Hofmeister效应对生物和化学体系的影响

Hofmeister效应涉及到的问题范围十分广泛,对很多化学、生物体系都有影响。总的说来,Hofmeister效应会影响到溶液的冰点、沸点、黏度、偏摩尔体积、饱和蒸汽压、传导率、pH、表面张力。文章主要介绍了Hofmeister效应的主要影响因素,以及相关理论的建立与完善,并对不同体系中Hofmeister效应的影响进行了描述。     

正交分析法在5种化武相关化合物硅烷化衍生方面的应用EI北大核心CSCD

以500,50和5μg/mL的甲基膦酸乙酯(EMPA)、甲基膦酸异丙酯(IMPA)、甲基膦酸(MPA)、甲基膦酸频哪酯(PMPA)、硫二甘醇(TDG)为研究对象,以气相色谱-质谱为检测手段,使用正交分析法对衍生时间、衍生温度和衍生试剂用量3个因素之间的交互作用及对衍生效果的影响进行了研究。在所选水平范围内,3个因素不存在交互关系;对于EMPA,IMPA,MPA,PMPA,衍生试剂用量影响>衍生时间影响>衍生温度影响,对于TDG,衍生试剂用量影响>衍生温度影响>衍生时间影响;在3个浓度条件下,衍生温度对于5种化合物的衍生效果没有显著影响;在5μg/mL质量浓度条件下,衍生温度、衍生时间、衍生试剂用量对5种化合物的衍生效果皆没有显著影响。     

加氢脱硫催化剂的研究 Ⅳ.TiO_2改性的CoO-MoO_3/γ-Al_2O_3加氢脱硫催化剂活化条件与催化性质的关系

通过反应活性评价、X射线衍射、程序升温还原、动态氧吸附等实验手段,考察了灼烧温度、预还原温度、硫化温度、氧化处理等活化条件对Co-Mo-Ti/Al_2O_3加氢脱硫催化剂性质的影响。实验表明,灼烧温度主要影响活性组分在载体表面的分散态,硫化温度既影响活性中心的数目也影响其性质,预还原温度和氧化处理主要影响催化剂的活性中心的数目。     

安息香缩合反应的影响因素

安息香缩合反应是重要的有机化学实验,影响实验的因素较复杂。本文通过反应温度、反应时间、pH、反应物料的投入方式等对安息香合成的影响进行了探讨。实验结果表明：反应温度、反应时间、pH是影响反应的重要因素,而反应前是否对反应物进行冷却以及苯甲醛与NaOH溶液的投料顺序对反应的影响不大。     

不同认识论学生的非智力因素对其化学探究学习的影响

用模糊综合评判法定量分析了非智力因素对化学探究学习各要素的影响,典型建构认识论者认为兴趣、意志是影响化学探究学习最重要的非智力因素,形成假设、收集证据是受非智力因素影响最显著的探究要素;典型机械认识论者认为动机是影响化学探究学习最重要的非智力因素,形成假设、得出结论是受非智力因素影响最显著的探究要素。最后,结合研究结果就如何搞好化学探究学习提出了具体建议。     

氢氧燃料电池实验的装置改进与实验条件优化

对氢氧燃料电池的实验装置进行简易化改进,确定电池性能指标、影响因素,设计正交实验方案,探讨正负极碳棒淬火的次数、电解时长、硫酸钠电解液浓度等4个因素对性能指标的影响,获得主要影响因素和最优实验条件。     

高分子片状板材热分析测试影响因素的研究

研究了高分子片状板材的取样位置、样品尺寸、升温速率、热历史及气流速率对DSC及(或)TGA测试结果的影响,简要分析了各因素影响测试结果的原因。结果表明,升温速率对测试结果影响很大,热历史对测试结果有一定影响,取样位置及一定范围内的样品尺寸对测试结果影响不大,气流速率对测试结果影响较微。     

磁场对乙酸乙酯合成影响的研究

近年来,有关外磁场对化学反应影响方面的研究十分引人注目,其研究范围以在非均相体系中进行的聚合反应、光化学反应和电化学反应居多,而对均相体系中的一些无机、有机反应却研究得很少。我们对在常温常压下磁场对合成乙酸乙酯反应的影响进行了一些探索,发现在均相体系中,磁场对该反应确有一定影响,该影响与磁处理时间、反应液流速、磁场的组合形式有关。     

制备条件对稀土复合氧化物粉体材料性能的影响

用柠檬酸络合法制备出双掺杂CeO2基粉体材料, 考察了柠檬酸用量、焙烧温度、升温速率和成胶温度等制备条件对粉体材料BET比表面积、孔容、平均孔径和平均粒径的影响. 柠檬酸用量和焙烧温度对粉体材料的这些性能影响较大, 升温速率只是对平均粒径产生影响, 成胶温度对BET比表面积没有影响, 对孔容和平均孔径影响也很小, 对平均粒径影响大一些. 通过对不同柠檬酸用量和不同焙烧温度所得样品进行XRD表征, 发现双掺杂并未改变CeO2晶型, 但晶胞参数略有增大, 表明掺杂离子进入CeO2晶格. 柠檬酸用量几乎不影响平均晶粒大小, 而焙烧温度对平均晶粒产生较大影响, 焙烧温度越高, 平均晶粒越大. 不同掺杂元素对粉体材料的表面性能也产生一定影响, 掺杂Ca2+的平均粒径比同主族的Mg2+和Sr2+小. 通过对不同制备条件的考察, 为制备固体氧化物电解质粉体材料提供了基础.     

H+反应对土壤重金属分级提取形态分析的影响

探讨了普遍存在于重金属分级提取形态分析体系中的H 反应的影响因素,分析了H 反应与提取剂的选择性、金属离子的重分配现象的关系,以及H 反应对分级提取法数据结果的影响,并对分级提取方法作了进一步的改进。研究表明提取剂pH、提取体系、土壤理化性质及土壤 溶液比是影响H 反应的主要因素;H 反应可降低提取剂选择性,减弱金属离子的重分配能力,影响分析结果的有效性,且对于不同的重金属离子、不同的提取体系,H 反应所造成的影响不同。     

Cationic polymerization of styrene with electrochemically generated perchloric acid—I

The electroinitiated polymerization of styrene in LiClO₄-propylene carbonate solutions leads to polystyrene at the anode through the formation of HClO₄. The influences on this polymerization of factors such as temperature, current, monomer and electrolyte concentrations, and dielectric constant of the medium, have been examined. The trends of the yields as functions of these factors show some anomalies. In particular, there is a maximum in the yield vs current curve. The molecular weights are relatively low, due to transfer processes, both spontaneous and involving monomer. The propagation proceeds by a cationic mechanism, in which free ions are in equilibrium with ion pairs.     

The Factors Influencing Nonlinear Characteristics of the Short‐Circuit Current in Dye‐Sensitized Solar Cells Investigated by a Numerical Model

A numerical model for interpretation of the light‐intensity‐dependent nonlinear characteristics of the short‐circuit current in dye‐sensitized solar cells is suggested. The model is based on the continuity equation and includes the influences of the nongeminate recombination between electrons and electron acceptors in the electrolyte and the geminate recombination between electrons and oxidized dye molecules. The influences of the order and rate constant of the nongeminate recombination reaction, the light‐absorption coefficient of the dye, the film thickness, the rate constant of geminate recombination, and the regeneration rate constant on the nonlinear characteristics of the short‐circuit current are simulated and analyzed. It is proposed that superlinear and sublinear characteristics of the short‐circuit current should be attributed to low electron‐collection efficiency and low dye‐regeneration efficiency, respectively. These results allow a deep understanding of the origin of the nonlinear characteristics of the short‐circuit current in solar cells.     

共晶基离子液体的钴电化学沉积

通过恒电流和恒电位方法,研究了不同温度下脲-氯化胆硷（氯仿）基或乙二醇-氯化胆硷（氯仿）基离子液体中氯化钴溶液在铜和钢阴极上的钴电化学沉积行为. 采用扫描电子显微镜和X射线衍射技术,考察了不同试验条件对钴电沉积行为及钴沉积层形貌的影响. 结果表明,当沉积电位达到-0.8 V和沉积电流密度达到-6.0 A·m^-2时,温度范围从30 °C到90 °C,添加0.05 mol·L^-1的五氧化二磷,可以从脲基和乙二醇基离子液体中沉积得到光滑、发亮和良好结合力的金属光泽钴层. 电化学沉积钴的阴极电流效率达到98%.     

基于氯化胆碱离子液体的铜电沉积研究（英文）

采用恒电流和恒电位方法,基于含有氯化铜溶液的乙二醇-氯化胆碱或硫脲-氯化胆碱离子液体,室温下在钢阴极上进行了铜的电沉积. 利用扫描电子显微镜和X-射线衍射技术研究了各种实验条件对电沉积的影响以及沉积层的形貌. 结果表明,室温下施加不超过-0.45 V的沉积电位和不超过-4.0 A·m^-2的沉积电流密度,可以同时从氯化胆碱基乙二醇和硫脲离子液体中沉积得到非常光滑、有光泽、致密且具有良好结合力、色泽鲜艳的铜金属涂层. 铜的电沉积阴极电流效率约为97%.     

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence (OD4MI-CL) were studied. The influences of these two factors on the complex OD4MI-CL reaction are discussed within a conceptual prototype for developing aqueous and non-aqueous capillary electrophoresis (ACE and NACE) devices with OD4MI-CL detection. The reaction channel length and OD4MI yield from the reaction between bis(2,4,6-trichlorophenyl) oxalate (TCPO) and 4-methylimidazole in the channel will be influenced by pH, water volume fraction, and cosolvent properties of the solution. Optimum OD4MI-CL efficiency is observed at pH 6.5 when 1-propanol, which has a low dielectric constant (epsilon = 20.8), is used as the NACE solvent in the separation channel. Water (epsilon = 80.1), the solvent in the ACE separation channel, acts similarly to a high dielectric constant organic solvent in NACE because the disadvantages normally associated with TCPO-CL reactions in water disappear due to the faster OD4MI-CL reaction versus OD4MI decomposition in aqueous solution. Therefore, it is expected that the OD4MI-CL detection system can be used in both NACE and ACE devices without requiring detector modifications. We also conclude that OD4MI-CL detection in NACE and ACE devices will be much more sensitive than the TCPO-CL detection used in current NACE devices.     

Amperometry with two polarisable electrodes-VII: chelometric determination of indium

Optimum conditions have been found for the chelometric determination of indium by biamperometric titration with EDTA. Two stationary platinum electrodes (Pt-Pt) or two graphite electrodes (C-C) may be used to indicate the end-point of the titration. At pH 1-1.5 the determination is highly selective. The applied potential only influences the absolute value of the current ; the accuracy of the determinations remains constant over a wide interval of applied potential. At a potential of 1.0-1.7 V the change of current during a titration with 0.05 M EDTA solution is of the order of 10 microA. Analytical applications of the method are discussed.     

高效毛细管区带电泳二肽类组分迁移行为的研究

本文考察了影响二肽类组分在高效毛细管区带电泳上迁移时间重复性的因素,提出了采用相对指标来作为高效毛细管区带电泳峰定性的依据,并考察了电流以及柱温对迁移时间和相对迁移时间的影响,发现在恒压lgt~m与T^-1有良好的线性关系;并从迁移时间的基本方程定量地解释了上述的变化规律.本文还发现,采用相对迁移时间指标后可以有效地消除操作电流以及柱温对迁移时间所引起的波动,是毛细管区带电泳的一个特征参数.     

四苯骈卟啉金属配合物轴向配位反应的热力学性质研究

金属卟啉在生命过程中起着重要的作用[1 - 4 ] 。CuTBP ,CoTBP与有机碱的反应,用光度法测定了轴配反应在不同温度下的速率常数和平衡常数,求得活化能及热力学参数,结果表明:它们与不同有机碱反应的活化能及平衡常数既与配体的碱性有关,也与空间位阻有关,同一温度下反应的平衡常数和速率常数的大小顺序均为:咪唑>吡啶>2 甲基吡啶>2 ,4 二甲基吡啶。1　实验部分1 .1　仪器与试剂日本产岛津UV 2 4 0G型分光光度计,上海分析仪器厂72 1型光度计(内装恒温套) ,重庆电机厂超级恒温槽。四苯骈卟啉金属配合物系自制[4] ,咪唑、吡啶、2 甲基吡…     

An in vitro method for studying the iontophoretic enhancement of drug transport through skin

An electrodiffusion cell and measurement system has been developed to study the factors governing the transport of ionized drugs through skin under the influence of an electric field. The system allows the determination of transport rates in vitro under conditions of either constant current or constant voltage across the skin. Both accelerating and retarding voltages may be applied. To test the method, the iontophoretic transport of a negatively charged bone resorption agent, etidronate disodium (ethanehydroxydiphosphonate, EHDP) was measured across excised human skin. An enhancement factor of 50-70 over passive diffusion was obtained using a constant current density of 140 μA-cm⁻², and a factor of approximately 100 was obtained with a constant applied voltage of -0.5 V. At the lowest power levels tested (14 μA-cm⁻² or -0.25 V) the enhancements were in reasonable agreement with the predictions of a constant field model for electrodiffusion; however, at higher power levels a phenomenological parameter, the drug transference number in the membrane, appeared to be more useful. Neither the constant current nor the constant voltage mode was found to be a completely satisfactory way of controlling drug delivery in this model. A current-voltage regimen in which both parameters are varied may be required in order to achieve consistent results.     

The synthesis and crystal structure of metal complexes S-alkyl-N-(ferrocenyl-1-methyl-methylidene)-dithiocarbazate and the study on their quenching the luminescence ofruthenium(bipyridine)_~3(2+)

The cobalt, nickel, copper, zinc and cadmium complexes of S-methyl-N-(ferrocenyl-l-methyl-methylidene)-dithiocarbazate (H-LSM) and S-benzyl-N-(ferrocenyl-l-methyl-methylidene)-dithiocarbazate (H-LSB) were synthesized and the crystal structure of Cd[Fe-C(CH3) = NNCSS. (CH3)]2 was solved by X-ray diffraction. The crystal is in the orthorhombic system with space group Pbca, cell parameters a=19.741(3), b=19.924(5), c=15.452(4) A, and the final factors of R=0.032. The study on quenching the luminescence of Ru(bpy)3 by those complexes showed that bimolecular quenching constants obtained from the Stern-Vohner constant and the excited-state lifetime were related to the redox potential of the quencher. Linear relationship is shown in the plot of logkq vs. E1/2(Q+/Q). The main factor which influences the quenching rate constant and the redox potential is the coordinating ability of the metal in the complex.