C12-s-C12•2Br和C12En混合水溶液的胶团化行为

季铵盐二聚表面活性剂C12 s C12•2Br（s=2、3、4、6）和非离子表面活性剂C12E10或C12E23在水溶液中生成混合胶团.其临界胶团总浓度cmcT值介于二元复配体系中各组分的临界胶团浓度和之间.当添加少量非离子型表面活性剂（在水溶液中的摩尔分数α2=0.1）时,混合胶团中C12E10或C12E23的摩尔分数均已超过0.35;随着溶液中非离子型表面活性剂含量的增大,混合胶团中逐渐以C12E10或C12E23成分为主.     

镓(Ⅲ)-茜素红体系的吸附伏安法

本文对镓(Ⅲ)与茜素红络合物在悬汞电极上的吸附伏安法作了研究,确定了电极过程.在HAc-NH_4Ac(pH4.06)缓冲溶液中茜素红存在下,用1.5阶微分吸附伏安法测定镓,其线性范围是1×10~(-10)～1×10~(-7)mol/L,其检测限为1×10~(-10)mol/L,并用此法测定了中草药中的痕量镓.     

Rapid and sensitive determination of protein by light-scattering technique with Eriochrome Blue Black R

Based on the interaction between Eriochrome Blue Black R (EBBR) and proteins, which causes a strong light-scattering signal with the maximum scattering peak located at 398 nm, a simple, rapid, sensitive and selective method is developed for the determination of proteins by the light-scattering technique using a common spectrofluoremeter. Under proper experimental conditions, the protein determination can be performed in the range of 0.1-25, 0.1-20 and 0.25-25 μg ml⁻¹ for bovine serum albumin (BSA), human serum albumin (HSA) and human immunoglobulin G (IgG), respectively. The detection limit, calculated as 3 times the S.D. of nine blank measurements, are 33 μg l⁻¹ for BSA, 25 μg l⁻¹ for HSA and 38 μg l⁻¹ for IgG. Moreover, there is no significant difference among the scattering signals yielded by HSA, IgG and BSA, and almost no interference of many amino acids and metal ions. The method has been satisfactorily applied to the direct determination of the total protein in human serum, saliva and urine samples. The results obtained from the studies on the binding characteristics of EBBR to BSA indicated that an electrostatic force existed in the binding system, and the binding constant (K) and the number of the binding sites (n) at 25 °C are 1.69×10⁵ l mol⁻¹ and 0.946, respectively.     

Quantitation of agmatine by liquid chromatography with laser-induced fluorescence detection

A high performance liquid chromatography (HPLC) method is described for the determination of agmatine, an endogenous neuromodulator. The method involves pre-column derivatization of the sample with a fluorescent tagging reagent, 7-fluoro-4-nitrobenzoxadiazole (NBD-F). The resulting agmatine derivative is stable and can be readily extracted into ethyl acetate at pH 8.5. The extraction enhances the quantification of low level agmatine because it eliminates chromatographic peaks caused by endogenous amino acids. The HPLC separation is carried out on a C₈ reversed phase column and completed in less than 10 min. With laser-induced fluorescence (LIF) detection, the detection limit is 5×10⁻⁹ M agmatine. Method precision (coefficient of variation) is 5% for agmatine in human plasma at the sub-μM level. This method has been validated by determination of agmatine in biological samples including human plasma and rat brain and stomach tissues.     

Remote substituent effects on bond dissociation energies of para-substituted aromatic silanes

UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified.     

Synthesis of Molecularly Imprinted Polymer Particles by Suspension Polymerization in Silicon Oil

Molecular imprinting is a method to prepare polymers with recognition site of desired and predetermined selectivity1. Molecularly imprinted polymers (MIP) are prepared by copolymerizing functional and cross-linking monomers in the presence of a molecular …     

Trace metal speciation measurements in waters by the liquid binding phase DGT device

The speciation measurements of trace metals by the diffusive gradients in thin-films technique (DGT) using a poly(4-styrenesulfonate) (PSS) aqueous solution as a binding phase and a cellulose dialysis membrane (CDM) as a diffusive layer, CDM-PSS DGT, were investigated and showed good agreement with computer modelling calculations. The diffusion coefficients of ethylenediaminetetraacetic acid (EDTA) complexes with Cd²⁺ and Cu²⁺ were measured and compared with those of the inorganic metal ions. CDM-PSS DGT device was tested for speciation measurement in sample solutions containing EDTA, tannic acid (TA), glucose (GL), dodecylbenzenesulfonic acid (DBS) and humic acid (HA) as complexing ligands forming organic complexes with varying stability constants. Lower percentages of DGT labile copper concentrations over total filterable copper concentrations obtained from the deployments in freshwater sites indicated that copper complexes with organic matter were basically not measured by the devices.     

多支链烷基苯磺酸钠水溶液的表面性质

用自制的四种高纯度多支链烷基苯磺酸钠,研究了支链结构对其表面性质的影响.结果表明,随支链烷基碳数增加,临界胶束浓度降低,标准吸附自由能DGadӨ更负;但是,饱和吸附量Γmax却随支链烷基碳数增加而减小,且临界胶束浓度时的表面张力γcmc随吸附量减小而降低,表现出与一般表面活性剂不同的变化趋势.从多支链烷基苯磺酸钠的分子结构特点,解释了随支链烷基碳数增加Γmax和γcmc的变化规律,探讨了分子的独占面积(as)对Γmax及γcmc的影响.     

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的表面碱性和表面活性氧种

利用ＣＯ２－ＴＰＤ方法考察了Ｔｉ－Ｌａ－Ｌｉ系多元氧化物催化剂的表面碱性，实验发现：Ｃ２选择性与表面碱强度呈顺变关系，而ＣＨ４转化率与ＣＯ２的脱附峰面积呈顺变关系。同时，利用ＸＰＳ，Ｏ２－ＴＰＤ等方法对该体系催化剂的表面活性氧种进行了表征与研究。结果表明：催化剂的表面晶格氧与Ｃ２选择性有关，表面吸附氧与甲烷转化（包括偶联和深度氧化）有关。Ｏ２－ＴＰＤ实验发现催化剂的表面存在三种氧。α（１００℃≤ｔ     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.