离子型-非离子型混合表面活性剂的协同增敏作用机理

本文研究了CTMAB-PeregalO混合表面活性剂对多羟基显色体系Cd-PAR及Al-CAS的协同增敏作用。认为除了形成混合胶束改变显色反应的微境外,两种表面活性剂对显色体系电子云分布的协同作用也是产生协同增敏作用的重要原因。     

表面活性剂对Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应作用的研究

我们曾研究了离子型-非离子型混合表面活性剂对Ag²⁺-5-Cl-PADAB和Cu²⁺-5-Cl-PADAB等显色反应的作用。本文研究了阴离子、阳离子、非离子及阴-非混合表面活性剂对一系列Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应的作用,试图寻求表面活性剂对显色体系增敏作用及协同增敏作用的原因,并对其作用机理作一初步探讨。     

离子型-非离子型混合表面活性剂对显色反应作用的研究及其应用 Ⅲ.显色剂在胶束相的分配系数

我们曾研究了离子型-非离子型混合表面活性剂对显色反应的作用.本文通过测定显色剂在表面活性剂胶束相和水相中的分配系数,考察了分配系数和显色反应灵敏度的关系,进一步探讨了阳离子型-非离子型混合表面活性剂对显色反应协同增敏作用的机理. 根据析相模型,显色剂(配位体)在胶束相和水相中的分配系数可表示如下:     

β-环糊精对显色反应作用的研究 Ⅱ.与表面活性剂的协同作用机理探讨

本文从β-环糊精(β-CD)的包合作用及其对表面活性剂(SF)包合后引起的包合常数增大等方面,探讨了β-CD-与离子表面活性剂对显色反应的协同增敏作用机理。研究表明:β-CD与SF形成包合物SF-β-CD及SF-β-CD对显色剂及其显色络合物包合作用的增强,是产生协同增敏作用的主要因素,但还须考虑对空白值的影响以及配合物的稳定性,还提出了对同一显色体系应用不同SF-β-CD估计协同增敏趋势的方法。     

胶束增敏 2,3,7-三羟基-9-[3,5-二溴-4-(2,5-二羟基)苯偶氮]苯基荧光酮与锆(Ⅳ)显色反应的研究

系统研究了在混合表面活性剂 CTMAB-Tween-80 存在下,新显色剂 2,3,7-三羟基-9-[3,5-二溴-4-(2,5-二羟基)苯偶氮]苯基荧光酮(DBAPPF) 与 Zr(Ⅳ)的显色反应及其光度性质并讨论了混合表面活性剂对显色反应的增敏机理.在浓度为 0.4mol/L 的 HCl 介质中,新试剂与 Zr(Ⅳ)和表面活性剂形成胶束络合物,混合表面活性剂有较强的增敏作用,络合物最大吸收波长为 539 nm,表观摩尔吸光系数为 1.55×105 L·mol-1·cm-1.锆(Ⅳ)的质量浓度在 0～0.32 mg/L 范围内服从比尔定律.方法已用于铝合金中微量锆的测定.     

阴、阳离子混合表面活性剂的一种适宜搭配

一般认为,离子型表面活性剂的主烃链长度若在C_8以下,由于分子间憎水相互作用力太弱,其表面活性很低,很难形成胶束,因此文献中尚未见采用澳化己基三甲铵(简写作C_6NBr)作为胶束增溶分光光度法的增敏剂。但阴、阳离子混合表面活性剂对显色反应有很强的增敏作用。本文将C_6NBr和长链阴离子表面活性剂适当地搭配起来,有可能增强其表面活性,和作     

β环糊精对显色反应作用的研究：Ⅱ.与表现活性剂的协同作用机理探讨

本文从β－环糊精（β－ＣＤ）的包合作用及其对表面活性剂（ＳＦ）包合后引起的包合常数增大等方面，探讨了β－ＣＤ－与离子表面活性剂对显色反应的协同增敏作用机理，研究表明：β－ＣＤ与ＳＦ形成包合物ＳＦ－β－ＣＤ及ＳＦ－β－ＣＤ对显色剂及其显色络合物包合作用的增强，是产生协同增敏作用的主要因素，但还须考虑对空白值的影响以及配合物的稳定性，还提出了对一同显色体系应用不同ＳＦ－β－ＣＤ估计协同增敏趋势的方法。     

十二烷基硫酸钠对酶抑制光度法测定农药残留的增敏作用

采用植物酯酶抑制法测定了蔬菜中农药的残留,研究了阴离子表面活性剂十二烷基硫酸钠对显色体系的作用.结果表明,十二烷基硫酸钠具有显著的增敏效果,其增敏幅度达到70%,同时对显色剂有增稳作用.用所建立的方法测定蔬菜中残留的敌敌畏,线性范围为0.11 mg/L~1.6 mg/L,最低检出限0.04 mg/L.     

显色反应中表面活性剂增溶及增敏机理的现状及分析(续)

(四)光度分析中胶束增敏机理研究的现状自从表面活性剂在光度分析中得到应用以来,关于表面活性剂的增敏机理曾经进行了广泛的研究。但是,表面活性剂究竟以什么形式参与增敏作用这一基本问题至今尚未取得比较一致的看法。目前,主要流行以下三种观点:(1)以胶束形式参与增敏作用,但与染料分子相互作用的是胶束中的表面活性剂分子,(2)以表面活性剂的单分子形式参与增敏作用,而极性端的电荷起着决定性的作用,(3)CMC值以前,表面活性剂以单分子形式增敏,而在CMC值以后则以胶束形式增敏,即单分子和胶束均有增敏作用。     

Al—CAS—PVA三元体系光度法测定微量铝

微量铝的络天青S(CAS)光度法测定灵敏度高,但稳定性较差。近年来许多分析工作者采用加入表面活性剂来改善其稳定性并进一步提高灵敏度,常用的有十四烷基吡啶(TPB)、聚乙二醇辛基苯基醚(OP)等等。这几类表面活性剂增敏作用一般较强,对痕量铝的测定显示了极大的优越性。然而对一般微量铝的测定则显得灵敏度过高,不太适宜。此时如采用增敏作用不强的表面活性剂聚乙烯醇(PVA)作增溶剂则较为理想,由于其与显色络合物形成三维立体空间结构的缔合物,并存在许多氢键,使显色体系异常稳定,其稳定性能甚至较前几种表面活性剂更佳。 本文讨论了Al-CAS-PVA三元体系显色反应的条件,并应用于石灰石中微量铝的测定。试验结果表明,该法稳定性高,准确度、精密度均好。     

Solid phase adsorption of crystal violet lactone on silica nanoparticles to probe mechanochemical surface modification

The solid phase adsorption of crystal violet lactone (CVL) on five types of Stober silica nanopowders with BET specific surface areas in the range of 50-800 m2/g under dry milling conditions was described for the first time. The hydrogen bonding between surface silanol and the carboxylate of the ring-opened triphenylmethane dye (CVL+) led to the formation of monolayers of CVL+ in a flat-laid configuration. The lambda max of CVL+ in diffusive reflection visible spectra was influenced by the particle size of silica powders, suggesting that the microenvironmental polarity of adsorbed CVL+ is considerably reduced along with the decrease of the particle size. The solid phase adsorption of CVL obeyed Langmuir adsorption isotherms to give a saturated amount of CVL+ for every silica nanoparticle. The surface concentration of CVL+ on nanoparticles at the saturation was estimated to be 0.31 mg/m2 on average, disclosing that about 52% of the surface can be covered by CVL+ under the assumption that the BET-specific surface areas are equivalent to the real surfaces active for the CVL adsorption. The generation of the blue color of CVL provided a convenient means to estimate qualitative and quantitative analysis of the surface coverage with surface-active reagents, which conceal surface silanols. Subsequently, silica nanoparticles were milled with a surface modifier, followed by milling with CVL to observe the intensity of the blue color in order to disclose that the surface coverage with oligo- and polyethylene glycols as well as with nonionic surfactants by dry milling was specifically determined by the number of repeating oxyethylene units. Although the surface-active reagents were easily desorbed in water, the desorption was notably suppressed by milling with CVL, suggesting that the surface-modified particles with the surface-active reagents are covered with ultrathin films of CVL.     

Reaction of β-nitrostyrenes with benzene catalyzed by trifluoromethanesulfonic acid. Formation and reaction of n,n-dihydroxyiminium-benzyl dications

β-Nitrostyrenes are diprotonated on the nitro group to yield N,N-dihydroxyiminium-benzyl dications in trifluoromethanesulfonic acid. These dications comprise a new class of reagents that can react with benzene. The reaction is dependent on the substituent (H or alkyl group) at the β-position of nitrostyrene: β-nitrostyrene yields diphenylacetophenoneoxime, and β-methyl-β-nitrostyrene yields acetophenoneoxime and triphenylmethane. An essentially common mechanism is suggested to be involved in both reactions. These reactions are novel examples of acidcatalyzed reactions of nitro olefins.     

Effect of metal ions on the determination of polymer flocculants using triphenylmethane dyes

Transition and heavy metals interfere with the spectrophotometric determination of flocculants based on the formation of their ion associates with triphenylmethane dyes (TPM). The absorption band of metal complexes with these reagents overlaps the absorption band of the associates; moreover, metal ions enhance the absorption of the associate. The increase in sensitivity is accompanied by a decrease in repeatability; therefore, the detection limits of flocculants change insignificantly. In the determination of flocculants in water at a level of 1 mg/L and above, these metals should be separated or masked in advance.     

Calculation of Partition Coefficients of Organic Reagents in Micellar Thin-Layer Chromatography

Equilibrium partition processes were quantitatively estimated for acidic reagents of the xanthene and triphenylmethane series in the system water–surfactant micelle–stationary phase. An anionic surfactant (sodium dodecyl sulfate) was used as the micelle-forming compound. Partition coefficients were calculated, and the preferential solubilization of reagents in surfactant micelles was demonstrated. Energies of reagent transfer to sodium dodecyl sulfate micelles and their adsorption energies at the stationary phase were calculated.     

A study of the chemiluminescence of some acidic triphenylmethane dyes

Chemiluminescence was observed when some acidic triphenylmethane dyes were oxidized with hydrogen peroxide in alkaline solution. Trace amounts of Co(II) catalysed this chemiluminescent reaction strongly, especially in the presence of the cationic surfactant cetyltrimethylammonium bromide. The chemiluminescence spectra of some compounds and the absorption spectra of some products of the chemiluminescent reactions were investigated, and some acidic triphenylmethane dyes were studied by the Hückel molecular orbital method. On the basis of these investigations, a possible mechanism for this chemiluminescent reaction, and an initial explanation for the relationship between the structure of the reagents and their chemiluminescent behaviour were proposed. The optimum conditions for use of some of the chemiluminescent reaction systems were selected by means of the modified simplex method, and a chemiluminescent analytical method for determination of ultratrace amounts of cobalt was established, with a detection limit of 5 pg/ml. It was used for analysis of natural water samples, and good results were obtained.     

The influence of substrate charge and molecular structure on interphase transfer in cloud point extraction systems

The specificity of interphase transfer of organic reagents of different types between water and the nonionic-surfactant-rich phases at the cloud point temperature was investigated. In contrast to organic solvents, the ability of the micellar phases to extract highly charged ions of organic reagents was shown. Further evidence of the specificity of interphase transfer in micellar-extraction systems is independent and cooperative influence of substrate molecular structure and hydrophobicity on their distribution. The appearance of host-guest phenomenon in cloud point extraction systems that is inherent in organized systems with molecules of the receptors was established. The possibility of describing reagent distribution using regressions that consider substrate hydrophobicity and molecular structure in the cloud point extraction systems was shown.     

Combination of silica sol and dyes on textiles

The embedding in sol-gel coatings can improve the fastness properties of dyes on textiles. The aim of this study is to investigate, whether it is necessary to apply dye and sol together in one step or the application of dye and sol can be performed in separate steps. For practical applications, it can be of high interest to apply sol and dye separately, because by this the fastness properties of once coloured textiles can be improved by sol-gel coatings or an uncolored sol-gel treated fabric can be dyed afterwards with higher fastness properties. For this, modified silica sols and dye molecules were applied in combination on textiles. The investigations were performed with the two triphenylmethane dyes Malachite Green and Guinea Green. These dyes were applied using four different methods – without sol, applied before or after sol treatment and together with the sol. The silica sols were applied in different concentration. It was demonstrated that the application together with the silica sol or the aftertreatment of dyed textile with silica sol lead to significant improvement of leaching fastness. Also the low bleaching fastness of the triphenylmethane dyes can be enhanced significantly.     

Synthesis of Fluoro-Contained Bisazo Chromotropic Acid Derivants and studies on Their Color Reactions with Rare Earth Elements

In this paper, a series of f1uoro-contained bisazo chromotropic acid derivants has been designed and synthesized. They are easily soluble in water, alcohol and acetone but insoluble in benzene, ether and chloroform. Some regularities of the effects of their molecular structure on the color reaction have also been studied. The result shows that in this series of reagents, DCF-chlorophosphonazo and DBF-chlorophosphonazo are excellent color reagents for the determination of the total amount of rare earth elements. The molar absor-ptivities of light and heavy rare earth elements are approach to each other. The tolerant quantity of Bi (Ⅲ) and Pb (Ⅱ) , Sn(Ⅳ) are larger than that of the other arsenazo or chlorophosphonazo type of color reagents. We also discover that p-fluorochlorophosphonazo can form β-type complexes with heavy rare earth elements, and p -fluoro-carboxyazo with light rare earth elements. If the reaction time is controlled, p -fluoro-carboxyao can form β-type complex only with La, and the     

Synthesis and characterization of poly(arylene ether)s containing triphenylmethane moieties for proton exchange membrane

A series of poly(arylene ether)s containing triphenylmethane moiety were synthesized by the nucleophilic displacement of aromatic dihalides with bisphenols in an aprotic solvent in the presence of excess potassium carbonate. High molecular weight and fibrous polymers in white color can be readily afforded in short reaction time. The structures of the synthesized monomers and polymers were investigated by ¹H NMR and MS techniques. The sulfonation position of the synthesized polymer can be easily controlled and the water-up-take can be conveniently tailored by changing the amount of sulfonation agent. This sulfonated polymer 4b is soluble in polar organic solvents, such as NMP, DMAc, DMSO, DMF, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The sulfonated polymers can be potentially used as the proton-exchange membranes for fuel-cells.     

Bias effects on the electronic spectrum of a molecular bridge

In this paper the effect of bias and geometric symmetry breaking on the electronic spectrum of a model molecular system is studied. Geometric symmetry breaking can either enhance the dissipative effect of the bias, where spectral peaks are disabled, or enable new excitations that are absent under zero bias conditions. The spectral analysis is performed on a simple model system by solving for the electronic response to an instantaneously impulsive perturbation in the dipole approximation. The dynamical response is extracted from the electronic equations of motion as expressed by the Keldysh formalism. This expression provides for the accurate treatment of the electronic structure of a bulk-coupled system at the chosen model Hamiltonian electronic structure level.