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91.
A series of diastereoisomers of beta-methyl-beta-phenylalanine analogues 1a-f have been prepared in enantiomerically pure form using a combination of chemo- and biocatalysis. Starting from l-threonine methyl ester 2, a range of beta,beta-disubstituted didehydroamino acids were obtained as their (Z)-isomers 6a-f. Asymmetric hydrogenation of these alkenes, using either the [Rh(R,R)-Et-DuPhos(COD)]BF4 or [Rh(S,S)-Et-DuPhos(COD)]BF4 catalyst, followed by hydrolysis yielded two of the four possible sets of diastereoisomers of the beta-branched amino acid. Subsequent stereoinversion, using a stereoselective amino acid oxidase in combination with a nonselective reducing agent, furnished the remaining two sets of diastereomers. 相似文献
92.
Cowley AR Dilworth JR Donnelly PS Gee AD Heslop JM 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2404-2412
A series of copper(II) and nickel(II) 1,3-bis(thiosemicarbazonato) complexes have been synthesised by the reaction of the metal acetates with pyrazoline proligands. In each case the complexes have an overall neutral charge with a dianionic ligand. The copper 1,3-bis(4-methyl-3-thiosemicarbazonato complex has been characterised by X-ray crystallography, which shows the copper is in an essentially square-planar symmetric N(2)S(2) environment. The nickel 1,3-bis(4-methyl-3-thiosemicarbazonato) and nickel 1,3-bis(4-phenyl-3-thiosemicarbazonato) complexes have been characterised by X-ray crystallography and show that in these cases the nickel is in a distorted square-planar environment, but the bonding mode of the ligands is unusual; the nickel binds to one of the aza-methinic nitrogen atoms and one hydrazinic nitrogen, creating one five-membered N-N-C-S-Ni chelate ring and one four-membered N-C-S-Ni chelate ring. Interestingly, the X-ray structure of the ethyl analogue [1,3-bis(4-ethyl-3-thiosemicarbazonato)nickel(II)] shows that in this case the nickel is symmetrically coordinated in the usual manner. The nickel complexes are diamagnetic and the different coordination modes are confirmed in solution by NMR spectroscopy. The complexes are susceptible to oxidation in air and a nickel complex, in which the central methylene carbon has been oxidised, has been characterised by X-ray crystallography and NMR spectroscopy. Electrochemical measurements show that the copper complexes undergo a reversible one-electron reduction at biologically accessible potentials. 相似文献
93.
It is argued that the partition of a quantum system into subsystems is dictated by the set of operationally accessible interactions and measurements. The emergence of a multipartite tensor product structure of the state space and the associated notion of quantum entanglement are then relative and observable induced. We develop a general algebraic framework aimed to formalize this concept. 相似文献
94.
Lloyd S 《Physical review letters》2003,90(16):167902
A communication channel is a physical system that transfers information from one place to another. Examples of communication channels include wires, optical fibers, and chains of spins that propagate spin waves through a medium. This Letter shows that the power-limited communication capacity of a multimode optical fiber or a set of parallel spin chains can be enhanced by introducing nonlinear couplings between the modes or chains. In particular, M coupled, entangled modes can send M bits in the same time it takes a single mode to send a single bit, and in the same time it takes M uncoupled, unentangled modes to send sqrt[M] bits. 相似文献
95.
Jahn M Marles J Warren RA Withers SG 《Angewandte Chemie (International ed. in English)》2003,42(3):352-354
96.
Gamblin DP Garnier P Ward SJ Oldham NJ Fairbanks AJ Davis BG 《Organic & biomolecular chemistry》2003,1(21):3642-3644
Controlled site-selective glycosylation can be achieved by combining site-directed cysteine mutagenesis with chemical modification of the introduced thiol; a new class of more efficient chemoselective reagents, glycosyl phenylthiosulfonates, allow rapid glycosylations of representative simple thiols, peptides and proteins. 相似文献
97.
An oil-soluble hexadecyl pyrene (HDP) probe is used to monitor coalescence of hexadecane oil-in-water emulsions, during emulsification, in stirred systems and in a high-pressure homogenizer (microfluidizer), when small molecule surfactants are used as emulsifiers. The effect of sodium dodecyl sulfate concentration and salt concentration on the amount of coalescence and final drop size is studied. The behavior of oil-soluble surfactants and mixtures of oil-soluble and water-soluble surfactants on emulsification performance is also discussed. For high-pressure homogenizers, the drop sizes obtained are found to depend mostly on the ability of surfactants to stabilize the drops against coalescence, rather than their ability to reduce the interfacial tension. Increasing oil phase fractions increase the coalescence rate, because of the increase in collision frequency, which, in turn, impacts the drop size of the homogenized emulsion. 相似文献
98.
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100.
K.N. Joshipura M. Vinodkumar B.K. Antony N.J. Mason 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,23(1):81-90
Total ionization cross-sections of electron impact are calculated for the molecular targets CHx, CFx, SiHx, SiFx (x = 1-4) and CCl4 at incident energies 20-3 000 eV. The calculation is based on Complex Scattering Potential approach, as developed by us recently.
This leads to total inelastic cross-sections, from which the total ionization cross-sections are extracted by reasonable physical arguments. Extensive comparisons are made here with the previous theoretical
and experimental data. The present results are satisfactory except for the CFx and SiFx (x = 1-3) radicals, for which the experimental data are lower than most of the theories by more than 50%.
Received 23 May 2002 / Received in final form 24 October 2002 Published online 21 January 2003
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ID="a"e-mail: knjoshipura@yahoo.com 相似文献