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931.
de Araújo ME Contesini FJ Franco YE Sawaya AC Alberto TG Dalfré N Carvalho Pde O 《Molecules (Basel, Switzerland)》2011,16(8):7171-7182
Response surface methodology (RSM) based on a five-level, three-variable central composite design (CCD) was employed for modeling and optimizing the conversion yield of the enzymatic acylation of hesperidin with decanoic acid using immobilized Candida antarctica lipase B (CALB) in a two-phase system containing [bmim]BF(4). The three variables studied (molar ratio of hesperidin to decanoic acid, [bmim]BF(4)/acetone ratio and lipase concentration) significantly affected the conversion yield of acylated hesperidin derivative. Verification experiments confirmed the validity of the predicted model. The lipase showed higher conversion degree in a two-phase system using [bmim]BF(4) and acetone compared to that in pure acetone. Under the optimal reaction conditions carried out in a single-step biocatalytic process when the water content was kept lower than 200 ppm, the maximum acylation yield was 53.6%. 相似文献
932.
Leung E Datti A Cossette M Goodreid J McCaw SE Mah M Nakhamchik A Ogata K El Bakkouri M Cheng YQ Wodak SJ Eger BT Pai EF Liu J Gray-Owen S Batey RA Houry WA 《Chemistry & biology》2011,18(9):1167-1178
ClpP is a cylindrical serine protease whose ability to degrade proteins is regulated by the unfoldase ATP-dependent chaperones. ClpP on its own can only degrade small peptides. Here, we used ClpP as a target in a high-throughput screen for compounds, which activate the protease and allow it to degrade larger proteins, hence, abolishing the specificity arising from the ATP-dependent chaperones. Our screen resulted in five distinct compounds, which we designate as Activators of Self-Compartmentalizing Proteases 1 to 5 (ACP1 to 5). The compounds are found to stabilize the ClpP double-ring structure. The ACP1 chemical structure was considered to have drug-like characteristics and was further optimized to give analogs with bactericidal activity. Hence, the ACPs represent classes of compounds that can activate ClpP and that can be developed as potential novel antibiotics. 相似文献
933.
Using energy methods, we prove some power-law and exponential decay estimates for classical and nonlocal evolutionary equations. The results obtained are framed into a general setting, which comprise, among the others, equations involving both standard and Caputo time-derivative, complex valued magnetic operators, fractional porous media equations and nonlocal Kirchhoff operators.Both local and fractional space diffusion are taken into account, possibly in a nonlinear setting. The different quantitative behaviours, which distinguish polynomial decays from exponential ones, depend heavily on the structure of the time-derivative involved in the equation. 相似文献
934.
Orth ES Medeiros M Bortolotto T Terenzi H Kirby AJ Nome F 《The Journal of organic chemistry》2011,76(24):10345-10348
We report a detailed kinetic and mechanistic study of the reaction of a widely used therapeutic agent, deferoxamine (DFO), which contains three nucleophilic hydroxamate groups, with the model phosphate diester bis-2,4-dinitrophenylphosphate BDNPP. We clarify the mechanism by detecting important phosphorylated intermediates in the model reaction and show that the mechanism can be extended to the reaction with DNA. The effectiveness of DFO in cleaving DNA was examined over a range of pH in the absence and presence of a biologically available metal (Zn(2+)). The results inform and complement ongoing studies involving DFO, which can act as a powerful nucleophile toward DNA and other targets susceptible to nucleophilic attack. 相似文献
935.
Orth ES Wanderlind EH Medeiros M Oliveira PS Vaz BG Eberlin MN Kirby AJ Nome F 《The Journal of organic chemistry》2011,76(19):8003-8008
The phosphorylation of imidazole by two activated phosphate diesters and a triester gives phosphorylimidazole derivatives that are stable enough in aqueous solution to be observed and identified by ESI-MS/MS and NMR. Half-lives ranging from hours to days (in the case of the monoethyl ester) show that it is possible to design molecules with variable half-lives with potential to be used for biological intervention experiments as possible inhibitors of biosignaling processes or as haptens for the generation of antibodies. 相似文献
936.
Giomi D Alfini R Micoli A Calamai E Faggi C Brandi A 《The Journal of organic chemistry》2011,76(22):9536-9541
1-(2-Pyridyl)-2-propen-1-ol, obtained by vinylation of commercially available picolinaldehyde, resulted a good starting material for the synthesis of the indolizidine skeleton. In particular, a simple process involving bromination, reduction, and nucleophilic substitution (via elimination and addition) allowed an easy conversion of the starting material into (±)-lentiginosine in ~27% overall yield. 相似文献
937.
Cliciane Guadalupe de Jesus Cristiane Maria Sampaio Forte Karen Wohnrath Christiana Andrade Pessôa Janete Elisa de Sá Soares Sérgio Toshio Fujiwara Pedro de Lima‐Neto Adriana Nunes Correia 《Electroanalysis》2011,23(8):1814-1820
A (SiPy+Cl?/CuTsPc)5 layer‐by‐layer film was employed for the electroanalytical determination of promethazine hydrochloride in BR buffer pH 5.0 with peaks at 0.48 and 0.79 V. After optimisation of the square‐wave parameters (f=100 s?1, a=40 mV and ΔEs=2 mV), the peak at 0.79 V was used for quantification and a detection limit of 8.71×10?9 mol L?1 and a quantification limit of 9.31×10?8 were calculated. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples, without any preliminary treatment. 相似文献
938.
Dr. Elena Arceo Dr. Elisa Montroni Prof. Dr. Paolo Melchiorre 《Angewandte Chemie (International ed. in English)》2014,53(45):12064-12068
We have found that an organic molecule as simple as p‐anisaldehyde efficiently catalyzes the intermolecular atom‐transfer radical addition (ATRA) of a variety of haloalkanes onto olefins, one of the fundamental carbon–carbon bond‐forming transformations in organic chemistry. The reaction requires exceptionally mild reaction conditions to proceed, as it occurs at ambient temperature and under illumination by a readily available fluorescent light bulb. Initial investigations support a mechanism whereby the aldehydic catalyst photochemically generates the reactive radical species by sensitization of the organic halides by an energy‐transfer pathway. 相似文献
939.
New evidence about the path followed in the photochemical reaction of 4-(2-nitrophenyl)-1,4-dihydropyridines such as the drugs nifedipine (Compound 1) and nisoldipine (Compound 2) to give the corresponding nitrosophenylpyridines has been found through determination of the steady-state photochemical parameters and a comparison of the photoreactions in solution and in matrix at 90 K. Additional support is given by comparison with the isomeric 4-(3-nitrophenyl)dihydropyridine as well as with simpler derivatives, such as the corresponding 4-methyldihydropyridine. In Compounds 1 and 2, the lowest lying singlet, localized on the dihydropyridine chromophore, is deactivated by (largely exothermic) electron transfer to the nitrobenzene moiety, as evidenced by the complete quenching of the blue fluorescence observed in analogues not containing the electron-accepting group. Intramolecular proton transfer ensues in the 2-nitrophenyl derivatives with a relatively medium-independent quantum yield of approximately 0.3 and leads to an aromatic zwitterion, which is detected in matrix at 90 K (photoionization of this intermediate takes place in 2-methyltetrahydrofuran secondary). The intermediate is smoothly converted into the end product upon melting the glass. The 3-nitrophenyl analog, for which such a path is not available, is less reactive by about three orders of magnitude at 366 nm, although the quantum yield arrives at approximately 0.01 by irradiation at 254 nm in MeOH, reasonably via the nitrophenyl localized triplet. 相似文献
940.
Two-dimensional (2D) electrophoresis is the most wide spread technique for the separation of proteins in biological systems. This technique produces 2D maps of high complexity, which creates difficulties in the comparison of different samples. The method proposed in this paper for the comparison of different 2D maps can be summarised in four steps: (a) digitalisation of the image; (b) fuzzyfication of the digitalised map in order to consider the variability of the two-dimensional electrophoretic separation; (c) decoding by principal component analysis of the previously obtained fuzzy maps, in order to reduce the system dimensionality; (d) classification analysis (linear discriminant analysis), in order to separate the samples contained in the dataset according to the classes present in said dataset. This method was applied to a dataset constituted by eight samples: four belonging to healthy human lymph-nodes and four deriving from non-Hodgkin lymphomas. The amount of fuzzyfication of the original map is governed by the sigma parameter. The larger the value, the more fuzzy theresulting transformed map. The effect of the fuzzyfication parameter was investigated, the optimal results being obtained for sigma = 1.75 and 2.25. Principal component analysis and linear discriminant analysis allowed the separation of the two classes of samples without any misclassification. 相似文献