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91.
CH3S CH2SH异化反应的理论研究 总被引:2,自引:1,他引:1
利用密度泛函理论(DFT)和从头算(ab initio)研究了CH3S←→CH2SH互异化的反应机理.采用HF、B3LYP、MP2理论水平和中等基组6-31(d),计算了CH3S、CH2SH及其过渡态的结构参数、谐振频率、零点能(ZPF)、总能量和相对能量,并利用B3LYP/6-31(d)的方法计算了反应的内禀反应坐标(IRC),给出了分子构型和自旋污染沿反应坐标的变化曲线,以及最小能量曲线(MEP)、绝热能量曲线.此外,利用传统过渡态理论(CTST)研究了该互异化反应的速率常数和平衡常数在200~1000K的变化. 相似文献
92.
Anette Munch Elmr Patric Jannasch 《Journal of polymer science. Part A, Polymer chemistry》2006,44(7):2195-2205
Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10?6 S cm?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006 相似文献
93.
94.
We consider a discrete-time stochastic model of an ECN/RED gateway where competing TCP sources share the link capacity. As
the number of competing flows becomes large, the asymptotic queue behavior (normalized by the number of flows) at the gateway
can be described by a simple recursion and the throughput behavior of individual TCP flows becomes asymptotically independent.
A Central Limit Theorem complement is also presented, yielding a more accurate characterization of the asymptotic queue size.
These results suggest a scalable yet accurate model of this complex large-scale stochastic feedback system, and crisply reveal
the sources of queue fluctuations.
This work was prepared through collaborative participation in the Communications and Networks Consortium sponsored by the
U.S. Army Research Laboratory under the Collaborative Technology Alliance Program, Cooperative Agreement DAAD19-01-2-0011.
This work was also supported by the Space and Naval Warfare Systems Center—San Diego under Contract No: N66001-00-C-8063.
The views and conclusions contained in this document are those of the authors and should not be interpreted as representing
the official policies, either expressed or implied, of the Army Research Laboratory or the U.S. Government. 相似文献
95.
R. B. King 《Russian Chemical Bulletin》1993,42(11):1772-1781
Reactions of disodium tetracarbonylferrate, Na2Fe(CO)4, with sterically hindered dialkylaminodichlorophosphines, R2NPCl2 (R2N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (i-Pr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993. 相似文献
96.
Santanu Bhattacharya Basudeb Saha Amitava Dutta Pradyot Banerjee 《Coordination chemistry reviews》1998,170(1):47-74
This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed. 相似文献
97.
Nadeem Saeed Basant K Puri Angela Oatridge Joseph V Hajnal Ian R Young 《Magnetic resonance imaging》1998,16(10):1237-1247
Two semi-automated methods for quantification of ventricular volume change from baseline and follow-up magnetic resonance imaging scans have been developed. Technique 1 employs direct segmentation of the ventricles from both the scans using thresholding and contour extraction. Technique 2 operates on difference images produced by voxel based intensity subtraction of the baseline from the registered follow-up images. Here, all voxels with intensities above a noise threshold and in a restricted area are monitored to compute volumetric changes. In phantom measurements the first technique was accurate to 0.0046%, the second to 0.167% of the phantom volume. Results from normal volunteers was that the average ventricular volume changed by 1.52% and 1.54% for images acquired within 9 months using techniques 1 and 2, respectively. With schizophrenic patients mean change of 10.78% and 9.43% were found employing the first and second procedures, respectively. All measurements agreed with a radiologist’s visual grading of the changes. Robust, objective, fast, easy-to-use, and fairly accurate procedures have been developed and validated to quantify volumetric changes. 相似文献
98.
C. N. Carducci S. E. Lucangioli V. G. Rodríguez G. C. Fernndez Otero 《Journal of chromatography. A》1996,730(1-2):313-319
Sample preparation procedures using octadecyl (C18) extraction disks were developed to obtain accurate and reproducible results for determinations of clenbuterol (20 μg per dose) and levothyroxine (100 μg per dose) in dissolution media of solid oral dosage forms. Preconcentration of samples allowed final concentrations of 1.1 μg/ml of clenbuterol and 4.0 μg/ml of levothyroxine to be reached prior to CE analysis. The results obtained by CE were in good agreement with those of HPLC. The precision of the migration time, peak area, peak height and accuracy were determined in both intea-day (n = 6) and inter-day (n =18) assays. Linearity was demonstrated over the ranges 0.5–80.0 μg/ml of clenbuterol and 1.0–30.0 μg/ml of levothyroxine. The mean recoveries were higher than 94.0%, ranging from 50 to 125% levels with respect to dose potencies. The proposed methodology may be generally applied to determine drugs at ng/ml concentrations. 相似文献
99.
100.
从芒果皮中提取果胶的工艺研究 总被引:5,自引:0,他引:5
果胶是一种大分子多糖类物质 ,具有良好的胶凝作用 ,用途广泛 ,在国内外市场上的销量很好。 1 990年世界上果胶总产量约 2 5 0 0 0吨 ,而我国 1 990年仅在食品工业上消耗的果胶就达 1 0 0 0吨 ,但国内市场上销售的果胶大部分为进口货[1] 。果胶在我国的生产仍处于开发阶段 ,所以发掘新的提取资源、提高果胶质量、降低果胶生产成本的意义十分重大。目前 ,已有以柑桔皮、向日葵盘、苹果皮、香蕉皮、马铃薯渣为原料提取果胶的研究报道 ,如何从芒果皮中提取果胶却未见报道。芒果在制造罐头和饮料中副产大量下脚料———芒果皮 ,未能得到充分利用… 相似文献