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Proton exchange membrane (PEM) water electrolysis offers several advantages compared to the traditional alkaline technologies including higher energy efficiencies, considerably higher specific production rates leading to more compact design, and avoiding a liquid and highly corrosive electrolyte. The oxygen electrode is the critical part in the energy consumption of such cells. To obtain high... [Conference Paper]

Electrospray ionisation mass spectrometry shows that arylstibonic acids, RSbO₃H₂, give rise to oxo-bridged clusters derived from [H₈(RSb)₁₂O₂₈] which act as inorganic crown ligands towards Na+ cations; structure determination of one derivative revealed a cage-like anion [Na₂H₉(p-O₂NC₆H₄Sb)₁₂O₃₀.4H₂O]-.This is an author's accepted version of an article published in the Journal: Chemical Communications. Copyright The Royal Society of Chemistry 2009. [Journal Article]

Downstream purification and analysis of a model biopharmaceutical protein (recombinant human myelin basic protein) is described. The recombinant protein was expressed in the milk of transgenic cows and was found exclusively associated with the casein micellar phase. Binding of milk calcium to the active sites of a cation exchanger resin was used beneficially in this study in order to gently... [Thesis or Dissertation]

This thesis investigated the formation of compositional gradients across 0.5 – 1 cm of porous silicon layers which had thicknesses of 2 – 10 μm. These compositional gradients were then characterised, and their potential use as vapour sensors was probed. Surface composition gradients have been reported on flat surfaces, but this is the first time that they have been reported on a... [Thesis or Dissertation]

Fabric has always been prominent throughout history. In the last 70 years new synthetic fabrics have been developed which mimic the natural fibres but have increased strength, durability and stretchability. Common fibres include Polyester, Nylon and Lycra(R). These fibres can be blended to incorporate the properties of both the individual fibre types. Gold nanoparticles have been found to give...

Note the addition of an erratum to “Investigation of the suitability of commercially available CVD diamond for megavoltage X-ray dosimetry”, added to the end of the full-text article.Sandwich-type X-ray detectors were fabricated on commercially available chemical vapour deposition diamond sourced from three manufacturers: Diamond Materials GmbH, Diamonex, and Element Six. These devices were investigated using Raman spectroscopy and 6 MV photons from a clinical linear accelerator. Parameters such as the level of the dark (leakage) current and photocurrent, necessary priming... [Journal Article]

The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the... [Thesis or Dissertation]

This thesis details the synthesis and coordination chemistry of twenty-five nitrogencontaining heterocyclic ligands, nineteen of which were previously unreported compounds. These ligands were designed for use as synthons for the formation of molecular cages, so contain multiple coordination sites capable of bridging multiple metal atoms. The majority of molecular cages in the literature are... [Thesis or Dissertation]

The envelope problem in macromolecular x-ray crystallography involves determining the boundary of a molecule from measurements of amplitudes of x-rays diffracted from a crystalline specimen. This represents a highly underdetermined image reconstruction problem with a large number of degrees of freedom. We regularize the problem by applying binary and connectivity constraints to the image, and... [Conference Paper]

X-ray detectors have been fabricated from a range of commercially-available chemical vapour deposition (CVD) diamond. They have been packaged and tested in a clinical environment, using clinical apparatus and following clinical procedures: 6 MV linear accelerator, solid water phantom, dosimeter. Some devices exhibited highly desirable characteristics, such as negligible dark currents (sub-pA),... [Conference Poster]

X-ray detectors were fabricated from a range of commercially-available synthetic diamond fabricated using chemical vapour deposition (CVD). As these detectors are intended as dosimeters for use in radiotherapy (beam calibration and profiling, in-situ dose measurements etc.), they were appropriately packaged and tested in a clinical environment, using clinical apparatus and following clinical... [Conference Paper]

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Dehydroquinate synthase (DHQS) catalyses the five-step transformation of the seven carbon sugar 3-deoxy-D-arabino-heptulosonate 7-phosphate (DAH7P) to the carbacycle dehydroquinate (DHQ). Multiple studies have described in detail the mechanism of most of the steps carried out by DHQS with the exception of the final cyclisation step. In this study, (3S)-3-fluoro-DAH7P and (3R)-3-fluoro-DAH7P... [Thesis or Dissertation]

The seventeenth-century technologist and colonist William White (ca. 1600–73) has been cited as an alchemical tutor to Gabriel Plattes and George Starkey, and hailed as an early modern “wizard of industrial efficiency.” This study — the first that focuses on White individually — pays particular attention to White’s extraordinary reputation for furnace design and manufacture. By... [Journal Article]

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The disposal of waste from agricultural activities has been recognised as a source of environmental contamination by endocrine disrupting chemicals (EDCs). The New Zealand dairy industry produces a large volume of dairy farm effluent, which contains EDCs in the form of estrogens. Most of this dairy farm effluent is applied onto the land for disposal. Groundwater and soil contamination by... [Thesis or Dissertation]

The cyclometallated Pd compound PdCl[PPh₂CH₂CH₂CHCH₂CH₂PPh₂] 1, obtained from PdCl₂(Ph₂P(CH₂)₅PPh₂) in refluxing DMF (N,N-dimethylformamide), was characterized by NMR and X-ray single-crystal diffraction analysis. The cyclometallation of MCl₂(Ph₂P(CH₂)₅PPh₂)(M = Pd, Pt) to give 1 and its Pt(II) analogue was probed using electrospray ionisation mass spectrometry... [Journal Article]

The normally robust monoalkylated complexes [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ can be activated towards further alkylation. Dialkylated complexes [Pt₂(μ-SR)₂(P–P)₂]²⁺ (P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4 -phenylacetophenone] and... [Journal Article]

The Lewis acidic pincer with a labile triflate ligand, viz. [Pd(OTf)(PCP)] (PCP = –CH(CH₂CH₂PPh₂)₂) 1 was prepared from [PdCl(PCP)] with AgOTf. It reacts readily with neutral bidentate ligands [L = 4,4 -bipyridine (4,4 -bpy) and 1,1 -bis(diphenylphosphino)ferrocene (dppf)] to give dinuclear PCP pincers [{Pd(PCP)}₂(μ-L)][OTf]₂ (L = 4,4 -bpy, 2; dppf, 3). [PdCl(PCP)] also reacts... [Journal Article]

Electrospray mass spectrometry (ESMS) provides a rapid and convenient technique for probing the nucleophilicity of the {Pt₂S₂} butterfly core. Positive-ion electrospray mass spectra have been recorded for a wide array of aggregates incorporating various metallo-fragments into the Pt₂(PPh₃)₄(μ-S)₂ 1 moiety. Such combinatorial-like screening allowed a large number of different... [Journal Article]

Two heterometallic complexes, [Pt₂MCl(bipy)(PPh₃)₄(μ₃-S)₂][PF₆] (M = Zn, 2, Cd, 3) were synthesized from [Pt₂(PPh₃)₄(μ-S)₂] and characterized by single-crystal X-ray diffraction and electrospray ionization mass spectrometry. Two unusual square-based pyramidal (sbp) Zn(II) and Cd(II) structures are evident. VT 31P-{1H} NMR studies showed that 2 and 3 are fluxional at rt... [Journal Article]

The composition of In–GaCl₃–benzene and In–BiCl₃–GaCl₃–benzene solutions was investigated by Raman, UV/Vis, 71Ga and 115In NMR spectroscopy as well as by X-ray absorption fine structure spectroscopy (EXAFS). Indium metal was found to be soluble in GaCl₃–benzene solution at room temperature through the reduction of GaIII, producing Ga⁺ and In⁺ species. The subvalent... [Journal Article]

Sea shells, bones and teeth are three examples of Nature's unrivalled ability to produce complex hierarchical structures from simple inorganic materials. Unlike the synthetic approach of using 'exotic' materials to introduce functionality, Nature has employed structural control to maximise properties. Key to this control is the use of an organic framework to guide inorganic...

Modified Mannich reactions of amines, amino acids and a model peptide with Ph₂PH and CH₂O gave bis(diphenylphosphinomethyl)amines (Ph₂PCH₂)₂NR [R=Ph (1), CH₂CH₂OH (2), CH₂COOCH₂Ph (3), CH₂CONHCH₂COOCH₂Ph (4), CH2COOH (5)] and (Ph₂PCH₂)₂NCH₂CH₂N(CH₂PPh₂)₂ (6). Reaction with [ReBr₃(CO)₃]²⁻ under mild conditions led to...This is an author’s accepted version of an article published in the Journal of Organometallic Chemistry. Copyright © 2002 Elsevier Science B.V. All rights reserved. [Journal Article]