Carbon disulfide binding at dinuclear and mononuclear nickel complexes ligated by a redox-active ligand: iminopyridine serving as an accumulator of redox equivalents for the activation of heteroallenes

The dinuclear complex Ni(2)L(1)(η(2)-CS(2))(2) (), featuring iminopyridine ligation, is prepared by COD substitution from Ni(2)L(1)(COD)(2) (). Spectroscopic, structural, and theoretical data reveals significant activation of the metal-bound C-S bonds, as well as the different oxidation states of the iminopyridine in (1-) and (0).     

Estimation of signal backgrounds on multivariate loadings improves model generation in face of complex variation in backgrounds and constituents

The present study is designed to understand further implications of using multivariate loadings for the correction of background signal, which has previously been shown to be highly reproducible even for very low quality signals. Singular value decomposition (SVD)‐based background correction was compared with the traditional per‐signal paradigm for a biomedical dataset to generate qualitative and quantitative models. The qualitative effect on a principal component analysis model and the quantitative effect on a partial least square regression model were assessed for these background correction methods. The chosen quantitative parameter was the concentration of a pathologically relevant protein modification, pentosidine. Of the approaches tested, the SVD‐based paradigm provided the regression model with the highest correlations, highest accuracy (lowest standard error of prediction) and repeatability (lowest sampling error). Contrasted against the traditional approaches, it was determined that the improved accuracy and repeatability of the SVD‐based approach arises from its ability to simultaneously handle very complex background shapes alongside the complex variation in biochemical species that resulted in Raman signals with incompatible baseline regions. A better understanding of the interaction of SVD‐based baseline correction, and data will give the reader more insight into the potential applicability of the procedure for other datasets. Copyright © 2012 John Wiley & Sons, Ltd.     

Methods for computing lower bounds to eigenvalues of self-adjoint operators

Summary. New approaches for computing tight lower bounds to the eigenvalues of a class of semibounded self-adjoint operators are presented that require comparatively little a priori spectral information and permit the effective use of (among others) finite-element trial functions. A variant of the method of intermediate problems making use of operator decompositions having the form is reviewed and then developed into a new framework based on recent inertia results in the Weinstein-Aronszajn theory. This framework provides greater flexibility in analysis and permits the formulation of a final computational task involving sparse, well-structured matrices. Although our derivation is based on an intermediate problem formulation, our results may be specialized to obtain either the Temple-Lehmann method or Weinberger's matrix method. Received December 12, 1992 / Revised version received October 5, 1994     

Lifting of Nichols algebras of typeB 2

We compute liftings of the Nichols algebra of a Yetter-Drinfeld module of Cartan typeB ₂ subject to the small restriction that the diagnonal elements of the braiding matrix are primitiventh roots of 1 with oddn≠5. As well, we compute the liftings of a Nichols algebra of Cartan typeA ₂ if the diagonal elements of the braiding matrix are cube roots of 1; this case was not completely covered in previous work of Andruskiewitsch and Schneider. We study the problem of when the liftings of a given Nichols algebra are quasi-isomorphic. The Appendix (with I. Rutherford) contains a generalization of the quantum binomial formula. This formula was used in the computation of liftings of typeB ₂ but is also of interest independent of these results. With an appendix “A generalization of theq-binomial theorem” with Ian Rutherford, Department of Mathematics and Computer Science, Mount Allison University, Sackville, N.B., Canada E4L 1E6. Research partially supported by NSERC. A visit to University of Bucharest in 1999 was partially supported by CNCSIS, Grant C12. She would like to thank the department for their warm hospitality. Received partial support from CNCSIS, Grants C12 and 199. Thanks to Mount Allison University for their hospitality in June 1999.     

The thermal degradation of polysiloxanes: Part 5—Synthesis,characterisation and thermal analysis of poly(tetramethyl-p-silphenylene siloxane) and copolymers with dimethylsiloxane

Poly(tetramethyl-p-silphenylene siloxane) and a series of copolymers with dimethylsiloxane have been prepared and characterised by means of ir and nmr spectroscopy and number average molecular weight measurements. Thermal gravimetry (TG) and Thermal Volatilisation Analysis (TVA) have been used to demonstrate the relationships which exist between stability and composition.     

Direct absorption measurement of the spin—orbit splitting of the ground state in atomic fluorine

We have measured the three hyperfine components of the spin—orbit split (²P_{$\text{3}\text{2}$} → ²P_{$\text{1}\text{2}$}) ground state in atomic fluorine by diode laser absorption spectroscopy. The measurement improves the accuracy of the two lines previously reported (404.175 and 403.969 cm^?1), with the third line at 404.210 cm^?1. This confirms the spacing of the hyperfine components measured by EPR, and establishes diode laser absorption as a viable technique for determining F-atom concentrations.     

Increasing throughput and information content for in vitro drug metabolism experiments using ultra-performance liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer

The field of drug metabolism has been revolutionized by liquid chromatography/mass spectrometry (LC/MS) applications with new technologies such as triple quadrupoles, ion traps and time-of-flight (ToF) instrumentation. Over the years, these developments have often relied on the improvements to the mass spectrometer hardware and software, which has allowed users to benefit from lower levels of detection and ease-of-use. One area in which the development pace has been slower is in high-performance liquid chromatography (HPLC). In the case of metabolite identification, where there are many challenges due to the complex nature of the biological matrices and the diversity of the metabolites produced, there is a need to obtain the most accurate data possible. Reactive or toxic metabolites need to be detected and identified as early as possible in the drug discovery process, in order to reduce the very costly attrition of compounds in late-phase development. High-resolution, exact mass measurement plays a very important role in metabolite identification because it allows the elimination of false positives and the determination of non-trivial metabolites in a much faster throughput environment than any other standard current methodology available to this field. By improving the chromatographic resolution, increased peak capacity can be achieved with a reduction in the number of co-eluting species leading to superior separations. The overall enhancement in the chromatographic resolution and peak capacity is transferred into a net reduction in ion suppression leading to an improvement in the MS sensitivity. To investigate this, a number of in vitro samples were analyzed using an ultra-performance liquid chromatography (UPLC) system, with columns packed with porous 1.7 mum particles, coupled to a hybrid quadrupole time-of-flight (ToF) mass spectrometer. This technique showed very clear examples for fundamental gains in sensitivity, chromatographic resolution and speed of analysis, which are all important factors for the demands of today's HTS in discovery.     

独居石微晶玻璃中玻璃相含量的红外光谱定量测定

独居石微晶玻璃由偏磷酸盐玻璃和独居石两相组成。玻璃和独居石的红外吸收谱带彼此不相重叠,且1275和616cm~(-1)谱带的吸收强度随玻璃相的含量变化而变化。两谱带的对数吸光度比值与玻璃相含量(w％)的相关系数r=0.9975,其回归方程为y=48.356 25.93x。合成独居石的IR谱中952和616cm~(-1)谱带的吸光度比值也随不同的Ce_2O_3/La_2O_3比值规律变化。其r=0.9917,回归方程为y=0.2211exp(0.0221x)。高的相关性表明IR技术可在磷酸盐微晶玻璃物相定量分析中得到实际应用。