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91.
F.D. De Körösy 《Journal of Electroanalytical Chemistry》1982,141(4):391-417
Biological cell membranes are compared to artificially produced permselective membranes. In spite of the difference in their thickness and electric resistance it is shown that they are similar in many important aspects, and the behaviour of synthetic membranes can explain very many points in the behaviour of cell membranes, especially axons. It is stressed that it is seldom necessary to assume unproven channels in biological membranes which are specific in the transport of a single ion species. Most of the phenomena of selectivity, opening and closing of such membranes can be explained by the influence of pH on membrane sites, by their poisoning with higly charged and/or large counter-ions. The borderline between two oppositely charged regions of a mosaic membrane opens up because it can be traversed by both positive and negative ions and permselectively is lost. Bipolar membranes rectify the current. Amphoteric membranes undergo very complex changes in conducting properties and permselectively with pH, especially when allowance is made for the weakly dissociated sites contained within these membranes. It is suggested that black lipid membranes made in the laboratory could be used to elucidate new points of similarity if they were used under similar conditions to our technical membranes. 相似文献
92.
The uncatalyzed 1,4-addition of phenylmagnesium bromide and furylmagnesium iodide to methyl 5-methoxy-1,5-cyclohexadienylcarboxylate (), directly followed by alkylation and hydrolysis leads to the corresponding cyclohexanones of type (R1 and R2 trans) in moderate to high yield. 相似文献
93.
A novel generally applicable synthesis of coumarins from phenolic substrates utilizing ring-closing metathesis is described. This sequence involves O-allylation of phenols followed by ortho-Claisen rearrangement, subsequent based-induced isomerization affording 2-(1-propenyl)phenols, acylation with acryloyl chloride, and finally ring-closing metathesis (RCM) with Grubbs’ second generation catalyst. 相似文献
94.
Résumé Les auteurs ont étudié le comportement chromatographique sur plusieurs phases stationnaires polaires et non polaires de composés cyclopropaniques stéréoisomêres: où R=H ou CH3 et X=CH, COOCH3 ou CH2OH. Les résultats sont interprétés en fonction de la configuration de X par rapport à , de la nature électronique de X et de l'orientation du phényle par rapport au plan du cyclopropane.
Relationship between chemical structure and retention. VII. Cyclopropane compounds
Summary The chromatographic behaviour, on several polar and non polar phases, of stereoisomeric cyclopropanes has been studied R=H or CH3 and X=CN, COOCH3, CH2OH. The results are interpreted in terms of the X versus configuration, the electronic nature of X and the orientation of the phenyl ring in relation to plane of the cyclopropane ring.相似文献
95.
F. De Meester J. M. Frre J. L. Piette P. Jacquemin L. Grooters G. Llabres S. Defays 《Journal of heterocyclic chemistry》1992,29(2):535-541
In an attempt to rationalize a synthesis of penicillin analogs modified at C(3), we have isolated the 3R(β)-carbinolamide derivative 4a. The trityl substituent on N(6′) seems to be responsible for the inversion of configuration which occurs at C(3) during the acid hydrolysis of the isocyanate intermediate. An hydrogen bond is formed on the β-face of the bell-shaped bicyclic skeleton between the N(6′)-nitrogen lone pair and the C(3) hydroxyl group. On standing, the carbinolamide analog slowly isomerizes to its expanded bicyclic isomer 4b , but the starting material may be easily recovered by treatment with acid. The postulated intermediate during isomerization, i.e., the open aldehyde form, does not accumulate. Substitutions of the hydroxyl group at C(3) lead to a variety of compounds with the biologically active 3S(α) configuration. These may be used to study the importance of the carboxyl group of penicillins in their interaction with β-lactamases at the molecular level. 相似文献
96.
The isolation of (2S,1'S,2'S)-2-(2'-carboxycyclopropyl)glycine (CCG I, 2) from Blighia sapida (Akee) was achieved through column chromatography on deactivated silica gel followed by ion-exchange chromatography. A HPLC method has also been devised in order to assess the purity of the isolated product. 相似文献
97.
Cyclization of suitable enamino ketones can produce hydroxyphthalides. 相似文献
98.
C.P. Boekel A. Jelsma J.H. Teuben H.J. De Liefde Meijer 《Journal of organometallic chemistry》1977,136(2):211-218
The thermolysis of compounds of the type Cp2VR (R = aryl) in the solid state has been studied. A distinct increase in thermal stability is observed upon substitution of the ortho-position of the aryl group. Thermal decomposition occurs with formation of RH, Cp2 V, a vanadocene homologue with the group R substituted in one of the Cp rings and, probably, a vanadocene homologue with two substituted Cp rings. It is shown that the abstraction of the hydrogen atom from the cyclopentadienyl ring, necessary for the formation of RH, is an intermolecular process, whereas the substitution of the aryl group in the Cp ring is intramolecular. A decomposition mechanism is proposed in which the group R is transferred from the vanadium atom to the C5H5 ring of the same molecule by interaction with an aryl group of another molecule. The thermal decomposition of Cp2VR is compared with that of the analogous titanium compounds. 相似文献
99.
L.J. Vanmaele P.J. De Clercq M. Vandewalle S.J. Halkes W.R.M. Overbeek 《Tetrahedron》1984,40(7):1179-1182
An efficient method for the preparation of crystalline α-hydroxy previtamin D3 is described. Also the stereoselective reduction of 1-keto previtamin is discussed; it was observed that with aluminum hydride is the most abundant product. This stands in contrast with previously reported LiAlH4 and NaBH4 mediated reductions. 相似文献
100.
De Wasch K De Brabander HF Van de Wiele M Vercammen J Courtheyn D Impens S 《Journal of chromatography. A》2001,910(1):79-86
Direct gas chromatographic methods to analyse phenylurea pesticides are discouraged by the thermal instability of these compounds, that in conventional hot splitless inlet systems leads to extensive and irreproducible formation of isocyanates and amines. However a careful control of the operating conditions, like the inlet temperature, the pressure and the presence of suitable chemical additives (as acetic acid, low-molecular-mass amines, organic anhydrides) can either: (i) minimise the thermal decomposition enabling the direct GC-MS analysis of phenylureas, or (ii) lead to reproducible conversion to isocyanates. Experimental design was employed to study the effect of the experimental variables on the thermal transformation of phenylurea pesticides in splitless inlet system. Two strategies were alternatively optimised: (i) the minimisation of degradation reactions to increase the signal of phenylureas; (ii) the maximisation of the degradation to isocyanates that are in turn determined. The maximal yields in isocyanate were obtained with high inlet temperatures, low carrier flows in the injection phase and the presence of acetic anhydride. By contrast, the use of relatively low inlet temperatures, high carrier flows during the injection and the presence of an amine maximise the response of the parent compounds. 相似文献