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121.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献
122.
辐照对聚己内酯结构和性能的影响 总被引:5,自引:2,他引:5
研究了γ 辐照对不同分子量的聚己内酯 (PCL)的力学性能、热性能、结晶行为的影响 ,在此基础上 ,研究了辐射交联后的PCL的形状记忆行为 .研究结果表明 ,PCL的分子量越大 ,辐射交联所需的凝胶化剂量越低 .溶胶分数S +S1 2 与 1 D的关系很好地符合Charlesby Pinner关系式 ,说明PCL的辐射交联属于无规交联 .剂量对PCL的力学性能影响显著 ,剂量越大 ,抗张强度和断裂伸长率下降越多 ,但分子量较高的PCL的抗张强度受剂量的影响较小 .DMA分析表明 ,聚己内酯辐照交联后的弹性模量和耐热性能显著提高 .交联度较高的PCL表现出高弹态 ,可以拉伸 ,并具有较好的形状记忆行为 .DSC分析表明 ,辐射交联使PCL的结晶度有所增加 ,但也使结晶熔点有所降低 相似文献
123.
《Journal of Molecular Structure》1995,343(1-3):125-132
A computer method has been developed which is an alternative to molecular dynamics in the sense that it pictures conformational motion. It simulates propagation in conformational movement based on conformational interconversion phenomena. The method starts with the knowledge of the topology of the conformational potential energy hyper-surface, which is described by the minima and the transition states. The topology is obtained by the recently described software
. The simulation of conformational motion is based on the Boltzmann statistics of movement between the minima and the transition states at a given temperature. The method is illustrated for methyl--glucopyranoside and -
-galNAc(1-3)[-
-Fuc(1-2)]Gal-O-Me molecules. Conformational transitions of hydroxyl groups as well as glycosidic linkages are discussed. 相似文献
124.
The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C5Me4(SiMe3)(SiMe2Cl) with MCl4 afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(η5-C5Me4SiMe2Cl)Cl3 [M=Ti (1), Zr (2)] with selective elimination of SiMe3Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl2}2 (3), which was converted into the μ-oxo complex {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl}2(μ-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(η5-C5Me4SiMe2R)R3 [R=Me (5), CH2Ph (6)] or partially alkylated {Ti[(η5-C5Me4SiMe2(CH2SiMe3)]Cl(CH2SiMe3)2} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Me2}2 (8), while the same reaction carried out with MgCl(CH2Ph) or Mg(CH2Ph)2·2THF gave the chloro-benzyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl(CH2Ph)}2 (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy. 相似文献
125.
126.
四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构 总被引:1,自引:0,他引:1
The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands. 相似文献
127.
《Electroanalysis》2005,17(2):178-181
Voltammetric behavior of water‐soluble endohedral metallofullerene derivatives Gd@C82(OH)5(NHCH2COOH)9 (GN) and Gd@C82(OH)6(NHCH2CH2SO3H)8 (GS) was characterized in 0.1 M KCl solution by CV and DPV. They showed similar redox behavior, that is, a reversible electroreduction process on HMDE was found; in the mean time, an irreversible oxidation process and an irreversible reduction process on GC electrodes were also observed. The results reveal that these two water‐soluble endohedral metallofullerene derivatives have good electron donating ability and poor electron accepting ability due to hydroxy groups, aminoacetic acid and aminoethyl sulfonic acid connected to the C82 cage in comparison with Gd@C82. 相似文献
128.
About the Structure and Reactivity of Diammonium Hexafluoromanganate(IV) Electrolytic oxidation of an aqueous suspension of MnF2 containing NH4F, and subsequent crystallization in 40% HF yields yellow crystals of (NH4)2MnF6. It crystallizes in the hexagonal K2MnF6 type structure with the space group P63mc and a = 5.903; c = 9.565 Å; Z = 2. With in situ powder diffraction studies it is shown, that (NH4)2MnF6 is gradually reduced in a NH3 atmosphere between 30 and 230 °C to afford (NH4)3MnF6, (NH4)2MnF5, and finally NH4MnF3. (NH4)3MnF6, thereby, forms a hitherto unknown cubic (a = 9.082 Å) high temperature modification with the cryolite type structure. Under N2 the thermal decomposition of (NH4)2MnF6 proceeds via NH4MnF4 to yield MnF2. 相似文献
129.
比较两种超高交联聚苯乙烯吸附树脂NJ-8、AM-1与Amberlite XAD-4(以下简称XAD-4)对对硝基苯乙酮的静态吸附行为,根据吸附等温线研究了吸附热力学性质.在298~318K和研究的浓度范围内,NJ-8,AM-1、XAD-4对对硝基苯乙酮的吸附平衡数据符合Freundlich吸附等温方程.结果表明:吸附为放热过程,适当降低温度有利于吸附.计算了对硝基苯乙酮在NJ-8,AM-1、XAD-4树脂上的吸附焓变、自由能变,吸附熵变.对吸附行为作了合理的解释。 相似文献
130.
The LC phase behavior of ternary mixtures of the two corresponding branched non-ionic surfactants 1,3-bis-(methoxy-tetraoxyethylene)-2-propoxy-tetradecane (Y-surfactant) and 1,3-bis-(heptyloxy)-2-propoxyoctaoxyethylene mono-methyl ether (V-surfactant) and water were studied by polarizing microscopy. The two branched surfactants, which have different molecular geometries but nearly the same hydrophilic-lipophilic volume ratio, exhibit extremely different phase behavior in binary surfactant/water systems. For the ternary mixtures of Y- and V-surfactant and water we found-according to established packing models-a continuous stabilization of the cubic and hexagonal phases and a destabilization of the lamellar phase with increasing amount of Y-surfactant. On the other hand, we observed a thermal stabilization of the lamellar phase. The maximal transition temperatures of the lamellar phase pass a maximum with increasing amount of Y-surfactant. 相似文献