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101.
An efficient hydrolase-catalyzed bioresolution of tertiary amino ester protic ionic liquids has been demonstrated. Protic ionic liquids have been prepared in one step from the corresponding tertiary amino alcohols by treatment with butyric anhydride. After bioresolution, unreacted esters can be easily separated from the corresponding alcohols by extraction with hexane. Bioresolution of quinuclidin-3-yl butyrate has been performed with excellent selectivity.  相似文献   
102.
A Moody  S Setford  S Saini 《The Analyst》2001,126(10):1733-1739
For desirable environmental reasons, peroxides have replaced halogenated substances for disinfection purposes in the food and beverage industry. However, cost issues and the requirement to remove these agents completely after disinfection necessitate simple, low-cost and sensitive test methods with a wide dynamic range and on-line capability. The development and performance of such a method is detailed here. Low-cost peroxide sensors were fabricated using a single deposition procedure, in which horseradish peroxidase enzyme and dimethylferrocene mediator were entrapped within a cellulose acetate membrane, over the working electrode area of a screen-printed three-electrode assembly. Optimum performance was obtained using HRP and DMFc loadings of 25 U and 0.03 micromol per electrode, respectively, and a mean cellulose acetate molecular weight of 37,000. The device had a detection limit of 49.5 microM hydrogen peroxide and mean RSD values of 21% across the concentration range 49.5-368 microM. In laboratory studies the sensor was shown to have a stability of > or = 4 d in continuous flow-mode maintaining an accuracy of +/- 16% that was considered acceptable for the intended on-line monitoring of the disinfection process. In a field study, it was successfully used on-line within a flow-cell to measure peroxide levels during disinfection of an industrial fermentation vessel.  相似文献   
103.
A series of resorcylic acid macrolactones, analogues of the natural product radicicol has been prepared by chemical synthesis, and evaluated as inhibitors of heat shock protein 90 (Hsp90), an emerging attractive target for novel cancer therapeutic agents. The synthesis involves acylation of an ortho‐toluic acid dianion, esterification, followed by a ring‐closing metathesis to form the macrocycle. Subsequent manipulation of the protected hydroxymethyl side chain allows access to a range of new analogues following deprotection of the two phenolic groups. Co‐crystallization of one of the new macrolactones with the N‐terminal domain of yeast Hsp90 confirms that it binds in a similar way to the natural product radicicol and to our previous synthetic analogues, but that the introduction of the additional hydroxymethyl substituent appears to result in an unexpected change in conformation of the macrocyclic ring. As a result of this conformational change, the compounds bound less favorably to Hsp90.  相似文献   
104.
105.
The first stereoselective total synthesis of a beta-d-mannosyl phosphomycoketide is reported. To introduce the stereogenic centers in the chain, three linear chiral building blocks were prepared using two different asymmetric catalytic conjugate addition protocols. Coupling of the various linear fragments was affected using a Julia-Kocienski sequence. This approach constitutes a general and convergent method for the construction of saturated oligoisoprenoid chains of any length and stereochemistry. In addition, an alternative approach for the formation of the difficult beta-mannosyl phosphate linkage was shown to be successful. Biological evalutation of the all-S compound revealed that its antigenic potency for T cells is identical to that of the natural product. This result implies that the fine structure of the lipid part has a strong influence on biological activity and that the T cell response is discriminating between different stereoisomers.  相似文献   
106.
[structure: see text] A family of cyclic 1-deoxysphingolipid derivatives of structure 4 has been designed and synthesized, which may serve as tumorigenesis suppressors for various cancers. Compound 4 is a second-generation analogue developed from sphingosine (1), in which a hydroxyl substituent is moved from C1 to C5 and a methylene is added for conformational rigidity between the C2-nitrogen substituent and C4. The synthetic chemistry for pyrrolidine ring closure at C3-C4 features ring-closing metathesis followed by hydroboration-oxidation.  相似文献   
107.
[structure: see text]The methyl ester of the naturally occurring macrocyclic pentapeptide stephanotic acid, containing an unusual beta-substituted alpha-amino acid with a tryptophan C-6 to leucine beta-carbon link, has been synthesized. The key steps include the formation of this amino acid through a thioxo-oxazolidine intermediate and a Horner-Wadsworth-Emmons reaction using a phosphonoglycine, derived by a dirhodium(II)-catalyzed N-H insertion reaction, to give a dehydroamino acid and subsequent rhodium(I)-catalyzed asymmetric hydrogenation to introduce the modified tryptophan residue.  相似文献   
108.
109.
Dislocation events are seen as excursions or pop-in events in the load–displacement curve of nanoindentation experiments. Two nanoindenters have been used to examine the difference between quasi-static and dynamic loading during indentation. Yield excursions were present in the load–displacement curves of both the statically and dynamically loaded single crystal nickel samples. Only one major excursion occurred in each quasi-static indent, nominally loaded at 100 μN/s while staircase yielding was observed under dynamic loading indentation with a 45 Hz oscillation of 2 nm superimposed on a 60 μN/s loading rate. Thermal activation analysis is used to explain the arrest and reinitiation of the yielding with activation volumes being modeled. For nanoindentation experiments differences between quasi-static and dynamic loading are described by the models presented. It is proposed that insight into the plastic deformation mechanisms associated with such plastic instabilities will provide one of the keys to length scale effects necessary to understanding nanostructures.  相似文献   
110.
The Trp-His-Gly-Arg derived macrocycle 4 of moroidin 1 containing the unusual tryptophan C-2 histidine N-1 link has been synthesised in protected form. The key steps are displacement of a 2-chloroindole with a histidine derived nucleophile, a Horner-Wadsworth-Emmons reaction followed by asymmetric hydrogenation to establish the tryptophan side chain, and incorporation of the Gly-Arg dipeptide by peptide coupling.  相似文献   
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