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The retinal chromophore (11Z)‐3‐diazo‐4‐oxoretinal ( 1 ) with two photo‐labile moieties has been synthesized by semi‐hydrogenation of an 11‐yne precursor with activated Zn in aqueous media. Incorporation of 1 into opsin yielded diazoketo rhodopsin (DK‐Rh), which, upon bleaching, gave rise to intermediates batho‐Rh, lumi‐Rh, meta‐Rh, and meta‐II‐Rh corresponding to those of native Rh but at lower temperatures. Photoaffinity labeling of DK‐Rh and these bleaching intermediates showed that the ionone ring cross‐linked to Trp265 of helix F in DK‐Rh and batho intermediate, and to Ala169 of helix D in lumi, meta‐I, and meta‐II intermediates. These results demonstrate the occurrence of large conformational changes along the visual transduction path, which, in turn, is responsible for activation of the G‐protein. 相似文献
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Hadi Gholami Dr. Mercy Anyika Jun Zhang Dr. Chrysoula Vasileiou Prof. Dr. Babak Borhan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9235-9239
The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization‐free manner, upon their complexation with Zn‐MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host–guest complex leads to observable exciton‐coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. 相似文献
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Babak Ebrahimian Ali Noorzad Mustafa I. Alsaleh 《Continuum Mechanics and Thermodynamics》2018,30(1):95-126
Recently, the authors have focused on the shear behavior of interface between granular soil body and very rough surface of moving bounding structure. For this purpose, they have used finite element method and a micro-polar elasto-plastic continuum model. They have shown that the boundary conditions assumed along the interface have strong influences on the soil behavior. While in the previous studies, only very rough bounding interfaces have been taken into account, the present investigation focuses on the rough, medium rough and relatively smooth interfaces. In this regard, plane monotonic shearing of an infinite extended narrow granular soil layer is simulated under constant vertical pressure and free dilatancy. The soil layer is located between two parallel rigid boundaries of different surface roughness values. Particular attention is paid to the effect of surface roughness of top and bottom boundaries on the shear behavior of granular soil layer. It is shown that the interaction between roughness of bounding structure surface and the rotation resistance of bounding grains can be modeled in a reasonable manner through considered Cosserat boundary conditions. The influence of surface roughness is investigated on the soil shear strength mobilized along the interface as well as on the location and evolution of shear localization formed within the layer. The obtained numerical results have been qualitatively compared with experimental observations as well as DEM simulations, and acceptable agreement is shown. 相似文献
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A simple, efficient, and general method has been developed for the synthesis of carbamoyl and thiocarbamoyl phosphonic esters using CaCl2 as an efficient Lewis base catalyst. Carbamoyl and thiocarbamoyl phosphonic esters were obtained in good yield (37%–65%) and purity under mild conditions by the reaction of diethyl phosphite with isocyanates and isothiocyanates in the presence of CaCl2. This method is easy, rapid, and good‐yielding reaction for the synthesis of carbamoyl and thiocarbamoyl phosphonic esters. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:250–253, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20538 相似文献
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An enantioselective total synthesis of the proposed structure of mucoxin (1) is described. Mucoxin, an annonaceous acetogenin isolated from bioactive leaf extracts of Rollinia mucosa, is the first acetogenin containing a hydroxylated trisubstituted tetrahydrofuran (THF) ring. This natural product is a highly potent and specific antitumor agent against MCF-7 (breast carcinoma) cell lines (ED50 = 3.7 x 10(-3) microg/mL compared to adriamycin, ED50 = 1.0 x 10(-2) microg/mL). The total synthesis described herein features two regio- and stereoselective THF ring-forming reactions. The 2,3,5-trisubstituted THF portion (C13-C17) was accessed using a highly regioselective cyclization of a methylene-interrupted epoxydiol, and the 2,5-disubstituted THF ring (C8-C12) was conveniently assembled via a 1,2-n-triol cyclization strategy. The spectral data of the synthetic material and two of its diastereomers did not match the reported data for the natural product. On the basis of detailed spectroscopic analysis of the synthesized molecule, we reason that the spectral discrepancies are due to stereochemical misassignment of the natural product. 相似文献