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排序方式: 共有676条查询结果,搜索用时 15 毫秒
671.
Christian A. Gomez Dibyendu Mondal Qian Du Natalie Chan Jared C. Lewis 《Angewandte Chemie (International ed. in English)》2023,62(15):e202301370
FeII- and α-ketoglutarate-dependent halogenases and oxygenases can catalyze site-selective functionalization of C−H bonds via a variety of C−X bond forming reactions, but achieving high chemoselectivity for functionalization using non-native functional groups remains rare. The current study shows that directed evolution can be used to engineer variants of the dioxygenase SadX that address this challenge. Site-selective azidation of succinylated amino acids and a succinylated amine was achieved as a result of mutations throughout the SadX structure. The installed azide group was reduced to a primary amine, and the succinyl group required for azidation was enzymatically cleaved to provide the corresponding amine. These results provide a promising starting point for evolving additional SadX variants with activity on structurally distinct substrates and for enabling enzymatic C−H functionalization with other non-native functional groups. 相似文献
672.
673.
Tomas Drevinskas Aaron C. Noell Florian Kehl Konstantin Zamuruyev Mauro S. Ferreira Santos Maria F. Mora Travis D. Boone Trinh Hoac Richard C. Quinn Antonio J. Ricco Peter A. Willis 《Electrophoresis》2023,44(13-14):1047-1056
Capillary electrophoresis (CE) holds great promise as an in situ analytical technique for a variety of applications. However, typical instrumentation operates with open reservoirs (e.g., vials) to accommodate reagents and samples, which is problematic for automated instruments designed for space or underwater applications that may be operated in various orientations. Microgravity conditions add an additional challenge due to the unpredictable position of the headspace (air layer above the liquid) in any two-phase reservoir. One potential solution for these applications is to use a headspace-free, flow-through reservoir design that is sealed and connected to the necessary reagents and samples. Here, we demonstrate a flow-through high-voltage (HV) reservoir for CE that is compatible with automated in situ exploration needs, and which can be electrically isolated from its source fluidics (in order to prevent unwanted leakage current). We also demonstrate how the overall system can be rationally designed based on the operational parameters for CE to prevent electrolysis products generated at the electrode from entering the capillary and interfering with the CE separation. A reservoir was demonstrated with a 19 mm long, 1.8 mm inner diameter channel connecting the separation capillary and the HV electrode. Tests of these reservoirs integrated into a CE system show reproducible CE system operation with a variety of background electrolytes at voltages up to 25 kV. Rotation of the reservoirs, and the system, showed that their performance was independent of the direction of the gravity vector. 相似文献
674.
675.
Dr. Phillip M. Danby Andrew Jeong Dr. Lyann Sim Dr. Ryan P. Sweeney Jacob F. Wardman Ryan Karimi Dr. Andreas Geissner Dr. Liam J. Worrall Prof. Dr. Jolene. P. Reid Prof. Dr. Natalie C. J. Strynadka Prof. Dr. Stephen G. Withers 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301258
Suitably configured allyl ethers of unsaturated cyclitols act as substrates of β-glycosidases, reacting via allylic cation transition states. Incorporation of halogens at the vinylic position of these carbasugars, along with an activated leaving group, generates potent inactivators of β-glycosidases. Enzymatic turnover of these halogenated cyclitols (F, Cl, Br) displayed a counter-intuitive trend wherein the most electronegative substituents yielded the most labile pseudo-glycosidic linkages. Structures of complexes with the Sulfolobus β-glucosidase revealed similar enzyme-ligand interactions to those seen in complexes with a 2-fluorosugar inhibitor, the lone exception being displacement of tyrosine 322 from the active site by the halogen. Mutation of Y322 to Y322F largely abolished glycosidase activity, consistent with lost interactions at O5, but minimally affected (7-fold) rates of carbasugar hydrolysis, yielding a more selective enzyme for unsaturated cyclitol ether hydrolysis. 相似文献
676.
Franck Schillinger Uwe Hahn Sebastiano Guerra Thi Minh Nguyet Trinh David Sigwalt Michel Holler Iwona Nierengarten Jean-François Nierengarten 《Helvetica chimica acta》2023,106(6):e202300026
Bis- and tris-malonates constructed around a silicon atom have been prepared by reaction of malonate derivatives bearing an alcohol function with di-tert-butylsilyl bis(trifluoromethanesulfonate) and tert-butyl(trichloro)silane, respectively. These compounds have been used for the regioselective bis- and tris-functionalization of C60 under Bingel conditions. By changing the nature of the linker between the central Si atom and the reactive malonate groups, the malonate precursors have been optimized to produce specific bis- and tris-adducts with excellent regioselectivity. A complete understanding of the electronic and stereochemical factors governing the regioselectivity has been obtained by combining computational studies with a complete analysis of the by-products formed during the reactions of the Si-tethered tris-malonates with C60. Finally, desilylation reactions of the resulting fullerene bis- and tris-adducts have been carried out to generate the corresponding acyclic fullerene bis- and tris-adducts bearing alcohol functions. 相似文献