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91.
Rousseau C Ortega-Caballero F Nordstrøm LU Christensen B Petersen TE Bols M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):5094-5101
alpha- and beta-Cyclodextrin 6(A),6(D)-diacids (1 and 2), beta-cyclodextrin-6-monoacid (14), beta-cyclodextrin 6(A),6(D)-di-O-sulfate (16) and beta-cyclodextrin-6-heptasulfate (19) were synthesised. Acids 1, 2 and 14 were made from perbenzylated alpha- or beta-cyclodextrin, by diisobutylaluminum hydride (DIBAL)-promoted debenzylation, oxidation and deprotection. Addition of molecular sieves was found to improve the debenzylation reaction. Sulfates 16 and 19 were made by sulfation of the appropriately partially protected derivatives and deprotection. Catalysis of 4-nitrophenyl glycoside cleavage by these cyclodextrin derivatives was studied. Compounds 1, 2 and 16 were found to catalyse the reaction, with the catalysis following Michaelis-Menten kinetics and depending first order on the phosphate concentration. In a phosphate buffer (0.5 M, 59 degrees C, pH 8.0), K(M) varied from 2-10 mM and the k(cat)/k(uncat) ratio from 80-1000 depending on the stereochemistry of the substrate and the catalyst, with 2 being the best catalyst and with the sulfated 16 also displaying catalytic ability. The monoacid 14 and the heptasulfate 19 were not catalytic. 相似文献
92.
Leleu S Penhoat M Bouet A Dupas G Papamicaël C Marsais F Levacher V 《Journal of the American Chemical Society》2005,127(45):15668-15669
A new and unprecedented exploitation of quinolinium thioester salts 2 in peptide bond formation is reported. These synthetic tools were assessed during the preparation of a number of dipeptides 3a-f obtained in good yields with complete stereochemical integrity. A sequential mechanism related to a prior amine capture strategy is well-established. Additionally, a tripeptide 3g was prepared according to a "safety-catch" approach, thus demonstrating the important potential of these new synthetic tools in the design of new safety-catch linkers exploitable in Solid-Phase Peptide Synthesis (SPPS). 相似文献
93.
The problem considered here is that of fitting a linear function to a set of points. The criterion normally used for this is least squares. We consider two alternatives, viz., least sum of absolute deviations (called the L1 criterion) and the least maximum absolute deviation (called the Chebyshev criterion). Each of these criteria give rise to a linear program. We develop some theoretical properties of the solutions and in the light of these, examine the suitability of these criteria for linear estimation. Some of the estimates obtained by using them are shown to be counter-intuitive. 相似文献
94.
95.
Cyril Mahaim Pierre-Alain Carrupt Jean-Pierre Hagenbuch Andr Florey Pierre Vogel 《Helvetica chimica acta》1980,63(5):1149-1157
Palladium-catalyzed double carbomethoxylation of the Diels-Alder adduct of furan and maleic anhydride yielded the methyl all-exo-7-oxanorbornane-2,3,5,6-tetracarboxylate (7) which was transformed in three steps into 2,3,5,6-tetramethylidene-7-oxanorbornane (1) , a useful synthon. Six isomeric methyl 7-oxanor-bornane-2,3,5,6-tetracarboxylates (7–12) have been isolated and their 1H- and 13C-NMR. data are compared. 相似文献
96.
Florence Bally Christophe A. Serra Cyril Brochon Georges Hadziioannou 《Macromolecular rapid communications》2011,32(22):1820-1825
Polymerization reactions can benefit from continuous‐flow microprocess in terms of kinetics control, reactants mixing or simply efficiency when high‐throughput screening experiments are carried out. In this work, we perform for the first time the synthesis of branched macromolecular architecture through a controlled/‘living' polymerization technique, in tubular microreactor. Just by tuning process parameters, such as flow rates of the reactants, we manage to generate a library of polymers with various macromolecular characteristics. Compared to conventional batch process, polymerization kinetics shows a faster initiation step and more interestingly an improved branching efficiency. Due to reduced diffusion pathway, a characteristic of microsystems, it is thus possible to reach branched polymers exhibiting a denser architecture, and potentially a higher functionality for later applications. 相似文献
97.
Christoph H. Braun Benjamin Schpf Chheng Ngov Cyril Brochon Georges Hadziioannou Edward J. W. Crossland Sabine Ludwigs 《Macromolecular rapid communications》2011,32(11):813-819
We report the synthesis of a series of block copolymers consisting of a rod‐like semiconducting poly(2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (DEH‐PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self‐assembling templates for bulk heterojunction donor–acceptor layers in organic solar cells. A lamellar microphase‐separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.
98.
D.I. Kolokolov H. Jobic A.G. Stepanov M. Plazanet M. Zbiri J. Ollivier V. Guillerm T. Devic C. Serre G. Férey 《The European physical journal. Special topics》2010,189(1):263-271
The low-frequency modes of MIL-47(V) and MIL-53(Cr) frameworks have been measured by inelastic neutron scattering. The librational
modes of benzene are very close in frequency in the two structures. First-principles calculations have been performed to assign
the measured spectra. The calculated values of the rotational barriers of the benzene rings are in reasonable agreement with
experimental data. The relatively large barriers (413–588 meV) explain the absence of quasi-elastic broadening on the neutron
time scale. 相似文献
99.
Fontaine-Gautrelet C Krafft JM Djéga-Mariadassou G Thomas C 《The journal of physical chemistry. B》2006,110(20):10075-10081
The low-temperature adsorption of N(2) on Rh/SiO(2) samples of various particle-size distributions was followed by FTIR. The addition of O(2) pulses on Rh(0) surfaces saturated with chemisorbed N(2) allowed us to reassign stretching frequencies attributed originally to N(2)-Rh(0) to N(2)-Rh(delta+). The formation of the latter oxidized Rh species is assumed to be induced by an electron withdrawal from adsorbed oxygen species on Rh surface centers neighboring those onto which N(2) species are chemisorbed. The present work, thus, enables us to delimit ranges of frequencies for which the adsorption of N(2) can be considered to occur on either Rh(0) or Rh(delta+) centers for nu(N2) lower or higher than 2243 cm(-1), respectively. The N(2)-FTIR experiments performed on the studied catalysts also suggest a lattice plane selectivity for N(2) adsorption on metallic Rh planes of different natures which, to our knowledge, has not been reported yet for Rh. 相似文献
100.
[reaction: see text] A palladium-catalyzed/norbornene-mediated sequential coupling reaction involving an aromatic sp(2) C-H functionalization as the key step is described, in which an alkyl-aryl bond and an aryl-heteroaryl bond are formed in one pot. A variety of highly substituted six- and seven-membered annulated pyrroles and pyrazoles were synthesized in a one-step process in good yields from readily accessible N-bromoalkyl pyrroles or pyrazoles and aryl iodides. 相似文献