N-酰基-L-丝氨酸钠表面活性剂的合成和胶束化热力学性质

以L-丝氨酸和长链酰氯为原料,合成了3种不同碳链长度（n=8,12,14）的N-酰基-L-丝氨酸。 并以1H NMR、ESI-MS和元素分析对3种目标产物进行了表征。 采用表面张力法研究了N-酰基-L-丝氨酸钠在298、308、318和328 K时水溶液中的聚集行为,确定了临界胶束浓度（cmc）、临界胶束浓度下的最低表面张力（γcmc）、表面饱和吸附量Γmax。 由cmc和温度的关系,应用相分离模型计算了胶束化热力学参数ΔGom、ΔHom和ΔSom。 结果表明,ΔGom＜0,ΔHom的绝对值比-TΔSom绝对值小的多,说明胶束化过程为熵驱动过程,随着温度的升高,胶束化过程是熵-焓补偿的过程。     

疏水链长对聚氧乙烯失水山梨醇脂肪酸酯界面扩张流变性质的影响

利用悬挂滴方法研究了系列聚氧乙烯失水山梨醇脂肪酸酯(TweenX)在正癸烷-水界面的扩张流变性质. 实验结果表明, 疏水烷基链长较短的Tween20 分子在界面上吸附量较大, 分子排列更紧密, Tween40 和Tween60具有大致相同的“有效截面积”, 导致饱和吸附时界面张力(γ_cmc)比较接近. TweenX浓度大于临界胶束浓度(cmc)时, 由于Tween20 分子排列的更加紧密, 模量和弹性大于Tween40 和Tween60. 当TweenX的疏水烷基链长达到一定长度时, TweenX的界面膜性质受疏水链长的影响减弱, Tween40和Tween60的扩张参数相差不大.     

聚甲基丙烯酸甲酯接枝聚氧乙烯共聚物溶液性质的研究

采用核磁共振 (NMR)、动态激光光散射 (DLS)、透射电子显微镜 (TEM )等方法研究了规整性聚甲基丙烯酸甲酯接枝聚氧乙烯共聚物溶液性质 ,研究表明两亲接枝共聚物在选择性溶剂中可形成球状胶束 ,溶液的浓度、温度和聚合物结构等因素影响其胶束的大小、形态     

正离子型疏水改性聚氧乙烯单成相组分双水相系统的相行为

对正离子型疏水改性聚氧乙烯(HM-EO)单成相组分双水相系统的相行为进行了考察,并分析其电荷特性.HM-EO在水溶液中呈现两亲性,可以形成胶束,进而形成带电的胶束簇集体.通过改变溶液的pH值、盐浓度及添加带相反电荷的表面活性剂SDS,可改变胶束簇集体的带电状态,从而影响系统的相行为.增大pH值,有利于系统的分相.盐的添加也可以增大双水相两相区域,正离子影响次序为K+>Na+,负离子次序为SO42->F->Cl->Br->I-.进一步考察了HM-EO和SDS之间的相互作用,结果表明SDS能与HM-EO形成混合胶束簇集体,改变HM-EO双水相系统的带电特性.     

聚氧乙烯月桂醚在含醇的非水体系中的热力学性质的微量量热法研究

对于非离子表面活性剂聚氧乙烯月桂醚(Brij-35)/N,N-二甲基甲酰胺(DMF)/长链醇(庚醇,辛醇,壬醇,癸醇)体系,利用滴定微量量热仪测定了胶束形成过程的热功率-时间曲线.根据热力学理论,测定了临界胶束浓度和胶束形成热(ΔHmθ),计算了热力学函数(ΔGmθ和ΔSmθ).讨论了温度、醇中的碳原子数、醇的浓度与临界胶束浓度和热力学函数之间的关系.结果表明:聚氧乙烯月桂醚(Brij-35)/DMF/长链醇体系:(1)在含有相同浓度的各种醇的体系中,ΔHmθ和ΔSmθ的值随着温度的升高而增大;CMC,ΔGmθ的值随着温度的升高而降低;(2)在相同温度及相同浓度的醇体系中,CMC,ΔHmθ,ΔGmθ和ΔSmθ的值都随着醇中碳原子数的增加而降低;(3)在相同温度及相同醇的体系中,CMC,ΔHmθ,ΔSmθ和ΔGmθ的值随着醇的浓度的增加都减小.     

冠醚化Schiff 碱配合物金属胶束催化BNPP水解动力学

研究了两种新的冠醚化Schiff 碱过渡金属配合物与表面活性剂Brij35(聚氧乙烯(23)十二烷基醚)形成的金属胶束对BNPP（对硝基苯酚磷酸二酯）的催化水解反应. 探讨了催化反应机理, 建立了一种金属胶束催化BNPP水解的动力学数学模型; 计算了模拟酶催化反应的相关参数和表观活化能. 结果表明, 此类金属胶束作为模拟水解金属酶对BNPP水解反应表现出良好的催化活性.     

硬脂酸聚氧乙烯酯与聚乙烯接枝共聚物的制备与表征

以聚氧乙烯为起始原料,合成了一系列硬脂酸聚氧乙烯酯及其丙烯酸酯,用FTIR和1H NMR测试技术对其结构进行了表征,用最大气泡法测定了其表面张力.以其作为接枝单体,利用反应挤出接枝方法制备了系列功能化聚乙烯,用FTIR确定了接枝共聚物的结构和接枝率;用DSC、接触角测量仪对接枝共聚物的热性能、结晶行为和表面性质进行了测试分析.结果表明,含有不同分子量(200、600、1 000、2 000和6 000)聚氧乙烯的硬脂酸聚氧乙烯酯的表面张力分别为30.19、32.22、35.30、38.39和43.37 mN/m;相应的聚乙烯接枝共聚物的结晶温度分别为109.30、109.08、110.18、109.74和109.74℃,水接触角分别为81.060、70.100、72.25°、76.加.和95.55°.随着聚氧乙烯分子量的增加,表面活性剂的表面活性降低;聚乙烯接枝共聚物的结晶温度高于线形低密度聚乙烯(LLDPE,T.=104.95℃),且其亲水性得到改善(纯聚乙烯的水接触角103°).     

可聚硼酸酯表面活性剂的表面化学性质及与LAS相互作用

用表面张力法研究了可聚合硼酸酯表面活性剂(BES)水溶液不同温度下(288-313 K)的表面活性和热力学函数变化；考察了BES与十二烷基苯磺酸钠(LAS)在0.5 mol·L-1 NaCl溶液中的相互作用. 结果表明, 298 K时, BES临界胶束浓度cmc达到0.066 mmol·L-1, γcmc为29.2 mN·m-1；在所考察的温度范围内BES胶束形成自由能(ΔG0m)在-22.4 - -25.8 kJ·mol-1之间, 胶束形成是熵驱动过程. BES/LAS混合体系为具有较大负偏差的非理想体系, BES/LAS分子间平均相互作用参数βm=-3.48；当溶液体相中BES摩尔分数αBES＝0.5时, 混合胶束中BES摩尔分数X1m为0.46, |βm|达到最大, 而且此时混合溶液cmc为0.017 mmol·L-1, 达到最低, γcmc为27.8 mN·m-1.     

手性赖氨酸基Gemini表面活性剂的表面性能

用表面张力法、电导法和稳态荧光法研究了手性Gemini表面活性剂[C₁₂-m-C₁₂] Na₂（m=2,4,6）和[C₁₂-T-C₁₂] Na₂的表面性能及临界胶束聚集数,并计算胶束形成的热力学参数,用圆二色谱法考察了[C₁₂-2-C₁₂] Na₂在不同浓度下的立体构型. 结果表明,手性Gemini表面活性剂的临界胶束浓度（cmc）和临界表面张力γ_cmc随着连接基链长增加或刚性增强而增大;ΔG_m⁰和ΔH_m⁰为负值,|ΔH_m⁰|比|-TΔS_m⁰|小很多,说明胶束化过程为熵驱动的自发放热过程;随着连接基链长增加或刚性增强,ΔG_m⁰和ΔH_m⁰逐渐增大,ΔS_m⁰和临界胶束聚集数逐渐减小,表明其胶束化能力随之降低;当浓度大于cmc时,手性Gemini表面活性剂可形成手性超分子聚集体.     

核磁共振谱研究PAA-F108-PAA 嵌段共聚物的胶束化行为

采用原子转移自由基聚合伴随水解的方法合成了聚丙烯酸-聚醚嵌段共聚物(PAA-F108-PAA), 并通过氢核磁共振波谱和二维核Overhauser效应谱(2D NOE)研究了温度、 羧酸基团中和度(α)及盐浓度对PAA-F108-PAA嵌段共聚物在水溶液中胶束化行为的影响. 结果表明, PAA-F108-PAA分子的临界胶束化温度受α影响较小, 受盐的种类和浓度影响较大. 当α=0.14(0.01 mol/L KCl)时, 在6 ℃条件下, PAA-F108-PAA分子处于塌缩状态, 而在60 ℃条件下, 聚氧化丙烯(PPO)链段发生疏水聚集形成胶束的核, PAA链段与PEO链段相互作用形成胶束的壳; 当α=0.80(0.01 mol/L KCl)时, 在6 ℃条件下, PAA-F108-PAA分子处于相对伸展状态, 而在60 ℃条件下, PPO链段仍发生疏水聚集形成胶束的核, PEO与PAA彼此分离形成胶束的壳. 增加KCl的浓度至1 mol/L, PAA-F108-PAA分子的临界胶束化温度显著降低, KCl对PPO和PEO链段都表现出脱水作用. 但KI的浓度增加至1 mol/L时, PAA-F108-PAA分子的临界胶束化温度仅略微增加, KI对PPO链段表现出脱水作用, 而对PEO链段表现出增溶作用.     

Synergism and foaming properties in binary mixtures of a biosurfactant derived from Camellia oleifera Abel and synthetic surfactants

A biosurfactant, named tea saponin (TS), was isolated and purified from the defatted seed of Camellia oleifera Abel. The characterization of TS including molecular weight, glycosyl composition, and thermal behavior as well as the surface and foaming properties was conducted. The synergistic interactions of binary systems of CTAB-TS, SDS-TS, and Brij35-TS were investigated. The results show that TS had a weight-average molecular weight of 809.12 g mol(-1) and contained four aglycones of L-rhamnose, D-galactose, D-glucose, and D-glucuronic acid. The critical micelle concentration (cmc) of 2.242 mmol L(-1) and the minimum surface tension (γ(cmc)) of 43.5 mN m(-1) were determined for TS. Synergisms in surface tension reduction efficiency, in mixed micelle formation, and in surface tension reduction effectiveness were observed in CTAB-TS and SDS-TS systems, whereas that was not shown in Brij35-TS mixtures. The mixtures of TS with CTAB and SDS showed synergism in foaming efficiency, but this synergism did not exist in Brij35-TS system with respect to the surface properties. Nevertheless, there appears to be no significant correlation between foam stability and the surface properties.     

C9pPHCNa与C10TABr混合水溶液的表面吸附和胶团形成

羧酸盐Gemini表面活性剂C9pPHCNa与季铵盐表面活性剂十烷基三甲基溴化铵(C10TABr)混合水溶液的胶团生成能力、降低水表面张力的能力和效率均出现明显的增效. 当C9pPHCNa在溶液中的摩尔分数(α1)为0.33时，cmcT(临界胶团总浓度)、γcmc(临界胶团总浓度对应的表面张力)、c20,T(降低20 mN•m^-1水表面张力所需的表面活性剂总浓度)这3个指标均达到最低值，分别为0.60 mmol•L^-1、23.5 mN•m^-1和1.58×10^-5 mol•L^-1. 在所有考察的溶液比例范围内，二组分在混合胶团和表面吸附层中的组成均接近等摩尔比，表现出强烈的分子间相互作用.     

Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

Spectroscopic studies of interaction of Safranine T with nonionic micelles and mixed micelles

The visible spectra of Safranine T (ST) in micellar solution of Brij 58, Tween 20 and Tween 40 and mixed micellar solution of Brij 58/Tween 20 and Brij 58/Tween 40 indicate formation of 1:1 charge transfer (CT) complex between acceptor ST and donor nonionic micelles and mixed micelles. The experimental CT transition energies are well correlated (through Mulliken's equation) with the vertical ionization potential of the donors. The solvent parameters, i.e. the intramolecular charge transfer energy ET(30) have been determined from the Stokes spectral shift. Variations of ionization potential and micropolarity in the mixed micellar region have been investigated as a function of surfactant composition and the obtained results in mixed micellar medium has been compared to the normal micelles. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic interaction. The interaction parameter (beta) and micellar stability has been calculated using regular solution theory.     

Analysis of interfacial and micellar behavior of sodium dioctyl sulphosuccinate salt (AOT) with zwitterionic surfactants in aqueous media

The interfacial and bulk properties of mixtures of the anionic surfactant (dioctyl sulphosuccinate sodium salt, AOT) with zwitterionic surfactants 3-(N,N-dimethyldodecylammonio) propane sulfonate (DPS), 3-(N,N-dimethyltetradecylammonio) propane sulfonate (TPS), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HPS) have been studied employing surface tension, fluorescence, and viscometric techniques in aqueous media at 25 °C. It is observed that these mixtures exhibit synergism and these synergistic interactions increase with the enhancement of the hydrocarbon chain of the zwitterionic surfactant. The various physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Г(max)), minimum area per molecule (A(min)), aggregation number (N(agg)), interaction parameters (β(σ), β(m)), and thermodynamic parameters such as standard Gibbs free energy of adsorption (ΔG(ads)(o)), excess free energy of micellization (ΔG(ex)), and standard Gibbs free energy of micellization (ΔG(m)(o)) have been evaluated. The negative values of ΔG(m)(o) and ΔG(ads)(o) show that the micelle formation and adsorption of surfactant at the air/solution interface is energetically favorable, while a negative value of ΔG(ex) ensures stability of the mixed micelles formed. The Regular Solution Approximation, Motomura and Rosen's approaches have been used to explain and compare the results. The packing parameter (p) ensures the formation of vesicles or bilayers for AOT+DPS/TPS mixtures, which can potentially be used as delivery agents for industrial applications.     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

Mixed Micellization Behavior of 12-2-12 Gemini Surfactant with Some Alkyltrimetyl Ammonium Bromide Surfactants

Mixed micellization behavior of dimeric cationic surfactant ethanediyl-1,2-bis (dimethyldodecylammonium bromide) (12-2-12) with a series of monomeric cationic surfactants dodecyltrimethyl ammonium bromide (DTAB), tetradecyltrimethyl ammonium bromide (TTAB), and cetyltrimethyl ammonium bromide (CTAB) has been studied in aqueous and aqueous polyvinylpyrrolidone (PVP) solutions at 298.15, 308.15, and 318.15 K, respectively, using conductometric method. Various thermodynamic parameters like mixed micelle concentration (C_m), micelle mole fraction (X₁), interaction parameter (β), and free energy of mixing (ΔG_ex) of the mixed systems have been determined and analyzed using Rubingh's regular solution theory. The results indicate that in aqueous solutions the binary mixtures of 12-2-12 with DTAB/TTAB behave nonideally with mutual synergism whereas that with CTAB shows almost ideal behavior at 298.15 K. At 318.15 K, all these binary mixtures exhibit antagonistic behavior. The effect of variation in chain length of alkyltrimethyl ammonium bromide surfactants on the interactions with 12-2-12 have also been evaluated and discussed.     

The interaction of an anionic gemini surfactant with conventional anionic surfactants

The interaction in two mixtures of an anionic gemini surfactant having N ,N -dialkylamide and carboxylate groups in a molecule, (CH2)2[N(COC11H23)CH(CO2H)CH2(CO2H)]2. 2NaOH (GA), and conventional anionic surfactants have been investigated in 0.1 M NaCl at pH 5.0. The two mixtures are GA/sodium dodecylsulfate (SDS) and GA/sodium N -dodecanoylglutamate (AGS) at a molar fraction of GA, alphaGA = 0.25 . Mixtures of both GA/SDS and GA/AGS exhibit synergism in surface tension reduction effectiveness. The GA/SDS mixture also exhibits synergism in surface tension reduction efficiency and mixed micelle formation, whereas the GA/AGS mixture does not. The interaction in mixed adsorption film formation is stronger than that in mixed micelle formation for the two mixtures. The interaction in the formation of the mixed adsorption film and the mixed micelle for the GA/SDS mixture is stronger in both formations than that for the GA/AGS mixture. The stronger interaction for the GA/SDS mixture may be caused by the combination of the smaller minimum area per molecule at the air/water interface (Amin) of the head groups in the GA molecule and the larger Amin in the SDS molecule.     

Mechanism of the Micellar Solubilization of Curcumin by Mixed Surfactants of SDS and Brij35 via NMR Spectroscopy

The micellar solubilization mechanism of curcumin by mixed surfactants of SDS and Brij35 was investigated at the molecular scale by NMR spectroscopy. Through the investigation of the micelle formation process, types and structures of mixed micelles and solubilization sites, the intrinsic factors influencing the solubilization capacity were revealed. For systems with α_SDS = 0.5 and 0.2, the obtained molar solubilization ratios (MSRs) are consistent with the MSR_ideal values. However, for α_SDS = 0.8, the solubilization capacity of curcumin is weakened compared to the MSR_ideal. Furthermore, only one single mixed SDS/Brij35 micelles are formed for α_SDS = 0.5 and 0.2. However, for α_SDS = 0.8, there are separate SDS-rich and Brij35-rich mixed micelles formed. In addition, NOESY spectra show that the interaction patterns of SDS and Brij35 in mixed micelles are similar for three systems, as are the solubilization sites of curcumin. Therefore, for α_SDS = 0.5 and 0.2 with single mixed micelles formed, the solubility of curcumin depends only on the mixed micelle composition, which is almost equal to the surfactant molar ratio. Although curcumin is solubilized in both separate micelles at α_SDS = 0.8, a less stable micelle structure may be responsible for the low solubility. This study provides new insights into the investigation and application of mixed micelle solubilization.