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991.
The molecular and electronic structure of the Fe 6S 6 H-cluster of [FeFe] hydrogenase in relevant redox and protonation states have been investigated by DFT. The calculations have been carried out according to the broken symmetry approach and considering different environmental conditions. The large negative charge of the H-cluster leads, in a vacuum, to structures different from those observed experimentally in the protein. A better agreement with experimental data is observed for solvated complexes, suggesting that the protein environment could buffer the large negative charge of the H-cluster. The comparison of Fe 6S 6 and Fe 2S 2 DFT models shows that the presence of the Fe 4S 4 moiety does not affect appreciably the geometry of the [2Fe] H cluster. In particular, the Fe 4S 4 cluster alone cannot be invoked to explain the stabilization of the mu-CO forms observed in the enzyme (relative to all-terminal CO species). As for protonation of the hydrogen cluster, it turned out that mu-H species are always more stable than terminal hydride isomers, leading to the conclusion that specific interactions of the H-cluster with the environment, not considered in our calculations, would be necessary to reverse the stability order of mu-H and terminal hydrides. Otherwise, protonation of the metal center and H 2 evolution in the enzyme are predicted to be kinetically controlled processes. Finally, subtle modifications in the H-cluster environment can change the relative stability of key frontier orbitals, triggering electron transfer between the Fe 4S 4 and the Fe 2S 2 moieties forming the H-cluster. 相似文献
992.
Gasparrini F Cancelliere G Ciogli A D'Acquarica I Misiti D Villani C 《Journal of chromatography. A》2008,1191(1-2):205-213
Two new chiral and restricted-access materials containing glycopeptide antibiotics as chiral selectors (chiro-Glyco-RAM) were designed, suitable for the direct HPLC injection of biological fluids containing chiral drugs without any sample pre-treatment or pre-columns coupling. The external surface of the porous silica support was covered with a bio-compatible hydrophilic polymeric network (polyvinyl alcohol, PVA) while the chiral phase based on either teicoplanin (TE) or teicoplanin aglycone (TAG) was exclusively confined to the internal region. The chiro-Glyco-RAM supports were synthesized by the following steps: (a) introduction of 3-aminopropyl groups on 100 A pore size silica gel; (b) activation of the aminopropylated silica with 1,6-diisocyanatohexane; (c) functionalization of the external region of the porous silica with PVA; (d) covalent linking of TE/TAG to the internal surface. The average pore diameter of the chiro-Glyco-RAM supports, calculated by inverse size-exclusion chromatography (ISEC), was about 80 A and able to exclude macromolecules heavier than about 20,000 Da (such as the most abundant serum proteins) from the pores. The recovery of bovine serum albumin (BSA) was almost quantitative. HPLC analyses of model chiral drugs were performed using hydro-organic mobile phases consisting of an organic solvent (acetonitrile or methanol) and aqueous solutions of ammonium acetate (0.020 M) or ammonium formate (0.0025-0.0050 M). 相似文献
993.
Optimization of the selectivity of a cyanopropyl stationary phase for the gas chromatographic analysis of trans fatty acids 总被引:2,自引:0,他引:2
Martin CA de Oliveira CC Visentainer JV Matsushita M de Souza NE 《Journal of chromatography. A》2008,1194(1):111-117
The quantification of monounsaturated and polyunsaturated trans fatty acids in partially hydrogenated fats by gas-liquid chromatography on a CP-Select CB-FAME capillary column was optimized using equivalent chain length values of fatty acids methyl esters that could coelute in the temperature range from 155 to 200 degrees C. The most appropriate temperature for the simultaneous determination of these trans isomers is around 197 degrees C. It is proposed a system to discriminate trans from cis octadecenoic fatty acid methyl esters based on the angular coefficient values of the equivalent chain length curves. The limits of detection and quantification were 0.28 and 0.93 mg g(-1). Quantification was performed in the range from 0.93 to 280 mg g(-1). Quantification accuracy was estimated by spike recovery of elaidic and trans-13-octadecenoic acids in hydrogenated fat samples. The obtained levels were from 97.60 to 103.28% for elaidic acid and from 98.12 to 99.27% for trans-13-octadecenoic acid. These results indicate that the accuracy of the methodology proposed for the quantification of monounsaturated and polyunsaturated trans fatty acids in hydrogenated fats is adequate. 相似文献
994.
Electrokinetic flow of non-Newtonian fluids in microchannels 总被引:1,自引:0,他引:1
995.
In this paper we introduce non-decreasing jump processes with independent and time non-homogeneous increments. Although they are not Lévy processes, they somehow generalize subordinators in the sense that their Laplace exponents are possibly different Bern?tein functions for each time t. By means of these processes, a generalization of subordinate semigroups in the sense of Bochner is proposed. Because of time-inhomogeneity, two-parameter semigroups (propagators) arise and we provide a Phillips formula which leads to time dependent generators. The inverse processes are also investigated and the corresponding governing equations obtained in the form of generalized variable order fractional equations. An application to a generalized subordinate Brownian motion is also examined. 相似文献
996.
Paola Mannucci Claudio Marchi Nicoletta Tchou 《NoDEA : Nonlinear Differential Equations and Applications》2016,23(4):47
We study existence and uniqueness of the invariant measure for stochastic processes with degenerate diffusion, whose infinitesimal generators are linear subelliptic operators in the whole space \({{\mathbb{R}}^N}\) with possibly unbounded coefficients. Such a measure together with a Liouville-type theorem will play a crucial role in two applications: the ergodic problem studied through stationary problems with vanishing discount and the long time behavior of the solution to a parabolic Cauchy problem. In both cases, the constants will be characterized in terms of the invariant measure. 相似文献
997.
Mathematische Annalen - We classify representations of compact connected Lie groups whose induced action on the unit sphere has the orbit space isometric to a Riemannian orbifold. 相似文献
998.
Marcus Henrique de Araujo Tulio Matencio Claudio Luis Donnici Hállen Daniel Rezende Calado 《Journal of Solid State Electrochemistry》2016,20(9):2541-2550
The present work reports the synthesis of four electron-acceptor beta-substituted thiophenes that were studied as monomers for electrochemical polymerization with 3,4-ethylenedioxythiophene (EDOT), an electron-donating monomer, aiming the combination of electron-acceptor and donor monomer thiophene to a simpler and convenient build up of novel donor–acceptor copolymeric materials via electrochemical polymerization. Four novel copolymers poly(EDOT-co-3-thiophene phenylacetate), (PEDOT-co-PPhTAc-2a), poly(EDOT-co-3-thiophene(4-nitrophenyl)acetate) (PEDOT-co-PPhTAc-2b), poly(EDOT-co-3-thiophenephenylcarboxylate) (PEDOT-co-PPhTCb), and poly(EDOT-co-3-(phenoxymethyl)thiophene) (PEDOT-co-PPhOMT) were electrochemically polymerized. The monomers were characterized by spectrometric techniques (FTIR, 1H NMR, and 13C NMR), and the copolymers were identified by electrochemical analyses and FT-IR. Although the corresponding homopolymers could not be obtained, in the presence of EDOT, the copolymers were formed in a quasi-reversible electrochemical kinetics. The infrared spectra of the copolymers as well the electrochemical profile corroborates their obtaining. The mass variation during the electrosynthesis was analyzed using a quartz crystal microbalance. The film’s morphologies were investigated by SEM. Interestingly, the combination of electron-rich monomer thiophene (EDOT) and these electron-deficient carboxy-substituted thiophenes might be a convenient building block couple to increase the performance control of physic-chemical properties of mixed polythiophenes with innovative applications and they also showed a possible applicability as charge storage device. 相似文献
999.
The steady-state UVA (350 nm) photolysis of ( E )-β-ionone ( 1 ) in aerated toluene solutions was studied by 1 H NMR spectroscopy. The formation of the 1,2,4-trioxane ( 2 ) and 5,8-endoperoxide ( 5 ) derivatives in the ratio of 4:1 was observed. Time-resolved laser induced experiments at 355 nm, such as laser-flash photolysis, photoacoustic and singlet oxygen 1 O2 phosphorescence detection, confirmed the formation of the excited triplet state of 1 with a quantum yield Φ T = 0.50 as the precursor for the generation of singlet oxygen 1 O2 ( Φ Δ = 0.16) and the isomeric α-pyran derivative ( 3 ), which was a reaction intermediate detected by NMR. In turn, the reaction of 1 O2 with 1 and 3 occurred with rate constants of 1.0 × 106 and 2.5 × 108 m −1 s−1 to yield the oxygenated products 5 and 2 , respectively, indicating the relevance of the fixed s-cis configuration in the α-pyran ring in the concerted [2+4] cycloaddition of 1 O2 . 相似文献
1000.
Berlin A Muñoz C Gilkes N Alamouti SM Chung P Kang KY Maximenko V Baeza J Freer J Mendonça R Saddler J 《Applied biochemistry and biotechnology》2007,137(1-12):267-280
The development of bioconversion technologies for production of fuels, chemicals, and power from renewable resources is currently a high priority for developed nations such as the United States, Canada, and the European Union as a way to improve national energy security and reduce greenhouse gas emissions. The widespread implementation of such technologies will require a sustainable supply of biomass from forestry and agriculture. Forests are a major source of feedstocks for biofuels production in Canada. Woody biomass includes residues from logging and forest thinning, and from wood processing and pulp production. More recently, damaged wood caused by beetle infestations has become available on a large scale in Western Canada. This study evaluates beetle-killed British Columbian hybrid spruce (HS) (Picea glauca x P. engelmannii) as a feedstock for the production of bioethanol. In the past 30 yr, attack by the beetle Dendroctonus rufipennis and associated fungi has resulted in estimated losses of more than three billion board feet in British Columbia alone. Here we describe the chemical and some physical characteristics of both healthy (HHS) and beetle-killed (BKHS) British Columbian HS and evaluate the technical feasibility of using these feedstocks as a source of biomass for bioethanol production. Untreated HHS and BKHS did not differ significantly in chemical composition except for the moisture content, which was significantly lower in BKHS (approx 10%) compared with HHS (approx 18%). However, the yields of carbohydrates in hydrolyzable and fermentable forms were higher at mild pretreatment conditions (H-Factor <1000) for BKHS compared with HHS. At medium (H-Factor 1000-2000) and severe (H-Factor >2000) pretreatment conditions HHS and BKHS behaved similarly. Organosolv pretreated HHS and BKHS demonstrated good ethanol theoretical yields, approx 70 and 80%, respectively. 相似文献