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91.
Hydrogen abstraction reaction, H C2H4 --H2 C2H2 was studied by using A initio SCF method. Ge-ometries were fully optimized at SCF level and energies were computed at STO-3G basis set for reactants and transition state. Vibrational analysis was performed thereupon. Finally, the rate constant calculations were carried out at different temperatures for all range of reaction temperature according to Eyring's sbwlute reaction rate theory. The calculated activation energy is 12. 68 kcal/mol, lower than observed value (H. S kcal/mol) by 1. 82 kcal/mol only. The agreement of the calculated rate constants with the experiments is satisfactory. 相似文献
92.
Ingo Pinnau 《先进技术聚合物》1994,5(11):733-744
During the past 20 years membrane systems have been applied to a limited number of commercial gas separations. To further advance membrane-based gas separations, current research efforts focus on optimization of (i) membrane materials, (ii) membrane structures and (iii) membrane system design. In this overview, recent developments in the formation of high-performance gas separation membranes are discussed. The gas separation properties of state-of-the-art integrally skinned asymmetric membranes and thin-film composite membranes are summarized. Future directions for the preparation of advanced gas separation membranes are highlighted. 相似文献
93.
The objective of this study was to characterize the fractionation profile of casein hydrolysates obtained with polysulfone hollow fiber ultrafiltration membranes. The two-step ultrafiltration process developed by Turgeon and Gauthier [J. Food Sci., 55 (1990) 106] was used: a caseinate solution was submitted to proteolysis with chymotrypsin or trypsin, and the reaction mixture (RM) was subsequently ultrafiltered using a 30 kDa (MWCO) hollow-fiber polysulfone membrane. The total hydrolysate permeating from this first step was further fractionated using a 1 kDa (MWCO) membrane, producing the mixture of polypeptides (retentate) and the amino acid fraction (permeate). The effect of enzyme specificity and of membrane retentivitiy on the total composition (total nitrogen, fat, lactose, minerals) and amino acid profile of the fractions was studied. The overall composition of the fractions was not significantly affected by the nature of the enzyme but the degree of hydrolysis and the molecular weight distribution profile analyses showed a marked effect of the enzyme specificity, with trypsin giving a larger proportion of small peptides (< 200 Da) in the mixture of polypeptides. Amino acid profile analyses provided useful information on the phenomena governing the fractionation of amino acids with a polysulfone membrane: (1) the target amino acids of the enzyme are concentrated in the permeate as a result of their presence in all peptides produced by hydrolysis, (2) polar amino acids are retained by the membrane, (3) non-polar amino acids are not selectively rejected by the membrane. Our results suggest that the charge/hydrophobicity balance of the peptides produced is the predominant factor determining the fractionation of casein hydrolysates. 相似文献
94.
95.
ZHANG Jun SUN Xiao-min CAI Zheng-ting FENG Da-cheng 《高等学校化学研究》2006,22(5):663-664
In the stratosphere,CF3Cl(CFC13)can either photodecompose or react directly with atomic oxygen to generate ozone-depleting agents such as Cl and ClO in the gas phase[1—3].Since the1970s,attention has been focused on the effects of these compounds on the … 相似文献
96.
In order to enhance the shelf-life of edible mature mushrooms Agaricus bisporus, 2 kGy ionising treatments were applied at two different dose rates: 4.5 kGy/h (I−) and 32 kGy/h (I+). Both I+ and I− showed 2 and 4 days shelf-life enhancement compared to the control (C). Before day 9, no significant difference (p>0.05) in L* value was detected in irradiated mushrooms. However, after day 9, the highest observed L* value (whiteness) was obtained for the mushrooms irradiated in I−. Analyses of phenolic compounds revealed that mushrooms in I− contained more phenols than I+ and C, the latter containing the lower level of phenols. The polyphenol oxidase (PPO) activities of irradiated mushrooms, analysed via catechol oxidase and dopa oxidase substrates, resulted in being significantly lowered (p0.05) compared to C, with a further decrease in I+. Analyses of the enzymes indicated that PPO activity was lower in I+, contrasting with its lower phenol concentration. Ionising treatments also increased significantly (p0.05) the phenylalanine ammonia-lyase (PAL) activity. The observation of mushrooms cellular membranes, by electronic microscopy, revealed a better preserved integrity in I− than in I+. It is thus assumed that the browning effect observed in I+ was caused by both the decompartimentation of vacuolar phenol and by the entry of molecular oxygen into the cell cytoplasm. The synergetic effect of the residual active PPO and the molecular oxygen, in contact with the phenols, allowed an increased oxidation rate and, therefore, a more pronounced browning in I+ than in I−. 相似文献
97.
采用密度泛函理论计算方法, 在B3LYP/6-311G*水平下, 计算并得到了SiHCl3与H2反应各反应通道上各驻点的构型、振动频率和能量. 结果表明, 在气相中SiHCl3分解的通道d和SiHCl3与H2反应的通道c为竞争反应, 但其均未还原出Si原子, 只有衬底Si参与SiHCl3-H2的反应, Si原子才淀积在Si衬底上. 相似文献
98.
Diaminocarboxylic acid carrier ampholytes, such as L-histidine, 2,3-diaminopropionic acid, L-ornithine, and L-lysine, were reacted with glycerol-1,3-diglycidyl ether (GDGE) and poly(vinyl alcohol) (PVA) in the presence of sodium hydroxide to produce hydrolytically and mechanically stable hydrogels, supported on a PVA substrate, for use as buffering membranes in isoelectric trapping (IET) separations. The pH values of the DACAPVA membranes were determined with the help of small-molecule pI markers and proteins and were found to be in the 6 < pH < 8.5 range. The membranes were successfully used to isoelectrically trap small ampholytes, desalt ampholyte solutions in IET mode, and effect the binary separation of chicken egg white proteins. 相似文献
99.
Silicalite-filled poly(siloxane imide) membranes for removal of VOCs from water by pervaporation 总被引:3,自引:0,他引:3
Silicalite-filled poly(siloxane imide) (PSI) membranes were prepared for the separation of volatile organic compounds (VOCs) from water via pervaporation. PSI copolymer was synthesized by polycondensation of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with a siloxane-containing diamine, e.g., poly(dimethylsiloxane), bis(3-aminopropyl) terminated (PSX), added with 3,3-diaminodiphenyl sulfone (DDS). 2,4,6-Triamine pyrimidine (TAP) was added into the casting solution in order to enhance the compatibility between the polymeric matrix and the filler, silicalite. The PSI membranes were characterized by SEM. The surface morphology for the membrane with the addition of TAP differs from that without TAP. The latter seems to be consisting of particles in the membrane surface. The sorption selectivity of the PSI membranes for chloroform/water solutions was investigated, and there was a highest value for it around 50 wt.% of PSX content. The pervaporation performance of the membranes was studied with the separation of chloroform/water mixture. The silicalite-filled membrane with 120 μm thickness exhibit a high total permeation flux of 280 g m−2 h−1 with separation factor of 52.2 for 1.2 wt.% of the chloroform/water mixture. 相似文献
100.
Lucia?MutihacEmail author Hans-Jürgen?Buschmann Radu-Cristian?Mutihac Eckhard?Schollmeyer 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):1-10
The ability of calix[n]arenes to form complexes, to act as extractants in liquid–liquid extraction, and run as carriers in transport through liquid membranes of different biological amine compounds (e.g., ammonium ion, amines, amino acids, and peptides) has been the central topics of many reports. These features recommend the calix[n]arenes as competitive candidates for studying the interactions involved in host–guest recognition as well as useful receptors in separation processes. Some specific aspects of their applications in binding and separation of various amine compounds by extraction, and in transport through liquid membranes have therefore been considered. The effect of the factors that might influence the separation of above compounds by extraction, and the transport through liquid membranes using the calix [n]arenes has been presented.This revised version was published online in July 2005 with a corrected issue number. 相似文献