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111.
112.
Pentacyclo[5.4.0.02,6.03,10.05,9]undecan-8-one 1 is readily sulfurated into pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8-thione 2 with Lawesson’s reagent in dry THF. Upon standing at ambient temperature the thione 2 formed the corresponding thio-dimer 3 within 10 days. When the thio-dimer 3 was exposed to oxygen and ultraviolet light an unexpected photochemical oxidation and rearrangement took place to form the stable disulfenate 5. 相似文献
113.
Tarek Agag Carlos R. Arza Frans H. J. Maurer Hatsuo Ishida 《Journal of polymer science. Part A, Polymer chemistry》2011,49(20):4335-4342
Two types of main‐chain type polybenzoxazines with amide and benzoxazine groups as repeating units in the main chain, termed as poly(amide‐benzoxazine), have been synthesized. They have been prepared by polycondensation reaction of primary amine‐bifunctional benzoxazine with adipoyl and isophthaloyl dichloride using dimethylacetamide as solvent. Additionally, a model reaction is designed from the reaction of 3,3′‐(4,4′‐methylenebis(4,1‐phenylene))bis(3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐amine) with benzoyl chloride. The structures of model compound and polyamides are confirmed by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) spectroscopies. Differential scanning calorimetry and FTIR are also used to study crosslinking behavior of both the model compound and polymers. Thermal properties of the crosslinked polymers are also studied by thermogravimetric analysis. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
114.
Feuz L Leermakers FA Textor M Borisov O 《Langmuir : the ACS journal of surfaces and colloids》2008,24(14):7232-7244
The two-gradient version of the Scheutjens-Fleer self-consistent field (SF-SCF) theory is employed to model the interaction between a molecular bottle brush with a polyelectrolyte backbone and neutral hydrophilic side chains and an oppositely charged surface. Our system mimics graft-copolymers with a cationic main chain (among which poly( L-lysine)- graft-poly(ethylene glycol) (PLL- g-PEG) or poly( L-lysine)- graft-polyoxazoline are well-known examples) interacting with negatively charged (metal oxide) solid surfaces. We aim to analyze the copolymer-surface interaction patterns as a function of the molecular architecture parameters. Two regimes are investigated: First, we compute the effective interaction potential versus the distance from the surface for individual bottle brush macromolecules. Here, depending on the grafting ratio and the degree of polymerization of the side chains, the interplay of electrostatic attractions of the main chain to the surface and the steric repulsion of the grafts results in different patterns in the interaction potential and, therefore, in qualitatively different adsorption behavior. In particular, we demonstrate that, at high side chain grafting density and short grafts, the molecular brushes are strongly adsorbed electrostatically onto negatively charged substrates, whereas, in the opposite case of low grafting ratio and high molecular weight of grafts, the steric repulsion of the side chains from the surface dominates the polymer-surface interaction. At intermediate grafting ratios, the adsorption/depletion scenario depends essentially on the ratio between the electrostatic screening length and the thickness of the molecular bottle brush. We further have analyzed the equilibrium adsorbed amount as a function of the macromolecular architecture. Our results are based on a detailed account of attractive and repulsive (including intermolecular in-plane) interactions, and suggest a nonmonotonic dependence of the adsorbed amount on the grafting ratio, in good agreement with the experimental studies for PLL- g-PEG adsorption onto Nb2O5 surfaces. The results of the theoretical modeling are discussed in the context of the optimization of the PLL-g-PEG molecular design parameters in order to create protein-resistant surfaces. 相似文献
115.
Susana Rocha Dr. James A. Hutchison Dr. Kalina Peneva Dr. Andreas Herrmann Prof. Dr. Klaus Müllen Prof. Dr. Michael Skjøt Dr. Christian I. Jørgensen Dr. Allan Svendsen Dr. Frans C. De Schryver Prof. Dr. Johan Hofkens Prof. Dr. Hiroshi Uji‐i Dr. 《Chemphyschem》2009,10(1):151-161
Many of the biological processes taking place in cells are mediated by enzymatic reactions occurring in the cell membrane. Understanding interfacial enzymatic catalysis is therefore crucial to the understanding of cellular function. Unfortunately, a full picture of the overall mechanism of interfacial enzymatic catalysis, and particularly the important diffusion processes therein, remains unresolved. Herein we demonstrate that single‐molecule wide‐field fluorescence microscopy can yield important new information on these processes. We image phospholipase enzymes acting upon bilayers of their natural phospholipid substrate, tracking the diffusion of thousands of individual enzymes while simultaneously visualising local structural changes to the substrate layer. We study several enzyme types with different affinities and catalytic activities towards the substrate. Analysis of the trajectories of each enzyme type allows us successfully to correlate the mobility of phospholipase with its catalytic activity at the substrate. The methods introduced herein represent a promising new approach to the study of interfacial/heterogeneous catalysis systems. 相似文献
116.
117.
Today, due to the ever increasing amount of data generated by analytical instruments, good compression methods are desired to keep computation time acceptable. The lower the volume and noise content of data, the easier it becomes to investigate and interpret the modeling results. Discrete Wavelet Transform (DWT) is an effective data compression and noise suppression tool. Compression can be performed at different levels, in each, the size of signal part of the data reduces to half the size. This work includes an approach for determining an acceptable level of compression of data where the aim is to achieve minimal loss of information and no significant change in the structure of data, which could mean, e.g. no loss in predictive ability or the effective rank of the data-set. The method is based on estimation of the Singular Values (SVs) from a data matrix and the Singular Values at each level of compression followed by the application of Median Absolute Deviation (MAD) of the correlation between original SVs and compression SVs as a simple statistical test for the determination of the optimum level of compression. We illustrate the method using FT-Raman data from aqueous solutions of three sugars (glucose, trehalose and sucrose) and NMR data from mixtures of three alcohols. A sudden change in prediction error sum of square plots from Partial Least Squares (PLS) modeling confirms the results from MAD statistics. 相似文献
118.
Steven De Feyter Petrus C. M. Grim Markus Rücker Peter Vanoppen Christian Meiners Michel Sieffert Suresh Valiyaveettil Klaus Müllen Frans C. De Schryver 《Angewandte Chemie (International ed. in English)》1998,37(9):1223-1226
The supramolecular packing mode of physisorbed monolayers built up by chiral isophthalic acid derivatives and coadsorbed achiral solvent molecules was imaged at the liquid/graphite interface with scanning tunneling microscopy (STM). The picture on the right shows the submolecularly resolved STM image of an enantiomorphous domain composed of the R enantiomer of the isophthalic acid derivative studied and 1-heptanol molecules; the latter express the chirality of the monolayer. Upon adsorption a racemic mixture is separated into enantiomorphous domains. 相似文献
119.
Dirk C. de Graaf Wolfgang Ritter Frans J. Jacobs Marleen Brunain Hein Imberechts Koen Mintiens Yves Van der Stede Bart Verheyden Aud Kari Fauske Patrick Boujon Gabriela Chioveanu Daniel Dezmirean Giovanni Formato Franco Mutinelli Hendrik-Jan Roest Dalibor Titĕra Stephen F. Pernal Katia Knapen 《Accreditation and quality assurance》2009,14(5):273-276
We report on the first proficiency test in the context of honey bee disease testing on a broad international scale. Honey
samples were distributed to 12 participating laboratories for isolation and identification of spores of the etiological agent
of American foulbrood, Paenibacillus larvae. Of the 11 laboratories responding to this proficiency testing event, only 6 (54%) provided data that were in full agreement
with the previously determined status of the honey samples; eight (72%) laboratories fell within the threshold for qualification
as defined a priori in this proficiency test (=level of agreement of at least 90%). Some lessons can now be drawn from the
organizational point of view and will certainly improve new initiatives to be taken. 相似文献
120.
Bon RS Hong C Bouma MJ Schmitz RF de Kanter FJ Lutz M Spek AL Orru RV 《Organic letters》2003,5(20):3759-3762
[reaction: see text] The three-component condensation between an amine, an aldehyde, and an alpha-acidic isocyanide efficiently provides substituted 2-imidazolines in a one-pot reaction under mild conditions. 相似文献