碳氟醇对阳离子表面活性及胶团反离子结合度的影响

用表面张力及电动势法研究了Ｃ１０Ｈ２１Ｎ（ＣＨ３）３Ｂｒ，Ｃ１２Ｈ２５Ｎ（ＣＨ３）３Ｂｒ和Ｃ３Ｆ７ＣＨ２ＯＨ混合水溶液的表面与胶团性质。结果表明，对于阳离子表面活性剂，Ｃ３Ｆ７ＣＨ２ＯＨ的加入一方面增加表面活性，另一方面降低胶团反离子结合度。后者不同于阴离子表面活性剂／Ｃ３Ｆ７ＣＨ２ＯＨ混合体系，可归因于Ｃ３Ｆ７ＣＨ２ＯＨ略有酸性，因而具备一些类似阴离子表面活性剂的性质。     

芳香反离子与离子表面活性剂胶团的相互作用

用紫外吸收光谱的方法研究了多种芳香反离子与离子表面活性剂胶团之间的相互作用。发现阳离子表面活性剂和阴离子表面活性剂胶团对芳香反离子的吸收光谱有着显著不同的影响,芳香反离子结构的细微变化可导致光谱特性显著不同。这被解释为阳离子表面活性剂胶团与芳香环之间的阳离子-π相互作用。阳离子-π相互作用需要阳离子表面活性剂分子与芳香反离子具有合适的相对位置与距离。通过测定各混合体系的吸附量证明,不同的芳香反离子在胶团表面有不同的排列方式。NMR的实验结果支持了上述解释。     

离子选择电极法测定胶团的反离子结合度

胶团的反离子结合度(K)对于胶团各种性质的研究是一个至关重要的参数^[1～3]。已有不少方法用于K值的测定,其中以离子选择电极法最为方便^[4～8],且此法赋予K值的含义也与热力学要求相同^[9]。     

反离子对氟表面活性剂的影响1. 表面活性及胶团化作用

通过表面张力和荧光探针法研究了全氟辛酸钠、全氟辛酸铵以及全氟辛酸四烷基铵[C₇F₁₅COON(C_nH_2n+1)₄, n＝1, 2, 3, 4]的表面活性以及胶团化作用, 系统地讨论了各种反离子, 特别是反离子大小的影响. 结果表明, 与普通碳氢表面活性剂不同, 反离子对这类氟表面活性剂的表面活性以及胶团化作用有很大影响. 表面活性剂的临界胶束浓度(cmc)随反离子的增大而下降; 饱和吸附层中平均每个分子所占的面积则大致随反离子的增大而增大. 而表面张力的变化则较为复杂. cmc时的表面张力随反离子的增大先上升(从全氟辛酸铵到全氟辛酸四乙铵)后下降(从全氟辛酸四乙铵到全氟辛酸四丁铵). 通过反离子的空间位阻、疏水性、插入以及电荷屏蔽效应对上述结果做了解释.     

碳氟醇对阳离子表面活性剂表面活性及胶团反离子结合度的影响

用表面张力及电动势法研究了C₁₀H₂₁N(CH₃)3Br、C₁₂H₂₅N(CH₃)3Br与C₃F₇CH₂OH混合水溶液的表面与胶团性质。结果表明,对于阳离子表面活性剂,C₃F₇CH₂OH的加入一方面增加表面活性,另一方面降低胶团反离子结合度。后者不同于阴离子表面活性剂/C₃F₇CH₂OH混合体系,可归因于C₃F₇CH₂OH略有酸性,因而具备一些类似阴离子表面活性剂的性质。     

碳氟醇对全氟辛酸钠表面活性及胶团反离子结合度的影响

The surface and micelle property of C_7F_(15)COONa/C_3F_7CH_2OH aqueous solution are investigated by surface tension, conductance, electromotive force methods. The results show that when adding C_3F_7CH_2OH into C_7F_(15)COONa solution the surface activity of C_7F_(15)COONa and the counterion binding degree of micelle can be enhanced.     

电解质对两性药物分子盐酸氯丙嗪的胶团生长的影响

The effect of electrolytes on the micellar behavior of an amphiphilic drug,chlorpromazine(CPZ)hydroehloride,was studied using cloud point(CP)and dye solubilization techniques.In the presence of KBr,increase because of deprotonation of drug molecules at high pH. The visible absorbance increased(due to dye solubilization)with the increase in pH from 6.5 to 6.9,which indicated micellar growth.At fixed pH(6.7),addition of inorganic salts(KF,KC1,effecfiveness being in the order:F-Na >K ,which Was explained by considering cognizance of their hydrated radii.Compared with anions,their effect was small.Increase in[CPZ]caused micellar growth and hence the CP as well as the visible absorbance increased.The overall behavior Was discussed in terms of electrostatic interactions and micellar growth.     

小分子有机添加物对胶团催化的影响

表面活性剂胶团对化学反应的催化作用具有重要的理论和实际意义^[1-2],在影响胶团催化的诸因素中,有机添加物的影响很受重视,这是因为有机物的加入既可能改变介质的性质,也可能对胶团的结构,大小,电性质产生影响,至今对添加有机物影响的研究大多为定性描述,缺少定量处理的结果,本文初步研究了小分子有机添加物异丙醇（i-PrOH),叔丁醇（t-BuOH),异戊醇（i-PeoH)和苯甲醛（PhCHO)对2－4－二硝基氯苯（DNCB）在溴代十六烷基三甲铵（CTAB）阳离子胶团训与NaOH反应的准一级反应速率常数k1 的影响,应用假相离子交换（PIE）模型的基本公式对实验结果进行了定量处理,并用胶团结构的变化对实验结果进行了解释。     

不同反离子对高效氯氰菊酯微乳液影响的研究

研究了结合不同反离子的十二烷基苯磺酸盐(DBS)与苯乙烯苯酚聚氧乙烯醚(NR600)形成的高效氯氰菊酯微乳液的导电机理, 以及反离子对体系相行为的影响. 研究结果表明, 由于阴离子表面活性剂的溶解度不同以及溶解后反离子结合度的差异, 使得反离子能改变微乳液界面的亲水亲油作用. 具有较小水化半径的K^＋使界面的亲水作用增强, 更有利于O/W型微乳液的形成, 而水化半径较大的Na^＋, Li^＋不如K^＋有利于O/W型微乳液的形成; Ca^2＋与表面活性剂的阴离子结合形成的油溶性的表面活性剂, 有利于微乳液界面亲油作用的增强, 不利于O/W型微乳液的形成. 这与热贮分解率的结果相一致.     

OXIDATION OF THE ALKYL-, ARYL-, AND AMINO-SULFONIUM IONS TO THE SULFOXONIUM IONS AND ITS REACTION MECHANISM

Abstract

Hitherto, the preparative method of the sulfoxonium ions has been practically limited to thealkylation of the sulfoxides with methyliodide. The yields of the desired sulfoxonium salts by this method are usually poor except that of trimethylsulfoxonium iodide, Diarylalkyl- or triaryl-sulfoxonium ions can not be prepared by this alkylation.     

SEQUENCE SPECIFICITY OF TETRAHYDROBENZOPSORALEN PHOTOBINDING TO DNA

Abstract— The sequence specificity of photobinding to DNA of two tetrahydrobenzopsoralen derivatives has been investigated by testing the photoreactivity toward a number of self-complementary oligonucleotides. The thermodynamic constant for noncovalent binding to each DNA sequence was evaluated. The extent of photoreactivity was greatly dependent upon base composition. The two tetracyclic compounds show similar behavior in comparison to other bifunctional derivatives. Their overall rate constants were greatly enhanced in comparison to classical psoralens. However, their high efficiency of covalent binding is counterbalanced by low affinity for noncovalent interaction with DNA.     

浊点萃取技术在金属离子分离和富集以及形态分析中应用的进展

介绍了新兴的环保型液液萃取方法——浊点萃取的原理及操作方法，讨论了影响浊点萃取效率的因素，重点回顾了近年来该技术在金属离子分离和富集以及形态分析中应用的进展，探讨了该技术的发展前景。     

INTERFACIAL ELECTRON TRANSFER INVOLVING RADICAL IONS OF CAROTENE AND DIPHENYLHEXATRIENE IN MICELLES AND VESICLES

Abstract— The radical cations and anions of diphenylhexatriene have been produced and characterized in homogenous and micellar solutions by pulse radiolysis and laser flash photolysis techniques. Both types of radical ions were formed in cyclohexane on pulse radiolysis. The radical cation was formed in dichloroethane on pulse radiolysis, and by two photon photoionization in ethanol, dichloroethane, and various micelles. Both radical ions have intense ( 10⁵ M ^-1 cm^-1) absorption peaks at600–650nm. The cation peak occurs at slightly shorter wavelengths than that of the anion.
In micelles and vesicles the radical anion of carotene was formed by electron transfer from e_a– on pulse radiolysis. The radical cation was formed on pulse radiolysis of micellar solutions containing Br^-₂ as counterion, presumably by electron transfer to Br₂^-. The spectra agree with those of the radical cation and anion of carotene that have previously been obtained in homogenous solutions (Dawe and Land, 1975).
Electron transfer in micelles and vesicles from the radical anion of biphenyl to carotene and diphenylhexatriene, and from the radical anions of these to inorganic acceptors has been studied.     

THE INTERACTION OF CHLOROPHYLL-A WITH DETERGENT MICELLES

Absorption and fluorescence spectra of Chl- a in ethanol, ethanol/water mixtures and aqueous sodium dodecyl sulphate are reported. Contrary to a previous report, it is found that Chl- a is not solubilized in the anionic detergent as a microcrystalline form.     

EFFECT OF METAL IONS ON THE LUMINESCENCE OF ACRIDINE DYES BOUND TO DNA

Abstract— The luminescence of acridine dyes intercalated in DNA was studied as a function of the concurrent binding of metal ions to DNA, in an effort to deduce specific site interactions of the dyes. Two dyes, proflavine (PF) and acridine orange (AO), and two metal ions, silver and mercuric, were used. Both ions quench the fluorescence of the dyes in aqueous solution at room temperature. The metal ions have a different effect on the fluorescence of these dyes when they are intercalated between the base pairs of DNA. The fluorescence of AO is decreased when silver is bound, while the fluorescence of PF is enhanced. Since Ag⁺ initially binds to GC sites in DNA, which quench the PF fluorescence, it ostensibly 'turns off' the quenching by DNA at these sites, and this effect is greater than the quenching effect of the silver ion itself. Hg²⁺ ion initially binds to AT sites in DNA. Since both dyes fluoresce from AT sites, Hg²⁺ is expected to quench their fluorescence. This behavior is observed at low r (metal ion/base). At higher r values, however, where Hg²⁺ is expected to begin binding to GC sites, the fluorescence of PF is enhanced. These quenching turn-off effects are tentatively interpreted in terms of a change in the structure of the dye/DNA complex which occurs when a metal ion binds at the intercalation site. At 77 K. no fluorescence enhancement is observed when metal ions bind; Ag⁺ quenches the fluorescence and enhances the phosphorescence of both dyes. Qualitatively similar results are obtained with Hg²⁺.     

2,6-二乙酰基吡啶缩二(氨基硫脲)与若干过渡金属离子的配位反应

用分光光度法研究了2.6-二乙酰基吡啶缩二(氨基疏脲)与 Cu²⁺,Co²⁺,Ni²⁺,Zn²⁺的配位反应,用作图法和自编的LEMIT-S程序计算了配合物的组成,摩尔吸光系数和稳定常数,两法所得的结果基本一致,结果表明,在乙醇中Cu²⁺与配体daptsc形成Cu₂(daptsc)和Cu(daptsc),二者在溶液中共存,而Cu²⁺在DMF中仅生成1:1配合物,其它金属离子在两种溶剂中均形成1:1型。在两种溶剂中lgβ₁₁的顺序为:Zn > Cu > Ni > Co.     

2,6—二乙酰基吡啶缩二(氨基硫脲)与若干过渡金属离子的配位反应

用分光光度法研究了2.6-二乙酰基吡啶缩二(氨基疏脲)与 Cu~(2+),Co~(2+),Ni~(2+),Zn~(2+)的配位反应,用作图法和自编的LEMIT-S程序计算了配合物的组成,摩尔吸光系数和稳定常数,两法所得的结果基本一致,结果表明,在乙醇中Cu~(2+)与配体daptsc形成Cu_2(daptsc)和Cu(daptsc),二者在溶液中共存,而Cu~(2+)在DMF中仅生成1:1配合物,其它金属离子在两种溶剂中均形成1:1型。在两种溶剂中lgβ_(11)的顺序为:Zn>Cu>Ni>Co     

THE EFFECT OF SURFACTANT MICELLES ON THE ALKALINE HYDROLYSIS OF DIMETHYLFORMAMIDE

The alkaline hydrolysis of dimethylformamide has been studied at 40'C in micellar solutions of single surfactant (CTAB. SDS. Brij 35) with the analog thermoanalytical curve method of thermokinetics. A kinetic equation of micellar catalysis under the condition of highter reactant concentration than micellar concentration ([S]>[M]) has been derived from the pseudophase model of micellar catalysis and some relative assumptions, The kinetic parameters. k_m, k_2mand the association constant of reactant with micelle K₁, have been calculated in this way. the results indicate that these surfactant micelles exhibit catalytic effect on the reaction. This is attributed to the micropolarity and local concentration effect of micelles.     

ELUTION OF TUNGSTEN BY SODIUM COMPOUNDS AND ACCELERATION EFFECTS OF COEXISTENT COUNTER IONS IN MIXED ELUANT

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