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421.
A new in-capillary derivatization method with naphtalene-2,3-dicarboxyaldehyde (NDA)/CN(-) has been developed for capillary electrophoresis with laser-induced fluorescence detection of brain microdialysate amino acids. Samples are sandwiched between two plugs of reagent mixture at the capillary inlet and subsequently separated. Highest derivatization yields are obtained by using a reagent to sample plug length ratio equal to 4, performing a first electrophoretic mixing followed by a zero potential amplification step before applying the separation voltage and using a NaCN to NDA concentration ratio equal to 1. This new single-step methodology allows the analysis of amino acid neurotransmitters in rat brain microdialysis samples. 相似文献
422.
Johanne Penafiel Prof. Dr. Laurent Maron Prof. Dr. Sjoerd Harder 《Angewandte Chemie (International ed. in English)》2015,54(1):201-206
Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal–alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca2+. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph2N?][Me4N+] and [Ph3C?][Me4N+]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (C?O and C?N) in the hydroamination of Ar? N?C?O and R? N?C?N? R (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated C?C bonds in H2C?CHCH2CPh2CH2NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study. 相似文献
423.
Dr. Julien Rodriguez Dr. Isabelle Beurroies Dr. Thierry Loiseau Dr. Renaud Denoyel Dr. Philip L. Llewellyn 《Angewandte Chemie (International ed. in English)》2015,54(15):4626-4630
In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal–organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL‐53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers. 相似文献
424.
Jean-Marc Ricaud Renaud Masson 《International Journal of Solids and Structures》2009,46(7-8):1599-1606
The Laplace–Carson transform classically used for homogenization of linear viscoelastic heterogeneous media yields integral formulations of effective behaviours. These are far less convenient than internal variables formulations with respect to computational aspects as well as to theoretical extensions to closely related problems such as ageing viscoelasticity. Noticing that the collocation method is usually adopted to invert the Laplace–Carson transforms, we first remark that this approximation is equivalent to an internal variables formulation which is exact in some specific situations. This result is illustrated for a two-phase composite with phases obeying a compressible maxwellian behaviour. Next, an incremental formulation allows to extend at each time step the previous general framework to ageing viscoelasticity. Finally, with the help of a creep test of a porous viscoelastic matrix reinforced with elastic inclusions, it is shown that the method yields accurate predictions (comparing to reference results provided by periodic cell finite element computations). 相似文献
425.
Valeria Tafintseva Tiril Aurora Lintvedt Johanne Heitmann Solheim Boris Zimmermann Hafeez Ur Rehman Vesa Virtanen Rubina Shaikh Ervin Nippolainen Isaac Afara Simo Saarakkala Lassi Rieppo Patrick Krebs Polina Fomina Boris Mizaikoff Achim Kohler 《Molecules (Basel, Switzerland)》2022,27(3)
The aim of the study was to optimize preprocessing of sparse infrared spectral data. The sparse data were obtained by reducing broadband Fourier transform infrared attenuated total reflectance spectra of bovine and human cartilage, as well as of simulated spectral data, comprising several thousand spectral variables into datasets comprising only seven spectral variables. Different preprocessing approaches were compared, including simple baseline correction and normalization procedures, and model-based preprocessing, such as multiplicative signal correction (MSC). The optimal preprocessing was selected based on the quality of classification models established by partial least squares discriminant analysis for discriminating healthy and damaged cartilage samples. The best results for the sparse data were obtained by preprocessing using a baseline offset correction at 1800 cm−1, followed by peak normalization at 850 cm−1 and preprocessing by MSC. 相似文献
426.
Infrared (IR) spectroscopy was used to study the surface (by means of external reflection) and the bulk (by means of transmission measurements on microtomed slices) of specimens obtained by injection moulding of a commercial polyamide-6 clay-based nanocomposite material (NCH = nylon clay hybrid) at different mould temperatures and with different part geometries. Comparisons were made with equivalent non-reinforced polymer (PA-6). For the PA-6, the mould temperature influences the crystalline structure, with the γ phase predominating at 50°C and the α phase at 80°C. However, in the NCH material the ( phase is favoured, even at 80°C. In all cases the crystallinity increases on going from the surface to the core. The polymer chains are oriented in the flow direction, and the orientation is higher for parts with more elongated shapes. It does not vary greatly across the part thickness, except for a thin surface layer, where it is significantly higher. Both at the surface and in the bulk, the crystalline phase orientation is higher for the NCH than for the PA-6. 相似文献
427.
Sauvinet V Parrot S Benturquia N Bravo-Moratón E Renaud B Denoroy L 《Electrophoresis》2003,24(18):3187-3196
gamma-Aminobutyric acid (GABA), glutamate (Glu), and L-aspartate (L-Asp) are three major amino acid neurotransmitters in the central nervous system. In this work, a method for the separation of these three neurotransmitters in brain microdialysis samples using a commercially available capillary electrophoresis (CE) system has been developed. Molecules were tagged on their primary amine function with the fluorogene agent naphthalene-2,3-dicarboxaldehyde (NDA), and, after separation by micellar electrokinetic chromatography, were detected by laser-induced fluorescence using a 442 nm helium-cadmium laser. The separation conditions for the analysis of derivatized neurotransmitters in standard solutions and microdialysates have been optimized, and this method has been validated on both pharmacological and analytical basis. The separation of GABA, Glu, and L-Asp takes less than 10 min by using a 75 mmol/L borate buffer, pH 9.2, containing 70 mmol/L SDS and 10 mmol/L hydroxypropyl-beta-cyclodextrin and + 25 kV voltage. The detection limits were 3, 15 nmol/L and, 5 nmol/L for GABA, Glu, and L-Asp, respectively. Moreover, submicroliter samples can be analyzed. This method allows a simple, rapid and accurate measurement of the three amino acid neurotransmitters for the in vivo brain monitoring using microdialysis sampling. 相似文献
428.
Two preparatively attractive methods for the azidation of alkyl radicals are described. Secondary and tertiary alkyl iodides and dithiocarbonates are easily converted into the corresponding azides, either by reaction with ethanesulfonyl azide in the presence of dilauroyl peroxide, or by treatment with benzenesulfonyl azide and hexabutylditin in the presence of a radical initiator. Interestingly, intramolecular tandem radical cyclization-azidation processes can be performed in high yields. 相似文献
429.
430.