Structural properties of a family of hydrogen-bonded co-crystals formed between gemfibrozil and hydroxy derivatives of t-butylamine, determined directly from powder X-ray diffraction data

We report the formation and structural properties of co-crystals containing gemfibrozil and hydroxy derivatives of t-butylamine H2NC(CH3)3-n(CH2OH)n, with n=0, 1, 2 and 3. In each case, a 1:1 co-crystal is formed, with transfer of a proton from the carboxylic acid group of gemfibrozil to the amino group of the t-butylamine derivative. All of the co-crystal materials prepared are polycrystalline powders, and do not contain single crystals of suitable size and/or quality for single crystal X-ray diffraction studies. Structure determination of these materials has been carried out directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm technique for structure solution followed by Rietveld refinement. The structural chemistry of this series of co-crystal materials reveals well-defined structural trends within the first three members of the family (n=0, 1, 2), but significantly contrasting structural properties for the member with n=3. © 2007 Elsevier Inc. All rights reserved.

Some historical extracts relevant to the discovery and application of the diffraction of X-rays by crystals to contribute to the centennial celebration and the International Year of Crystallography

Illustrative extracts from the writings of Paul P. Ewald and of Max von Laue are presented. The latter in turn contains extensive text contributions from William Lawrence Bragg. These selections we have chosen so as to indicate the nature of the discovery of X-ray diffraction from crystals (experiments undertaken by Friedrich, Knipping and von Laue) and its early and prompt application in crystal structure analyses (by William Henry Bragg and William Lawrence Bragg). The platform for these discoveries was provided by a macroscopic physics problem dealt with by Ewald in his doctoral thesis with Arnold Sommerfeld in the Munich Physics Department, which is also where von Laue was based. W.L. Bragg was a student in Cambridge who used Trinity College Cambridge as his address on his early papers; experimental work was done by him in the Cavendish Laboratory, Cambridge, and also with his father, W.H. Bragg, in the Leeds University Physics Department. Of further historical interest is the award of an Honorary DSc (Doctor of Science) degree in 1936 to Max von Laue by the University of Manchester, UK, while William Lawrence Bragg was Langworthy Professor of Physics there. © 2012 Copyright Taylor and Francis Group, LLC.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Information transfer for multi-trauma patients on discharge from the emergency department : mixed-method narrative review

Aim. This paper is a report of a review conducted to identify (a) best practice in information transfer from the emergency department for multi-trauma patients; (b) conduits and barriers to information transfer in trauma care and related settings; and (c) interventions that have an impact on information communication at handover and beyond. Background. Information transfer is integral to effective trauma care, and communication breakdown results in important challenges to this. However, evidence of adequacy of structures and processes to ensure transfer of patient information through the acute phase of trauma care is limited. Data sources. Papers were sourced from a search of 12 online databases and scanning references from relevant papers for 1990–2009. Review methods. The review was conducted according to the University of York’s Centre for Reviews and Dissemination guidelines. Studies were included if they concerned issues that influenced information transfer for patients in healthcare settings. Results. Forty-five research papers, four literature reviews and one policy statement were found to be relevant to parts of the topic, but not all of it. The main issues emerging concerned the impact of communication breakdown in some form, and included communication issues within trauma team processes, lack of structure and clarity during handovers including missing, irrelevant and inaccurate information, distractions and poorly documented care. Conclusion. Many factors influence information transfer but are poorly identified in relation to trauma care. The measurement of information transfer, which is integral to patient handover, has not been the focus of research to date. Nonetheless, documented patient information is considered evidence of care and a resource that affects continuing care.

A Raman spectroscopic study of M2+M3+ sulfate minerals, römerite Fe2+Fe23+ (SO4)4· 14H2O and botryogen Mg2+Fe3+ (SO4)2(OH)·7H2O

The mixed valency (M2+M3+) sulphate minerals, römerite Fe2+Fe23+(SO4)4•14H2O and botryogen Mg2+Fe3+(SO4)2(OH).7H2O have been studied by Raman spectroscopy. The Raman spectra of the two types of crystals proved very similar but not identical. The observation of two symmetric stretching modes confirmed the presence of the two non-equivalent sulphate units in the römerite structure. The observation of multiple bands in the antisymmetric stretching region and in the bending regions proves the symmetry of the sulphate anion is significantly reduced in the römerite structure. The number of Raman bands related to the (SO4)2- symmetric and antisymmetric vibrations support the X-ray single crystal structure conclusion that two symmetrically distinct S6+ are present in the structure of botryogen. Römerite is a mineral of environmental significance as it is commonly found in tailings and dumps.

Deformation behaviours of coarse-grained and nanocrystalline Mg-5wt% Al alloys

Magnesium alloys have been of growing interest to various engineering applications, such as the automobile, aerospace, communication and computer industries due to their low density, high specific strength, good machineability and availability as compared with other structural materials. However, most Mg alloys suffer from poor plasticity due to their Hexagonal Close Packed structure. Grain refinement has been proved to be an effective method to enhance the strength and alter the ductility of the materials. Several methods have been proposed to produce materials with nanocrystalline grain structures. So far, most of the research work on nanocrystalline materials has been carried out on Face-Centered Cubic and Body-Centered Cubic metals. However, there has been little investigation of nanocrystalline Mg alloys. In this study, bulk coarse-grained and nanocrystalline Mg alloys were fabricated by a mechanical alloying method. The mixed powder of Mg chips and Al powder was mechanically milled under argon atmosphere for different durations of 0 hours (MA0), 10 hours (MA10), 20 hours (MA20), 30 hours (MA30) and 40 hours (MA40), followed by compaction and sintering. Then the sintered billets were hot-extruded into metallic rods with a 7 mm diameter. The obtained Mg alloys have a nominal composition of Mg–5wt% Al, with grain sizes ranging from 13 μm down to 50 nm, depending on the milling durations. The microstructure characterization and evolution after deformation were carried out by means of Optical microscopy, X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Scanning Probe Microscopy and Neutron Diffraction techniques. Nanoindentaion, compression and micro-compression tests on micro-pillars were used to study the size effects on the mechanical behaviour of the Mg alloys. Two kinds of size effects on the mechanical behaviours and deformation mechanisms were investigated: grain size effect and sample size effect. The nanoindentation tests were composed of constant strain rate, constant loading rate and indentation creep tests. The normally reported indentation size effect in single crystal and coarse-grained crystals was observed in both the coarse-grained and nanocrystalline Mg alloys. Since the indentation size effect is correlated to the Geometrically Necessary Dislocations under the indenter to accommodate the plastic deformation, the good agreement between the experimental results and the Indentation Size Effect model indicated that, in the current nanocrystalline MA20 and MA30, the dislocation plasticity was still the dominant deformation mechanism. Significant hardness enhancement with decreasing grain size, down to 58 nm, was found in the nanocrystalline Mg alloys. Further reduction of grain size would lead to a drop in the hardness values. The failure of grain refinement strengthening with the relatively high strain rate sensitivity of nanocrystalline Mg alloys suggested a change in the deformation mechanism. Indentation creep tests showed that the stress exponent was dependent on the loading rate during the loading section of the indentation, which was related to the dislocation structures before the creep starts. The influence of grain size on the mechanical behaviour and strength of extruded coarse-grained and nanocrystalline Mg alloys were investigated using uniaxial compression tests. The macroscopic response of the Mg alloys transited from strain hardening to strain softening behaviour, with grain size reduced from 13 ìm to 50 nm. The strain hardening was related to the twinning induced hardening and dislocation hardening effect, while the strain softening was attributed to the localized deformation in the nanocrystalline grains. The tension–compression yield asymmetry was noticed in the nanocrystalline region, demonstrating the twinning effect in the ultra-fine-grained and nanocrystalline region. The relationship k tensions < k compression failed in the nanocrystalline Mg alloys; this was attributed to the twofold effect of grain size on twinning. The nanocrystalline Mg alloys were found to exhibit increased strain rate sensitivity with decreasing grain size, with strain rate ranging from 0.0001/s to 0.01/s. Strain rate sensitivity of coarse-grained MA0 was increased by more than 10 times in MA40. The Hall-Petch relationship broke down at a critical grain size in the nanocrystalline region. The breakdown of the Hall-Petch relationship and the increased strain rate sensitivity were due to the localized dislocation activities (generalization and annihilation at grain boundaries) and the more significant contribution from grain boundary mediated mechanisms. In the micro-compression tests, the sample size effects on the mechanical behaviours were studied on MA0, MA20 and MA40 micro-pillars. In contrast to the bulk samples under compression, the stress-strain curves of MA0 and MA20 micro-pillars were characterized with a number of discrete strain burst events separated by nearly elastic strain segments. Unlike MA0 and MA20, the stress-strain curves of MA40 micro-pillars were smooth, without obvious strain bursts. The deformation mechanisms of the MA0 and MA20 micro-pillars under micro-compression tests were considered to be initially dominated by deformation twinning, followed by dislocation mechanisms. For MA40 pillars, the deformation mechanisms were believed to be localized dislocation activities and grain boundary related mechanisms. The strain hardening behaviours of the micro-pillars suggested that the grain boundaries in the nanocrystalline micro-pillars would reduce the source (nucleation sources for twins/dislocations) starvation hardening effect. The power law relationship of the yield strength on pillar dimensions in MA0, MA20 supported the fact that the twinning mechanism was correlated to the pre-existing defects, which can promote the nucleation of the twins. Then, we provided a latitudinal comparison of the results and conclusions derived from the different techniques used for testing the coarse-grained and nanocrystalline Mg alloy; this helps to better understand the deformation mechanisms of the Mg alloys as a whole. At the end, we summarized the thesis and highlighted the conclusions, contributions, innovations and outcomes of the research. Finally, it outlined recommendations for future work.

Mixed methods research approach to the development and review of competency standards for dietitians

Aim: Competency standards support a range of professional activities including the accreditation of university courses. Reviewing these standards is essential to ensure universities continue to produce well equipped graduates, who can meet the challenge of changing workforce requirements. This paper has two aims: a) to provide an overview of the methodological approaches utilised for compilation and review of the Competency Standards for Dietetics and b) to evaluate the Dietitians Association of Australia’s Competency Standards and capture emerging and contemporary dietetic practice. Methods: A literature review of the methods used to develop Competency Standards for dietitians in Australia, including entry level, advanced level and DAA Fellow competencies and other specific areas of competency, such as public health nutrition and nutrition education is outlined and compared to other allied health professions. The mixed methods methodology used in the most recent review is described in more detail. Results: The history of Dietetic Competency Standards development and review in Australia is compared to dietetic Competency Standards internationally and within other health professions in Australia. The political context in which these standards have been developed in Australia and which has determined their format is also discussed. The results of the most recent Competency Standards review are reported to highlight emerging practice in Australia. Conclusion: The mixed methods approach used in this review provides rich data about contemporary dietetic practice. Our view supports a planned review of all Competency Standards to ensure practice informs education and credentialling and we recommend the Dietitians Association of Australia consider this in future

The role of randomly mixed-layered chlorite/smectite in the transformation of smectite to chlorite

Vesicular and groundmass phyllosilicates in a hydrothermally altered basalt from the Point Sal ophiolite, California, have been studied using transmission electron microscopy (TEM). Pore-filling phyllosilicates are texturally characterized as having coherent, relatively thick and defect-free crystals of chlorite (14 Å) with occasional 24-Å periodicities. Groundmass phyllosilicates are texturally characterized as 1) randomly oriented crystals up to 200 Å in width and 2) larger, more coherent crystals up to 1000 Å in width. Small crystallites contain predominantly 14-Å layers with some 24-Å units. Large crystals show randomly interlayered chlorite/smectite (C/S), with approximately 50% chlorite on average. Adjacent smectite-like layers are not uncommon in the groundmass phyllosilicates. Electron microprobe analyses show that Fe/Mg ratios of both groundmass and vesicular phyllosilicates are fairly constant. Termination of brucite-like interlayers has been identified in some of the TEM images. The transformation mechanisms represented by these layer terminations are 1) growth of a brucite-like interlayer within smectite interlayer regions and 2) the dissolution and reprecipitation of elements to form chlorite layers. Both mechanisms require an increase in volume as smectite transforms to chlorite. The data, combined with that from previously published reports, suggest that randomly interlayered C/S is a metastable phase formed in microenvironments with low water/rock ratios. Chlorite forms in microenvironments in the same sample dominated by higher water/rock ratios. The relatively constant number of Mg's in the structure (Mg#) of both structures indicates that in both microenvironments the bulk rock composition has influence over the composition of phyllosilicates.

Integrated TEM, XRD and electron-microprobe investigation of mixed-layer chlorite smectite from the Point-Sal ophiolite, California

Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite-smectite identified for each specimen: (i) L2036 almost-equal-to 50%, (ii) L2035 almost-equal-to 70 and 20%, (iii) 1A-13 almost-equal-to 70%, (iv) 1B-42 almost-equal-to 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that 'chlorite' analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate. Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-angstrom layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-angstrom periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (< 0.5)-smectite exists. Images of lower lava sample 1B-55 show predominantly 14-angstrom layers. Units of 24 angstrom tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.

Ordered mixed-layer structures in the Mighei carbonaceous chondrite matrix

High resolution transmission electron microscopy of the Mighei carbonaceous chondrite matrix has revealed the presence of a new mixed layer structure material. This mixed-layer material consists of an ordered arrangement of serpentine-type (S) and brucite-type (B) layers in the sequence ... SBBSBB. ... Electron diffraction and imaging techniques show that the basal periodicity is ~ 17 Å. Discrete crystals of SBB-type material are typically curved, of small size (<1 μm) and show structural variations similar to the serpentine group minerals. Mixed-layer material also occurs in association with planar serpentine. Characteristics of SBB-type material are not consistent with known terrestrial mixed-layer clay minerals. Evidence for formation by a condensation event or by subsequent alteration of preexisting material is not yet apparent. © 1982.

YBa2Cu3O7-x films on yttria-stabilized ZrO2 substrates : influence of the substrate morphology

c-axis-oriented YBa2Cu3O7-x (YBCO) thin films were laser deposited on (001) yttria-stabilized ZrO2 (YSZ) substrates with different surface morphologies. The in-plane orientation of the films on smooth substrates was sensitive to the deposition conditions, often resulting in mixed orientations. However, a strongly dominating [110] YBCO//[110]YSZ orientation was obtained at a deposition temperature of 770°C. Films on substrates with surface steps, induced by depositing a homoepitaxial buffer layer or by thermally annealing the substrate, had a [110]YBCO//[100]YSZ orientation when deposited at the same temperature. It was concluded that the [110]YBCO//[100] YSZ orientation was promoted by a graphoepitaxial mechanism. Films prepared under identical conditions on smooth and stepped substrates grew with extended c axes on the former. It is proposed that the extension can be induced by disorder, invoked by a low oxygen pressure and a low density of adsorption sites. The disorder may be eliminated by either an increase of the oxygen pressure or an increase of the density of adsorption sites in the form of steps. The film microstructure influenced the microwave surface resistance, which was similar for films with one exclusive in-plane orientation and higher for films with mixed orientations. The films on the stepped surfaces had superior superconducting properties; inductive measurements gave a Tc onset of 88 K, a ΔT(90%-10%) c of 0.2 K, and the transport jc was 1.5×106 A/cm2 at 83 K, for films on substrates with homoepitaxial buffer layers.

Vibrational spectroscopy of the borate mineral gaudefroyite Ca4Mn3+3-x(BO3)3(CO3)(O,OH) from N’Chwaning II mine, Kalahari, Republic of South Africa

Gaudefroyite Ca4Mn3+3-x(BO3)3(CO3)(O,OH)3 is an unusual mineral containing both borate and carbonate groups and is found in the oxidation zones of manganese minerals, and it is black in color. Vibrational spectroscopy has been used to explore the molecular structure of gaudefroyite. Gaudefroyite crystals are short dipyramidal or prismatic with prominent pyramidal terminations, to 5 cm. Two very sharp Raman bands at 927 and 1076 cm-1are assigned to trigonal borate and carbonate respectively. Broad Raman bands at 1194, 1219 and 1281 cm-1 are attributed to BOH in-plane bending modes. Raman bands at 649 and 670 cm-1 are assigned to the bending modes of trigonal and tetrahedral boron. Infrared spectroscopy supports these band assignments. Raman bands in the OH stretching region are of a low intensity. The combination of Raman and infrared spectroscopy enables the assessment of the molecular structure of gaudefroyite to be made.

Synthesis and spectroscopic characterization of magnesium oxalate nano-crystals

Synthesis of MgC2O4⋅2H2O nano particles was carried out by thermal double decomposition of solutions of oxalic acid dihydrate (C2H2O4⋅2H2O) and Mg(OAc)2⋅4H2O employing CATA-2R microwave reactor. Structural elucidation was carried out by employing X-ray diffraction (XRD), particle size and shape were studied by transmission electron microscopy (TEM) and nature of bonding was investigated by optical absorption and near-infrared (NIR) spectral studies. The powder resulting from this method is pure and possesses distorted rhombic octahedral structure. The synthesized nano rod is 80 nm in diameter and 549 nm in length.