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161.
Top S el Hafa H Vessiéres A Huché M Vaissermann J Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(22):5241-5249
In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha. 相似文献
162.
Patrick Gredin Ariel De Kozak Michel Quarton Jean Renaudin Grard Ferey 《无机化学与普通化学杂志》1993,619(6):1088-1094
The liquid-solid phase diagram of the binary system BaF2? ScF3 is established by D.T.A. and radiocrystallography. Three fluorides are disclosed: Ba3Sc2F12, Ba5Sc3F19 and a cubic high temperature phase Ba1?xScxF2+x (x = 0.17), the structure of which derives from that of BaF2. A solid solution between BaF2 and ScF3 is also evidenced at high temperature. The ternary system BaF2? CuF2? ScF3 is investigated by radiocrystallography and an isothermal section at 670°C is given. It shows the existence of four phases: a complex quaternary fluoride Ba10Cu12ScF47, two “polytypic” phases the structure of which derives from that of BaCuF4 and a tetragonal solid solution Ba5Sc3?xCuxF19?x with 0 ≤ x ≤ 1. 相似文献
163.
A general stochastic theory of size exclusion chromatography (SEC) able to account for size dependence on both pore ingress and egress processes, moving zone dispersion and pore size distribution, was developed. The relationship between stochastic-chromatographic and batch equilibrium conditions are discussed and the fundamental role of the 'ergodic' hypothesis in establishing a link between them is emphasized. SEC models are solved by means of the characteristic function method and chromatographic parameters like plate height, peak skewness and excess are derived. The peak shapes are obtained by numerical inversion of the characteristic function under the most general conditions of the exploited models. Separate size effects on pore ingress and pore egress processes are investigated and their effects on both retention selectivity and efficiency are clearly shown. The peak splitting phenomenon and peak tailing due to incomplete sample sorption near to the exclusion limit is discussed. An SEC model for columns with two types of pores is discussed and several effects on retention selectivity and efficiency coming from pore size differences and their relative abundance are singled out. The relevance of moving zone dispersion on separation is investigated. The present approach proves to be general and able to account for more complex SEC conditions such as continuous pore size distributions and mixed retention mechanism. 相似文献
164.
Multianalytical Study of Patina Formed on Archaeological Metal Objects from Bliesbruck-Reinheim 总被引:1,自引:0,他引:1
Michael Wadsak Ina Constantinides Guido Vittiglio Annemie Adriaens Koen Janssens Manfred Schreiner Freddy C. Adams Philippe Brunella Michel Wuttmann 《Mikrochimica acta》2000,133(1-4):159-164
Patinas naturally formed on archaeological bronze alloys were characterized using light microscopy (LM), micro energy dispersive
X-ray fluorescence analysis (μ-EDXRF), time of flight secondary ion mass spectrometry (TOF-SIMS) and scanning electron microscopy
in combination with energy dispersive X-ray microanalysis (SEM/EDX). The examinations carried out on cross-sections of samples
have shown that in all samples the copper content in the corrosion layer is lower than in the bulk, while an increase of tin
and lead could be observed. Two different types of corrosion were found: first type, a corrosion formation leading to a three
layer structure was observed on lead bronze. The outer layer consists mainly of Cu(II) compounds and soil material, followed
by a fragmented layer of cuprous oxide and the surface layer of the alloy, where a depletion of copper and an enrichment of
tin and high amounts of Cl could be detected. The second type of corrosion is characterized by a two layer structure on the
tin bronze sample consisting of an outer layer with copper containing corrosion products and a layer with cracks, which reveals
a depletion of copper whereas tin and lead are enriched. Also high amounts of Si were detected in this surface layer. 相似文献
165.
166.
Ugo Bussy Illa Tea Véronique Ferchaud-Roucher Michel Krempf Virginie Silvestre Nicolas Galland Denis Jacquemin Moa Andresen-Bergström Ulrik Jurva Mohammed Boujtita 《Analytica chimica acta》2013
The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope 18O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope 18O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions. 相似文献
167.
Mohamed Brakta Denis Sinou Michel Becchi Joseph Banoub 《Journal of mass spectrometry : JMS》1992,27(5):621-624
A series of anomeric unsaturated C-glycosides were studied by negative ion mass spectrometry following keV ion bombardment The compounds bearing an acidic hydrogen show a prominent [M ? H]? peak; in the other cases, the [M ? H]? peak is of very low intensity. A retro-Diels–Alder fragmentation and the abstraction of a hydrogen atom from the aglycon residue are observed in all cases. 相似文献
168.
A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products. 相似文献
169.
Karen Wright Marco CrismaClaudio Toniolo Roland TörökAntal Péter Michel WakselmanJean-Paul Mazaleyrat 《Tetrahedron letters》2003,44(16):3381-3384
Amination of 3-carboxymethyl-1-oxyl-2,2,6,6-tetramethyl-4-piperidone with (R)-α-methylbenzylamine, NaBH3CN reduction of the resulting enamine and removal of the chiral auxiliary from the separated diastereoisomers, led to enantiomerically pure (3S,4S) and (3R,4R) methyl 4-amino-1-oxyl-2,2,6,6-tetramethylpiperidine-3-carboxylates. 相似文献
170.
Alain Merschaert Laurent DelhayeJean-Paul Kestemont Willy BrionePieter Delbeke Vincent MancusoFreddy Napora Khalid DikerDaniel Giraud Michel Vanmarsenille 《Tetrahedron letters》2003,44(24):4531-4534
A stereoselective approach has been developed for the synthesis of cis- and trans-2-methyl-4-arylpiperidines from a common intermediate. The Ni-catalyzed hydrogenolysis of N-Boc-2-methyl-4-aryl-4-piperidinols, obtained by addition of organometallic reagents on N-Boc-2-methyl-4-piperidone, afforded the trans derivatives with up to 95% selectivity whereas the corresponding cis isomers were obtained in the presence of palladium catalysts. 相似文献