高含量钒的钼钒磷杂多化合物的合成和性质研究

本工作改进了文献[4]报导的几种原料同时混合、加热煮沸合成的方法采用分步加入原料,控制反应温度、多次重结晶的方法合成了6、7、8个钒原子取代的钼钒磷杂多酸铵;并以铵盐为原料,用离子交换、冷冻分离和真空抽吸相结合的提纯方法制备了未见文献报导的相应的固体杂多酸;H₅[PMo₅V₇O_37.5]·xH₂O,H₆[PMo₄V₈O_37.5]·xH₂O。通过元素组成分析确定了它们的组成。这些杂多酸在水溶液、非水溶液中的电位滴定表明,杂多阴离子在分解前没有发生自电离、水解等情况,它们在水溶液中是稳定的。酸的碱度分别为5、5、6。通过纸上色谱实验,讨论了杂多酸的分解过程。由热重分析和溶解性实验得到它们的分解温度,本文还讨论了这些化合物的红外、紫外光谱,x光粉末衍射及极谱性质。光谱结果表明,它们可能具有Keggin结构,由导数脉冲极谱得到它们的峰电位。     

毛细管离子交换电色谱的分离行为

在离子交换毛细管色谱柱上实施电色谱，并对其分离行为进行了研究，采用７５μｍ（ｉ．ｄ．）２０ｃｍ的毛细管强阳离子交换柱（３μｍ）以ＮａＨ２ＰＯ４－Ｈ３ＰＯ４缓冲液为淋洗剂，紫外柱上检测（２１４ｎｍ）考察了流动相的ｐＨ值，有机改性剂及分离电压等因素对分离的影响，研究表明，不同的ｐＨ溶质的流出次序发生改变，随着有机改性剂含量增加，溶质的保留时间减小，而电渗流却增大，同时，对分离的柱效和方法的重现性进行了     

Immobilization of thiabendazole-specific monoclonal antibodies to silicon substrates via aqueous silanization

Monoclonal antibodies specific for thiabendazole were immobilized to silicon, silicon dioxide, stoichiometric silicon nitride, and silicon-rich silicon nitride surfaces. This work provides the foundation for the development of a homogeneous sensor system for rapid detection and quantification of thiabendazole residues in produce and animal tissue. Immobilization was performed via aqueous silanization of the substrate followed sequentially by treatment with glutaraldehyde and contact with antibody solution in the presence of detergent. Surfaces were challenged with thiabendazole-horseradish peroxidase conjugate in an ELISA format to estimate immobilized antibody load. A stable and reproducible surface loading of 2 x 10¹¹ antibodies/cm² was obtained only after surfaces received postimmobilization treatments to remove nonspecifically adsorbed antibody. No difference in surface loading was noted when using 30% hydrogen peroxide rather than nitric acid for silanol activation. Little difference was noted among the antibody loadings achieved on the various silicon substrates. Bound antigen-enzyme conjugate was eluted with 0.1N acetic acid and reproducible surface activity was measured for up to four consecutive antigen challenges. Immobilized antibody surfaces were stabilized with 2% sucrose, dehydrated at 37‡C and stored in vacuum or stored at 4‡C in phosphate buffered saline containing 0.01% sodium azide without significant loss of activity.     

Synthesis of monodisperse poly(chloromethylstyrene-co-divinylbenzene) beads and their application in separation of biopolymers

The monodisperse, porous poly(chloromethylstyrene-co-divinylbenzene) beads of 7.9 microm were prepared by a single-step swelling and polymerization method. The seed particles prepared by dispersion polymerization exhibited good absorption of the monomer phase. Based on this media, a weak cation-exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages of biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The dynamic protein-loading capacity of the synthesized WCX packings was 18.2 mg/g. Five proteins were separated in 3.0 min using the synthesized WCX stationary phase. The experimental results show that the obtained WCX resin has very weak hydrophobicity. The WCX resin was also used for the rapid separation and purification of lysozyme from egg white in 5.0 min with only one step. The purity and specific bioactivity of the purified lysozyme were found to be more than 93% and 70 245 U/mg, respectively.     

纯硅MCM-41中孔分子筛合成因素的研究Ⅰ.Na~+、K~+阳离子对合成的影响

本文采用表面活性剂十六烷基三甲基溴化铵（Ｃ１６ＴＡＢｒ，以下为１６３１），在（Ｎａ，Ｋ）ＯＨＳｉＯ２Ｃ１６ＴＡＢｒＨ２Ｏ体系中分别利用室温、水热及干粉法进行了纯硅ＭＣＭ４１中孔分子筛的合成，考察了阳离子Ｎａ＋、Ｋ＋对ＭＣＭ４１合成及稳定性的影响。通过ＸＲＤ对结晶度的测定，发现ＮａＭＣＭ４１的晶化速率明显高于ＫＭＣＭ４１，而热稳定性和水热稳定性较差，且ａ０值小于后者。同时发现，就合成方法而言，室温法得到的产物具有很高的结晶度，利用水热法合成的样品的热稳定性明显较高，而干法得到的分子筛产品具有优良的水热稳定性。     

目视催化褪色计时法测定超痕量钒的研究

本文基于在酸性介质中钒(V)催化溴酸钾氧化酸性铬蓝K褪色的新指示反应,建立了一个催化褪色计时法测定超痕量钒的新方法。在体系中引入活化剂抗坏血酸,灵敏度达2×10~(-12)ng/ml,测定范围在0.0l～3.0ng/ml,同时探讨了反应机理。确立了反应速率方程,方法简便经济,已用于天然水中痕量钒的测定。     

蝎型钒氧配合物的合成、结构及量子化学研究

设计合成了两种新型的以聚类吡唑硼酸盐为配体的钒氧配合物VO(acac)[HB(pz)3](1)和VO(acac)[HB(3,5-Me2pz)3]·CH3CN(2). 运用元素分析、 红外光谱和紫外光谱对所合成的配合物进行了表征, 并用X射线衍射测定了它们的晶体结构. 同时, 采用量子化学的Hartree Fock方法和自然轨道分析方法(NBO), 使用3-21G*(6d, 7f)基组计算得到了两个分子体系的分子轨道、原子电荷以及键级, 并对其结构进行了分析.     

Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.     

容量法测定氧化钒中的各种价态钒

用NaOH溶液处理样品，分离V（V）然后以Fe(Ⅱ）滴定测定之。定量加入过量的V（V）到上述残渣中并用H2SO4溶解，用Fe(Ⅱ）滴定，计算出V（Ⅱ），V（Ⅲ）的含量。V（Ⅳ）的测定是通过从总钒量中扣除V（Ⅱ）、V（Ⅲ）、V（Ⅴ）的含量得到。V（Ⅱ）、V（Ⅲ）和V（Ⅴ）的回收率均大于96％，其8次测定结果的相对标准偏差分别为：9．8％、0．4％、1．2％；本法快速、简便，在实际应用中效果良好。     

Alginate Properties and Heavy Metal Biosorption by Marine Algae

The physical properties of the alginate component in four different brown seaweeds (Sargassumfluitans, Ascophyllum nodosum, Fucus vesiculo-sus, andLaminaria japonica) were characterized using potentiometric titration,¹³C-nuclear magnetic resonance (NMR), chemical analysis, and viscosity measurements. The heavy metal binding capacities of the corresponding seaweeds were directly proportional to their respective total carboxyl group content, and related to the electronegativity of the elements investigated (Ca, Zn, Cd, Cu, and Pb). The uronic acid composition or sequence of the alginate component did not affect the metal uptake properties of the biosorbents studied here. However, the alginate leaching owing to its solubilization by Na ions was observed to decrease with increasing intrinsic viscosity of the extracted alginate, related to its molecular weight, and with increasing apparent acidic dissociation constant, related to the alginate density inside the biomass.