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121.
Dr. Romain Ramozzi Dr. Nicolas Chéron Dr. Laurent El Kaïm Dr. Laurence Grimaud Dr. Paul Fleurat‐Lessard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):9094-9099
Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles. 相似文献
122.
Cheng Zhang Laurence Bensaid Donna McGregor Xikui Fang Robertha C. Howell Benjamin Burton-Pye Qunhui Luo Louis Todaro Lynn C. Francesconi 《Journal of Cluster Science》2006,17(2):389-425
Lanthanide complexes of polyoxometalates, including the α2-P2W17O61
10− ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α2-P2W17O61
10− ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H2O)X(α2-P2W17O61)]2
14− species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α2-P2W17O61
10− ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K1/log K2 ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α2-P2W17O61
10− species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field. 相似文献
123.
Laurence Muhr Steve Pontvianne Katalin Selmeczi Cdric Paris Sandrine Boschi‐Muller Laetitia Canabady‐Rochelle 《Journal of separation science》2020,43(11):2031-2041
Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental tR with the simulated tR obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of tR were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance. 相似文献
124.
Serge Ello Laurence Pirault-Roy Attila Wootsch Zoltán Paál 《Reaction Kinetics and Catalysis Letters》2008,94(2):301-310
Platinum-germanium catalysts supported on a non-acidic Al2O3 have been prepared by adding Ge in amounts corresponding nominally to 1/8 (PtGe1/8/Al2O3); 1/2 (PtGe1/2/Al2O3); 1 (PtGe1/Al2O3) and 2 (PtGe2/Al2O3) monolayers by controlled surface reaction of Ge(n-C4H9)4 to Pt/Al2O3. These catalysts were characterized by electron microscopy (TEM), FTIR of CO adsorption and H2 chemisorption. The ring opening of ethylcyclopentane (ECP) was studied as a test reaction between 543 and 633 K. PtGe1/8/Al2O3 catalyst produced the most ring opening products (ROP) in the whole temperature range. A good agreement with statistical
values of ROP was observed at low temperature, but at higher temperature, the opening became selective, producing mostly heptane.
Bimetallic catalysts PtGe1/Al2O3 and PtGe2/Al2O3 led to a nonselective hydrogenolysis, similar to the monometallic platinum catalyst Pt/Al2O3. The catalysts PtGe1/Al2O3 and PtGe2/Al2O3 produced ROP with the lowest selectivity; instead, much aromatics and fragments were formed, in increasing amounts above
600 K. 相似文献
125.
A versatile synthesis leading to either C-linked alpha- or beta-glucopyranosyl serines is presented from a common, advanced synthetic intermediate. Cyclization of the penultimate carbinol onto the alkene and methanolysis of the lactone yields selectively the alpha-linkage. A transposition of these last steps leads to the beta-linked isomer selectively. 相似文献
126.
127.
Grandjean C Boutonnier A Guerreiro C Fournier JM Mulard LA 《The Journal of organic chemistry》2005,70(18):7123-7132
[reaction: see text] The nature of a linker used for preparing glycoconjugate vaccines is of utmost importance as it may lead to immunogenic biomolecules. We report the conjugation of carbohydrate haptens to protein carriers leading to potential vaccines using the traceless Staudinger ligation. The ligation relies on the selective transfer of a phosphane substituent to an azide to form a native amide bond in the final product upon release of an oxidized phosphane byproduct. We designed new phosphino-functionalized cross-linkers suitable for protein carrier derivatization. We evaluated their utility in preparing conjugates using both synthetic and purified bacterial carbohydrates. The use of a borane-protected phosphane which is deprotected at the time of the ligation reaction led to the best results observed thus far in terms of stability toward oxidation and reactivity. 相似文献
128.
Laurence S. Rothman 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(11):1514-1515
The publication by G.H. Dieke and H.M. Crosswhite (JQSRT 1962;2:97-199) is a classic paper detailing the spectroscopy of the A2Σ+←X2Π bands of the hydroxyl radical (OH) in the ultraviolet region. It soon became the basis of astrophysical modeling, most subsequent theoretical and laboratory studies of the OH individual line parameters, and a host of other applications. 相似文献
129.