全氟壬烯氧基苯磺酸钠与烷基季铵盐的相互作用

通过六氟丙烯三聚体(全氟壬烯)氧基苯磺酸钠(C₉F₁₇OC₆H₄SO₃Na, OBS)与阳离子碳氢表面活性剂C_nNR[C_nH_2n+1N(CH₃)₃Br, C_nNM, n=8, 10和C_nH_2n+1N(CH₂CH₃)₃Br, C_nNE, n=8, 10, 12]复配, 研究了OBS与C_nNR的摩尔比、 C_nNR疏水链长及C_nNR亲水基团大小对此类阴、 阳离子碳氟-碳氢表面活性剂混合体系的临界胶束浓度(cmc)、 最低表面张力(γ_cmc)、 总饱和吸附量(Γ_tm)及极限分子面积(A_min)的影响. 结果表明, 通过与C_nNR复配, OBS的cmc和γ_cmc均大幅下降, 达到了全面增效的结果. 不同摩尔比的OBS-C₈NE混合体系中, 摩尔比为1:1时表面活性最好, cmc和γ_cmc均最小; 偏离等摩尔比时, OBS过量时混合体系的cmc小于C₈NE过量时混合体系的cmc, 但γ_cmc相差不大. 与单体系相比, OBS-C₈NE混合体系的Γ_tm明显增大、 A_min明显变小. OBS与不同疏水链长的C_nNE复配时, cmc的变化规律为C₈NE>C₁₀NE>C₁₂NE, 表明C_nNE疏水链长的增加能降低混合体系的cmc. 通过比较C_nNM和C_nNE(n=8, 10)的表面活性发现, 改变混合体系中C_nNR的亲水基团大小对混合体系的表面活性无明显影响.     

C12EO4与氨丙基三乙氧基硅烷水溶液自组装和流变性研究

研究了3-氨丙基三乙氧基硅烷(APTES)和非离子表面活性剂十二烷基聚氧乙烯(C₁₂EO₄)水溶液的相行为、溶液自聚集作用和流变性, 小角度X-射线散射(SAXS)、低温透射电子显微镜(cryo-TEM)和氘谱核磁共振(²H NMR)测定确定了溶液中聚集体结构, 测定了聚集体混合物溶液的流变性质. 结果表明: 随着溶液混合物组分的变化, 溶液聚集体结构发生了改变, 在L_α相区内, 恒定C₁₂EO₄浓度, 随着APTES浓度增加聚集体结构由高曲率聚集体转变为低曲率的层状结构; 而在恒定APTES浓度时, 随着C₁₂EO₄增加, L_α相由低粘弹性的囊泡溶液转变为粘弹性极高的密堆积囊泡和平面层状结构共存的类凝胶相, 溶液聚集体结构和结构转变是由于APTES水解产物插入至C₁₂EO₄胶束引起的. 非离子表面活性剂和氨基硅烷混合物溶液相结构及结构转变的新结果对于完全理解该类混合物的实际应用, 特别是作为模板合成硅材料的应用具有重要理论意义.     

不同寡聚度磺酸盐表面活性剂与支化羧酸盐混合体系的聚集行为

采用表面张力、Zeta电位和小角中子散射技术,研究了pH 11条件下2-己基癸酸、异硬脂酸对具有单头单链十二烷基磺酸钠（SDoS）和星状四聚磺酸盐表面活性剂EDA-（C₁₂SO₃Na）₄的气液界面性质、胶束化行为和乳化性能的影响.结果表明,在气液界面和胶束中支化羧酸盐分子与磺酸盐表面活性剂间有不同程度的相互吸引作用,而且在降低表面张力效率方面具有协同作用,但胶束中分子间相互吸引作用更强的四聚磺酸盐表面活性剂混合体系在聚集体形成方面却未表现出协同作用.同时,随着羧酸盐的加入,SDoS和EDA-（C₁₂SO₃Na）₄呈现出不同的聚集体转变规律,羧酸盐与SDoS的混合聚集体随着浓度增大逐渐由球形胶束转变为棒状胶束,而羧酸盐与EDA-（C₁₂SO₃Na）₄的棒状胶束随着羧酸盐摩尔分数的增大而增长,随着总浓度的增大而减小.此外,在同等乳化烷烃的效果下,支化羧酸盐分子的加入可以大幅减少寡聚磺酸盐表面活性剂的使用量.     

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。     

碳氟表面活性剂与碳氢表面活性剂混合水溶液的表面吸附与胶团形成(Ⅳ)——非离子-非离子体系

测定了25℃不同比例的C₁₀F₁₉O(C₂H₄O)₉H与C₈H₁₇C₆H₄O(C₂H₄O)₁₀H混合水溶液的表面张力,研究混合水溶液的表面性质与胶团形成。用两种不同方法计算在表面上的表面成份、分子之间相互作用参数(β_σ)。结果表明,在非离子型碳氟和碳氢表面活性剂混合水溶液中,两种表面活性剂基本上各自形成胶团;表面分子相互作用参数皆为正值;表明此混合体系中碳氟链与碳氢链之间互疏作用的存在。     

尾链长度高度不对称的阴/阳离子表面活性剂自组织

通过引进新的溶液制备方法,以光散射、流变、电镜等方法研究了烷烃链长度不对称的阴/阳离子表面活性剂等摩尔混合体系,其中阳离子为二十二烷基三甲基溴化铵(C₂₂TABr),阴离子是烷基羧酸钠(C_n-1COONa, n = 4, 6, 8, 10, 12, 14, 16).结果表明,烷烃链长度高度不对称时(C22/n4)生成了球状胶束,随着降低不对称度,聚集体向棒状、蠕虫状直至囊泡转变.在构成囊泡的体系中,随着降低链长不对称度,聚集体尺寸明显增大.机理分析表明,阴/阳离子对的几何形状决定了聚集体的形貌以及它们的转变.     

Imidazolium ionic liquid-supported sulfonic acids: efficient and recyclable catalysts for esterification of benzoic acid

Several imidazolium ionic liquid（IL）-supported sulfonic acids with different anions,[C₃SO₃Hmim]HSO₄,[C₃SO₃Hmim]BF₄, [C₃SO₃ Hmim]PF₆,and[C₃SO₃Hmim]CF₃SO₃,were synthesized and applied as catalysts for esterification reaction of benzoic acid. The experimental results indicate that imidazolium IL-supported sulfonic acid containing anion of HSO₄^- shows the best catalytic activity.Only when less[C₃SO₃Hmim]HSO₄（0.3 equiv.） applied,was the product obtained with high yield of 97%.Furthermore, the produced esters could be separated by decantation,and the catalyst could be reused after the removal of water.     

NMR研究溶液中正十四烷基硫酸钠/正十四烷基聚氧乙烯醚(3)表面活性剂之间的相互作用

采用¹HNMR弛豫、自扩散系数和二维相敏(2DNOESY)实验研究了正十四烷基硫酸钠[n-CH₃(CH₂)₁₃OSO₃Na(STS)]和正十四烷基聚氧乙烯醚(3)[n-CH₃(CH₂)₁₃O(C₂H₄O)₃H(C₁₄E₃)]在溶液中的自聚集以及二者混合后的相互作用.结果表明,STS与C₁₄E₃混合后存在相互作用,并形成混合胶束;弛豫实验表明,混合胶束中STS疏水链质子运动更加受阻,C₁₄E₃的α-(4″)和β-CH₂(3″)处链堆积紧密.C₁₄E₃的亲水端(CH₂CH₂0)₃链卷曲紧贴在疏水壳表面外链堆积较紧密处.自扩散系数测量表明,混合胶束比单一阴离子表面活性剂形成的胶束大.单一非离子型胶束和混合胶束的亲水端(CH₂CH₂0)₃(5″)链构成相应较软和松散的外壳.单一C₁₄E₃在极性溶剂氯仿溶液中,质子运动比在水中自由度大,但2DNOESY谱中出现了少量分子间的交叉峰,也可能形成了一些小的聚集体.     

季铵盐表面活性剂与卵磷脂囊泡相互作用的研究

采用动态光散射、ζ电势等方法研究了季铵盐二聚表面活性剂(C₁₂-8-C₁₂•2Br)和十二烷基三甲基溴化铵(DTAB)在卵磷脂囊泡中的增溶作用. C₁₂-8-C₁₂•2Br使囊泡粒径增大, 促进脂双层向胶团的转变, 过程明显分为三个阶段; 而DTAB与囊泡的作用则相对缓和, 72 h内未见明显变化. 此外, 用亲水头基总体积的大小, 讨论了这两种表面活性剂在脂质体中的吸附行为, 并对实验现象加以解释说明.     

十二烷基混合糖苷与其它表面活性剂二元体系表面吸附和胶束形成的顺序研究

摘要绿色表面活性剂烷基糖苷C₁₂G _1.46具有混合糖苷组成, 将其分别与十二烷基三氧乙烯磺酸钠C₁₂E₃S、 十二烷基三甲基氯化铵C₁₂TAC、 三硅氧烷非离子表面活性剂BE-6、 聚醚类表面活性剂 TMN-6复配, 在25 ℃下测定它们在0.1 mol/L NaCl溶液中的表面活性, 通过其混合表面层和混合胶束的分子交换能(ε, ε_m)的计算得出如下结论: (1) C₁₂G_1.46的活性高于C₁₂G₁和C₁₂G₂, 即烷基混合糖苷的活性高于相同烷基的纯糖苷的结论得到了进一步证实. 利用MM2分子力场计算的能量数据可合理地解释这种混合产品活性提高的原因. (2) 在该烷基混合糖苷的二元体系溶液中, 对其表面吸附和胶束化两个过程的顺序问题进行探讨, 一种情况是先建立表面吸附, 再形成胶束(C₁₂G_1.46/BE-6 和 C₁₂G_1.46/TMN-6 体系); 另一种情况是表面吸附和胶束化同时进行(C₁₂G_1.46/C₁₂TAC和C₁₂G_1.46/C₁₂E₃S体系).     

Interactions of beta-lactoglobulin with sodium decylsulfonate, decyltriethylammonium bromide, and their mixtures

The interactions of beta-lactoglobulin (BLG) with anionic surfactant sodium decylsulfonate (C10SO3), cationic surfactant decyltriethylammonium bromide (C10NE), and the mixtures of cationic-anionic surfactants (C10NE-C10SO3) were investigated by circular dichroism (CD) and fluorescence methods. At pH 7.0, C10NE and the C10NE-rich surfactant mixtures of C10NE-C10SO3 could form precipitates with BLG, while C10SO3, equimolar mixtures of C10NE-C10SO3, or C10SO3-rich mixtures of C10NE-C10SO3 form homogeneous solutions with BLG. CD observed that both C10NE and C10SO3 could change the BLG structure. The effects of the mixtures of C10NE-C10SO3 on BLG structure depended on the ratio of C10NE to C10SO3. The C10NE-rich or the C10SO3-rich mixtures of C10NE-C10SO3 could significantly affect BLG structure, while the equimolar mixtures of C10NE-C10SO3 exhibited weaker interaction with BLG. Fluorescence measurements showed that both C10NE and C10SO3 could induce the enhancement of fluorescence of BLG, and C10NE enhanced the BLG fluorescence more than C10SO3 did. The effect of the mixtures of C10NE-C10SO3 on the fluorescence of BLG became stronger with the increase of the molar fraction of C10NE in C10NE-C10SO3 mixtures.     

Interaction between bovine serum albumin and equimolarly mixed cationic-anionic surfactants decyltriethylammonium bromide-sodium decyl sulfonate

The interactions of bovine serum albumin (BSA) with the anionic surfactant sodium decylsulfonate (C10SO3), the cationic surfactant decyltriethylammonium bromide (C10NE) and equimolarly mixed cationic-anionic surfactants C10NE-C10SO3 were investigated by surface tension, viscosity, dynamic light scattering (DLS) and circular dichroism (CD). It was shown that the single ionic surfactant C10SO3 or C10NE has obvious interaction with BSA. The presence of C10SO3 or C10NE modified BSA structure. However, the equimolarly mixed cationic-anionic surfactants C10NE-C10SO3 showed very weak interactions with BSA. The surface tension-log concentration (gamma-logC) plot for the aqueous solutions of C10NE-C10SO3/BSA mixtures coincided with that of C10NE-C10SO3 solutions. Viscometry showed that there is no significant change in the rheological properties for the C10NE-C10SO3/BSA mixed solutions. DLS showed that BSA monomers and mixed aggregates of C10NE-C10SO3 existed in the C10NE-C10SO3/BSA mixed solutions. From CD spectra no obvious modification of BSA structure in the presence of C10NE-C10SO3 mixtures was observed. The weak interactions between BSA and C10NE-C10SO3 might be explained in terms of the very low critical micelle concentration (cmc) of C10NE-C10SO3 mixtures that made the concentration of ionic surfactant monomers much lower than that needed for inducing the modification of BSA structure. In other words, the very strong synergism between oppositely charged cationic and anionic surfactants makes the formation of cationic-anionic surfactant mixed aggregates in the bulk solution a more favorable process than binding to proteins.     

Interaction between lysozyme and mixtures of cationic-anionic surfactants decyltriethylammonium bromide-sodium decylsulfonate

The interaction of lysozyme with the mixtures of cationic-anionic surfactants decyltriethylammonium bromide-sodium decylsulfonate (C10NE-C10SO3) was investigated by turbidity, circular dichroism (CD) and lysozyme activity assay. At pH 3.0, the mixtures of C10NE-C10SO3 formed precipitates with lysozyme at a wide range around the equal molar ratio of C10NE to C10SO3. Homogeneous solutions were formed when the mixtures of C10NE-C10SO3 were far from equimolar. CD and lysozyme activity assay showed that lysozyme was in different state in the C10SO3-rich and C10NE-rich mixtures of C10NE-C10SO3. Lysozyme structure changed in C10SO3-rich C10NE-C10SO3 mixtures, while was almost kept in native state in C10NE-rich ones.     

Effect of polymer chain in coexisting liquid phases by refractive index measurements

The behavior of polyethylene oxide (PEO, molecular weight, M(w) = 9 x 10(5), as an impurity) was studied in the critical binary mixture of nitroethane (NE) + 3-methylpentane (MP) by refractive index measurements. The measurements were performed at three different PEO concentrations (C = 0.373, 0.759, and 1.509 mg/cc) in the near critical composition of NEMP. We observed that the coexisting phase region shifts down with increasing PEO concentration and the critical temperature (T(c)) decreases linearly with C. At temperatures T close enough to T(c), the critical exponent beta [defined by the relation (n1-n2) proportional (T(c)-T)beta, with n1 and n2 being the refractive indices of the coexisting phases] was found to decrease from 0.456 to 0.372 when the PEO concentration changes from 0.373 to 1.509 mg/cc. These values are higher than that of 0.345+/-0.015 of pure NEMP, which is compatible with the three-dimensional Ising value beta = 0.325. It appears that the shape of the PEO in NEMP coexistence curves is similar from that of pure NE + MP.     

Polymer electrolytes based on room temperature ionic liquid: 2,3-dimethyl-1-octylimidazolium triflate

Room temperature ionic liquid (DMOImTf) based upon 2,3-dimethyl-1-octylimidazolium cation and trifluoromethanesulfonate or triflate (CF(3)SO(3))(-) anion has been synthesized and shows conductivity of 5.68 mS/cm and viscosity of 26.4 cP at 25 degrees C. Ion conducting polymer electrolytes based on polymers (poly(ethylene oxide) (PEO) and polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP)) and ionic liquid (DMOImTf) were prepared in film form by the casting technique. The conductivity of polymer electrolytes containing 0.5 M LiCF(3)SO(3) in PEO:DMOImTf taken in equal weight ratio increases with the addition of propylene carbonate (PC) while its mechanical stability improved by dispersing nanosize fumed silica. However, polymer electrolytes containing PVdF-HFP and ionic liquid show a high value of conductivity (10(-4)-10(-3) S/cm) alongwith better mechanical stability.     

Microstructures of Aqueous Two‐Phase Systems Formed by Mixture of Polymer and Cationic‐Anionic Surfactants

Microstructure and phase behavior of decyltriethylammonium bromide (C₁₀NE)/sodium decylsulfonate (C₁₀SO₃)/poly(ethylene oxide) (PEO)/water quaternary systems were studied by freeze‐fracture transmission electron microscopy, small angle X‐ray diffraction, and dynamic light scattering methods. Aqueous two‐phase systems (ATPS) could be prepared by properly mixing the aqueous solution of PEO and equimolar mixed C₁₀NE and C₁₀SO₃. It was shown that the top phase of the ATPS was surfactant‐enriched and mainly composed of multi‐lamellar structure, while the bottom phase of the ATPS was polymer‐enriched in which some vesicles were observed.     

Determination of LiCF(3)SO(3) and gamma-LiAlO(2) in composite PEO-based polymer electrolytes by flame atomic absorption spectrometry

A simple and rapid method for the determination of LiCF(3)SO(3) and gamma-LiAlO(2) in composite PEO (poly(ethylene)oxide)-based polymer electrolytes, both in mixtures and thin films, is described. The method is based on the dissolution of LiCF(3)SO(3) in anhydrous ethanol at room temperature and subsequently dissolution of PEO in water for the separation of gamma-LiAlO(2). Determination of the lithium content in LiCF(3)SO(3) and gamma-LiAlO(2) was performed by flame atomic absorption spectrometry (FAAS). A fast and total recovery of the components is achieved, being within 99-100%. The analysis of variance (ANOVA) is used to estimate the contribution of variance of chemical analysis and sampling procedure to the total variance. The results from ANOVA show a high level of homogeneity of the samples.     

Aggregation behavior of a series of anionic sulfonate gemini surfactants and their corresponding monomeric surfactant

A series of anionic sulfonate gemini surfactants with the general structure of [(Cn H2n+1)(C3H6SO(-)3) NCsN(C3H6SO(-)3)(CnH2n+1)].2Na+ have been synthesized. While the spacer group Cs represents p-xylyl or (CH2)3, the surfactants are abbreviated as CnCpxCn(SO3)2 (n=8,10,12) or C12C3C12(SO3)2(n=12), respectively. A corresponding monomeric surfactant C12H25N(CH3)(C3H6SO(-)3).Na+(C12NSO3) has also been prepared. The aggregation behavior of these surfactants has been studied at pH 9.2 and ionic strength of 30 mM. The gemini surfactants exhibit stronger aggregation tendencies and much less endothermic enthalpy changes of micellization (DeltaH mic) compared with the monomeric surfactant. The critical micelle concentrations (CMC) of the gemini surfactants decrease with the increase of the hydrophobic chain length from C8CpxC8(SO3)2 to C10CpxC10(SO3)2, but the CMC values of C10CpxC10(SO3)2 and C12CpxC12(SO3)2 are very close. The DeltaH mic values vary from endothermic for C8CpxC8(SO3)2 to almost zero for C12CpxC12(SO3)2. Besides, vesicles are observed above the CMC for all these surfactants. The water-mediated intermolecular hydrogen bonding between the tertiary nitrogen groups may assist C12NSO3 and C12C3C12(SO3)2 in their vesicle formation, while the pi-pi interaction between aromatic rings should be another additional driving force for the vesicle formation of CnCpxCn(SO3)2. Meanwhile, the hydrogen bonding, pi-pi interaction, and strong hydrophobic interaction provide the possibility of a multilayer formation for C12CpxC12(SO3)2 and C12C3C12(SO3)2 at the air/water interface, which is a possible reason for the extremely small minimum area occupied per surfactant molecule at the air/water interface for these two gemini surfactants.     

Li1.5Al0.5Ge1.5(PO4)3基固体复合电解质的制备及锂离子导电行为

将聚氧化乙烯(PEO)和二(三氟甲基磺酰)亚胺锂(LiTFSI)混合(固定EO/Li摩尔比为13)后, 采用溶液浇注法制备了一系列不同Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP)与PEO质量比的LAGP-PEO(LiTFSI)固体复合电解质体系. 结合电化学阻抗法、 表面形貌表征以及与惰性陶瓷填料(SiO₂, Al₂O₃) 性能的对比分析, 探讨了LAGP在固体复合电解质中的作用机理以及锂离子的导电行为. 结果表明, 在以LAGP为主相的固体复合电解质中, PEO主要处于无定形态, 整个体系主要为PEO与LiTFSI的络合相、 LAGP与PEO(LiTFSI)相互作用形成的过渡相和LAGP晶相. 其中LAGP作为主要的导电基体不仅起到降低PEO结晶度、 改善两相导电界面的作用; 同时自身也可以作为离子传输的通道, 降低锂离子迁移的活化能, 从而使离子电导率得到提高. 当LAGP与PEO的质量比为6:4时, 固体复合电解质的成膜性能最好, 离子电导率最高, 在30 ℃时为2.57×10^-5 S/cm, 接近LAGP的水平, 电化学稳定窗口超过5 V.