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31.
Vishal Sipani Ann Kirsch Alec B. Scranton 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4409-4416
The effective propagation rate constant (kp; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the kp as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the kp values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004 相似文献
32.
Jack Harrowfield Dominique Matt 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(3-4):133-150
The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion. 相似文献
33.
DongXiangLI WanGuoHOU ShuPingLI MingTuHAO GaoYongZHANG 《中国化学快报》2004,15(2):224-227
The relation of the isoelectric point (IEP) and the point of zero net charge (PZNC) of the hydrotalcite-like compounds was discussed. It was found that the IEP does not equal to the PZNC and the IEP is higher than the PZNC. The structural positive charges existing in the HTlc,which cause the difference between the IEP and the PZNC. The effects of the structural positive charges of the HTlc on its IEP and PZNC are the same as the specific adsorption of metal cations. 相似文献
34.
R. Gerbaldo G. Ghigo G. Giunchi L. Gozzelino F. Laviano E. Mezzetti 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,26(3):297-300
We present results from an extended magneto-optical (MO) analysis of two samples cut from high-density pellets of MgB2. The first sample was studied in order to show that no matter how large the sample is and despite the bulk granularity, the
material enters into a critical state in a crystal-like fashion. The second sample was chosen for the quantitative analysis.
A numerical approach based on an inverted 2D Biot-Savart model was used to calculate the current paths across the homogeneous
polycrystalline bulk, as well as in the vicinity and across some morphological defects. Local current densities in the homogeneous
part were estimated as a function of the applied magnetic field at different temperatures, in three regimes: below full penetration,
at full penetration and above full penetration, respectively. A hypothesis of interpretation of the apparent absence of magnetic
granularity inside the polycrystalline microstructure is presented. It is related to a critical state likely reached by a
network of strongly coupled Josephson junctions.
Received 31 May 2001 and Received in final form 5 December 2001 相似文献
35.
Long range one-dimensional ordering of lead phthalocyanine monolayer on InSb(1 0 0) (4 × 2)/c(8 × 2)
Sub-monolayer and monolayer of lead phthalocyanine deposited on InSb(1 0 0) (4 × 2)/c(8 × 2) surface have been investigated by scanning tunneling microscopy and low energy electron diffraction. Molecules first adsorb on the indium rows of the (4 × 2)/c(8 × 2) structure in the [1 1 0] direction and diffuse at the surface in order to form two-dimensional islands. The molecule-substrate interaction stabilizes the PbPc molecules on the In rows. It weakens the interaction between molecules located in adjacent rows resulting in numerous gliding planes between the molecular chains, in the direction parallel to the rows. At monolayer completion, a long-range one-dimensional order is adopted by the molecules in the [1 1 0] direction. 相似文献
36.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
37.
38.
饲喂频率对鲈鱼生长及体生化成分的影响 总被引:2,自引:0,他引:2
选取同一种饵料设置1次·d-1、2次·d-1、3次·d-1、4次·d-14个饲喂频率,采用静水连续充气养殖系统,在盐度为26.0%~27.0%、温度为26~30℃条件下对鲈鱼(85.95±2.04)g进行为期40d的生长实验.结果表明:(1)饲喂频率影响鲈鱼的生长是由食物转化率和摄食率的提高共同引起的.(2)水分含量随饲喂频率的增高而保持不变;蛋白质含量随饲喂频率的增加,基本保持不变;脂肪含量随饲喂频率的增高而明显减少;灰分含量随饲喂频率的增多而明显增加.(3)鲈鱼的适宜饲喂频率为2次·d-1. 相似文献
39.
Leonard M Khalilov Ludmila V Parfenova Askhat G Ibragimov Usein M Dzhemilev 《Journal of organometallic chemistry》2004,689(2):444-453
This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt3 and i-Bu2AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp2ZrCl2. 相似文献
40.
Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献