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81.
Matsumoto K Davis BG Jones JB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4129-4137
A significant enhancement of the applicability of the serine protease subtilisin Bacillus lentus (SBL) in peptide synthesis was achieved by using the strategy of combined site-directed mutagenesis and chemical modification to create chemically modified mutant (CMM) enzymes. The introduction of polar and/or homochiral auxiliary substituents, such as X=oxazolidinones, alkylammonium groups, and carbohydrates at position 166 at the base of the primary specificity S(1) pocket created SBL CMMs S166C-S-X with strikingly broad structural substrate specificities. These CMMs are capable of catalyzing the coupling reactions of not only L-amino acid esters but also D-amino acid esters as acyl donors with glycinamide to give the corresponding dipeptides in good yields. These powerful enzymes are also applicable to the coupling of L-amino acid acyl donors with alpha-branched acyl acceptor, L-alaninamide. Typical increases in isolated yields of dipeptides of 60-80 % over SBL-WT (e.g. 0 % yield of Z-D-Glu-GlyNH(2) using SBL-WT-->74 % using S166C-S-(CH(2))(2) NMe(3) (+)) demonstrate the remarkable synthetic utility of this "polar patch" strategy. Such wide-ranging systems displaying broadened and therefore similarly high, balanced yields of products (e.g. 91 % Z-L-Ala-GlyNH(2) and 86 % yield of Z-D-Ala-GlyNH(2) using S166C-S-(3R,4S)-indenooxazolidinone) may now allow the use of biocatalysts in parallel library synthesis. 相似文献
82.
A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures. 相似文献
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The interplay between electronic and geometric structure is investigated for covalently bonded phosphorus clusters. We use a modification of the molecular dynamics/ density functional (MD/DF) method of Car and Parrinello, describing the electronic structure by a simplified linear combination of atomic orbitals (LCAO) approach. The results show clearly the tendency of phosphorus to threefold coordination, and substantial variations in bond angles lead to a large variety of isomers. 相似文献
85.
Kohtani M Jones TC Schneider JE Jarrold MF 《Journal of the American Chemical Society》2004,126(24):7420-7421
High-temperature ion mobility measurements have been performed for alpha-helical Ac-A15K+H+ and globular Ac-KA15+H+ peptides. The alpha-helical and globular conformations do not melt into random coils as the temperature is raised. Instead, both conformations survive to the point where the peptide signals vanishes due to fragmentation. This occurs at 600 K for the globular Ac-KA15+H+ peptide and at 725 K for the alpha-helical Ac-A15K+H+. For the helical Ac-A15K+H+ peptide it appears that fragmentation is triggered by disruption of the helical conformation. 相似文献
86.
The infrared spectrum for the vapour, liquid and solid states of epifluorohydrin has been studied, and evidence has been obtained for the presence of rotational isomers. The dominant conformer in all phases corresponds to a gauche structure, which was the only form identified in the vapour by microwave spectroscopy [1]. Similar evidence for conformational equilibria has been found for the chloro, bromo and iodo derivatives, and the enthalpy differences between the rotational isomers of these compounds were measured respectively as 4580 ± 970, 3950 ± 400, and 2350 ± 170 J mol?1 respectively. At low temperatures, epiiodohydrin was found to crystallize in one of two possible crystalline phases. These two phases correspond to the two rotational isomeric conformations of the molecule. 相似文献
87.
A decamer duplex model of Domain II of the hammerhead ribozyme was synthesized with [8-13C-1,7,NH2-15N3]-guanosine at the known metal binding site, G10.1 and, for comparison, [2-13C-1,7,NH2-15N3]-guanosine at G16.2. The 15N NMR chemical shifts of the labeled N7s monitored during addition of Mg2+, Cd2+, and Zn2+ showed the same preference for binding at G10.1 over G16.2 for each metal. These results demonstrate that 15N labeling can be used to evaluate the binding of different metals, including Mg2+, to a given nitrogen, as well as to compare the binding potential of different sites. 相似文献
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90.
Abernethy Colin D. Baker Robert J. Cole Marcus L. Davies Aaron J. Jones Cameron 《Transition Metal Chemistry》2003,28(3):296-299
The reactivity of the carbene stabilised indium trihydride complex, [InH3(IMes)] IMes = 1,3-dimesitylimidazol-2-ylidene, toward a variety of transition metal complexes has been investigated. The study has shown that the InH3 complex can act as a carbene and/or hydride transfer reagent to transition metal centres but does not yield heterobimetallic materials. Two new complexes, [Cp2Ti(-Cl)2Zn(IMes)Cl] and [CpNi(H)(IMes)], have resulted from this work, both of which have been spectroscopically and structurally characterised. 相似文献