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101.
Analogues of MKC-442 capable of undergoing Michael addition reactions were synthesised in order to investigate the activity against the HIV-1 mutant (Y181C). An improved activity was postulated on the basis of a possible covalent binding to the mercapto group of Cys181. Lithiation of the C-6 position of 1-ethoxymethyl-5-ethyl-1H-pyrimidine-2,4-dione (5) was followed by reaction with alpha,beta-unsaturated aldehydes and oxidation of the alcohols formed to give the alkenoyl analogues 1a-3a. Analogues 1b-3b containing an allyloxymethyl group in the N-1 position instead of the ethoxymethyl group could not be synthesised due to isomerisation of the allylic group during the metallation reaction. The NMR data for compounds 1a-3a showed a hindered rotation, which was more pronounced for the 6-cyclohexenylcarbonyl derivative 3a than for the propenyl derivatives 1a and 2a. Moderate activity against wild type HIV-1 was observed for the alcohol 8 and the ketones 2a-3a. However, no activity was observed against the Y181C mutant. 相似文献
102.
Giles GI Fry FH Tasker KM Holme AL Peers C Green KN Klotz LO Sies H Jacob C 《Organic & biomolecular chemistry》2003,1(23):4317-4322
Oxidative stress is implicated, either directly or indirectly, in the pathology of a range of human diseases. As a consequence, the development of efficient antioxidants for medical use has become increasingly important. We have synthesised a range of structurally related organo-sulfur, -selenium and -tellurium agents and demonstrated that a combination of electrochemical methodology, in vitro assays and cell culture tests can be used to rationalise the antioxidant activity of these catalytic agents. Based on its exceptionally low anodic oxidation potential (Epa) and high activity against the representative oxidative stressors tert-butyl hydroperoxide and peroxynitrite, 4,4'-dihydroxydiphenyltelluride is predicted to be a potent antioxidant. This compound exhibits a correspondingly high activity with a remarkably low IC50 value of 20 nM, when tested in PC12 cell culture using a bioassay indicative of the early stages of Alzheimer's disease. 相似文献
103.
[RuCl2(PPh3)3] reacts with thallium(I) fluoride to give either [Tl(mu-F)3Ru(PPh3)3] (1) or [Tl(mu3-F)(mu2-Cl)2Ru2(mu2-Cl)(mu2-F)(PPh3)4] (2) depending on the excess of TlF used. Both 1 and 2 were fully characterized, including X-ray structure determinations. Complex 1 reacts with dihydrogen to form the known ruthenium hydride complex [Ru(H)2(H2)(PPh3)3] upon hydrogenolysis of the Ru-F bond. The reaction of 1 with activated alkyl bromides (R-Br) gives the corresponding alkyl fluorides and the trinuclear complex [Tl(mu3-F)(mu2-F)(mu2-X)Ru2(mu2-Br)(mu2-F)(PPh3)4] (X=Br, F) (3), whose structure closely resembles that of 2. However, 1 is not active as catalyst for the nucleophilic fluorination of R-Br in the presence of thallium fluoride. The effect of the bridging coordination mode of fluoride on the Ru-F bond is discussed in terms of the HSAB principle, which suggests a more general model for predicting the stability of d6 and d8 complexes containing hard ligands (such as fluoro, oxo, and amido). 相似文献
104.
The electrostatic self-assembly monolayer process has been utilized for what is believed to be the first time to deposit quarter-wavelength stacks on the end faces of cleaved and polished optical fibers. Standard multimode optical fibers as well as single-mode optical fibers were used as substrates with different coating materials to fabricate broadband filters, and the experimentally measured spectral responses of these devices are shown. These optical filter structures were employed to develop chemical sensors that use an unperturbed reference wavelength to normalize the output signal. 相似文献
105.
Claus Scheiderer 《Transactions of the American Mathematical Society》2000,352(3):1039-1069
Let be an affine algebraic variety over (or any other real closed field ). We ask when it is true that every positive semidefinite (psd) polynomial function on is a sum of squares (sos). We show that for the answer is always negative if has a real point. Also, if is a smooth non-rational curve all of whose points at infinity are real, the answer is again negative. The same holds if is a smooth surface with only real divisors at infinity. The ``compact' case is harder. We completely settle the case of smooth curves of genus : If such a curve has a complex point at infinity, then every psd function is sos, provided the field is archimedean. If is not archimedean, there are counter-examples of genus .
106.
107.
108.
109.
For every odd prime number p, we give examples of non-constant smooth families of curves of genus 2 over fields of characteristic p which have pro-Galois (pro-étale) covers of infinite degree with geometrically connected fibers. The Jacobians of the curves
are isomorphic to products of elliptic curves. 相似文献
110.