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991.
含规整聚环氧乙烷枝链的聚硅氧烷的合成及表征 总被引:3,自引:0,他引:3
以萘钾为引发剂,二甲基亚砜为溶剂制备了以烯丙基为末端基的聚环氧乙烷大单体,并利用末端双键的硅氢化反应合成了相对分子质量规整的聚环氧乙烷接枝聚硅氧烷的共聚物。产物经萃取精制后,用IR、 ̄1HNMR等方法进行了表征。 相似文献
992.
The carborane–siloxane copolymers Dexsil 300, a 34.5% bis(dimethylsilyl)-m-carborane–65.5% dimethylsiloxane copolymer, and Dexsil 400, a 24.9% bis(dimethylsilyl)-m-carborane–50.8% dimethyl, 24.3% methylphenylsiloxane copolymer, were coated on fused silica capillary columns and their gas
chromatographic properties were evaluated. Their selectivity was evaluated using both Rohrschneider–McReynolds constants and
triacylglycerol indices. The bis(dimethylsilyl)-m-carborane unit turned out to be equivalent to two dimethylsiloxy units and one half of a diphenylsiloxy unit. The m-carborane unit was found to cause a 15–25 K shift in the elution temperature between 120 and 360 °C. The working range was
from 20 and 0 °C to 380 °C for Dexsil 300 and Dexsil 400, respectively. The column bleeding levels at 380 °C were below 20
and 15 pA for Dexsil 300 and Dexsil 400, respectively. 相似文献
993.
Preparation and characterization of high-specific-surface-area activated carbons from K2CO3-treated waste polyurethane 总被引:2,自引:0,他引:2
Hayashi J Yamamoto N Horikawa T Muroyama K Gomes VG 《Journal of colloid and interface science》2005,290(2):437-443
An activated carbon with high specific surface area was prepared from polyurethane foam by chemical activation with K2CO3 and the influences of carbonization temperature and impregnation ratio on the pore structure of the prepared activated carbon were investigated. It was found that the specific surface area of the activated carbon was at a maximum value (about 2800 m(2)/g) at a carbonization temperature of 1073 K and at an impregnation ratio of 1.0. It was concluded that the polyurethane foam structure was modified during impregnation by K2CO3, K2CO3 promoted charring during carbonization, and then the weight loss behavior was changed below 700 and above 1000 K, carbon in the char was consumed by K2CO3 reduction, and this led to the high specific surface area. The prepared activated carbon had a very sharp micropore size distribution, compared with the commercial activated carbon having high specific surface area. The amounts of three organic vapors (benzene, acetone, and octane) adsorbed on the prepared activated carbons was much larger than those on the traditional coconut shell AC and the same as those on the commercial activated carbon except for octane. We surmised that the high specific surface area was due to the modification of the carbonization behavior of polyurethane foam by K2CO3. 相似文献
994.
ZHOU Hai-cheng XU Sheng PENG Qing LI Ya-dong 《高等学校化学研究》2006,22(1):11-13
IntroductionNano-sized semiconductors are of great interestdue to their special optical and electronic proper-ties[1,2].As one of the mostimportantⅡ—Ⅵsemicon-ductors,CdS has importantapplications in many fields,such as the solar cell field,non linear o… 相似文献
995.
HUANG Yongmin XIAO Xingqing LIU Honglai** HU Ying Department of Chemistry Lab for Advanced Material East China University of Science Technology Shanghai China 《Chinese Journal of Reactive Polymers》2006,(2)
1. INTRODUCTION The extensive applications of block copolymer have been studied in detail due to their special molecular architecture and characteristic [1,2]. Recently, many studies including theoretical analysis and experimental techniques have addressed the polymer blend system of diblock copolymer/homopolymer [3~9]. An early investigation presented a quantitative analysis of homopolymer distributions in well-ordered copolymer microdomains through mixing polystyrene (PS) or poly methyl… 相似文献
996.
Wenjuan Yin Shihai Yan Mei Qin Zhiqiang Li Yuxiang Bu 《International journal of quantum chemistry》2006,106(7):1528-1543
In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol?1, and the forward/backward barriers are 32.27/12.66 kcal · mol?1, decreased by 33.25/31.21 kcal · mol?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
997.
Olga?V.?DorofeevaEmail author Igor?F.?Shishkov Lev?V.?Vilkov István?Hargittai 《Structural chemistry》2005,16(6):617-628
The conformational composition of gaseous MTMNB and the molecular structures of the rotational forms have been studied by
electron diffraction at 130∘C aided by results from ab initio and density functional theory calculations. The conformational potential energy surface
has been investigated by using the B3LYP/6-31G(d,p) method. As a result, six minimum-energy conformers have been identified.
Geometries of all conformers were optimized using MP2/6-31G(d,p), B3LYP/6-31G(d,p), and B3LYP/cc-pVTZ methods. These calculations
resulted in accurate geometries, relative energies, and harmonic vibrational frequencies for all conformers. The B3LYP/cc-pVTZ
energies were then used to calculate the Boltzmann distribution of conformers. The best fit of the electron diffraction data
to calculated values was obtained for the six conformer model, in agreement with the theoretical predictions. Average parameter
values (ra in angstroms, angle α in degrees, and estimated total errors given in parentheses) weighted for the mixture of six conformers
are r(C–C) = 1.507(5), r(C–C)ring, av = 1.397(3), r(C–S)av = 1.814(4), r(C–N) = 1.495(4), r(N–O)av = 1.223(3), ∠(C–C–C)ring = 116.0–122.5, ∠ C6–C4–C7 = 118.2(4), ∠ C–C–S = 113.6(6), ∠ C–S–C = 98.5(12), ∠ N–C–C4 = 121.9(3), ∠(O–N–C)av = 116.8(3), ∠ O–N–O = 127.0(4). Torsional angles could not be refined. Theoretical B3LYP/cc-pVTZ torsional angles for the
rotation about C–N bond, φC−N, were found to be 30.5–36.5∘ for different conformers. As to internal rotation about C–C and C–S bonds, values of φC−C = 68–118∘ and φC−S = 66–71∘ were obtained for the three most stable conformers with gauche orientation with respect to these bonds.
Some conclusions of this work were presented in a short communication in Russ. J. Phys. Chem. 2005, 79, 1701. 相似文献
998.
Holcapek M Volná K Jandera P Kolárová L Lemr K Exner M Církva A 《Journal of mass spectrometry : JMS》2004,39(1):43-50
High-performance liquid chromatography/mass spectrometry (HPLC/MS) analysis of anionic species such as sulphonic acid dyes and intermediates requires volatile ion-pairing mobile phase additives. Six di- and trialkylammonium acetates were compared with tetraalkylammonium salts and ammonium acetate in the concentration range 0-20 mmol l(-1) as mobile phase additives for HPLC/MS of polysulphonated compounds. The effects of the structure and concentration of the ion-pairing reagents on the electrospray response of mono-, di- and tetrasulphonic aromatic acids and acid dyes were studied in detail. Further, five different mass analysers and instrument geometries were compared. A higher signal decrease is observed with linear geometry instruments in comparison to orthogonal or even Z-spray geometry mass spectrometers. The concentration of mobile phase additives has a significant influence on the abundance ratios of multiply charged ions in the mass spectra of polysulphonated compounds. The competing ions of sulphonic acids may also cause significant signal suppression. 相似文献
999.
Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight Mn = 29,700 g mol−1 (MPS = 9300 g mol−1MPMMA = 20,100 g mol−1, PD = 1.15, χPS = 0.323, χPMMA = 0.677) and Mn = 63,900 g mol−1 (MPS = 50,500 g mol−1, MPMMA = 13,400 g mol−1, PD = 1.18, χPS = 0.790, χPMMA = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 °C for 24 h led to a change in surface structure. 相似文献
1000.
To investigate the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine, this study uses a method based on microdialysis technique and liquid chromatography that allows continuous and concurrent in vivo monitoring of extracellular caffeine in the blood, brain and bile of anesthetized rats following the administration of caffeine (3 or 10 mg/kg, i.v.) through the femoral vein. Dialysates of the blood, brain and bile were directly injected onto the liquid chromatographic system and no further clean-up procedures were required. The study design consisted of two groups of six rats in parallel: the rats of the control group received caffeine (3 or 10 mg/kg, i.v.) alone and those of the cyclosporine treated-group were injected cyclosporine (10 mg/kg, i.v.) 10 min prior to caffeine administration (3 or 10 mg/kg, i.v.). The decline of caffeine in the blood, brain striatum and bile suggested that caffeine had rapid exchange and equilibration between the peripheral compartment and the central nervous system. In addition, the results indicated that caffeine underwent hepatobiliary excretion and was distributed into brain. When cyclosporine was co-administered, the pharmacokinetic parameters were not significantly altered. The results of this study reveal that the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine might not relate to P-glycoprotein. 相似文献