Application of Response Surface Methodology to laser-induced breakdown spectroscopy: Influences of hardware configuration

Response Surface Methodology (RSM) was employed to optimize LIBS analysis of single crystal silicon at atmospheric pressure and under vacuum conditions (pressure  10^− 6 mbar). Multivariate analysis software (StatGraphics 5.1) was used to design and analyze several multi-level, full factorial RSM experiments. A Quality Factor (QF) was conceived as the response parameter for the experiments, representing the quality of the LIBS spectrum captured for a given hardware configuration. The QF enabled the hardware configuration to be adjusted so that a best compromise between resolution, signal intensity and signal noise could be achieved. The effect on the QF of simultaneously adjusting spectrometer gain, gate delay, gate width, lens position and spectrometer slit width was investigated, and the conditions yielding the best QF determined.     

Modelling photoionised plasma experiments

A low runtime DCA model, ALICE, is used to model the few available photoionised plasma experiments that use both laser and pulse power devices. Modelling photoionised plasmas provides a computationally intensive problem which must therefore be solved by careful approximation emphasising the underlying physics. We will demonstrate the relative importance of the completeness of the set of configurations considered compared to the set of rates used in the model and draw conclusions as to how ALICE and other models may be improved for future use.     

Orbital correlations in doped manganites

We review our recent X-ray scattering studies of charge and orbital order in doped manganites, with specific emphasis on the role of orbital correlations in Pr_1-xCa_xMnO₃. For x=0.25, we find an orbital structure indistinguishable from the undoped structure and long-range orbital order at low temperatures. For dopings 0.3≤x≤0.5, we find scattering consistent with a charge and orbitally ordered CE-type structure. While in each case the charge order peaks are resolution limited, the orbital order exhibits only short-range correlations. We report the doping dependence of the correlation length and discuss the connection between the orbital correlations and the finite magnetic correlation length observed on the Mn³⁺ sublattice with neutron-scattering techniques. The physical origin of these domains, which appear to be isotropic, remains unclear. We find that weak orbital correlations persist well above the phase transition, with a correlation length of 1–2 lattice constants at high temperatures. Significantly, we observe similar correlations at high temperatures in La_0.7Ca_0.3MnO₃, which does not have an orbitally ordered ground state, and we conclude that such correlations are robust to variations in the relative strength of the electron–phonon coupling. Received: 22 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

Extreme-Value Moment Goodness-of-Fit Tests

A general goodness-of-fit test for scale-parameter families of distributions is introduced, which is based on quotients of expected sample minima. The test is independent of the mean of the distribution, and, in applications to testing for exponentiality of data, compares favorably to other goodness-of-fit tests for exponentiality based on the empirical distribution function, regression methods and correlation statistics. The new minimal-moment method uses ratios of easily-calculated, unbiased, strongly consistent U-statistics, and the general technique can be used to test many standard composite null hypotheses such as exponentiality, normality or uniformity (as well as simple null hypotheses).     

Determination of organometallic compounds by capillar gas chromatography – inductively coupled plasma mass spectrometry

The separation and detection of volatile organometallic compounds containing tin, iron, and nickel has been achieved using capillary GC–inductively coupled plasma–mass spectrometry (capillary GC-ICP-MS). Detection limits range from 3.0 to 7.0 pg/s. The presence of volatile organotin compounds in a harbor sediment has been confirmed. The retention range of the organometallic compounds analyzed by capillary GC-ICP-MS has been extended considerably beyond that possible in earlier studies (retention indices up to 3400).     

Cyclophane bis(sulfoxides) a thermal analysis study

A thermogravimetry study of a series of cyclophane bis(sulfoxides) (1–6) has shown that thermal decomposition of these compounds occurs in two stages with a stepwise loss of the sulfoxide groups at well defined decomposition temperatures. The stepwise thermal cleavage has been rationalized in terms of the stereochemistry of the sulfoxide groups and the strain associated with the resultant elimination products.

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Zusammenfassung Eine thermogravimetrische Studie einer Reihe von Cyclophan-bis(sulphoxiden) (1–6) zeigte, dass die thermische Zersetzung dieser Verbindungen in zwei Stufen unter stufenweisem Verlust der Sulphoxidgruppen bei gut definierten Zersetzungstemperaturen vor sich geht. Die stufenweise thermische Spaltung wurde aufgrund der Stereochemie der Sulphoxidgruppen und der mit den resultierenden Eliminationsprodukten verbundenen Belastung erörtert.

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Résumé Une étude thermogravimétrique d'une série de bis (sulfoxydes) de cyclophane (1–6) a montré que la décomposition thermique de ces composés se déroule en deux étapes avec pertes graduelles des groupes sulfoxydes à des températures de décomposition bien définies. Le clivage thermique graduel est expliqué par la stéréochimie des groupes sulfoxydes et la contrainte associée aux produits éliminés.

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A DTA study of phenols

A comprehensive DTA study is reported of 17 halophenols and of the corresponding p-nitrobenzoylchloride 3,5-dinitrobenzoylchloride and p-phenylazobenzoylchloride derivatives, prepared “in-situ”by heating intimate mixtures of phenol and acid chloride in the DTA system. The thermal analysis data, in particular, the derivative formation temperatures, are interpreted in terms of the inductive, mesomeric and steric effects associated with the ring substituents of the phenol and acid chloride and the extent of inter- and intramolecular hydrogen-bonding existing in these systems. The DTA data collectively provide a reference base for the identification and characterization of halophenols via thermal analysis.     

Bacterial lantibiotics: strategies to improve therapeutic potential

Lantibiotics are ribosomally-synthesised antimicrobial peptides produced by Gram-positive bacteria that are characterised by the presence of lanthionine and/or methyllanthionine residues. Other unusual post-translationally modified amino acids, most frequently dehydroalanine and dehydrobutyrine, can also be present. While it has been frequently suggested that these peptides have the potential to be utilised in a wide range of medical applications, to date no actual therapeutic applications have been convincingly described. More recently, however, they have been the focus of much attention as a consequence of improved biotechnological capabilities, an improved understanding of lantibiotic biosynthesis and mode of action, and their high specific activity against multi-drug resistant bacteria. This review concerns the fundamental analyses that have revealed the importance of individual amino acids in these peptides and has permitted the implementation of rational mutagenesis strategies ('intelligenetics') to alter individual residues with a view to ultimately widening the active pH range, improve stability, and enhance binding to cell wall targets with the ultimate aim of optimising their antimicrobial activity. It is hoped that as a consequence of this improved knowledge the most suitable application of individual lantibiotics will become apparent. It should also prove possible, in the near future, to generate tailor-made lantibiotics and utilise biosynthetic enzymes to incorporate modified amino acids into non-lantibiotic peptides. In the shorter term, the extensive characterisation of lantibiotics will be instrumental in reassuring drug industry regulators of their safety and facilitate the widespread application of these novel antimicrobial agents in medicine.     

Thermal stability of the crystallisation nucleant

The 2,2',4,4',6,6'hexanitrostilbene, HNS, nucleant, used in the crystallisation of 2,4,6,trinitrotoluene, TNT, was precipitated from molten TNT and examined by differential scanning calorimetry, DSC, at several stages during purification by vacuum sublimation. During purification a broad endotherm, associated with nucleant decomposition, which could be resolved into two endotherms, depending on the sublimation temperature, was observed. Pure nucleant prepared at 70C showed a similar behaviour during thermal annealing for extended periods of time at >85C. Thus TNT, retained in the recrystallised HNS nucleant, may be migrating during the purification process or may occupy a range of lattice sites, which exhibit different activation energies for migration to the surface of the solid during thermal decomposition of the nucleant. Loss of TNT from the nucleant, during purification, could produce some free HNS. The activation energy for nucleant decomposition, which may be a two-stage processes with the initial mobility of the TNT being the limiting reaction, was estimated to be 210 kJ mol^–. The lattice sites available for the TNT in the host HNS nucleant require elucidation and are the subject of further studies to be published at a later date.