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991.
Wagner FR Bezugly V Kohout M Grin Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(20):5724-5741
The novel functional electron localizability indicator is a useful tool for investigating chemical bonding in molecules and solids. In contrast to the traditional electron localization function (ELF), the electron localizability indicator is shown to be exactly decomposable into partial orbital contributions even though it displays at the single-determinantal level of theory the same topology as the ELF. This approach is generally valid for molecules and crystals at either the single-determinantal or the explicitly correlated level of theory. The advantages of the new approach are illustrated for the argon atom, homonuclear dimers N2 and F2, unsaturated hydrocarbons C2H4 and C6H6, and the transition-metal-containing molecules Sc(2)2+ and TiF4. 相似文献
992.
Short polypeptides with four pentad repeats, (VPGVG)(4) and (VPAVG)(4), were synthesised by manual fluorenylmethoxycarbonyl/tert-butyl (Fmoc/t-Bu) solid phase peptide synthesis using a convergent approach. In the next step, the peptides were coupled via their N-terminus with activated semi-telechelic poly(ethylene glycol) O-(N-Fmoc-2-aminoethyl)-O'-(2-carboxyethyl)undeca(ethylene glycol) (Fmoc-PEG-COOH) to yield monodisperse Fmoc-PEG-peptide diblock copolymer. Both the presence of the terminal hydrophobic Fmoc group and the hydrophilic PEG chain in the copolymers were shown to play a crucial role in their self-associative behaviour, leading to reversible formation of supramolecular thermoresponsive assemblies. The peptides and their PEG derivatives were characterised by HPLC, NMR and MALDI-TOF MS. The associative behaviour of the peptides and their PEG derivatives was studied by dynamic light scattering, MAS NMR and phase contrast microscopy. [image: see text] 相似文献
993.
An assay of L-tyrosine (Tyr) hydroxylating activity operating in lincomycin biosynthesis is described. The assay development consisted of HPLC procedure development, assessing the effect of reaction mixture components on non-enzymatic Dopa and Tyr oxidation, and sample stability evaluation. The HPLC procedure with isocratic elution and fluorescence detection was developed and validated. The method showed a wide linear range of Dopa determination of 0.125-25 micromol/L with lower limit of quantification (LLOQ) of 0.125 micromol/L, RSD of 7.2% and accuracy of 101.7%. The studied linear range of Tyr was 15.625 mmol/L to 500 mmol/L with LLOQ of 15.625 mmol/L, RSD of 1.1%, and accuracy of 98.1%. Recoveries for Dopa and Tyr were 100.66 +/- 0.89% and 94.76 +/- 0.94%, respectively. The inter- and intra-day accuracies and precisions were all within 10%. Samples of the reaction mixture were stable for at least 24 h at room temperature (RT) and 28 days at -20 degrees C. The method was tested for the enzyme activity monitoring in purified as well as crude preparations and enabled micro preparation of the enzyme product during confirmation of its identity. The influence of pH and ascorbic acid content in reaction mixture was studied with respect to non-enzymatic Tyr oxidation. 相似文献
994.
E. V. Budarina T. S. Dolgushina M. L. Petrov N. N. Labeish A. A. Kol’tsov V. K. Bel’skii 《Russian Journal of Organic Chemistry》2007,43(10):1516-1525
Reactions of 4-methyl-1,3-thiazole-2(3H)-thiones with various C,N-disubstituted nitrile imines occurred by the common [3+2]-cycloaddition scheme leading to the formation in general of stable spiro compounds. In reactions of o-nitrophenylnitrile imines acyclic compounds were the main products. 相似文献
995.
V. A. Pal’chikov I. N. Tarabara S. V. Shishkina O. V. Shishkin N. Yu. Kol’tsov L. I. Kas’yan 《Russian Journal of Organic Chemistry》2007,43(5):660-673
Reaction products were obtained from bicyclo[2.2.1]hept-5-ene-endo,endo-2,3-dicarboxylic (endic) acid anhydride and ammonia, methyl-, benzyl-, dimethyl-, methylbenzyl-, dibenzyl-, diethyl-, dipropyl-, diisopropyl-, and dipentylamines. The synthesized amido acids were subjected to epoxidation by organic peracids. The structure of compounds obtained was confirmed by IR, 1H and 13C NMR spectra, and in some instances, by X-ray diffraction analysis. 相似文献
996.
Five optically active imidazole derivatives have been synthesized via a facile 4-step reaction sequence starting from commercially available and inexpensive N-Cbz amino acids. While microwave assisted condensation was unsuccessful, the condensation of the corresponding alpha-bromoketones with formamidine acetate in liquid ammonia was revealed to be a useful method for the synthesis of such imidazole derivatives. The derivatives thus prepared are structurally-related to histamine. 相似文献
997.
Miroslav Jan
o David Sýkora Frantisek Svec Jean M. J. Frchet Johannes Schweer Reimer Holm 《Journal of polymer science. Part A, Polymer chemistry》2000,38(15):2767-2778
Rapid high‐performance liquid chromatography (HPLC) of polystyrenes, poly(methyl methacrylates), poly(vinyl acetates), and polybutadienes using a monolithic 50 × 4.6 mm i.d. poly(styrene‐co‐divinylbenzene) column have been carried out. The separation process involves precipitation of the macromolecules on the macroporous monolithic column followed by progressive elution utilizing a gradient of the mobile phase. Depending on the character of the separated polymer, solvent gradients were composed of a poor solvent such as water, methanol, or hexane and increasing amounts of a good solvent such as THF or dichloromethane. Monolithic columns are ideally suited for this technique because convection through the large pores of the monolith enhances the mass transport of large polymer molecules and accelerates the separation process. Separation conditions including the selection of a specific pair of solvent and precipitant, flow rate, and gradient steepness were optimized for the rapid HPLC separations of various polymers that differed broadly in their molecular weights. Excellent separations were obtained demonstrating that the precipitation‐redissolution technique is a suitable alternative to size‐exclusion chromatography (SEC). The molecular weight parameters calculated from the HPLC data match well those obtained by SEC. However, compared to SEC, the determination of molecular parameters using gradient elution could be achieved at comparable flow rates in a much shorter period of time, typically in about 1 min. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2767–2778, 2000 相似文献
998.
Jan Koláček 《Computational Statistics》2008,23(1):63-78
The problem of bandwidth selection for non-parametric kernel regression is considered. We will follow the Nadaraya–Watson
and local linear estimator especially. The circular design is assumed in this work to avoid the difficulties caused by boundary
effects. Most of bandwidth selectors are based on the residual sum of squares (RSS). It is often observed in simulation studies
that these selectors are biased toward undersmoothing. This leads to consideration of a procedure which stabilizes the RSS
by modifying the periodogram of the observations. As a result of this procedure, we obtain an estimation of unknown parameters
of average mean square error function (AMSE). This process is known as a plug-in method. Simulation studies suggest that the
plug-in method could have preferable properties to the classical one.
Supported by the MSMT: LC 06024. 相似文献
999.
Dietmar Kunkel Axel H. E. Müller Miroslav Janata Lubomír Lochmann 《Macromolecular Symposia》1992,60(1):315-326
The kinetics of the anionic polymerization of methacrylates and acrylates in THF as well as the MWD of the polymers formed depend on the concentration of active centres and of additives, such as lithium halides and lithium alkoxides. These results are discussed on basis of multiple equilibria between non-associated, associated, and complexed ion pairs which are supported by viscosity measurements. The position of these equilibria determines the rate of polymerization, whereas the dynamics of interconversion determine the polydispersity. In the absence of additives the rate of monomer addition to non-associated ion pairs competes with the rate of association. Addition of lithium chloride mainly affects the rate of interconversion between dormant and active species, whereas lithium tert-butoxide forms adducts which stabilize the active centre. 相似文献
1000.
Momir Stevanovic Dragica Selakovic Miroslav Vasovic Biljana Ljujic Suzana Zivanovic Milos Papic Marko Zivanovic Nevena Milivojevic Milica Mijovic Sasa Z. Tabakovic Vukoman Jokanovic Aleksandra Arnaut Pavle Milanovic Nemanja Jovicic Gvozden Rosic 《Molecules (Basel, Switzerland)》2022,27(5)
Reconstruction of jaw bone defects present a significant problem because of specific aesthetic and functional requirements. Although widely used, the transplantation of standard autograft and allograft materials is still associated with significant constraints. Composite scaffolds, combining advantages of biodegradable polymers with bioceramics, have potential to overcome limitations of standard grafts. Polyethyleneimine could be an interesting novel biocompatible polymer for scaffold construction due to its biocompatibility and chemical structure. To date, there have been no in vivo studies assessing biological properties of hydroxyapatite bioceramics scaffold modified with polyethyleneimine. The aim of this study was to evaluate in vivo effects of composite scaffolds of hydroxyapatite ceramics and poly(lactide-co-glycolide) and novel polyethyleneimine on bone repair in swine’s mandibular defects, and to compare them to conventional bone allograft (BioOss). Scaffolds were prepared using the method of polymer foam template in three steps. Pigs, 3 months old, were used and defects were made in the canine, premolar, and molar area of their mandibles. Four months following the surgical procedure, the bone was analyzed using radiological, histological, and gene expression techniques. Hydroxyapatite ceramics/polyethyleneimine composite scaffold demonstrated improved biological behavior compared to conventional allograft in treatment of swine’s mandibular defects, in terms of bone density and bone tissue histological characteristics. 相似文献