亚甲蓝双分子聚集体的解离平衡

本通过光主地研究了作为新的光敏剂－亚甲蓝（Ｍｅｔｈｙｌｎｅ Ｂｌｕｅ，ＭＢ）在水溶液中的溶液状态，以及其在不同温度时双分子聚集体的解离平衡，通过差示光谱监测了亚甲蓝在水溶液中，其双分子二聚体在温度３０－６０℃范围内的构成方式的变化：其单分子倾角９α）为４８．３－４６．１°，双分子面间距离（ｒ）为０．５７６－０．５８０ｎｍ，监测了亚甲蓝在水溶液中其单最大吸收波长吸收值随温度的变化，算得其二聚体的解     

用吸收光谱法研究亚甲蓝在表面活性剂存在时的聚合状态

应用紫外－可见吸收光谱研究了光敏试剂亚甲蓝在溶液中的聚合状态及其与表面活性剂之间的关系。当添加阴离子表面活性剂的浓度于其临界胶束浓度时，亚甲蓝二聚体的比例将出现一极大值；用环己烷剂萃取后，测得亚甲蓝二聚体的吸收光谱，其最大吸收波长位于６０４ｎｍ。     

分光光度法测定脱氧核糖核酸——基于其与亚甲蓝的反应

试验发现在pH 6.5的B-R缓冲溶液中在加脱氧核糖核酸(DNA)后亚甲蓝溶液在其吸收峰666 nm波长处的吸收明显减弱(即色泽减褪),而且吸光度的减弱(ΔA)程度与DNA的质量浓度在10.0 mg.L-1以内保持线性关系,其相关系数为0.9998,此反应对DNA的检出限为0.10 mg.L-1,分别以蛋白酶、胰蛋白酶及溶菌酶作为基体定量加入DNA配制成3种合成样品,按所提出方法进行分析,测得回收率结果在98.4%~101.0%之间,分析结果的RSD(n=11)值在1.1%~3.1%之间。对反应条件(包括亚甲蓝的浓度、反应的温度、酸度及时间等因素)作了试验和选定,还对反应机理作了简要的讨论。     

重氮树脂与十二烷基硫酸钠相互作用研究

重氮树脂与十二烷基硫酸钠相互作用研究罗杨磊曹维孝（北京大学化学与分子工程学院北京１００８７１）关键词重氮树脂，十二烷基硫酸钠，负性ＰＳ版随着化学与生命科学领域的发展，大分子与小分子在溶液的相互作用越来越受到关注．表面活性剂因其具有自组装能力，...     

十二烷基硫酸钠减慢二苯胺-4-重氮盐及重氮树脂在水溶液中热分解反应的机理

以二苯胺重氮盐(DDS)为模型化合物, 系统考察了其在水中热分解反应与十二烷基硫酸钠(SDS)的浓度以及溶液中小分子电解质的关系, 结合荧光分析结果, 证实了DDS及重氮树脂(DR)在SDS溶液中热稳定性的提高是由于DDS和DR分子与SDS分子间的疏水相互作用和静电吸引作用使它们同SDS分子共同形成混合预胶束或胶束, 通过预胶束或胶束的静电及极性效应使其中的DDS和DR分子上的重氮基得到保护. 随着SDS浓度和小分子电解质(NaCl)浓度的增加, 进入预胶束或胶束中的DDS和DR的量越多, 体系的热稳定性提高得越大. 由于DDS和DR在远低于SDS的临界胶束浓度时(≈10-5 mol/L)形成了预胶束, 从而在SDS浓度很低时即能对DDS和DR起明显的保护作用.     

光敏剂亚甲蓝与不同溶剂的相互作用研究

应用光谱法研究了新光敏剂亚甲蓝在不同溶剂中的电子光谱特性，通过Ｋａｓｈａ理论推测了其在不同溶剂中二聚体的分子构造模式，其二聚体的面－面间距离为１．３４５～１．４２５ｎｍ，面间角为８２．９°～８７．５°确认由ＭｃＲａｅ式对亚甲蓝与不同溶剂间的相互作用下方式进行评价是可行的，提出了亚甲蓝在不同溶剂中分子间力的相互结合作用导致亚甲蓝在溶液中的结构变化，产生光谱差异的原因，阐述了溶液状态与选择性分子间力的     

十二烷基硫酸钠与羟乙基纤维素的相互作用

本文用表面张力(γ)和电导率(κ)方法研究了阴离子表面活性剂十二烷基硫酸钠(SDS)与天然纤维素的水溶性改性物羟乙基纤维素(HEC)的相互作用.实验结果表明,SDS-HEC溶液的γ-lgcSDS曲线和κ～CSDS曲线均呈现双拐点特征,并且γ-lgcSDS曲线上两个SDS临界浓度值(c1 )γ及(c2)γ,与κ～CSDS...     

钯-8-羟基喹啉-5-磺酸络合物电极反应和十二烷基硫酸钠的增敏机理

钯 8 羟基喹啉 5 磺酸形成的络合物的峰电流 (pH 8.6 ,- 0 .6 8V)具有吸附特性 ,为不可逆电极反应过程。其电子转移数 (n)、电子转移系数 (α)及饱和吸附量 (Γs)分别为 2、0 .4 6和 2 .2× 10 - 9mol cm2 ;钯 与8 羟基喹啉 5 磺酸的络合比为 1∶2 ;稳定常数 (K)为 8.73× 10 7。加入阴离子表面活性剂十二烷基硫酸钠未形成三元络合物 ,催化电流是由与十二烷基硫酸钠共吸附在电极表面上的超氧阴离子自由基氧化了络合物的电极反应中间体所产生的。     

二苯胺重氮盐与十二烷基硫酸钠在水溶液中的相互作用

报道了二苯胺-4-重氮盐(DDS)与十二烷基硫酸钠(SDS)在水溶液中的相互作用.实验结果表明,体系粘度随SDS/DDS物质的量比(ξ)的变化而急增急降.当ξ=0～0.9时,二者形成沉淀,体系的粘度基本不变;当ξ=1.9～2.3时,沉淀溶解并伴随着体系粘度急增,最高粘度达初始值的2520倍;之后,随ξ的增大,体系粘度迅速下降至初始值.对DDS-SDS聚集体的微观结构与体系粘度的关系进行了初步讨论.同时发现体系粘度是光敏性的,紫外光照可使其迅速下降.     

石墨烯/十二烷基硫酸钠复合物修饰碳糊电极测定氯霉素

以液体石蜡和硅油为混合粘合剂,与石墨粉混合制备了碳糊电极基底电极,将石墨烯/十二烷基硫酸钠复合物修饰在基底碳糊电极上,得到了基于石墨烯复合物的新型修饰碳糊电极。应用扫描电镜和循环伏安法分别研究了该电极的表面特性和电化学性质,结果表明,石墨烯和十二烷基硫酸钠修饰的碳糊电极增大了比表面积,有利于电子传递。在pH 3.0的HAc-NaAc缓冲溶液中,该修饰碳糊电极对氯霉素具有良好的电化学响应,氧化峰电位为0.194 V,氧化峰电流是基底碳糊电极的10倍。在最优实验条件下,该氧化峰电流与氯霉素的浓度在1.0×10~(-8)~5.0×10~(-4)mol/L范围内呈良好的线性关系,检出限为5.0×10~(-9)mol/L。该方法简便,重现性及选择性好,用于测定氯霉素滴眼液和虾中氯霉素残留,结果满意。     

静电场诱导十二烷基硫酸钠结晶行为的研究

用透射电镜、X射线衍射及DSC等方法 十二烷基硫酸钠（SDS）极稀水溶液（溶液介于临界聚集浓度和临界胶束浓度之间）在静电场作用下的结晶行为,静电场作用诱导SDS形成规则的四方单晶与从甲醇中重结晶所得样品的晶体结构相同,DSC结果表明,从有序到无序结构变化的一级相转变热焓相同,但由于电场诱导结晶的晶体较小而表现为转变温度的降低,没有施加静电场处理的样品只具有较低的有序程度。     

十二烷基硫酸钠对甲烷水合物生成过程影响研究

根据甲烷水合物含气率高、分解速度慢等特性,提出利用高压注水技术和表面活性剂促进作用促使矿井瓦斯水合化以预防煤与瓦斯突出的思路。进行了3·6~12℃、7·82~12·26MPa条件下两种浓度体系(10mmol/L和0·3mmol/L)中十二烷基硫酸钠(SDS)对甲烷水合物作用效果的实验研究,结合水合物诱导时间、生成速度及含气率等计算对实验数据进行了分析,并运用表面张力法测得8℃时SDS溶液的临界胶束浓度(CMC)为2·5mmol/L。结果表明,高浓度体系对水合物生成速度、含气率的影响较之低浓度体系的更强,但是低浓度体系中水合物生成的诱导时间却较短,表面活性剂溶液浓度超过其CMC后对水合物的生成影响显著。     

Extraction Spectrophotometric Determination of Trace Chlorine Dioxide with Methylene Blue

Abstract

The coloration reagent - leucomethylene blue, the reduction product of methylene blue, is used to determine the concentration of chlorine dioxide in the presence of Cl₂ and anion species such as OCl^?, ClO₂ ^? and ClO₃ ^?. This simple spectrophotometric method is performed by using the extractant 1,2-dichloroethane at pH 1.3. The linear range of ClO₂ measurement extends to 0.95 mgl^?1 with a detection limit of 0.02 mgl^?1. The presence of chlorine and hypochlorite ion can be masked by oxalic acid. The permissible maximum concentration of ClO₂ ^? is 2.0 mgl^?1, and ClO₃ ^? anion does not interfere with the measurement.     

Micellization of Sodium Dodecyl Sulfate in Glycerol Aqueous Mixtures

The effect of glycerol on both micellar formation and the structural evolution of the sodium dodecyl sulfate (SDS) aggregates in the context of the action mechanism of the cosolvent has been studied. The critical micelle concentration and the degree of counterion dissociation of the surfactant over a temperature range from 20°C to 40°C were obtained by the conductance method. The thermodynamic parameters of micellization were estimated by using the equilibrium model of micelle formation. The analysis of these parameters indicated that the lower aggregation of the surfactant is mainly due to a minor cohesive energy of the mixed solvent system in relation to the pure water. The effect of glycerol on the mean aggregation number of the micelles of SDS was analyzed by the static quenching method. It was found that the aggregation number decreased with the glycerol content. This reduction in the micellar size seems to be controlled by an increase in the surface area per headgroup, which was ascribed to a participation of glycerol in the micellar solvation layer. Studies on the micropolarity of the aggregates, as sensed by the probe pyrene, indicated that this microenvironmental parameter is almost unaffected by the presence of glycerol in the mixture. However, an increase in the micellar microviscosity at the surface region was observed from the photophysical behavior of two different probes, rhodamine B and auramine O. These results suggest a certain interaction of the cosolvent in the micellar solvation of SDS micelles.     

Photophysical Properties of Ethidium Bromide in Low Concentration of Sodium Dodecyl Sulfate

Sodium dodecyl sulfate (SDS) is widely utilized in biomolecules separation, but high residue SDS in biomolecules samples interfere mass analysis. Ethidium bromide (EtdBr) interacts with SDS, and the formation of EtdBr‐SDS complex at low SDS concentration (0–0.1 %) results a large red shift of the n→π* transition of EtdBr from 480 nm to 530 nm. The ion pairs become non‐emissive and cause low emission intensity. While the concentration of SDS is above 0.1 %, SDS starts aggregating to form micelle. Micelle formation destabilizes the complex and the absorption maxima shift back to 513 nm while emission intensity increases. Based on the change of absorption and emission of EtdBr, a SDS concentration assay was developed. If absorption maximizes at 480 nm, the concentration of SDS of the sample is below 0.005 %. If absorption maximum is at longer wavelength than 480 nm, a second parameter, the ratio of absorbance at 513 nm and 550 nm is introduced. If the ratio is smaller than 1.5, the concentration of SDS is between 0.01–0.1 %. If the ratio is larger than 1.5, the concentration of SDS is above 0.15 %. Despite the suitable range is small, the lower limit is around the range of no mass interference.     

十二烷基硫酸钠水溶液的动态表面吸附性质

利用MPTC型气泡压力张仪研究了十二烷基硫酸钠(SDS)溶液在不同NaCl 浓度下的动态表面吸附性质, 分析了离子型表面活性剂在表面吸附层和胶束中形成双电层结构产生表面电荷对动态表面扩散过程和胶束性质的影响. 结果表明, SDS在表面吸附过程中, 表面电荷的存在会产生5.5 kJ·mol^-1的吸附势垒(E_a), 显著降低十二烷基硫酸根离子(DS^-)的有效扩散系数(D_eff). 十二烷基硫酸根离子的有效扩散系数与自扩散系数(D)的比值(D_eff/D)仅为0.013, 这表明SDS与非离子型表面活性剂不同, 在吸附初期为混合动力控制吸附机制. 加入NaCl可以降低吸附势垒. 当加入不小于80 mmol·L^-1 NaCl后, E_a小于0.3 kJ·mol^-1, D_eff/D在0.8-1.2之间, 表现出与非离子型表面活性剂相同的扩散控制吸附机制. 同时, 通过分析SDS胶束溶液的动态表面张力获得了表征胶束解体速度的常数(k₂). 发现随着NaCl 浓度的增大, k₂减小, 表明SDS胶束表面电荷的存在会增加十二烷基硫酸根离子间的排斥力, 促进胶束解体.     

A Simple and Highly Selective Determination of Telmisartan at Sodium Dodecyl Sulfate Modified Pyrolytic Graphite Surface

A simple, facile, selective and cost effective electrochemical method is proposed for the determination of telmisartan (TMS); a drug used for hypertension. A sodium dodecyl sulfate (SDS) modified edge plane pyrolytic graphite (EPPG) is prepared by simple immersion of EPPG in SDS solution at concentration greater than critical micelle concentration (CMC). The modified sensor exhibited superior sensing properties towards the oxidation of TMS. The modified surface was characterized by using the Energy dispersive X‐ray analysis, Field Emission Scanning Electron Microscopy, Electrochemical Impedance Spectroscopy and cyclic voltammetry. The quantitative investigations of the TMS were performed by applying the square wave voltammetry. The micelles of SDS form a pseudo complex with cation radical of TMS and catalyse the oxidation. The proposed sensor shows the linear calibration plot in the concentration range of 5–100 μM with sensitivity 0.2983 μA/μM and the limit of the detection of the sensor was found to be 0.082 μM. The specificity of the developed sensor was also evaluated in the presence of commonly present interfering substances in biological samples. The amount of TMS excreted in urine of the patients undergoing treatment has also been determined. The proposed method can be effectively applied for the investigation of TMS in pharmaceutical formulations and biological samples.     

偶氮蓝分光光度法测定硫酸卡那霉素

在pH 4.10的B-R缓冲溶液中,偶氮蓝与硫酸卡那霉素相互作用生成离子缔合物导致偶氮蓝色泽减褪,或换言之,当在偶氮蓝溶液中加入硫酸卡那霉素后,在偶氮蓝的吸收峰552 nm波长处吸光度降低,吸光度差值与硫酸卡那霉素浓度成正比,最佳条件下,硫酸卡那霉素的质量浓度在0.1～4.0 mg·L-1范围内遵守比耳定律,表观摩尔吸光率ε=7.3×104L·mol-1·cm-1,检出限(3σ)为7.6×10-2mg·L-1.将方法应用于硫酸卡那霉素注射液试样中卡那霉素的测定,测定结果的RSD(n=7)值为1.1%,按标准加入法测得的平均回收率为96.5%.     

用弱电解质理论研究水溶液中SDS胶团的电离行为

在临界胶团浓度以上,十二烷基硫酸钠(SDS)在溶液中形成聚集态的胶团,从而表现出不同于一般强电解质的电导行为.针对这一特点提出了一种胶团电离模型,即将胶团作为一种弱电解质,用弱电解质电导理论来描述其溶液电导的变化规律,导出SDS胶团电离度的计算式,并得到该溶液电导实测数据的验证.     

Modified Calcium Alginate Beads with Sodium Dodecyl Sulfate and Clay as Adsorbent for Removal of Methylene Blue

In present study, we have investigated the effect of an anionic surfactant sodium dodecyl sulfate (SDS) and clay on calcium alginate beads was studied to remove methylene blue (MB) and to improve the adsorption capacity. The effects of various experimental parameters, such as shaking rate, initial dye concentration, temperature, and pH on the adsorption rate, have been studied. Equilibrium studies showed that the sorption of the dye was enhanced in presence of SDS. Scanning electron microscope (SEM) analysis showed that SDS entrapped beads have more pores and cavities which could be responsible for improved adsorption of MB. The kinetics of cationic dye adsorption nicely followed pseudo-second-order process. The evaluated thermodynamic parameters (ΔG ^o, ΔH ^o, ΔS ^o) suggest endothermic adsorption of MB. The results revealed that the surfactant entrapped alginate could be considered as potential adsorbents for MB removal from aqueous solutions.