retirement in 1972, and later was appointed head of the Medical Chemistry Group in the JCSMRuntil his retirement at the end of 1985. He then became a Visiting Fellow in the Research School of Chemistry (RSC, ANU)where hewas providedwith an office and facilities for writing books (1986 to 2012). The Department of Medical Chemistry consisted of a fourstorey wing of the JCSMR building in which a very large space that spanned three storeyswas designated ‘TheHighLaboratory’. Des was in charge of this area which was used for very large scale syntheses and when the purification of large quantities of chemicals was required. This laboratory was converted to provide more laboratory space to accommodate new areas of research after 1972. Des’s research was mainly in the areas of pyrimidine, purine, and pteridine chemistry, substances that have central biological importance. He published most of his work in several series of papers, but only the first and the last parts of the series are referenced here. These include Improved Syntheses in the Pyrimidine Series (six parts), Simple Pyrimidines (17 parts), PyrimidineReactions (27 parts),TheDimrothRearrangement (18 parts), Isomerizations Akin to the Dimroth Rearrangement (five parts), Purine Studies (19 parts), Pteridine Studies (12 parts), Aza-analogues of Pteridines (eight parts), Triazolopteridines (three parts), and Naphthimidazoles (three parts). Other papers that he wrote did not belong to any series and stood alone. These included papers on triand tetrazolopurinones, a new route to pyrazolo[2,4-b] pyrazine, triazolopyrimidines, and triazolopurines, among several others. An important aspect of Des’s research was the study of the physico-chemical properties of many of the compounds that he, his students, and co-workers prepared. The studies specifically included the ionisation constants of the substances as well as the electronic spectra of the neutral and ionic species, photoelectron spectra of pteridines, and C NMR of tautomerism in N-heterocycles. Together with Adrien Albert and their co-workers, the department had amassed a tremendous amount of physico-chemical data which is now indispensible in the field ofmedicinal chemistry. The amount of data collected and published nowmakes it possible to predict with some degree of accuracy the dissociation constants of ionisable drugs

The study of pyrolysis (thermolysis) reactions has a long tradition in Australia. In the 1950s, G. M. Badger and his students at the University of Adelaide carried out extensive studies on the gasphase pyrolysis of aromatic hydrocarbons under flow conditions at atmospheric pressure. Experiments with low-pressure gasphase pyrolysis, later to be known as flash vacuum thermolysis (FVT) or flash vacuumpyrolysis (FVP) – a term coined byEddie Hedaya – were started by Wilfred D. (Bill) Crow and R. F. C. (Roger) Brown in the Chemistry Department, School of General Studies, at the ANU in 1965. At that time, there were two places in Canberra where one could do chemical research: the Medical Chemistry Department in the John Curtin School of Medical Research under Professor Adrien Albert, and the Chemistry Department in the School of General Studies. The Research School of Chemistry was being built in 1966 and it opened for business in 1967withArthur Birch as FoundationDean. Nobody liked the name ‘School of General Studies’, which authors abbreviated SGS or dropped entirely in their publications, and in 1979 this unhappy name was changed to ‘The Faculties’. Roger Brown arrived at the SGS as a young lecturer in 1961, and Bill Crow from CSIRO (Melbourne) accepted an associate professorship at about the same time. At the SGS, Bill Crow purchased a Lindberg tube furnace for hisM.Sc. student from Western Australia, Richard K. (Dick) Solly to commence FVP experiments in 1964. He later purchased a mass spectrometer in order to pursue the then-popular line of research on analogies (or differences) between thermal and mass spectrometric fragmentations. Other researchers, inter alia M. P. Cava, E. K. Fields, and S. Meyerson in the USA had similar interests. However, Bill Crowwent on study leave with Nelson J. Leonard at the University of Illinois, Urbana-Champaign, in 1965 and left it to Roger to supervise Dick, which led to a series of very topical papers on the formation of benzyne and hetarynes, a subject that remained close to Roger’s heart throughout his career. After his move to Monash University in 1968, methyleneketenes and methylenecarbenes became a major research topic in collaboration with Frank. W. Eastwood, and this is where the ‘Roger Brown rearrangement’, viz. 1,2-dyotropic shifts in acetylenes, R–C1 C2–R0 #R0–C1 C2–R, taking place via transient vinylidene intermediates, was discovered. According to Richard Johnson (University of New Hampshire, USA), during the Gordon Conference on Physical Organic Chemistry in Holderness, New Hampshire, in 2001 he and Roger Brown discussed this chemistry as they hiked up Rattlesnake Mountain, and later that afternoon, Richard and Maitland Jones, Jr (Princeton University) decided (over a beer) to name the rearrangement after Roger. During the evening session, Maitland drew the alkyne-vinylidene rearrangement on a chalkboard in the centre of the stage and suggested to the assembled crowd to honour Roger by naming the reaction after him. The August issue of Aust. J. Chem. is dedicated to the memory of Roger Brown, who passed away on 1 September 2013. Many scientists from all over the world have contributed papers to this issue, which thereby becomes a celebration of FVP and the chemistry of reactive intermediates and unusual molecules as well as organic synthesis, structure determination, and inorganic chemistry. The apparatus and techniques used in flash (vacuum) pyrolysis are reviewed. Anna Chrostowska and Stanislaw Lesniak from Pau, France, and Lodz, Poland, respectively, review the use of photoelectron spectroscopy in the study of pyrolysis reactions. Ian Rae, Roger’s first Ph.D. student, reveals some of Roger’s first research projects at the SGS in Canberra, which were concerned with 1,2-dithiole chemistry and nitrones. Carl Th. Pedersen (Odense, Denmark) with colleagues in Belgium, Japan, and Singapore describe the elusive ethene diselone, Se1⁄4C1⁄4C1⁄4Se. Oliver Kappe (Graz, Austria) reports on the (non-)existence of special microwave effects, Hassan Sheibani (Kerman, Iran) on new reactions of chlorocarbonylketenes, and Wolfram Sander et al. (Bochum, Germany) on matrix-isolation of pyridyl radicals formed by FVP of azopyridines as well as the pyridylperoxy radicals derived from them. Arvid Kuhn and Curt Wentrup (UQ) with co-workers from Japan report on the characterisation of 1,2-dehydroheptafulvene (heptafulvyne) and rearrangements of C8H6 hydrocarbons under FVP conditions, which includes a Roger Brown rearrangement. Joel Hooper, J. W. White, and Andrew Holmes (Melbourne) describe the use of a Claisen rearrangement with an organocatalytic, intramolecular Diels-Alder reaction in natural product synthesis, Mary Garson et al. (UQ) report the isolation of a new 3-alkylpiperidine from Indonesian waters, and John Bremner and Z. Wu (Wollogong) detail annulation of eightto ten-membered oxaza rings to benzo[b] thiophene. ChrisMoody (Nottingham, UK) reports the use of Rh-catalyzed carbene insertion in the synthesis of indoxylic acid esters. Jonathan White, Ken Ghiggino and co-workers (Melbourne) elucidate solvatochromism in diketopyrrolopyrrole derivatives with the aid of calculations, Jason Smith (UTas), Rolf Prager (Flinders) and co-workers report on the synthesis of heterocyclic fused imidazoles by FVP of isoxoazol-5(2H)ones, and Ross McGeary (another former Roger Brown student) and his co-workers (UQ) use ethyl (benzothiazol-2ylsulfonyl)acetate in malonic ester-type syntheses of carboxylic acids and esters. Roger Brown spent an extended period on sabbatical at Nijmegen University, The Netherlands, in Binne Zwanenburg’s group, and two papers from this laboratory report CSIRO PUBLISHING

This special open access edition of the Australian Journal of Chemistry represents a collection of papers from the first international conference dedicated to creating a Global Artificial Photosynthesis (GAP) or Global Solar Fuels (GSF) project, held at LordHowe Island on 14–18August 2011. Conceived and coordinated by the author of this article, the conference had endorsement from theUNESCONatural Science Sector andwas an official event of the UNESCO 2011 International Year of Chemistry. The federal Department of Industry, Innovation, Science and Research (DIISR, as it was then called) contributed to the funding, as did the Australian National University (ANU) College of Medicine, Biology and the Environment and ANU College of Law. Speakers included over 50 national and international experts in various aspects of artificial photosynthesis, as well as related areas including photovoltaics, hydrogen fuel cells, quantum coherence in electron transfer, and international governance systems. Lord Howe Island is a jewel in the UNESCOWorld Heritage List with its unique southerly coral reefs, mountain microclimate, flora, and fauna (Fig. 1). It provided a perfect symbolic backdrop for discussions about how nanochemistry in particular could devise new mechanisms for powering the planet for this and future generations and what governance structures could assist our move from the Anthropocene towards what has been termed the Sustainocene era. An expert naturalist (Ian Hutton) who was closely involved in that UNESCO listing process for Lord Howe Island gave a presentation to the conference about the energy and pollution challenges facing this beautiful island and donated copies of his illustrated book as gifts for the conference presenters. An innovative feature of the inaugural GAP conference was the involvement of over 40 high-achieving senior year Australian high school science students (from James Ruse Agricultural College in Sydney, Geelong Grammar in Victoria and Narrabundah High School, Radford College, and Canberra Boys Grammar in the ACT). Proceedings began each day at 8 a.m. in the beautifully renovated 1930s-era community hall overlooking the lagoon. There were no parallel sessions and afternoons were free to allow collaborative discussions whilst exploring the island. The island community generously assisted with accommodation and food. Sessions recommenced for a couple of hours after dinner. Each session was constructed to be a multidisciplinary mix of topics and concludedwith short presentations by the high school students that provided an insightful and often hilarious commentary on the presentations. Endingmost evenings was a panel discussion on how to advance governance of global artificial photosynthesis. We are very grateful that many of the GAP conference presenters have produced contributions for this special edition of theAustralian Journal of Chemistry. Amongst these and other attendees were world leaders in many fields connected with solar fuels. Their active contributions during question time vitally helped shape the papers in this issue. Videos of their talks are available at the GAP conference website: http://law. anu.edu.au/coast/tgap/conf.htm. A brief survey of the overall GAP conference contributions is important in understanding the unusually high quality, interdisciplinary context in which this edition of the journal evolved. Some notable presentations at the GAP conference included those on the use of gallium phosphide nanowires in light-driven hydrogen production by Peidong Yang, one of the leaders of the newly established Joint Centre on Artificial Photosynthesis at Berkeley. Dan Nocera from MIT spoke about his ‘artificial leaf’ that configures a triple junction silicon photovoltaic cell with a cobalt catalyst (Co-OEC) for O2 evolution and a ternary alloy (NiMoZn) as the H2-evolving catalyst. [3] Professor Nocera

The symposium Frontiers in Optical Bio-Imaging and Microscopy took place at the Suntec Conference Centre in Singapore from 26 June to 1 July 2011 as part of the wider Materials Research Society of Singapore’s (MRS-S) International Conference on Materials for Advanced Technologies (ICMAT) series. This symposium was held over six days and was chaired by Colin Sheppard, Brahim Lounis, Dave Fernig, and Jonathan Hobley, combining their respective knowledge on optical design, biological imaging, spectroscopy, and photochemistry. The parent biennial ICMAT event has been held on six previous occasions since its inauguration in 2001 and aims to promote multidisciplinary materials research, not only in Singapore, but especially in Asia and beyond. In this context the subject of this particular symposium typifies the scope of the ICMAT series, since modern microscopy is no longer just an exercise in advanced optics – it is in fact a combination of optical design, the chemistry of probe design, and chemistry required to attach novel probes to relevant targets that wewish to observe. In addition, the spectroscopic and photochemical features of probes need to be understood and harnessed in order to enhance their usefulness. For this reason, modern advanced microscopy can truly be considered to be a highly multidisciplinary research field. In the field ofmodern optics, it is no longer enough to simply envisage a concept in imaging alone; once the concept is born, it is often necessary to work with organic chemists and preparative nanoparticle scientists in order to produce an appropriatemodel probe system for the desired observation. For example, the most modern super-resolution techniques of PALM, STORM, and STED all require specific fluorescent probes with well tailored photochemistry in order towork. Equally recent developments in photo-thermal tracking of biomolecules require specifically designed noble metal nanoparticle probes as labels for the biomolecule of interest. Probe design is therefore now nearly as important as optical design in this field. Each of the individual component parts of a new bio-imaging methodology is of equal importance in the success and applicability of the technique. This Research Front comprises a selection of papers that exemplify the current trends in modern microscopy and optical methods presented in the Frontiers in Optical Bio-Imaging and Microscopy symposium, with particular emphasis on the chemical design of probes and the observation of chemical phenomena. In particular, two papers deal with advanced optical design, and three papers deal with advanced probe design. In optical design, Yakovlev et al. present work on the use of stimulated Raman photo-excitation coupled with acoustic detection as means of locating and imaging specific chemical signatures in a sample. Siebenhofer et al. describe the development of a novel optical design for determining the nanosecond kinetics of processes in bio-mimetic films based on Brewster-angle reflectometry. In probe design, Free et al. present work on the development of monovalently labelled silver nanoparticles stabilised by peptide shells that are resistant to ligand exchange and nonspecific binding for use in bio-imaging applications. Paramelle et al. describe their work on the stabilisation of gold nanoparticles for use as bio-imaging probes. In particular, they show how the shell design affects the overall stability of the nanoparticle. In this work, they present a rapid screening protocol for determining nanoparticle stability. Zhang et al. describe the preparation of polyethylene glycol-protected gold nanorods that are bio-compatible for use inmultiphoton luminescence imaging in cells. In this way, their paper describes both state-of-the-art nanoprobe development and cutting edge imagingmethodology. The next ICMAT event will be held in the summer of 2013, and it will once again combine multidisciplinary research in biology, materials science, and optics. We will be looking forward to hosting international scientists in Singapore once again for this event.

Synchrotron light sources are highly versatile research tools, with applications in a vast range of science from medicine to earth science. In fact, there are few areas of science to which synchrotron radiation cannot make a contribution, which is a credit to the designers of the many synchrotron light sources around the world and to those who have conceived and implemented the many beamlines and end-stations that make such a diverse range of experiments possible. Australia has recently joined the ranks of countries with an advanced third-generation light source since the opening of the Australian Synchrotron (AS) in Clayton, Victoria, in 2007. Synchrotron science in Australia dates back well before the opening of the AS, from the early days when intrepid scientists travelled to early light sources without the support structures that are taken for granted today, through the period of the Australian National Beamline Facility to the Australian Synchrotron Research Program (ASRP). The ASRP was a visionary programme that provided the experience and much of the impetus needed for Australian scientists to push for the establishment of a synchrotron light source in AustraliaandfromthatcametheASasweknowittoday.Although still in its earlystages of development and with only9 of apossible 38 beamlines,theAS has auser base of over 3000 scientists and an output of over 250 papers with AS data in 2011 alone. Many of the current beamlines are useful to those in the chemical sciences. Some, such as infrared spectroscopy, are methods that are quite familiar to chemists. The synchrotron infrared microspectroscopy beamline offers advantages over its laboratory counterpart such as greatly increased signal-to-noise ratio and the ability to perform mapping rapidly and with high spatial resolution, but is nevertheless quite similar at heart to an instrument that may be found in a lab, albeit with a synchrotron as the source of IR radiation. Others, with the X-ray absorptionspectroscopy(XAS)beamlinebeingagoodexample, rely on the unique properties of synchrotron radiation and offer capabilitiesthatcannotbeachievedwithoutasynchrotron.XAS offers unique opportunities for structural studies of metal centres that are of enormous value to chemists, biologists and materials scientists. This issue of Aust. J. Chem. contains a selection of papers by Australian groups that demonstrate some of the power of synchrotron radiation when applied to chemical problems. While some are more in the style of reviews and others are research articles, all give a useful perspective on how this versatile tool is a powerful weapon in the chemist’s armoury. A short review on applications of synchrotron radiation to medicinal chemistry [1] gives a summary of the way several beamlines (microprobe X-ray fluorescence imaging, XAS and infrared microspectroscopy) can individually and in combinationbeusedtohelpsolveimportantproblemsinthechemistryof health, while applications of infrared spectroscopy to biological systems is the focus of another review. [2] Other papers come from a materials chemistry perspective, highlighting the use of synchrotron powder diffraction for the structural elucidation of perovskite oxides, [3] the application of small angle scattering to the study of superhydrophobic surfaces, [4] structure determination of triiron carbonyl sulfide clusters using X-ray absorption spectroscopy [5] and finally a demonstration of the power of insitu measurements combining electrochemistry and X-ray diffraction to study electrocrystallization. [6] As more sources come into service and beamlines are constructed and upgraded, synchrotron techniques will continue to grow in importance to chemists. It is encouraging to see the breadth and quality of science being produced by Australian scientists using these techniques, and provided governments continue to recognize the importance and power of synchrotron science, there are exciting times ahead.

This Research Front features papers selected from the 39th International Conference on Coordination Chemistry held in Adelaide (24–30 July 2010). This meeting, the premier inorganic coordination chemistry conference worldwide, had not been held in Australia since 1989. In 2010 it coincided with the RACI Inorganic Chemistry Divisional (IC’10) conference. This internationalmeeting featured excellent contributions across the various themes of the conference including materials chemistry, metals in synthesis, solar energy conversion, metals in catalysis, supramolecular chemistry, and metals in biological systems. It is from this last theme that papers have been chosen for this Research Front, and these span a wide range of topics within the ‘bioinorganic’ area. Inorganic chemistry taken literally in its original meaning from the days of ‘Vital Force Theory’, excludes the chemistry of life. Nearly 200 years after Friedrich Wohler rescued inorganic chemistry from biological irrelevance the roles of metals in biological systems are now, more than ever, the focus of intense research in biological chemistry. Within this Research Front we have two reviews. One a personal perspective by David Parker (Durham) on the development of fluorescent complexes for bio-imaging. The long fluorescent lifetimes of lanthanoid excited states enable time resolution to be used in fluorescence imaging with essentially zero background interference from any other fluorescent molecules in the sample. A second review is fromZhiguang Xiao and Tony Wedd (Melbourne) on the topic of metallo-oxidases, a fascinating family of enzymes that catalyze the oxidation of important low valent metals such as Cu(I), Fe(II), and Mn(II) bymolecular oxygen. These reactions are critical to maintaining balanced levels of redox active metals within cells and to their transport and uptake by other metalloproteins. The full papers in this Research Front are equally comprehensive in their coverage of contemporary biological inorganic chemistry. The emergence of organometallic complexes in medicinal chemistry has challenged traditional views on metal-based drugs and their interactions with biomolecules (see also the Research Front published in Aust. J. Chem. 2010, 63, issue 11). In this vein, a paper by Gilles Gasser (Zurich), Nils Meztler-Nolte (Bochum), and coworkers report new peptide nucleic acid containing ligands and their Re and Tc carbonyl complexes, the latter being of great interest in radio-imaging. The stability of these complexes and ease of formation is investigated and discussed. Water solubility can be challenge in developing ligands and complexes that exhibit suitable pharmacological properties. Paul Donnelly (Melbourne) and coworkers have developed new water soluble bisthiosemicarbazone ligands that strongly bind Cu, a suitable isotope for positron emission tomography diagnostic imaging. The effects on cellular uptake and the redox properties of their Cu(II) complexes are discussed. The use of synchrotron radiation as a tool for imaging metals within cells is covered in two different papers using distinct techniques. Trevor Hambley (Sydney) and coworkers, using X-ray absorption near-edge spectroscopy, have developed a way of extracting information about the relative proportions of Pt(II) and Pt(IV) within cells. Pt(II) complexes comprise the most thoroughly investigated metal-based anticancer drugs to date but their side effects, linked to reactions with other biomolecules, have led to new approaches including the use of more chemically inert Pt(IV) analogues. The present paper shows how the relative proportions of the Pt(II) and Pt(IV) forms of some complexes change over time within cells. Lou Rendina (Sydney), Hugh Harris (Adelaide), and colleagues have used synchrotron X-ray fluorescence (XRF) spectroscopy to identify the cellular location of a DNA-intercalating Pt-terpyridyl complex bearing a carborane thiolate ligand; a potential target in boron neutron capture therapy. Rather than localising within the nucleus, the bifunctional complex is found to be distributed throughout the cell both within and outside the nucleus. Addition of the Pt complex also has significant effects on the concentrations of other elements within the cell (alsomeasured with XRF) with an increase in Cl, K, and Cu being found while Fe levels decreased. The purple acid phosphatase (PAP) family are an interesting group of enzymes that require two metal ions in proximity, one in a trivalent and the other in a divalent oxidation state for activity. Lawrie Gahan and coworkers report a new binucleating ligand and its Fe(III)/Zn(II) complex that mimics the PAP active site found in the plant enzyme in structure and in function. This ligand also bears an olefinic substituent for future copolymerization of the complex. Only a relatively small selection of the work presented at ICCC39 was able to be included in this Research Front but the quality of these contributions, and the contributors, herein is representative of the meeting. I was fortunate to be a PhD student in 1989 when ICCC last came to Australia. It was a long wait of 21 years to see the conference return to Australia and then from a different perspective as one of the organizing committee. If this pattern is to be repeated I will have retired CSIRO PUBLISHING

Organized by the Singapore A*STAR Institute of Materials Research and Engineering (IMRE), in partnership with other A*STAR institutes, the inaugural Molecular Materials Meeting (M3) held on the 10th and 11th of January 2011 in Singapore was a resounding success.Withmore than 60 talks by prominent scientists from across the globe and almost 90 poster presentations, this was an ambitious first meeting in many regards (Fig. 1). The conference also marked the inauguration of the International Year of Chemistry 2011 in Singapore. This conference was strategically named to cover a broad spectrum of materials research. The term ‘molecular materials’ puts emphasis on creating materials with new applications by studying, designing, and engineering their basic building blocks, i.e. their molecules, using chemical methods and processing techniques. By bringing together top minds from diverse fields, M3@Singapore aimed to foster new connections among scientists to discuss ideas targeted at the major technological challenges in selected application domains, i.e. health, urban lifestyle, high-value manufacturing, and sustainability. The theme of the meeting was ‘Big Ideas in Molecular Materials’. This theme set the expectation for the 2-day meeting during which there were candid discussions. This special issue of M3@Singapore comprises a selection of papers that epitomizes the current sentiments in molecular materials research, a sampling of which is mentioned in the following. In the focus article by J.M. MacLeod and F. Rosei (Universite du Quebec, Canada), the self-organization of molecules at solution/solid interfaces was investigated as a function of temperature. A related paper on self-organization, i.e. the self-assembly of block copolymer molecules in aqueous solutions is presented by A. M. H. Leung et al. (University of Waterloo, Canada). On a sustainability-related topic, K. J. Young et al. (Yale University, USA) contribute a paper on a photocatalytic cell for water splitting that was inspired by molecular studies of the photosystem II protein complex, and W. Zhang et al. (National University of Singapore) contribute a paper on TiO2 nanorod photoelectrodes for dyesensitized solar cells. In the area of health technology, a paper on functionalized polymers for the detection of cells is presented by U. Latif et al. (University of Vienna, Austria), together with two papers by X. D. Su et al. (Institute of Materials Research and Engineering, Singapore) on metallic nanoparticle interactions with DNA. In addition, the readers will find several other stimulating papers in this issue. In this molecular age, if we can creatively design, synthesize, process, and applymaterials usingmolecular techniques, we can certainly expect quantum leaps in advances in materials research. We believe that the solution to the hard problems in science and technologywill be found in the scrutiny of materials from the molecular level to the nano-scale. The advances of the likes of carbon-materials such as fullerenes and graphene and hybrid materials like nano composites and hetero-structures are just some successful examples. If chemistry can energize the biology field to the extent that it could create a new field called ‘chemical biology’, there is every reason to be enthusiastic

The Australian Journal of Chemistry is pleased to publish a collection of papers commemorating the 100th anniversary of the Nobel Prize in chemistry awarded to Marie Curie (nee Marya (Maria) Sk"odowska) for the discovery of two new radioactive elements, polonium and radium. Her first Nobel Prize, in physics in 1903, was shared with Henri Bequerel and her husband Pierre Curie for their work on the radiation phenomena discovered by Becquerel – the so-called Becquerel rays, which were later determined by Rutherford and Royds in 1907 to be a-particles (He2þ nuclei). It wasMarie Curie who in 1898 coined the term radioactivity for this new property of matter. Although Marie and Pierre had discovered and isolated two new highly radioactive elements, Po and Ra from the uranium mineral pitchblende in 1898, the Nobel physics committee appeared to have reservations about this and made no mention of it, thereby making it possible for the chemistry Nobel committee to award her the second prize in 1911. The Curie story is reviewed herein by Clarence Hardy. It is important to realize that these discoveries were made before the structure of the atom was understood. Neither the proton nor the neutron nor indeed the atomic nucleus were known, and the electron had only just been discovered by J. J. Thomson in 1897. The bestmodel of the daywas J. J. Thomson’s ‘plum pudding model’, in which the corpuscular electrons were sitting like the plums in an ill-defined nuclear fluid. Rutherford’s ‘solar system’ model came in 1911, and Bohr’s now familiar quantummodel of the atom in 1913. The Becquerel rays were at first thought to be similar to Rontgen’s X-rays, i.e. electromagnetic in nature. The a-particles emitted by polonium became crucially important in the discovery of the neutron, which earned Chadwick the Nobel Prize in Physics in 1935, and Irene Curie and her husband Frederic Joliot the Chemistry Nobel, also in 1935, for the discovery of the transmutation of elements by a-particle bombardment of lighter elements, e.g. Alþ a(He)Pþ n. The Joliot-Curies first thought the neutron rays emanating from light elements such as beryllium and aluminium on a-bombardment were a powerful variant of g-rays (high energy electromagnetic radiation), but Chadwick realized their particulate nature. The P isotope formed in the Joliot-Curie experiment is radioactive, emitting positrons with a half-life of 3min. Thus, they discovered artificial radioactivity. Similarly, radioactive isotopes of nitrogen and silicon were produced by a-bombardment of boron and magnesium, respectively. Positrons are nowadays immensely important in positron emission tomography (see paper by Greguric et al. below). The fascinating story of the neutron – the Curie family’s legacy – is reviewed expertly by John and Alsia White. The discoveries of Po, Ra, radioactivity, the atomic nucleus, and the neutron paved the way to our current understanding of the atom and the associated advances in chemistry, physics, and medicine. The development of radiation chemistry since the Curies and till the present day is reviewed briefly by Ronald Cooper. Alison Edwards highlights modern uses of neutron diffraction in structure determination in cases where X-ray diffraction is unable to provide definitive answers. This takes advantage of the different scattering properties of X-rays and neutrons: because the neutrons are electrically neutral, they are diffracted more readily by the nuclei rather than the electrons in a molecule, thereby enabling them to reveal the precise locations of the nuclei of hydrogen and other light elements or to ascertain their absence. While neutron diffraction used to be a technique firmly in the realm of physics because forbiddingly large crystals were needed in order to obtain chemical structures, technical advances using Laue neutron diffractometers have made it possible to undertake such studies on crystals of manageable sizes (fractions of mm). Radioactive elements and isotope labelling are of practical importance in several areas of medicine. Radium and other radionuclides were introduced very early byMarie Curie herself and are still used in radiotherapy to combat malignant tumours. More recently, g-rays from e.g. Co, electron (b-rays), and proton beams from particle accelerators have come into use. The synthesis of radioactively labelled drugs (radiosynthesis) is interesting because it permits the location of the molecule on the target and elsewhere by means of 3D positron emission tomography. Ivan Greguric and coworkers describe a synthesis of positron-emitting F-labelled nicotinamide (half-life of F 110min) designed to target random metastasis of melanoma tumours. Because the ingestion of radionuclides is harmful and potentially lethal, it is of crucial importance to be able to determine their presence in drinking water – not least in Australia with its large deposits of uraniumore.MeganCook andRossKleinsmith describe a method for the simultaneous determination of a-emitting Ra-226 and b-emitting Ra-228 in water by liquid scintillation spectrometry. CSIRO PUBLISHING

This review paper updates the previous literature in relation to the continued and developing use of stable isotope ratio analysis in samples which are relevant to forensic science. Recent advances in the analysis of drug samples, explosive materials, and samples derived from human and animal samples are discussed. The paper also aims to put the use of isotope ratio mass spectrometry into a forensic context and discuss its evidential potential.

This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition–fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379–410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669–692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a diverse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

This Special Issue of the Australian Journal of Chemistry is dedicated to Professor Alan M. Sargeson whose contributions to not only inorganic chemistry but Australian and international science were extraordinary. Over his career, Alan published more than 400 papers and more than 50 were published in Aust. J. Chem. Alan passed away in December 2008. There are several accounts of Alan’s life in chemistry. For those wishing to gain a personal insight to his academic career, particularly in the early days, his published interview with Len Lindoy makes great reading.[1] The papers in this issue come from all around the globe. All of the contributors accepted their invitation enthusiastically and without hesitation. Given space restrictions, there were only a limited number of papers that could be included here. Several contributions are from former postdoctoral fellows or graduate students who worked in his group at the Research School of Chemistry, Australian National University, and then went on to establish their own research programs. Others are international collaborators or those who simply admired and appreciated Alan’s contributions to chemistry. The chemistry of Alan Sargeson spanned all areas. Apart from his truly innovative macrocyclic ‘cage’ chemistry, his research was also groundbreaking in areas of inorganic reaction mechanisms and bioinorganic chemistry; these areas all feature prominently in this issue. My first appreciation of Sargeson chemistry came as a 3rd year chemistry undergraduate in 1985 when given the task of following synthesis of the complex [Co(diNOsar)]3+ that had been published a year before (Scheme 1).[2] The reaction involves the seemingly incongruous self assembly of nine molecules to give a crystalline product in high yield. The synthesis followed on from the groundbreaking publication reporting the analogous chemistry with ammonia, instead of nitromethane, as the capping reagent to create the first cage ligand sepulchrate complexed to CoIII and CoII.[3,4] There can be few better examples of the elegance of Sargeson ‘cage chemistry’ than this. HN HN

Robert V. Stick is a carbohydrate chemist; and so am I. Carbohydrate chemistry is a special branch of organic chemistry. The carbohydrates differ from the common organic chemicals in many ways: they do not dissolve in organic solvents, they cannot be distilled; and when a pure sugar is dissolved in water, a solution results that contains six different compounds. Carbohydrate chemists have their own journals and textbooks. Carbohydrate chemistry did not develop until the end of the 19th century; then Emil Fischer[1] determined the structures and configuration of all the simple sugars, established conversions, and studied their reactions. I worked for my Ph.D. degree in sugar chemistry with Zemplen, a former student of Fischer; he was not a brilliant chemist, and was a poor supervisor. When I completed my degree, I decided not to work on sugars any more: I thought that the problems there had already been solved by Fischer himself and his team. I went into the pharmaceutical industry. But soon I realised that my judgment was not right: there was plenty to learn still about the properties of sugars. Thus, we did not know why d-glucose is mainly in the β-pyranose form but d-mannose mainly the α-pyranose. Why does the equilibrium of d-glucose contains very little furanose but that of d-idose quite a lot? Why do some sugars readily form a 1,6-anhydride but others do not? When I obtained a university position in 1946, I returned to carbohydrate chemistry. In the middle of the century, three new methods revolutionized carbohydrate chemistry: NMR spectroscopy,[2] X-ray crystallography,[3] and conformational analysis.[4] NMR spectroscopy allowed the determination of the exact proportions of isomers in equilibrium; the X-ray method indicated the exact shapes of the molecules; and conformational analysis supplied the explanations and allowed predictions of behaviour. It became now much easier to deal with the structures and synthesis of complex carbohydrates, such as oligosaccharides and glycosides. And synthesis has been improved by new methods and new reagents, and by better control of conditions. Separation methods were also improved, for example chromatography – originally an analytical technique – was turned into an efficient method of preparative separation. When Stick established his group in the Department of Chemistry at the University of Western Australia his collaborators and Ph.D. students carried out a range of reactions with a variety of sugars. Many of the compounds thus obtained were natural products, but others were artefacts. These, of course, were compounds of interest to biochemists because they could be tested for potential biological activity. Soon many papers appeared on the biochemical behaviour of sugar derivatives. By now, there were biochemists in some chemistry departments and chemists in some biochemistry departments. Ideally, close cooperation was desired between them but, in fact, was seldom achieved. In most universities, the chemistry and the biochemistry departments are in different faculties and not even close to each other. [In my case, the two schools do not even inform each other of their seminars.] By contrast, by the time of the retirement of Robert Stick in 2008, his department had been renamed the School of Biomedical, Biomolecular and Chemical Sciences. The changes in carbohydrate chemistry are easily surveyed by looking at two sources of information: the series Advances in Carbohydrate Chemistry, published annually since 1945, and the programs of the International Symposia on Carbohydrate Chemistry, held biennially since 1960. The Advances contain chapters of current interest on carbohydrates; the symposia consist of talks on subjects in which work was currently carried out. Both indicate which way carbohydrate research is moving. Both organizations realised how much it was tending towards biochemistry. In 1989 Advances in Carbohydrate Chemistry added the words ‘and Biochemistry’ to its title; in 1980, the Symposia made room for biochemistry in the opposite way by omitting in Vancouver the word ‘Chemistry’ and becoming International Carbohydrate Symposia. Neither of these bodies used the term ‘Glycoscience’, much liked by some of the biochemists. [However, a recent book on carbohydrate chemistry and biochemistry is entitled Glycoscience; Chemistry and Chemical Biology. It contains more than 9000 references!] At the Symposium in Hamburg (in 2000), about one-third of the presented papers and the posters were on biochemistry and biotechnology. By then, interest in carbohydrates had grown very much: there were almost 1000 talks and posters presented. At the latest Symposium, in 2007 in Oslo, again about onethird of the papers and posters were on biochemical subjects. Curiously, the proportion was smaller for the plenary and invited lectures; apparently there were few biochemists on the organizing committee. Unfortunately, Robert Stick missed this meeting, his first absence in over 20 years. All this development affected Robert Stick’s interest and research too. Most of his work was published in the Australian Journal of Chemistry but gradually shifted to journals of

You are looking at the first issue of the sixtieth volume of the Australian Journal of Chemistry. The journal has changed enormously over the last sixty years but some crucial elements remain. AJC, as the journal is affectionately known, continues to be a major forum for the publication of some of the country’s and the region’s best chemical science. SinceAJC has a fine tradition of publishing papers on all aspects of chemistry, it also remains an important vehicle by which all researchers can promulgate their research to colleagues outside their own specific area(s) of the discipline.A survey of the authorship over the last six decades reveals the names of some of our most distinguished chemists, including Birch and Cornforth, while a glance at more recent issues of the journal provides the names of many rising stars in chemistry, especially those on the local scene. Although the journal has had anAustralasian-focus in the past, the current editorial direction, with an emphasis on ensuring proper coverage of a range of internationally recognized research priorities, means that this is less so now. As a consequence, and as evidenced by looking at the most highly cited papers published in AJC during 2004,[1–3] 2005,[4–6] and 2006,[7–9] the work produced by Australasian authors is receiving greater attention, while increasing numbers of papers arising from groups working in the Northern Hemisphere are now appearing in the journal. There is a basket of indicators that highlight the vigorous nature of AJC as a sixty year old. The impact factor is increasing steadily, as is the journal’s citation ranking. The web-based delivery of the journal has seen an almost exponential growth in the number of articles downloaded and thus confirming the continued enthusiasm for the journal within the research community. Equally importantly, submissions to the journal continue to increase while the introduction of Research Fronts has provided a remarkably popular forum for the publication of cutting-edge

This paper provides a first update to the review of living radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of Reversible Addition–Fragmentation chain Transfer (RAFT) published in June 2005. The time since that publication has witnessed an increased rate of publication on the topic with the appearance of well over 200 papers covering various aspects of RAFT polymerization ranging over reagent synthesis and properties, kinetics, and mechanism of polymerization, novel polymer syntheses, and diverse applications.

This issue of the Australian Journal of Chemistry features papers from the Australian Colloid and Interface Symposium (ACIS), held at Coogee Beach, Sydney, in February 2003. ACIS is the new biennialAustralian conference of colloid and surface science. It provides a regular opportunity for Australian and international researchers to meet and exchange ideas far from the cold of the northern winter, and acts as a permanent venue for the A. E. Alexander Lecture of the Colloid and Surface Science Division of the Royal Australian Chemical Institute (RACI). ACIS2003 also incorporated the Australia–Japan Colloid Symposium, an event we hope will also continue as a regular part of the program. The Alexander Lecture for 2003, reproduced in this issue,[1] was presented by Mats Almgren of Uppsala University and entitled Cubosomes, Vesicles, and Perforated Bilayers inAqueous Systems of Lipids, Polymers, and Surfactants. The lecture commemorates the contributions of Albert ‘Alex’ Alexander FAA FRACI, who was Professor of Physical Chemistry at the University of Sydney from 1957 to 1970, and is presented by an eminent colloid and surface scientist who has contributed particularly to the discipline inAustralia. Some of Mats Almgren’s numerous outstanding contributions are discussed in his paper. These, together with his long connections with various Australian research groups, combined to make him a welcome addition to the distinguished list of Alexander lecturers, Table 1. Previous Alexander lecturers, Bob Hunter and Toyoki Kunitake, also both presented at ACIS2003 and have papers in this issue. ACIS2003 was structured around four themes that the organizing committee hoped would showcase the modern

Open a text-book on Electrochemistry today and the lay reader will be enthused (and perhaps slightly confused) by the exploits of researchers of yesteryear including Faraday, Nernst, Fermi, Cotrell, Butler, and others. Its pages will reveal delightful descriptions of diffusion layers, dielectric constants, and double layers, intermingled with theories on solvation effects, electron transfer, and solid–liquid interfaces. The practical applications chapters will include descriptions of charge storage devices (such as batteries and capacitors), electrowinning of metals, electrosynthesis of polymers, and the voltammetric analysis of trace elements. By the end the reader will have grappled with most of the fundamental concepts underpinning the very essence of electrochemical science—the movement and separation of charge. And since most chemical reactions involve charge transfer, the reader will have been exposed to the very essence of chemistry itself. The Electrochemistry text-books of tomorrow will, rightfully, be more diverse and interdisciplinary than the very much physical nature of today’s texts. This will be particularly true in the chapters on applications. Like their present day counterparts, the content of tomorrow’s texts will be based on the research exploits of those in the past (today’s researchers). As such, we will read about applications of electrochemistry in areas as diverse as nanotechnology, biochemistry, microbiology, genetics, new materials, molecular biology, and so on; indeed, any field in which the movement and/or separation of charge is important. At the recent Interact 2004 Conference held at the Gold Coast, Australia, electrochemical researchers from around the world presented their latest findings in many of these areas. The Interact event included the 12th Australasian Electrochemistry Conference (12AEC), hosted by the Electrochemical Division of the Royal Australian Chemical Institute (EDRACI). This volume of the Australian Journal of Chemistry includes a selection of papers from electrochemical researchers who presented at 12AEC. The selected papers that appear in this volume involve applications of electrochemistry in microbiology (by means of electrochemically mediated catabolism of yeasts and bacteria), molecular biology (employing DNA hybridization and metal–protein interactions), nanoscale surface modification (through protein adsorption), new materials (involving the conducting polymers polyaniline and polypyrrole), as well as more traditional electrochemical applications in metal deposition and the thermodynamics of solid–solid interfaces. The application of electrochemistry in the catabolic processes of microorganisms has received considerable renewed interest in the last few years. Of particular interest has been the use of soluble electron mediators to shuttle electrons derived from oxidative catabolic processes to electrode surfaces. While these mediated microbial processes have been predominantly studied employing prokaryote cells (such as bacteria), their use in eukaryote cells has received much less attention. Keith Baronian and his team have addressed this issue with the use of single and double mediator studies on yeast species to determine the mechanisms and sites of interactions of the redox mediators within the catabolic pathways.[1] Neil Pasco and colleagues also report the use of double mediated systems in bacterial cells for the development of a rapid assay for biochemical oxygen demand (BOD).[2] A review of the considerable work carried out worldwide in this field over the last five years is presented by Kristy Morris et al.[3] This review focusses on the use of the ferricyanide ion as the electron mediator and its application to environmental monitoring—particularly for rapid BOD and rapid toxicity assays. The study of conducting polymers (plastics that conduct electricity!) has been a central theme for many electrochemical researchers over the last decade or more. Ben Mattes and his team at Santa Fe Science and Technology Inc. lead the world in the electrochemical synthesis of polyaniline fibres for ‘smart fabric’ and ‘interactive textile’ manufacture. Here they report their latest work on the use of ionic liquids as the electrolyte in polyaniline fibre synthesis.[4] The stress generation from these electromechanical actuators exceeds that of skeletal muscle! Dennis Tallman and colleagues have been studying the electrochemical deposition of conducting polymers at various metal surfaces for some years with an eye on the age-old problem of corrosion protection.[5] In their paper they report on the problems of depositing polypyrrole onto aluminium surfaces (due to the concomitant oxidation of the aluminium electrode) and of the use of an electron mediator which lowers the deposition potential as well as serves as the counter-ion in the polymer structure. The coupling of electrochemistry and molecular biological techniques also finds prevalence in this volume with the

The theme for the most recent New Zealand Institute of Chemistry (NZIC) conference held in Nelson was ‘Chemistry at the Interface’ and that’s exactly what the twelve plenary speakers, invited speakers, section lecturers, and hundreds of posters presented. Close to 400 delegates, from a range of chemical backgrounds, were treated to the best of international and local speakers in a programme that provided a glimpse into the future of chemistry and also, importantly, an insight into the discipline’s past and evolution. This issue of theAustralian Journal of Chemistry compiles some of the outstanding science presented within the framework of the conference symposia; the interface of chemistry and biology, techniques of chemistry at the interface, the interface of chemistry with the commercial sector, and the interface of chemistry with materials and nanotechnology (Fig. 1). Bill Denny[1] provides an insightful discussion on the design of drugs that target tumor hypoxia. This approach to tumour-selective agents has lead to some internationally important findings and a deeper understanding of the biology of tumours. Ted Baker[2] reviews recent advances in the area of structural analysis in his article. This work highlights a critical link between advances in molecular biology and in structural determination by X-ray crystallography. David Fairlie[3] continues the theme of the biology/chemistry interface, presenting an outstanding summary of some minimalistic approaches to structural mimetics of amino acids and of strand, turn, and helix segments of proteins. Gary Evans[4] presents an overview on the design and synthesis of transition state analogue inhibitors of N-ribosyl transferases and their current therapeutic uses and potential. This is a real success story in New Zealand-based medicinal chemistry.The medicinal chemistry theme continues in a paper by Andrew Abell and coworkers[5] on the synthesis and anti-cataract properties of peptidic aldehydes. A true highlight of the conference was a presentation by Dieter Seebach[6] on his pioneering work on the creation of new secondary structures derived from βand γ-peptides, and aspects of this work are discussed here. This special issue also contains two papers that present work at the interface of organic and inorganic chemistry. Peter Steel and coworkers[7] present the first examples of 2,2′-bipyrimidine ligands incorporating bulky or chiral substituents, and Jonathan White and coworkers[8] present Fig. 1. The interface of chemists with the Nelson environment.

In this paper, a dataset of 11 fluorinated compounds containing a variety of functional groups (amides, esters, indoles, and ethers) as well as mono, gem-difluoro, erythro-difluoro, and threo-difluoro patterns were synthesised and their octanol–water partition coefficients (log P) were measured using a shake-flask method. The resulting data was used to assess the performance of several popular empirical fragment-based methods as well as quantum chemical implicit solvent models (SMD and SM12). Overall, the empirical miLOGP, ALOGPS, and ALOGP methods performed the best with a mean absolute deviation (MAD) of ~0.25 log units, while the best performing implicit solvent model SMD has a slightly higher MAD of 0.36 log units. Based on the present work and previous studies, the miLOGP and ALOGP empirical methods are recommended for fast and moderately accurate prediction of log P for neutral organic solutes.

Growth hormone deficiency (GHD) is a severe pathology that greatly affects the quality of life, and increases morbidity and mortality of patients owing to the augmentation of cardiovascular events. Treatment of GHD is challenging, mainly because there is no specific characteristic sign or symptom that can be used to make a clear diagnosis. There is need for an unequivocal diagnosis of GHD to avoid unnecessary treatment with GH, because the available provocative tests (GH stimulation tests) are not specific and sensitive enough, and are contraindicated in some patients. Ghrelin is an endogenous peptide that stimulates GH secretion by interacting with a G-protein-coupled receptor named ghrelin receptor (GH secretagogue receptor 1a, GHS-R1a). Given this, a GH stimulation test using ghrelin or its analogues appears to be attractive. In this paper, a modified tripeptide first named JMV-1843 in the laboratory is briefly presented. It is potent and selective in stimulating the release of GH and is orally active. It has been recently commercialised for the diagnosis of adult GH deficiency under the tradename Macrilen. The test using this compound appears to be reliable, well tolerated, and simple.

金沢大学ナノマテリアル研究所 / 金沢大学理工研究域生命理工学系, A polar carboxylate-type zwitterion with a small volume of water can dissolve cytochrome c without significant disruption, compared with the case of a popular polar carboxylate-type ionic liquid, 1-ethyl-3-methylimidazolium acetate. A change in the Soret, Q, and 615 nm bands was not observed in the 80 wt-% polar zwitterion solution, whereas a shift in the Soret band, diminishing Q band, and appearance of the 615 nm band was found in the 80 wt-% polar ionic liquid solution. It suggests that concentrated polar ionic liquid solutions critically disrupt the structure of cytochrome c, and the polar zwitterion solution used in this study was better than a 1-ethyl-3-methylimidazolium acetate solution in a high concentration range., This paper has supplementary information.

This study investigated two student cohorts enrolled in an introductory tertiary chemistry unit designed for students with little or no previous education in chemistry. Emeritus Professor Graham Chandler was instrumental in the design and development of this unit almost 30 years ago. Therefore, this study has particular interest in this special issue of the Australian Journal of Chemistry, which celebrates Emeritus Professor Graham Chandler’s contribution to Australian chemistry. This paper is divided into two distinct parts that provide two unique perspectives of the unit. The first perspective, Part A, is a historical account of the origins of this unit and is based on an interview with E/Prof. Chandler and Dr Peter Simpson OAM. Both E/Prof. Chandler and Dr Simpson provide an excellent reflection on the need for an introductory chemistry unit in tertiary education, which was not as common then as it is in the present day. The second perspective, Part B, is a research study focussing on the perceptions of students taking this unit in 2013 and 2014. In this study, it was found that the number of students who perceived chemistry to be applicable to real world problems increased during the unit, as did the number of students who enjoyed the unit. However, many students, most of whom did not intend to study chemistry further, did not recognise the application of the content to their future careers. There are many similarities between the aims of E/Prof. Chandler and Dr Simpson for the unit and the perceptions of students taking this unit 30 years later, which is testament to Graham’s contribution to chemistry education at the University of Western Australia.

In the present paper, we finalize some threads in our investigations into the effects of chain-length-dependent propagation (CLDP) on radical polymerization kinetics, confirming all our previous conclusions. Additionally, and more significantly, we uncover some unexpected and striking effects of chain-length-dependent chain transfer (CLDTr). It is found that the observed overall rate coefficients for propagation and termination (and therefore the rate of polymerization) are not significantly affected by whether or not chain transfer is chain-length dependent. However, this situation is different when considering the molecular weight distributions of the resulting polymers. In the case of chain-length-independent chain transfer, CLDP results in a considerable narrowing of the distribution at the low molecular weight side of the distribution in a chain-transfer controlled system. However, the inclusion of both CLDP and CLDTr yields identical results to classical kinetics – in these latter two cases, the molecular weight distribution is governed by the same chain-length-independent chain transfer constant, whereas in the case of CLDP only, it is governed by a chain-length-dependent chain transfer constant that decreases with decreasing chain length, thus enhancing the probability of propagation for short radicals. Furthermore, it is shown that the inclusion of a very slow first addition step has tremendous effects on the observed kinetics, increasing the primary radical concentration and thereby the overall termination rate coefficient dramatically. However, including possible penultimate unit effects does not significantly affect the overall picture and can be ignored for the time being. Lastly, we explore the prospects of using molecular weight distributions to probe the phenomena of CLDP and CLDTr. Again, some interesting insights follow.

Zwitterionic liquids composed of a tethered cation and anion were synthesized and their thermal properties and ionic conductivity were investigated as novel ionic liquids especially for electrochemical applications. We prepared nine zwitterions in this study. In addition, this paper includes 36 kinds of zwitterions already reported in order to discuss the relationship between the zwitterion structure and their properties. Most zwitterions melt above 100°C; their melting points are generally higher than that of simple ionic liquids. When an equimolar amount of lithium salt (LiTFSI, LiBETI, LiCF3SO3, LiBF4, or LiClO4) was added to the zwitterion, the mixture showed only a glass transition temperature Tg. The Tg values of the zwitterionic liquid/salt mixture showed the lowest value of –37°C when mixed with LiTFSI. This mixture also showed the highest ionic conductivity of 8.9 × 10–4 S cm–1 at 100°C. There is a good relationship between Tg and the ionic conductivity of the zwitterionic liquid/lithium salt mixtures.

Transition metal-mediated arylation chemistry is emerging as a powerful tool for the selective modification of native peptides and proteins, providing new opportunities in the field of bioconjugation. This highlight paper will summarize recent methodologies for the regio- and chemoselective arylation of select proteinogenic side chains and backbone amide N–H bonds within unprotected peptides and proteins. The importance of the metal–ligand complex in achieving tunable selectivity and the inherent benefits of arylation as a mode of covalent protein modification will be highlighted.

In this paper, we give a succinct derivation of the fundamental equation of classical equilibrium thermodynamics, namely the Gibbs equation. This derivation builds on our equilibrium relaxation theorem for systems in contact with a heat reservoir. We reinforce the comments made over a century ago, pointing out that Clausius’ strict inequality for a system of interest is within Clausius’ set of definitions, logically undefined. Using a specific definition of temperature that we have recently introduced and which is valid for both reversible and irreversible processes, we can define a property that we call the change in calorimetric entropy for these processes. We then demonstrate the instantaneous equivalence of the change in calorimetric entropy, which is defined using heat transfer and our definition of temperature, and the change in Gibbs entropy, which is defined in terms of the full N-particle phase space distribution function. The result shows that the change in Gibbs entropy can be expressed in terms of physical quantities.

The September issue of Aust. J. Chem. contains a selection of papers authored by speakers at the National Congress of the Royal Australian Chemical Institute held in Adelaide, 7–12 December 2014, which integrated all areas of chemistry under one roof in the Adelaide Convention Centre. Neil Vasdev and Steven Liang (Massachusetts General Hospital and Harvard Medical School) present an account on a new avenue to synthesize radiotracers aimed at the eventual ability to radiolabel just about any substance for medicinal purposes. Rainer Koch (University of Oldenburg, Germany), H.-J. Wollweber (University of Marburg, Germany), and the present author (The University of Queensland) report on the synthesis of a-oxo oximes of isoxazolones, pyrazolones, and 1,2,3-triazolone and the elucidation of stereochemical preferences. Toshihide Horikawa (Tokushima University, Japan), Duong Do (The University of Queensland), and their colleagues describe their research on the adsorption of water and methanol on highly graphitized carbon black and activated carbon fibre. John Gladysz and co-workers (Texas A&M University) report on the syntheses of three series of trigonal bipyramidal trans-bis(phosphine) complexes, which can potentially undergo three-fold intramolecular ring closing metatheses to yield gyroscope-like complexes. Frederic Paul, Jean-Francois Halet, and their co-workers (Universite de Rennes 1, France) report a theoretical analysis of electronic structures and optical properties of a series of phenylalkynyl iron complexes, Fe(dppe)(Z-C5Me5). Unexpected hypsochromic shifts of the lower energy absorption bands upon carbon chain lengthening were observed. Bradley Smith et al. (University of Notre Dame, Indiana, USA) report enhanced squaraine rotaxane endoperoxide chemiluminescence in acidic alcohols. The squaraine rotaxane endoperoxides are storable chemiluminescent compounds that undergo a clean cycloreversion reaction, releasing singlet oxygen and emitting near-infrared light when warmed to body temperature. Acidic alcohols such as hexafluoroisopropanol greatly increase the chemiluminescence, which takes place from a squarine excited state. Interlocked rotaxanes are necessay for the effect. Philip E. Thompson (Monash Institute of Pharmaceutical Sciences) and co-workers applied click chemistry to produce linear and cyclic peptide conjugates derived from Fmocpropargyloxyprolines. The conjugates can retain the binding affinity and/or binding conformation of the parent peptide. Frances Separovic (The University of Melbourne) and her co-workers describe C-terminal modifications with hydrazide and alcohol functions that extend the antibacterial activity of a proline-rich peptide towards other Gram-negative species. Furthermore, the new analogues did not show cytotoxicity towards mammalian cells. Jianbo Wang and co-workers at Peking University, China, report Rh-catalyzed cross-coupling of diazoesters with arylstannanes as a first Stille-type coupling using diazo compounds. The reaction is operationally simple, can be carried out under mild conditions, and provides an alternative approach to the synthesis of a-aryl esters. RichardO’Hair (TheUniversity ofMelbourne) et al. report that decarboxylation takes precedence over loss of acetonitrile in silver propiolate complexes of the type [CH3C CCO2Ag2(CH3CN)n] (n1⁄4 1 or 2). Massimiliano Massi and Mark Ogden (Curtin University, Perth), Evan Moore (The University of Queensland), and coworkers have prepared a one-dimensional Eu3þ coordination polymer bearing a-nitrile-substituted b-diketonate and 1,10phenanthroline ligands, which exhibit red emission in the solid state. The sensitization process from the b-diketonate to the Eu3þ is thought to occur via an antenna effect. Aleksey Vasilev (University of Sofia, Bulgaria), Katharina Landfester (Max Planck Institute for Polymer Research, Mainz, Germany), and their co-workers report their work on assembling new two-in-onemerocyanine chromophoreswith a 1,8-naphthalimide core by using the NO2 function as a leaving group in SN-Ar reactions, thus overcoming limitations of the conventional use of halogenide leaving groups. Timothy Long et al. (Virginia Tech, USA) have synthesized a biocompatible, biodegradable, and 3D-printable polyester [poly(tri(ethylene glycol) adipate) dimethacrylate] suitable for building vascularized soft-tissue scaffolding. The polyester exhibited highly efficient photocuring, hydrolyzability, and 3D printability in a custom micro-stereolithography system. The photocured polyester film demonstrated significantly improved cell attachment and viability.

Curt Wentrup was educated at the University of Copenhagen (Cand. Scient. 1966 with K. A. Jensen; D.Sc. 1976) and the Australian National University (Ph.D. 1969 with W. D. Crow). After post-doctoral periods with Hans Dahn (Lausanne), W. M. Jones (Gainesville, FL) and Maitland Jones, Jr (Princeton, NJ), he held academic positions at the Universite de Lausanne, Switzerland, and a professorship at the Universitat Marburg, Germany, before returning to Australia in 1985 as Professor and Chair of Organic Chemistry and Head of the Organic Chemistry Section at the University of Queensland, where he is now Emeritus Professor. Since 2008, he has been the editor-in-chief of the Australian Journal of Chemistry, and he is the immediate-past chair of the National Committee for Chemistry. He has published over 350 research papers, reviews, and books on reactive intermediates and unusual molecules. He is a Fellow of the Australian Academy of Science, and a recipient of the Centenary Medal of the Australian Commonwealth (2003), the David Craig Medal of the Academy of Science as well as the A. J. Birch Medal of the RACI (2014). He collaborates strongly with research groups in Europe and was awarded an honorary doctorate from the Universite de Pau, France, in 2014.

The April issue of Aust. J. Chem. is dedicated to the memory of Sir John Warcup Cornforth (usually known as Kappa to friends and colleagues), who passed away in December 2013. Cornforth studied chemistry at The University of Sydney (he entered at the age of 16), where he worked for his B.Sc. degree (obtained in 1937 with first class honours and a University Medal) with Francis Lions and Gordon K. Hughes, with whom he published several papers in J. Proc. Roy. Soc. New South Wales on such topics as the pyrolysis of phenyl cyclohexenyl ether, coumarono [3,2-b]indoles, and (with Arthur J. Birch and others) pyrroles derived from acetonylacetone. Birch, who was a year ahead of Cornforth at Sydney, recounts how Francis Lions used to make cocktails from distilled alcohol, and that ‘his student John Cornforth in about 1938 invented a ‘‘cocktail’’ that contained absolute ethanol flavouredwith ethyl acetate and vanillin –which effectively smooths down the tissues – coloured by methylene blue and named ‘‘Satan’s Sparking Plugs’’. It produced chromatic urinary effects after imbibing, dismaying to the uninitiated’. Cornforth was known for his quick wit and making up limericks on the run. He got his own back on Birch

This research paper describes a second-generation, enantioselective synthesis of (+)-GR24. This new strategy circumvents the need for ozonolysis, which may not be suitable for reactions performed on scale. This flexible new approach is then used to synthesise a novel bromo-GR24 analogue. Finally, the optimal solvent for making GR24 stock solutions is identified.

The 6th Heron Island Conference on Reactive Intermediates and Unusual Molecules - Synthesis and Mechanism was held at the Heron Island Resort on the Great Barrier Reef, 7- 13 July 2013, with some 80 scientists in attendance from all over the world, presenting highlights of their work in lecture and poster format ( Fig. 1). These meetings, which enjoy an excellent international reputation, present unique opportunities for interaction between Australian and overseas chemists in subject areas varying from organic synthesis to reaction mechanism, computational and theoretical chemistry, physical/ materials chemistry, inorganic chemistry, biological/ medicinal chemistry, and spectroscopy. This issue of Aust. J. Chem. presents a collection of papers authored by delegates at the meeting and comprise a wide range of topics, including amine boranes ( S.- Y. Liu et al.),[ 1] rhodium carbenoids ( A. Padwa et al.),[ 2] singlet oxygen ( T. Linker et al.),[ 3] hydrogen peroxide fuel cells ( S. Fukuzumi et al.),[ 4]

This paper discloses for the first time the effects of the gas phase (GP) and the tar of cigarette smoke on lipid peroxidation (LPO) and on the structure of different lipid regions in liposomes. The LPO development was analysed in terms of the total unsaturation of lipids (double-bond, DB, content) and the formation of dienic conjugates (DC), ketodienes (KD), and malonic dialdehyde (MDA). As expected, the exposure of liposomes to either the GP or the tar led to a significant decrease in the DB content. However, the formation of oxidation products revealed different dynamics: MDA generation was inhibited, while the formation of DC and KD increased during the first few hours of the LPO development followed by its inhibition. The smoke constituents exhibited opposite effects on the structure of the lipid bilayer of liposomes: the GP markedly enhanced the microviscosity of liposomal membranes, whereas the tar caused a drastic lowering of microviscosity.

Physical organic chemistry is broadly defined and of fundamental importance for the development of interdisciplinary areas that link together chemical synthesis and biological and material sciences with theoretical and physical chemistry. In its classical sense, physical organic chemistry can be defined as the study ofmechanism, reactivity, structure, and binding in organic systems, which leads to the quantitative understanding of their properties at the molecular level. Modern physical organic chemistry also encompasses a wider range of contexts and interactions, which extend beyond reaction pathways. Some important current topics include supramolecular interactions and molecular recognition, aggregation and reactivity, computation of reaction pathways, reactions and catalysis in biology, materials where molecular structure controls function, structure activity correlations, mechanisms in synthesis and catalysis, and interactions and reactivity in organised assemblies and interfaces. The program of the Gordon Research Conference on Physical Organic Chemistry (conference title: Understanding Chemical Reactivity – New Concepts and Applications), which was held in June 2013 at the Holderness School, New Hampshire, USA, spanned the wide area of modern physical organic chemistry. This Research Front on physical organic chemistry is dedicated to this highly interdisciplinary field by showcasing research that ranges from mechanistic organic and bio-organic chemistry to materials chemistry. Fluorescence spectroscopy is a powerful method for monitoring conformational changes in proteins and protein–protein associations. Petersson and co-workers describe in their review strategies for labelling proteins with fluorescence probes with a particular focus on evaluating the balance between size and utility of the fluorophores, since large sizes can be disruptive to the protein’s fold or function, but on the other hand provides valuable characteristics such as visible wavelength absorption and emission or brightness. Formation of C–C bonds mediated by transition metals are amongst the most important reactions in organic synthesis. The search for new types of reactions requires a detailed understanding of the mechanism of these reactions. O’Hair and colleagues have used multi-stage mass spectrometric techniques to obtain mechanistic insight of the cobalt-mediated Glaser-type decarboxylative homocoupling of alkynyl carboxylic acids. These studies revealed that dinuclear cobalt clusters are superior to mononuclear complexes at promoting both decarboxylation steps as well as the reductive coupling itself. Reversible bond formation and dissociation of radical species (p-dimers) in solution phase can be applied to control the mechanical motion of molecules. Nishinaga and co-workers studied the diradical character of benzoand naphtho-annelated thiophene-pyrrole mixed oligomer dications and their application in p-dimer based supramolecular chemistry. Organic semiconductors have become increasingly important as substitutes for conventional inorganic materials. Jeffries-EL and co-workers have explored the optoelectronic properties of two-dimensional cross-shaped ‘cruciform’ molecules possessing two extended conjugation axes, which enable independent manipulation of the HOMO and LUMO levels by incorporating electron-donating and -withdrawing substituents at different positions along the two axes. This selection of invited papers in this Research Front is just a snapshot of the variety of research that is currently being performed under the broad category ‘physical organic chemistry’. It is this diversity of science and the constant developments that will keep this field exciting in the future.

Curt Wentrup was educated at the University of Copenhagen (Cand. Scient. 1966; D.Sc. 1976) and the Australian National University (Ph.D. 1969). After post-doctoral periods with Hans Dahn (Lausanne), W. M. Jones (Gainesville, FL), and Maitland Jones, Jr (Princeton), he held an assistant professorship at the Universite de Lausanne, Switzerland, and a professorship at the Universitat Marburg, Germany, before returning to Australia in 1985 as Professor and chair of organic chemistry and head of the organic chemistry section at the University of Queensland, where he is now Emeritus Professor. Since 2008, he has been the editor-in-chief of the Australian Journal of Chemistry, and since 2009 chair (now immediate-past chair) of the National Committee for Chemistry of the Australian Academy of Science. He is a Fellow of the Australian Academy of Science and has published over 300 research papers. His interests are in the fields of both experimental and computational chemistry of reactive intermediates and unusual molecules using photochemistry, flash vacuum thermolysis, andmicrowave-induced chemical reactions; in particular, chemistry of nitrenes, carbenes, nitrile ylides, and nitrile imines, pericyclic rearrangements of cyanates, isocyanates, thioand isothiocyanates, and nitrile oxides and sulfides, and the chemistry of extended cumulenes. He collaborates extensively with groups in Australia and Europe, and frequently holds visiting professorships in Europe.

This paper discusses the binding of a laser dye, Coumarin 314 with β-cyclodextrin, studied mainly by UV-visible spectroscopy, 2D rotating-frame nuclear Overhauser effect spectroscopy (ROESY), steady-state spectroscopy and time-resolved fluorescence spectroscopy. The role of β-cyclodextrin on the binding of Coumarin 314 with calf thymus DNA was investigated. Coumarin 314 shows a hyperchromic shift of absorption and a quenching of fluorescence due to binding with β-cyclodextrin. The fluorescence quenching is non-linear and the reason for the non-linearity is discussed. The unusual fluorescence quenching on Coumarin 314–β-cyclodextrin binding is rationalised from the effect of acidity on absorption, fluorescence, and molecular modelling studies. Additional proof for the mode of binding is given by 2D ROESY. The capped and exposed portions of the Coumarin 314 molecule in the Coumarin 314–β-cyclodextrin complex when binding with calf thymus DNA were visualised based on spectral and molecular modelling studies.

Curt Wentrup was educated at the University of Copenhagen (Cand. Scient. 1966; D.Sc. 1976) and the Australian National University (Ph.D. 1969). After post-doctoral periods with Hans Dahn (Lausanne), W. M. Jones (Gainesville, FL), and Maitland Jones, Jr (Princeton), he held an assistant professorship at the Universite de Lausanne, Switzerland, and a professorship at the Universitat Marburg, Germany, before returning to Australia in 1985 as Professor and chair of organic chemistry and head of the organic chemistry section at the University of Queensland, where he is now Emeritus Professor. Since 2008 he is editor-in-chief of the Australian Journal of Chemistry, and since 2009 chair of the National Committee for Chemistry of the Australian Academy of Science. He is a Fellow of the Australian Academy of Science and has published over 300 research papers. His interests are in the fields of both experimental and computational chemistry of reactive intermediates and unusual molecules using photochemistry, flash vacuum thermolysis, and microwave-induced chemical reactions, in particular chemistry of nitrenes, carbenes, nitrile ylides and nitrile imines, pericyclic rearrangements of cyanates, isocyanates, thioand isothiocyanates, and nitrile oxides and sulfides, and the chemistry of extended cumulenes. He collaborates extensively with groups in Australia and Europe and frequently holds visiting professorships in Europe.

The Beckwith Memorial Symposium on Free Radical Chemistry was held in Philadelphia, USA, on 19 August 2012, as part of the 244th American Chemical Society National Meeting and Exposition, ‘Materials for Health and Medicine’. It was organised by Professor Derek Pratt of the University of Ottawa and Professor Igor Alabugin of Florida State University, as part of the program of the Organic Chemistry Division, at the invitation of the American Chemical Society. It follows other international meetings dedicated to the memory of Professor Athelstan (Athel) L. J. Beckwith, including the 11th International Symposium on Organic Free Radicals (ISOFR-11) held in Bern, Switzerland, in July 2012. Athel’s outstanding contributions to chemistry have also been acknowledged in many other ways, including through his election to the Fellowship of the Australian Academy of Science (1973) and the Royal Society of London (1989), and Membership of the Order of Australia (2004); with a special issue of Aust. J. Chem. celebrating his 65th birthday and posthumous issues of Aust. J. Chem. and Organic and Biomolecular Chemistry; and in obituaries published in Historical Records of Australian Science and Biographical Memoirs of Fellows of the Royal Society. These are all a reflection of a quite remarkable man and his chemistry, but the Beckwith Symposium stood out as an opportunity for some of his close friends to reflect on their memories of Athel, sufficiently after his untimely, accidental death in May 2010 for some of the raw emotions to have passed. Invited lectures were presented at the symposium by Professor Carl Schiesser (University of Melbourne – ‘Building Bridges Using Homolytic Substitution Chemistry’), Professor Curt Wentrup (University of Queensland – ‘Rearrangement of Triplet Nitrenes and Carbenes to Triplet 1,5-Biradicals’), Professor Leo Radom (University of Sydney – ‘Influence of Connector Groups on the Stabilities of Radicals’), Professor Wes Borden (University of North Texas – ‘Effects of Tunnelling by Carbon on the Ring Opening of Cyclopropylcarbinyl Radicals’), Professor David Crich (Wayne State University – ‘Lessons from Radical Chemistry and their Application to Glycochemistry’), Dr Chrys Chatgilialoglu (Consiglio Nazionale delle Richerche (Bologna) – ‘Bio-Inspired Synthetic Strategies of Purine 50,8-Cyclonucleoside Derivatives’), Professor Chris Easton (Australian National University – ‘Effect of Radical Modifications of Amino Acids on Protein Synthesis, Structure and Function’), Professor John Murphy (University of Strathclyde – ‘Super-Electron Donors (SEDs): New Frontiers’), Professor Michelle Coote (Australian National University – ‘New Insights into the Catalytic Cycle of Nitroxide Activation and Regeneration’), Professor Marc Greenberg (Johns Hopkins University – ‘Free Radical Mediated Nucleic Acid Damage’), Professor Louis Fensterbank (Universite Pierre et Marie Curie (Paris) – ‘New Developments in Tin-Free Radical Chemistry’), Professor Armido Studer (Westfalische Wilhelms-Universitat Munster – ‘Applications of Nitroxides and Quinones as Mild Oxidants in Catalysis’), Professor David Procter (University of Manchester – ‘SmI2-Mediated Cyclisation Cascades: An Approach to Pleuromutilin’), Professor Robert Flowers (Lehigh University – ‘Unravelling the Mechanism of Single-Electron Oxidation and Reduction in Important Synthetic Reactions’), Professor Dennis Curran (University of Pittsburgh – ‘Radical Reactions of N-Heterocyclic Carbene Boranes’) and Professor Philippe Renaud (University of Bern – ‘Boron: A Unique Element in Radical Chemistry’). Following the scientific program, many of the symposium participants adjourned to Zahav, a nearby Israeli restaurant, and following that to a local bar. As when Athel was present, the social interactions were as important as, and inseparable from, the science. This issue of Aust. J. Chem. contains a selection of papers authored by Athel’s ex-students, colleagues, and friends who attended the Beckwith Symposium. They cover new methods for the generation of radicals in ‘Convenient Ambient Temperature Generation of Sulfonyl Radicals’ by I. V. Alabugin et al. and ‘New Elements on the Behaviour of a Bissulfinylmethyl Radical’ by L. Fensterbank and co-workers, as well as studies that establish new fundamental principles of free radical chemistry reported in articles by C. H. Schiesser and his

Coordination polymers, which are also widely known as metalorganic frameworks (MOFs), are infinite solid-state networks that can be synthesised from combinations of organic links and metals or metal oxide clusters. By careful choice of both precursor metal salt and the bridging organic ligand, materials with varying 1-D, 2-D, and 3-D topologies; tailored pore sizes, pore shapes, and internal pore chemistry; and properties can be synthesised. Research into the field of coordination polymers and MOFs appears to know no limits. A Web of Science search of both terms as part of the title of published manuscripts (Fig. 1) shows a continual and notable growth over the past 20 years; first of the term ‘coordination polymer’ and then more recently the term ‘metal-organic framework’ or ‘MOF’. This Research Front inAust. J. Chem. highlights examples of the current state of research in the field of coordination polymer or MOF chemistry and indicates briefly where some of the future challenges and opportunities in the field may lie. Australasia has strong links to the field of coordination polymers with Hoskins and Robson publishing one of the seminal papers in this area. By combining tetrahedral organic links and tetrahedral Cu metals ions, Hoskins and Robson were able to form a 3-D coordination polymer with a diamond-like cationic framework. This primary contribution outlined a strategy by which judicious choice of both metal ion and organic ligand could lead to the synthesis of coordination polymers with 1-D, 2-D, and 3-D topologies (Scheme 1). By modifying the structure metrics of a link or ligand, the pore size and chemistry could be systematically manipulated to generate desirable materials. A flurry of activity in the field has elucidated numerous structurally novel materials from a vast array of metal and ligand combinations, along with the observation of various fundamental phenomenon such as the mechanical interlocking – catenation or interpenetration – of the polymeric structures and the intrinsic physical properties of the frameworks, for example, magnetism and non-linear optics. The appreciation that such materials could be made permanently porous altered the focus of the field to the properties of coordination polymers that take advantage of the high surfaces areas and large pore volumes; to on-board gas storage initially and hence to separations, catalysis, sensing, and delivery, for example. The identification of a third class of coordination polymers, namely materials with dynamic structures, has added a further focus to the field with the ability to tie changes in the properties of a material to structural changes that occur in the framework. As noted, the robust frameworks obtained from combinations of metal ions, or metal-oxide clusters, and organic ligands possess high surfaces areas and large pore volumes that make them suitable for gas storage. Potential for onboard storage of gases such as hydrogen and methane for transportation has been investigated in considerable detail, with control over surface areas and pore volume by extension of the ligands, control of catenation, and generation of open metal sites having been shown to enhance gas uptake. More recently considerable attention has been directed towards the use of coordination polymers for gas separations, particularly for the separation of CO2 frommixtures of gases that include predominantlymethane (natural gas sweetening), hydrogen (pre-combustion CO2 capture), or nitrogen (post-combustion CO2 capture) to counter the increasing levels of CO2 in the atmosphere. [13] Two main strategies have been used to enhance the gas separation performance ofMOFs: increasing the affinity of the framework for the gas (e.g. generation of exposed metal sites, post-synthetic metallation, and functionalising pores with Lewis basic sites), or by separating on the basis of different kinetic diameters. Other separations that have been studied included olefin/alkane separations, capture of organosulfur compounds, and enantioseparations. The open, crystalline structures of coordination polymers have also led to studies of their potential as catalytic materials, including as shape-selective catalysts, framework catalysts (e.g. Lewis acid catalysis due to structural metal ions), and for heterogenising – embedding – existing homogenous catalysts. Properties of the frameworks such as luminescence, solvatochromism, or vapochromism, and localised Surface Plasmon Resonance have been utilised for sensing, while the large pore volumes have been explored for delivery of pharmaceutical

In April 2013, the second biennial SynthCon meeting, SynthCon2, was held in the Yarra Valley at Fergusson’s Winery. Building upon the success of SynthCon1, which had around 45 attendees, 55 delegates attended and presented recent results from their laboratories. SynthCon focuses on the needs of the synthetic organic chemistry community within Australia. Although the tyrannies of distance no longer impede the timely delivery of the latest international discoveries, conducting research in Australia still presents a unique range of challengesyand advantages. A central motivation behind the creation of these meetings was a desire to address the challenge of performing research within smaller institutes, and often in the absence of colleagues working in closely related fields. By providing a meeting focused on academics, without the distractions of international speakers, it was hoped that an environment conducive to the open and frank development of novel ideas could be created. While we have some way to go, our second meeting allowed delegates from the Australian National University, Biota International, CSIRO, Curtin University, Deakin University, Griffith University, Monash University, Queensland University of Technology, University of Adelaide, University of Melbourne, University of New England, University of New South Wales, University of Queensland, University of Sydney, University ofWestern Australia and University ofWollongong to meet and discuss new and unpublished chemistry. This Research Front presents a taste of the chemistry from this meeting, with research papers examining the synthesis and biological activity of Sunitinib analogues, facial selectivity in benzonitrile oxide cycloaddition, the enantioselective synthesis of kopsia and aspidosperma natural products, temperature responsive amphiphiles, and the ozonolysis of endoperoxides. Several highlights focused on emerging areas, such as ionic liquid conjugated proline catalysis, chemical activation of nitrenes and azides, and the role of peptide secondary structure in electron transfer, are presented. Finally, a focus article highlights 1-(acyloxy)benzotriazoles, and examines its utility. SynthCon2, and SynthCon1, was financially supported by Davies Collison Cave, CSIRO, Australian Journal of Chemistry, Biota International and Monash University. Thanks also to Amanda Lee, for her help behind the scenes, and in the creation of the cover art for this issue; Simon Lee, our trusted bus driver; Michael Blair, for the homebrew; and the Lupton doctoral students for venue set-up. Planning is under way for SynthCon3, which will be held in Victoria’s Yarra Valley in 2015. Our chair, Richard Payne, will be in contact in due course. Hopefully, SynthCon3 will see some familiar faces, along with new members of the community, as we continue to foster excellence in organic synthesis within the Australian chemistry community.

The indolin-2-one fused-ring system and the 2,4-dimethylpyrrole unit represent key structural motifs in the anticancer drug sunitinib (Sutent®) and predecessor angiogenesis inhibitors that have undergone anticancer clinical trials (e.g. semaxanib, SU5416). In pursuit of novel anti-angiogenic scaffolds, we were interested in identifying whether the indolin-2-one group in these structures could be modified without losing activity. This paper describes novel condensation chemistry used to prepare a test series of (E)- and (Z)-alkenes related to SU5416 that retain the 2,4-dimethylpyrrole unit while incorporating ring-opened indolin-2-ones. Unique structural characteristics were identified in the compounds, such as intramolecular hydrogen bonds in the (Z)-alkenes, and several examples were shown to possess significant anti-angiogenic activity in a rat aorta in vitro model of angiogenesis. The work demonstrates that the indolin-2-one moiety is not an absolute requirement for angiogenesis inhibition in the sunitinib/SU5416 class.

Native state mass spectrometry (MS) has been recognised as a rapid, sensitive, and high throughput method to directly investigate protein-ligand interactions for some time, however there are few examples reporting this approach as a screening method to identify relevant protein–fragment interactions in fragment-based drug discovery (FBDD). In this paper an overview of native state MS will be presented, highlighting the attractive properties of this method within the context of fragment screening applications. A summary of published examples using MS for fragment screening will be described and reflection on the outlook for the future adoption and implementation of native state MS as a complementary fragment screening method will be presented.

The world needs new, environmentally friendly, and renewable fuels to exchange for fossil fuels. The fuel must be made from cheap, abundant, and renewable resources. The research area of solar fuels aims to meet this demand. This paper discusses why we need a solar fuel, and proposes solar energy as the major renewable energy source to feed from. The scientific field concerning artificial photosynthesis is expanding rapidly and most of the different scientific visions for solar fuels are briefly reviewed. Research strategies for the development of artificial photosynthesis to produce solar fuels are overviewed, with some critical concepts discussed in closer detail.

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.