正负离子表面活性剂在短链脂肪醇/水中沉淀-囊泡转化和双水相的形成

首次报道在短链脂肪醇/水溶剂中十二烷基硫酸钠和辛基三甲基溴化铵混合体系由沉淀转化为囊泡，并出现表面活性剂双水相的新现象，以期探索正负离子表面活性剂混合体系研究的新途径。     

DTAB-月桂酸钠体系表面活性剂双水相研究

绘制和分析了十二烷基三甲基溴化铵（DTAB） 月桂酸钠（SL）组成的表面活性剂混合体系相图,系统研究了温度和无机盐等因素对该体系表面活性剂双水相 (ASTP) 影响的规律性.结果表明:与富含负离子表面活性剂双水相 (ASTP A) 相比较,富含正离子表面活性剂双水相(ASTP C)区域更大、更稳定;温度升高,无机盐(NaBr)的浓度增大,都引起 ASTP 体系上相体积的减小和下相体积的增加;囊泡普遍存在于ASTP的上下相之中.     

离子液体在多水相液液平衡体系中的作用

通过用短链离子液体(1-乙基-3-甲基咪唑溴盐[C2mim]Br、1-丁基-3-甲基咪唑溴盐[C4mim]Br)部分或全部取代SDS/DTAB/PEG/NaBr/H2O多水相体系中的无机盐NaBr,用长链离子液体十二烷基-3-甲基咪唑溴盐[C12mim]Br部分取代体系中阳离子表面活性剂DTAB,系统研究了离子液体在分相体系中的作用及其对分相体系性质的影响.研究表明,SDS/DTAB/PEG/NaBr/H2O混合体系形成的四水相体系可以看作"聚合物双水相"与"表面活性剂双水相"共存的结果.短链离子液体([C2mim]Br、[C4mim]Br)较强的亲水性能赋予其较强的盐析能力,在混合体系中表现出明显的盐效应,保证了四水相体系中"聚合物双水相"的存在.短链离子液体与聚合物之间的相互作用及其对表面活性剂之间相互作用的影响均不可忽略.对混合体系的相行为,共存多相的性质有重要的影响.而长链离子液体[C12mim]Br主要通过自身的疏水作用影响"表面活性剂双水相"的性质,充当表面活性剂的角色.然而,[C12mim]Br与DTAB分子结构上的差异,导致表面活性剂分子在"表面活性剂双水相"的两相重新分配,影响了对应两相的体积及萃取能力.可见,通过调节离子液体的烷基链长、混合体系中的含量等可获得具有特定性质的多水相体系.     

正负离子表面活性剂/离子液体双水相性质研究

本文把短链离子液体(IL)四氟硼酸1-乙基-3-甲基咪唑鎓[C2mim]BF4引入正负离子表面活性剂十二烷基硫酸钠(SDS)和十二烷基三甲基溴化铵(DTAB)双水相体系(SDS/DTAB/H2O)中,研究了IL对双水相相图及相分离体系性质的影响。结果表明,[C2mim]BF4的阳离子性质是影响阴离子表面活性剂过量区域性质的主要因素,IL通过静电作用、氢键作用等改变体系中聚集体的形貌,最终导致阴离子双水相(ATPSa)的消失。IL的阴离子对阳离子双水相(ATPSc)区域性质起着决定作用;IL的盐效应引起的对表面活性剂混合胶束扩散双电层的压缩作用,不但促进胶团的形成,缩短了形成稳定胶团所需要的时间,加快了双水相的相分离速度,而且也造成了形成ATPSc所需DTAB含量的提高。IL的引入改变了ATPSc上、下相表面活性剂的组成及含量,使富含表面活性剂的上相中阳离子表面活性剂含量更高,进而提高了双水相的萃取性能,其上相对甲基橙的萃取效率可高达96.67%。     

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.     

寡聚核苷酸/单链阳离子表面活性剂囊泡与沉淀共存(英文)

DNA(包括寡聚核苷酸)和阳离子表面活性剂可形成难溶复合物.本文通过浊度测试和透射电子显微镜观察,发现单链阳离子表面活性剂可以诱使寡聚核苷酸/单链阳离子表面活性剂沉淀转变成为寡聚核苷酸/单链阳离子表面活性剂囊泡,且寡聚核苷酸/单链阳离子表面活性剂囊泡可以与寡聚核苷酸/单链阳离子表面活性剂沉淀共存.在寡聚核苷酸/单链阳离子表面活性剂沉淀向囊泡的转变过程中,表面活性剂和沉淀之间的疏水作用力发挥了重要作用.此外,当体系温度达到寡聚核苷酸开始融解的温度后,寡聚核苷酸/单链阳离子表面活性剂体系更容易形成囊泡.因此,寡聚核苷酸的链越伸展,越易于寡聚核苷酸/单链阳离子表面活性剂囊泡的生成.据我们所知,有关寡聚核苷酸/阳离子表面活性剂囊泡的报道尚不多见.因此,考虑到DNA(包括寡聚核苷酸)/两亲分子体系在医学、生物学、药学和化学中的重要性,该研究应该有助于我们进一步了解该体系并对其进行更合理有效的应用.     

N-烷基-N-(2-羟乙基)-N,N-二甲基溴化铵与十二烷基硫酸钠复配系统的双水相

合成了N-十二烷基-N-(2-羟乙基)-N,N-二甲基溴化铵、N-十四烷基-N-(2-羟乙基)-N,N-二甲基溴化铵和N-十六烷基-N-(2-羟乙基)-N,N-二甲基溴化铵等3个季铵盐阳离子表面活性剂. 研究了它们以及N-十六烷基-N,N,N-三甲基溴化铵(CTAB)与阴离子表面活性剂十二烷基硫酸钠(SDS)复配系统在313.15 K时的双水相行为. 复配系统在两个非常狭窄的区域能形成双水相, 两相区近似以等摩尔线为中心对称分布, 随着阳离子表面活性剂碳链长度的增长, 富含阳离子表面活性剂的双水相区向阴阳离子表面活性剂摩尔比减小的方向稍有移动.     

类水滑石诱导囊泡的自发形成

报道了一种新的囊泡合成方法——荷电固体纳米颗粒诱导囊泡的自发形成. 研究发现, 将5.0 g/L带结构正电荷的Mg₃Al类水滑石(HTlc)溶胶和0.02 mol/L由两性表面活性剂十二烷基甜菜碱(C₁₂BE)和阴离子表面活性剂双(2-乙基己基)琥珀酸磺酸钠(AOT)组成的溶液(C₁₂BE与AOT物质的量比为3∶2)混合, 当HTlc溶胶与表面活性剂溶液的体积比在1∶9～4∶6范围内, 在HTlc纳米颗粒的诱导下可自发形成囊泡, 并获得稳定的HTlc-囊泡复合分散体系.     

pH及有机小分子物质对SDS/CTAB/H2O系统双水相性质的影响

正离子表面活性剂与负离子表面活性剂混合物能产生比单一表面活性剂更高的表面活性[1 ] 。在适当条件下 ,正负离子表面活性剂的水溶液能产生两个互不相溶的水相 ,即表面活性剂双水相系统[2 ] (ＡｑｕｅｏｕｓＴｗｏ -ＰｈａｓｅＳｙｓｔｅｍ -ＡＴＰＳ)。作者曾指出双水相上相为液晶 (ＬｉｑｕｉｄＣｒｙｓｔａｌ -ＬＣ)结构 ,下相为各向同性溶液 ,盐离子通过改变双水相中表面活性剂有序组合体的反离子层的状态而对双水相的组成、结构等产生重要的影响[3,4] 。本文进一步研究ｐＨ及有机小分子物质在十二烷基硫酸钠 /十六烷基三甲基溴化铵 /…     

外加盐作用形成的正负离子表面活性剂双水相

癸基三乙基溴化铵-癸基磺酸钠（C10NE-C10SO3）等摩尔混合均相体系（即使在表面活性剂总浓度高达0.2 mol•L－1时仍然可形成稳定的均相溶液）在外加盐NaF、Na2SO4和Na3PO4的作用下可自发分离成两个水相（双水相）.研究了该类双水相体系的形成、相行为及其对牛血清蛋白（BSA）的分配，并与普通的正负离子表面活性剂混合双水相体系进行了比较.结果表明，该类双水相体系克服了普通的正负离子表面活性剂混合双水相体系的一些不足，具有一些独特的优点.该类双水相体系的相行为可以通过外加盐进行调控,通过外加盐的种类来调控和优化BSA的分配行为.图1表2参8     

正负离子表面活性剂混合体系中高稳定性囊泡的形成

对总浓度为0.01 mol/L，摩尔比为2：1的十二烷基硫酸钠/溴化十二烷基三乙 铵的正负离子表面活性剂混合体系形成的囊泡的稳定性进行了研究。发现这一体系 形成的囊泡在长放置（5个月）后依然存在。在加入较大量的无机盐（0.15 mol/L NaBr）、较大幅度pH变化（pH = 2～12）、温度变化（从80 ℃到-22 ℃）情况下 体系中的囊泡依然呈现出优异的稳定性。在非水溶剂乙醇（100%）中这类正负离子 表面活性剂仍然可以形成囊泡。     

表面活性剂对3-甲基吡啶电氧化制取烟酸的影响

研究了在阳极液中加入不同类型和不同浓度表面活性剂对3-甲基吡啶电氧化的影响. 结果表明, 十六烷基三甲基溴化铵、脂肪醇聚氧乙烯醚硫酸钠、十二烷基苯磺酸钠、十二烷基二甲基甜菜碱和山梨醇酐单硬脂酸酯的胶团对3-甲基吡啶电氧化有明显的促进作用. 实验结果还表明, 在低浓度的硫酸为支持电解质阳极液中加入表面活性剂与不加表面活性剂相比, 3-甲基吡啶电氧化制取烟酸的选择性和电流效率明显提高.     

Effects of additives on the cloud points of selected nonionic linear ethoxylated alcohol surfactants

Effects of various additives including inorganic salts, nonionic and ionic surfactants, water-soluble polymers and alcohols on the cloud points of three linear nonionic surfactants, Tergitol 15-S-7, Tergitol 15-S-9 and Neodol 25-7, were investigated. These surfactants are readily biodegradable and either linear primary or secondary ethoxylated alcohols. Cloud points of these surfactants were functions of their concentrations and concentrations of additives. The cloud points of nonionic surfactant mixtures lay in between the cloud points of individual component surfactants. Presence of two ionic surfactants, sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB), increased the cloud point of 1 wt% Tergitol 15-S-7 micellar solution dramatically when concentrations of ionic surfactants approaching their critical micelle concentration. Addition of water-soluble polymers decreased the cloud point, while addition of inorganic salts can either increase or decrease the cloud points. However, the effect of an alcohol additive on cloud point was dependent on its chain length or its water solubility. Interestingly, synergistic effects between sulfate or phosphate and pentanol on depression of cloud points of Tergitol 15-S-9 were discovered. A linear model predicting cloud points of Tergitol 15-S-X (X = 7, 9 and 12) surfactants and Neodol 25-X (X = 7, 9 and 12) surfactants were proposed with a correlation to logarithm of their ethylene oxide numbers.     

Effect of 1-hexanol on the phase behavior of SDS/CTAB/NaBr/H2O system

Abstract

The influence of 1-hexanol on the phase behavior of sodium dodecyl sulfate (SDS)/cetyltrimethyl ammonium bromide (CTAB)/NaBr/H₂O system has been systematically investigated in this paper. The results showed 1-hexanol effectively dissolved the precipitate formed by the CTAB and SDS surfactants, while liquid crystal (LC) and aqueous two phase system (ATPS) were formed in a wider range. When the molar ratio of 1-hexanol to surfactant is higher than 1, the precipitation in the system disappeared completely and was transformed into ATPS and LC, indicating that alcohol inserted at least evenly between every two surfactant molecules and hence effectively weakened the electrostatic interaction between the anionic and cationic surfactants and limited the formation of precipitation. Polarizing microscope (POM) with crossed polarizers was employed to investigate the textures of liquid crystals. It was shown that the existence of lamellar LC was confirmed by “Maltese crosses” textures. Additionally, we showed that the thermal stability of LC was promising. The ATPS and LC regions remained stable and changed slightly when the temperature was increased from 40 to 70?°C. The results indicated that ATPS and LC of the system were quiet resistant to temperature with the addition of 1-hexanol.     

Binding of hexadecylammonium surfactants to water-soluble neutral polymers

The binding of hexadecyltrimethylammonium bromide and hexadecyldimethyl-2-hydroxyethylammonium bromide to neutral polymers was measured by a potentiometric titration method using surfactant selective electrodes. Binding to poly(vinyl alcohol) was slightly cooperative, while that to poly(ethylene oxide) lacked the co-operativity. Poly(vinyl pyrrolidone) did not bind them at all. Binding affinity as estimated by a distribution coefficient of the cationic surfactants between the bulk and polymer phases is about 2 orders of magnitude smaller than that of anionic sodium dodecyl sulfate. The heat of binding was estimated from the temperature dependence of the distribution coefficient and found to be endothermic. It is imagined that the cationic surfactants are simply partitioned between the aqueous bulk phase and the polymer coil phase which is regarded as aqueous organic mixed solvent.     

Effect of Surfactants and Ionic Strength on Dissociation of Hydrochlorides of Phenothiazine Derivatives

Abstract

A study of the effect of the anionic surfactant dodecyl sulfate, the cationic surfactant carbethoxypentadecyl trimethyl ammonium bromide (Septonex), nonionic surfactant p-octyl phenyl polyoxyethylene (Triton X-100), and a strong electrolyte (KBr) on the dissociation of the hydrochlorides of two derivatives of phenothiazine (diethazine and fluphenazine) was made. It was found that sodium dodecyl sulfate increases the pKa value, whereas Septonex and Triton X-100 decrease this value. The presence of KBr suppresses the effect of the surfactants. A new method for the potentiometric determination of fluphenazine in an aqueous medium was proposed.     

Control of phase behavior and properties of vesicle gels by admixing ionic surfactants to the nonionic surfactant Brij 30

The effect of the addition of two cationic surfactants of different chain length (decyl and dodecyl trimethylammonium bromide, DeTMABr and DTMABr, respectively) and one anionic surfactant of identical chain length (sodium dodecyl sulfate, SDS) on phase behavior, structure, and macroscopic properties of a bilayer forming nonionic surfactant (Brij 30) has been investigated by means of phase studies, rheology, turbidity measurements, dynamic light scattering, and freeze-fracture transmission electron microscopy. We concentrated on DTMABr because of the generically similar behavior for the other ionic surfactants. It is found that already very small amounts of added ionic surfactant have a very pronounced effect on the phase behavior of these systems. The pure nonionic surfactant forms bilayers and has a tendency for the formation of vesicles which becomes enhanced by charging the bilayer through the incorporation of the ionic surfactant. The presence of the ionic surfactant leads to much more viscous systems, which already at a total surfactant concentration of 150 mM become gel-like. For a given surfactant concentration, the elastic properties of the gels increase largely upon the addition of ionic surfactant. This effect is strongly synergistic, requiring only very small amounts of added ionic surfactant, and the elastic properties pass through a maximum for a content of ionic surfactant of about 3-5 mol %. This behavior can be explained in a self-consistent way by a simple rheological model and by combining it with light scattering data. For the addition of larger amounts, the elastic properties decrease again and the formed vesicles become structurally less defined as one is leaving the range of conditions for forming well-defined vesicles, which are required for forming elastic vesicle gels.     

Adsorption, association and precipitation in hexadecyltrimethylammonium bromide/sodium dodecyl sulfate mixtures

The phase equilibria of surfactant aqueous mixtures, hexadecyltrimethylammonium bromide and sodium dodecyl sulfate, have been studied by polarizing microscopy, quasielastic light scattering, conductivity, potentiometric, electrophoretic, and surface tension measurements. Adsorption at the air/solution interface, association and precipitation in bulk solution strongly depended on the molar ratio and the concentration of surfactants. Catanionic vesicles coexisted with crystalline catanionic salts in a broad concentration range. The relative proportions of crystallites and vesicles varied according to the concentration and the molar ratio of the surfactants. The solid crystalline phase was progressively converted to catanionic vesicles with increasing surfactant molar ratio. At the highest excess of one of the surfactants transition from catanionic vesicles to mixed micelles occurred. The formation and stability of different phases are discussed in terms of surfactant molecular packing constraints and electrostatic interactions in the headgroup region. Surfactant tail-length asymmetry and the change of electrostatic interactions in the headgroup region from attractive to repulsive are governing factors for the transition from planar to curved bilayers. Received: 9 June 1998 Accepted: 18 August 1998     

Effects of addition of short-chain alcohol solvents on micellization and thermodynamic properties of anionic surfactants sodium dodecyl sulfate and sodium dodecyl sulfonate in aqueous solutions

Micellar and thermodynamic properties of anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodecyl sulfonate (SDSn) in aqueous solutions of 5 wt% short-chain alcohols methanol, ethanol, and 1-butanol were investigated by experimental electrical conductivities, densities and sound velocities at 298.15 K. It was found that methanol behaves like a cosolvent and increases the critical micelle concentration (CMC) of both surfactants in aqueous solutions. However, the other investigated alkanols act as a cosurfactant and decrease the CMC by their presence. The values of the degree of counterion association on the micelles of both surfactants in aqueous methanol solution are same as those in pure water, and they decrease with increasing the alkyl chain length of alcohol. Furthermore, the values of the apparent molar volume and isentropic compressibility of the monomeric and micellar forms of the investigated surfactants were obtained from the experimental density and sound velocity data. It was found that the values of the apparent molar properties of both micellar and monomeric forms of the studied surfactants increase by increasing the alkyl chain of the alcohols.