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71.
P. Molina Ma. J. Vilaplana P. L. Andreu J. Mller 《Journal of heterocyclic chemistry》1987,24(5):1281-1284
N-Aryl-N-(α-phenylphenacyl)oxamoyl chlorides react with N3-arylsubstituted amidrazones to give functionalized 1,2,4-triazoles which undergo ring-closure by the action of thionyl chloride to give 1,2,4-triazolo[1,5-a]-pyrazinium chlorides in excellent yields. 相似文献
72.
Ethanol production from steam-explosion pretreated wheat straw 总被引:1,自引:0,他引:1
Ignacio Ballesteros Ma José Negro José Miguel Oliva Araceli Cabañas Paloma Manzanares Mercedes Ballesteros 《Applied biochemistry and biotechnology》2006,130(1-3):496-508
Bioconversion of cereal straw to bioethanol is becoming an attractive alternative to conventional fuel ethanol production
from grains. In this work, the best operational conditions for steam-explosion pretreatment of wheat straw for ethanol production
by a simultaneous saccharification and fermentation process were studied, using diluted acid [H2SO4 0.9% (w/w)] and water as preimpregnation agents. Acid-or water-impregnated biomass was steam-exploded at different temperatures
(160–200°C) and residence times (5, 10, and 20 min). Composition of solid and filtrate obtained after pretreatment, enzymatic
digestibility and ethanol production of pretreated wheat straw at different experimental conditions was analyzed. The best
pretreatment conditions to obtain high conversion yield to ethanol (approx 80% of theoretical) of cellulose-rich residue after
steam-explosion were 190°C and 10 min or 200°C and 5 min, in acid-impregnated straw. However, 180°C for 10 min in acid-impregnated
biomass provided the highest ethanol yield referred to raw material (140 L/t wheat straw), and sugars recovery yield in the
filtrate (300 g/kg wheat straw). 相似文献
73.
Regioselectivity in acylation of oligosaccharides catalyzed by the metalloprotease thermolysin 总被引:2,自引:0,他引:2
Investigation of the acylation scope of carbohydrates by metalloprotease thermolysin immobilized on Celite as biocatalyst has been carried out. The reactions were performed in DMSO, a good solvent for carbohydrates, where the enzyme has previously shown its activity in transesterifications of sucrose, maltose and maltose-containing oligosaccharides. Surprisingly, no reaction was observed for glucose or the glucose-containing disaccharides, trehalose and lactose. In contrast, laurate monoesters of several sucrose-containing tri- and tetrasaccharides were synthetized through a one step transesterification using vinyl laurate as the acylating agent. Enzyme regioselectivity was accurately determined by HPLC/MS and the structure of the main regioisomers was established by a combination of NMR experiments. The preferred position of acylation in all cases was the 2-OH of the α-d-glucopyranose moiety linked 1→2 to the β-d-fructofuranose unit. These results correlate with the regioselectivity observed in the case of the disaccharide sucrose. A general carbohydrate binding motif for catalysis by thermolysin is proposed. 相似文献
74.
Ruggero Curci Sergio Giannattasio Oronzo Sciacovelli Luigino Troisi 《Tetrahedron》1984,40(14):2763-2771
The oxidation of organic sulphides (n-Bu2S, PhSCH3, Tolyl-SCH3, p-Cl-C6H4SCH3, and Ph2S by (HMPT)CrO(O2)21′ in CHCl3 has been studied. The reaction produces the corresponding sulphoxides in nearly quantitative yields according to a 2:1 stoichiometry of sulphide to metaldiperoxide. A second-order-overall (order one in each of the reagents) kinetic law is obeyed. In parallel, the oxidation of organic sulphides by (HMPT)MoO(O2)21' has been studied. Kinetic data, the observed rate laws, and the effect of inhibitors (HMPT, DABCO) have pointed out that-although 1' is significantly more reactive than 1′—considerable similarity exists between the two metaldiperoxides, in that both appear to act as electrophilic oxidizers. Also, through 1H, 31P and 13C NMR investigations have permitted to assess the relevance of equilibria (HMPT)MO(O22 MO(O2)2 + HMPT [with M = Mo(VI) or Cr(VI)]in solution, whereas no NMR evidence could be found for significant substrate coordination under the given conditions. 相似文献
75.
Roberto Dallocchio Barbara Sechi Alessandro Dessì Bezhan Chankvetadze Sergio Cossu Victor Mamane Robin Weiss Patrick Pale Paola Peluso 《Electrophoresis》2021,42(17-18):1853-1863
2’-(4-Pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs (TCIBP = 3,3’,5,5’-tetrachloro-2-iodo-4,4’-bipyridyl) are chiral compounds that showed interesting inhibition activity against transthyretin fibrillation in vitro. We became interested in their enantioseparation since we noticed that the M-stereoisomer is more effective than the P-enantiomer. Based thereon, we recently reported the enantioseparation of 2’-substituted TCIBP derivatives with amylose-based chiral columns. Following this study, herein we describe the comparative enantioseparation of both 2’-(4-pyridyl)- and 2’-(4-hydroxyphenyl)-TCIBPs on four cellulose phenylcarbamate-based chiral columns aiming to explore the effect of the polymer backbone, as well as the nature and position of substituents on the side groups on the enantioseparability of these compounds. In the frame of this project, the impact of subtle variations of analyte and polysaccharide structures, and mobile phase (MP) polarity on retention and selectivity was evaluated. The effect of temperature on retention and selectivity was also considered, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van ’t Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal were observed. In particular, the EEO was shown to be dependent on polysaccharide backbone, the elution sequence of the two analytes being P-M and M-P on cellulose and amylose tris(3,5-dimethylphenylcarbamate), respectively. In this regard, a theoretical investigation based on molecular dynamics (MD) simulations was performed by using amylose and cellulose tris(3,5-dimethylphenylcarbamate) nonamers as virtual models of the polysaccharide-based selectors. This exploration at the molecular level shed light on the origin of the enantiodiscrimination processes. 相似文献
76.
Product distribution, total quenching rate (kT), and rate of chemical reaction (kr) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines. 相似文献
77.
Octavio Surez-Iglesias Ignacio Medina Consuelo Pizarro Julio L. Bueno 《Fluid Phase Equilibria》2007,260(2):279-286
The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities. 相似文献
78.
UVB irradiation of normal human skin favors the development of type-2 T-cells in vivo and in primary dermal cell cultures 总被引:1,自引:0,他引:1
Di Nuzzo S Sylva-Steenland RM Koomen CW Nakagawa S van Breemen M de Rie MA Das PK Bos JD Teunissen MB 《Photochemistry and photobiology》2002,76(3):301-309
To determine the effect of UVB exposure on the balance of type-1 or type-2 T-cells in skin, we examined the expression of key markers interferon (IFN)-gamma and interleukin (IL)-4 in cryostat sections. IFN-gamma mRNA was clearly detectable in nonirradiated control skin, and IFN-gamma protein was found in 2% of the dermal CD3pos T-cells, whereas IL-4 mRNA was hardly detectable, and no IL-4 protein was found. In contrast, IL-4 mRNA expression increased upon irradiation, and IL-4 was found in 2% of the T-cells at day 2 after UVB-exposure. Concomitantly, IFN-gamma mRNA expression decreased, and IFN-gamma protein became absent. We also analyzed T-cells present in primary dermal cell cultures, which were used as an in vitro equivalent of the in vivo situation. As compared with T-cells from control skin, T-cells in dermal cell cultures from UVB-exposed skin displayed an increased IL-4 and decreased IFN-gamma expression. No such skewing occurred when the T-cells from irradiated skin were cloned in the absence of a dermal microenvironment. Except for an occasional positive T-cell, type-1-associated cell-surface markers (CCR5, CXCR3) or type-2 markers (CCR3, CD30, CRTH2) were undetectable in situ. But these markers were expressed on cultured dermal T-cells from UVB-exposed and control skin at a comparable level, but did not correlate with the IFN-gamma and IL-4 production. Altogether, UVB-induced changes of the dermal microenvironment favor the development of type-2 T-cells. 相似文献
79.
Viñas P Aguinaga N López-García I Hernandez-Córdoba M 《Journal of AOAC International》2002,85(3):736-743
Procedures were developed for determining cadmium, aluminium, and copper in beer and the products used in its manufacture by electrothermal atomic absorption spectrometry. Beer samples were injected into the furnace and solid samples were introduced as suspensions after preparation in a medium containing hydrogen peroxide, nitric acid, and ammonium dihydrogen phosphate for cadmium atomization. Calibration was performed with aqueous standards, and characteristic masses and detection limits were, respectively, 1 and 0.3 pg for cadmium, 18 and 5.4 pg for aluminium, and 5.6 and 6.8 pg for copper. Different samples of beer, wort, brewer's yeast, malt, raw grain, and hops were analyzed by the proposed procedures. Cadmium was found in low concentrations (0.001-0.08 microg/g and 0-1.3 ng/mL); copper (3-13 microg/g and 25-137 ng/mL) and aluminium (0.6-9 microg/g and 0.1-2 microg/mL) were found at higher levels. The reliability of the procedure was confirmed by comparing the results obtained with others based on microwave oven sample digestion, and by analyzing several certified reference materials. 相似文献
80.
Pedro Molina Angeles Lorenzo Rosa Ma Claramunt José Elguero 《Tetrahedron letters》1984,25(47):5427-5428
A number of mesoionic compounds derivatives of the bicyclic system 1,2,4-triazolo(4,3-b)-1,2,4-triazole have been prepared from 4-amino-1-methyl-3,5-bis(methylthio)-1,2,4-triazolium iodide and aryl isothiocyanates. 相似文献