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41.
Carolina Toloza Porras Dagmar R. D'hooge Marie‐Franoise Reyniers Guy B. Marin 《Macromolecular theory and simulations》2013,22(2):136-149
The potential of initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) for the synthesis of well‐defined poly(n‐butyl acrylate) is analyzed by means of simulations. The kinetic model accounts for reactivity differences between secondary and tertiary macrospecies and considers the possible influence of diffusional limitations. CuBr2 is used as transition metal salt and the commercially available N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand. For targeted chain lengths (TCLs) up to 1000, the ICAR ATRP can be performed relatively quickly, and with ppm levels of ATRP catalyst. For moderate TCLs, slightly higher ppm levels are required if excellent control over chain length is also desired. In all cases, limited loss of end‐group functionality (EGF) results.
42.
Dagmar Medková Emma Skopin Werner Varnhorn 《Mathematical Methods in the Applied Sciences》2013,36(16):2237-2242
We study the Robin problem for the scalar Oseen equation in an open n‐dimensional set with compact Ljapunov boundary. We prescribe two types of Robin boundary conditions, and prove the unique solvability of these problems as well as a representation formula for the solution in form of a scalar Oseen single layer potential. Moreover, we prove the maximum principle for the solution to the Robin problem of the scalar Oseen equation. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
43.
As shown in this study, the solvatochromic behavior of polyenes depends exclusively on the polarizability of the medium and, even more interestingly, their solvatochromism increases markedly with increasing length of the polyene chain. By virtue of the electronic nature of the interaction of polyenes with the medium, their solvatochromic response to a polarizability change is instantaneous, making these compounds extremely effective polarizability probes for molecular environments. The extreme sensitivity of polyenes to the polarizability of their environment is consistent with the fact that changes in molecular architecture such as those occurring in photosynthetic systems can give rise to polarizability gradients resulting in red shifts in the 1Ag --> 1Bu transition, thereby opening up new channels directing the energy transfer involved to energy trapping sites in such systems. 相似文献
44.
The all-trans pentaene, 3,12-di(tert-butyl)-2,2,13,13-tetramethyl-3,5,7,9,11-tetradecapentaene (ttbP5) fluoresces in two different regions of the visible spectrum. It produces an extremely weak emission in the gas phase that can also be detected in the condensed phase; such an emission exhibits a negligible Stokes shift with respect to the 1Ag-->1Bu absorption transition and can in principle be assigned to the 1Bu-->1Ag emission of the compound. ttbP5 also exhibits a second fluorescence emission at approximately 520 nm in both the gas phase and the condensed phase. The emission in the condensed phase increases in strength and structure, with no change in spectral position, as the solvent viscosity increases by effect of the solution temperature being lowered. The spectral behavior of this pentaene (ttbP5) is different enough from that reported [J. Catalan et al., J. Chem. Phys. 128, 104504 (2008)] for its tetraene counterpart (ttbP4) to warrant a separate analysis in order to facilitate a better understanding of the way the photophysics of these polyenes changes as their chain is lengthened. 相似文献
45.
Kapeller DC Brecker L Hammerschmidt F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(34):9582-9588
Several homochiral oxymethyllithiums, chiral by virtue of the hydrogen isotopes protium and deuterium, were prepared. They were tested for their microscopic configurational stability in intramolecular isomerizations, such as the silyl- and germyl-[1,2]-retro-Brook and the sigmatropic[2,3]-Wittig rearrangement. The influence of temperature, solvent, and migrating group on the stability of the intermediate carbanions was studied. Furthermore, the stereochemical course of these rearrangements was elucidated, resulting in highly enantioenriched alcohols (90-97% ee; ee=enantiomeric excess) up to temperatures of 0 degrees C. 相似文献
46.
Holger Moroder Jessica Steger Dagmar Graber Katja Fauster Krista Trappl Viter Marquez Dr. Norbert Polacek Priv.‐Doz. Dr. Daniel N. Wilson Dr. Ronald Micura Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(22):4056-4060
Translation of specific small peptides on the ribosome can confer resistance to macrolide antibiotics. To reveal the molecular details of this and related phenomena, stable RNA–peptide conjugates that mimic peptidyl‐tRNA would be desirable, especially for ribosome structural biology. A flexible solid‐phase synthesis strategy now allows efficient access to these highly requested derivatives without restriction on the RNA and peptide sequences.
47.
A fully automated, qualitative screening HPLC method for the identification of basic compounds in urine has been developed. A 1-ml volume of urine was extracted by on-line extraction and separated on two coupled strong cation-exchange (SCX) columns (2 x LunaSCX, 150 mm x 4.6 mm, 5 microm) under isocratic conditions. The mobile phase consisted of a mixture of potassium dihydrogenphosphate buffer (pH 2.3) and acetonitrile. The use of photodiode-array detection (DAD, lambda = 190-800 nm) gave access to a library of approximately 2600 toxicologically relevant compounds. The validated method is reliable, simple and in addition successfully proven with the analysis of real biological specimen for the routine use. 相似文献
48.
A new method for the electrophoretic separation of nine phenolic acids (derivatives of benzoic and cinnamic acids) with contactless conductometric detection is presented. Based on theoretical calculations, in which the mobility of the electrolyte co- and counterions and mobility of analytes are taken into consideration, the electrolyte composition and detection mode was selected. This approach was found to be especially valuable for optimization of the electrolyte composition for the separation of analytes having medium mobility. Indirect conductometric detection mode was superior to the direct mode as predicted theoretically. The best performance was achieved with 150 mM 2-amino-2-methylpropanol electrolyte at pH 11.6. The separation was carried out in a counter-electroosmotic mode and completed in less than 6 min. The LODs achieved were about 2.3-3.3 microM and could be further improved to 0.12-0.17 microM by using a sample stacking procedure. The method compares well to the UV-Vis detection. 相似文献
49.
Flodrová D Ralplachta J Benkovská D Bobálová J 《European journal of mass spectrometry (Chichester, England)》2012,18(3):323-332
This study was undertaken to investigate the effect of the malting process on hordein composition. For this purpose, combination of sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and the method of isotopic peptides labeling iTRAQ was used. Barley proteins are essential components determining the quality of both malt and beer. Since hordeins represent the most abundant proteins accounting for about 40-50% of total protein fraction of mature barley grain, our research was focused on them. In this respect, the proteins of interest were extracted from milled samples of barley grain, germinated barley grain (samples collected at different time intervals), green malt and malt, respectively. Particular hordein extracts were firstly fractionated via SDS- PAGE, which was used as a relatively rapid and reliable technique providing information about hordein profile of analyzed samples. Then, separated proteins were in-gel digested and resulting peptides were measured by mass spectrometry. In addition, the chosen proteins, after in-gel digestion, were subjected to the iTRAQ method and the screening of proteins during malting process was evaluated. Our results have revealed that most of the hordein components present in the barley grain can be found in all stages of the malting process as well as in the final malt. The amount of hordeins decreases during the malting process; in the case of C hordein, the protein decrease is approximately 65%. On the other hand, significant degradation of D hordein was detected. The suggested procedure can be used to follow the development of the hordein profile during germination, which is of great technological importance in beer production. 相似文献
50.
Zuzana Bujdo?ová Katarína Gy?ryová Dagmar Mudroňová Daniela Hudecová Jana Ková?ová 《Journal of Thermal Analysis and Calorimetry》2012,110(1):167-176
New zinc(II) 4- and 5-chlorosalicylate complexes of general formula [Zn(X-sal)2(L) n (H2O) x ] (where X-sal?=?4-Clsalicylate, 5-Clsalicylate; L?=?N,N-diethylnicotinamide, isonicotinamide, theophylline; n?=?1, 2; x?=?0, 1, 2, 4) were prepared. The complexes were determined by elemental analysis and characterised by infrared spectroscopy. The thermal behaviour of the complexes was studied by simultaneous TG, DTG and DTA methods under dynamic air conditions. The thermal decomposition is a multi-step process. In the first step of the thermal decomposition, water is released in hydrated compounds. The anhydrous compounds start to decompose by the release of organic ligand, followed by chlorosalicylic acid, chlorophenol and carbon monoxide. The final solid product of the thermal decomposition is zinc oxide. The volatile products of the thermal decomposition were determined by mass spectrometry. The antimicrobial activities of the complexes were evaluated against selected pathogen and probiotic bacteria, yeasts and fungi strains. Bioactivities of the tested compounds are different against bacteria, yeasts and filamentous fungi. It was found that bacteria were more sensitive to the studied zinc(II) complex compounds than yeasts or filamentous fungi. 相似文献