Characterization of Microemulsion Systems Formed by a Mixed 1,3-Dioxolane Ethoxylate/Octyl Glucoside Surfactant System

The phase behavior of microemulsion systems containing water (or 1.0 wt% NaCl_aq), isooctane, and the binary surfactant system consisting of n-octyl-β-d-glucopyranoside, C₈βG₁, and the acid-cleavable alkyl ethoxylate, 4-CH₃O (CH₂CH₂O)_7.2, 2-(CH₂)₁₂CH₃, 2-(CH₂)CH₃, 1,3-dioxolane, or “cyclic ketal” (“CK-2,13”), was determined. Large temperature-insensitive one, two, and three-phase microemulsion-phase regions were obtained when equal masses of the two surfactants were employed, suggesting that C₈βG₁ reduces the temperature sensitivity of CK-2,13’s ethoxylate group. Addition of C₈βG₁ to CK-2,13 greatly improves the latter’s low efficiency, evidenced by the formation of a three-phase microemulsion system for surfactant concentrations at low fractions of total surfactants for systems with equal mass ratios of water to oil and CK-2,13 to C₈βG₁. Analysis of the phase diagrams also suggests that CK-2,13 and C₈βG₁ impart hydrophobic and hydrophilic character, respectively, to the surfactant mixture, and that addition of salt further increases the hydrophilicity of C₈βG₁, presumably because of the salting-in of the latter. Analysis of small-angle neutron scattering data revealed that the mixed surfactant system formed spherical oil-in-water microemulsions, and that increasing the CK-2,13 fraction among the surfactants reduced the critical microemulsion concentration but slightly increased the nanodroplet size.

Studies on aggregation of AOT and NaDEHP via the energy transfer between AO and RB molecules

The aggregation behaviours of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium bis(2-ethylhexyl)phosphate (NaDEHP) solutions are studied via the energy transfer of acridine orange (AO) and rhodamine B(RB) molecules. The approximate apparent energy transfer efficiency (ϕ_a) of the dye molecules reaches its maximum value when the concentrations of AOT and NaDEHP are far lower than their cmc. This might be caused by the formation of surfactant–dye mixtures. The anionic surfactants (SDS, AS, AOT and NaDHEP), cationic surfactant (CTAB) and nonionic surfactant (Triton-X-100) are chosen to investigate the effect of the structure of surfactant on the ϕ_a between AO and RB molecules. The results indicate that the effective energy transfer may occur in the anionic surfactant systems and it is not obvious in the nonionic and cationic surfactant systems.     

1-丁基-3-甲基咪唑表面活性离子液体的界面膨胀流变行为研究

研究了1-丁基-3-甲基咪唑十二烷基硫酸盐([bmim][DS])和1-丁基-3-甲基咪唑二(2-乙基己基)磺基琥珀酸酯盐([bmin][AOT]两种表面活性离子液体在正庚烷/水界面的动态界面张力和膨胀特性。比较了[bmim][DS]或[bmin][AOT]和传统表面活性剂十二烷基硫酸钠(SDS)或二(2-乙基己基)磺基琥珀酸酯钠(Na[AOT])之间的膨胀弹性,并且考察了1-丁基-3-甲基咪唑阳离子之间静电相互作用对界面膜特性的影响。另外,通过对比[bmim][DS]和[bmim][AOT]在不同浓度下的膨胀弹性,验证了烷基链数量的改变对界面膨胀流变行为的影响。     

Effect of Self-Assemblies on the Dynamics of the Briggs–Rauscher Reaction

The study involves the dynamic evolution of the Briggs–Rauscher (BR) reaction in the presence of various surfactants—SDS (sodium dodecyl sulphate) as anionic, CTAB (cetyl trimethylammonium bromide) as cationic and TritonX‐100 [4‐(1,1,3,3‐(tetramethylbutyl) phenyl polyethylene glycol] as a neutral one in single as well as mixed mode conditions (SDS + TX‐100 and CTAB + TX‐100). The reaction has been monitored potentiometrically at 30 °C under CSTR conditions. These surfactants affect the reaction dynamics to an extent which depends on the nature and concentration of the surfactant and the formation of their self‐assemblies. The experimental findings indicate that the oscillatory behavior of the BR reaction in the presence of surfactants is due to the efficacy of organized surfactant assemblies to selectively distribute the key species involved in the reaction, and their interaction with the counter ions in cases of ionic micelles. The study reveals that the evolution of oscillatory behavior is a characteristic feature of the surfactant.     

In vitro solubilization of antibiotic drug sulfamethazine: An investigation on drug–micelle aggregate formation by spectroscopic and scattering techniques

Micellar solubilization has been used extensively for the dissolution of sparingly soluble drugs for effective drug delivery. Apart from improving the solubility and bioavailability, micelles can help reduce toxicity and improve permeability in the system. In this article, solubilization of a well-known antibiotic, sulfamethazine (SMZ) upon micellization, is studied by employing various spectroscopic and scattering techniques like, ultraviolet–visible, fluorescence, small angle neutron scattering (SANS), and zeta potential (ZP) studies. The size(s) and charge(s) of the micelles were monitored by SANS and ZP. A positively charged/cationic surfactant, cetyl trimethyl ammonium bromide (CTAB) and a negatively charged/anionic surfactant, sodium dodecyl sulfate (SDS) are used for micelle formation. Regardless of the surfactant type, the solubility of SMZ increases linearly with the increase in the surfactant concentration, as a result of association between the drug and micelles. However, the solubility of SMZ is found to be better with CTAB than SDS. Upon interaction with SMZ, we observed that the critical micelle concentration of CTAB occurred at a lower concentration than that of SDS surfactant. As fitted in the ellipsoidal core–shell model, SANS results also show the formation of charged micelles. This comparative study can help us to select an appropriate medium for SMZ solubilization to improve selective drug delivery in biomedical applications.     

阴离子表面活性剂对聚乙二醇水溶液粘度的影响

测定了聚乙二醇（PEG）在十二烷基硫酸钠（SDS）和琥珀酸双-2-乙己酯磺酸钠（AOT）水溶液中的粘度,讨论了SDS和AOT在水溶液中聚集形态的差异对PEG与SDS和AOT相互作用的不同影响,结果表明：PEG-SDS与PEG-AOT体系粘度均明显增加,而PEG-SDS与PEG-AOT体系粘度变化机制不同,根本原因是表面活性剂在高分子溶液中聚集行为不同,SDS分子在PEG链上聚集,形成类胶束,使高分子链带电,表现出聚电解质的粘度行为;PEG链吸附于AOT囊泡,不同PEG链对囊泡的吸附可能造成高分子链更加伸展,PEG特性粘数增大,使溶液粘度上升。     

Magnetic and Phase Behavior of Magnetic Water-in-Oil Microemulsions

Magnetic water-in-oil microemulsions with anisotropic morphology have been generated by mixing single-chain magnetic surfactants (dodecyltrimethylammonium trichloromonobromoferrate, DTAF) with non-magnetic di-chain analogues (didodecyldimethylammonium bromide, DDAB). Full phase diagrams have been mapped as a function of surfactant composition, water content, and temperature. It was shown that for all surfactant concentrations [Surfactant_total], on replacing 30 wt% DDAB with DTAF optimum (i.e. wt% of the total surfactant) w ratios (w = [water]/[surfactant]) could be achieved; up to w = 120 for [Surfactant_total] = 0.050 M. Small-angle neutron scattering (SANS) indicated that microemulsion droplets have a rod-like morphology with a radius commensurate with the surfactant tail length and an aspect ratio between 6 and 35. In the presence of a large magnetic field (6.7 T) no reorientation of the droplets was observed by SANS.     

Enzymatic activity of Chromobacterium viscosum lipase in an AOT/Tween 85 mixed reverse micellar system

To enhance the Chromobacterium viscosum lipase (glycerol‐ester hydrolase; EC 3.1.1.3) activity for the reaction of water‐insoluble substrates, the AOT/isooctane reverse micellar interface was modified by co‐adsorption of a non‐ionic surfactant. Polyoxyethylene sorbitan trioleate (Tween 85) was used as the non‐ionic surfactant and olive oil as a water‐insoluble substrate. An appreciable increase of lipase activity was observed and at higher W_o values (where W_o = molar ratio of water to total surfactants of the micellar system) there was no sharp fall of the enzyme activity such as a typical bell‐shaped profile. The kinetic model for the lipase‐catalysed hydrolysis of olive oil in AOT/isooctane reverse micellar system was applied to the enzymatic reaction in this mixed reverse micellar system. It was found that the predictions of the model agree well with the experimental kinetic results and that the adsorption equilibrium constant of olive oil molecules between the micellar phase and the bulk phase of the organic solvent is smaller in AOT/Tween 85 mixed reverse micellar systems than in simple AOT reverse micellar systems. © 1999 Society of Chemical Industry     

脂肪酸双酯双磺酸盐型双子表面活性剂的合成及性能

以脂肪酸、二甘醇、氯磺酸为原料,经酯化、磺化反应制备了4种二甘醇双(α-磺酸钠)烷基羧酸酯表面活性剂。用红外光谱、元素分析对产物进行了表征,并对其表面活性和聚集行为进行了研究。结果表明,该类脂肪酸双酯双磺酸盐型双子表面活性剂比十二烷基硫酸钠的临界胶束浓度低1～2个数量级和更强的降低表面张力的能力。稳态荧光猝灭实验表明,表面活性剂胶束聚集数随着烷烃链碳原子数的增加而逐渐减小。     

Synergistic Effects between Anionic and Sulfobetaine Surfactants for Stabilization of Foams Tolerant to Crude Oil in Foam Flooding

In foam flooding, foams stabilized by conventional surfactants are usually unstable in contacting with crude oil, which behaves as a strong defoaming agent. In this article, synergistic effects between different surfactants were utilized to improve foam stability against crude oil. Targeted to reservoir conditions of Daqing crude oil field, China (45 °C, salinity of 6778 mg L⁻¹, pH = 8–9), foams stabilized by typical anionic surfactants fatty alcohol polyoxyethylene ether sulfate (AES) and sodium dodecyl sulfate (SDS) show low composite foam index (200–500 L s) and low oil tolerance index (0.1–0.2). However, the foam stability can be significantly improved by mixing the anionic surfactant with a sulfobetaine surfactant, which behaves as a foam stabilizer increasing the half-life of foams, and those with longer alkyl chain behave better. As an example, by mixing AES and SDS with hexadecyl dimethyl hydroxypropyl sulfobetaine (C₁₆HSB) at a molar fraction of 0.2 (referring to total surfactant, not including water), the maximum composite foaming index and oil tolerance index can be increased to 3000/5000 L s and 1.0/4.0, respectively, at a total concentration between 3 and 5 mM. The attractive interaction between the different surfactants in a mixed monolayer as reflected by the negative β^s parameter is responsible for the enhancement of the foam stabilization, which resulted in lower interfacial tensions and therefore negative enter (E), spreading (S), and bridging (B) coefficients of the oil. The oil is then emulsified as tiny droplets dispersed in lamellae, giving very stable pseudoemulsion films inhibiting rupture of the bubble films. This made it possible to utilize typical conventional anionic surfactants as foaming agents in foam flooding.     

反胶团酶催化研究新进展

评述了近年来反胶团酶催化研究的新进展。在AOT/异辛烷反胶团中加入非离子型表面活性剂如Tween 85、小相对分子质量聚乙二醇等可有效降低酶与表面活性剂间的静电和疏水作用 ,显著提高酶的活性。对AOT进行化学修饰及合成结构与磷脂类似的新表面活性剂以用其构建新的反胶团体系 ,酶的活性较常用的AOT/异辛烷反胶团体系有显著提高。在反胶团酶反应动力学研究中考虑水含量或底物在反胶团表面吸附的影响等 ,提出了进一步研究的设想 ,包括开发新型表面活性剂以进一步提高酶的活性和稳定性及有利于产物分离     

Mixtures of anionic and cationic surfactants with single and twin head groups: Adsorption and precipitation studies

This research reports on the adsorption and precipitation of mixtures of anionic and cationic surfactants having single and twin head groups. The surfactant mixtures investigated were: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), in a mixture with the twin-head cationic surfactant pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD)—adsorption was studied on negatively charged silica; and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), and the single-head cationic surfactant dodecylpyridinium chloride (DPCI)—adsorption was studied on positively charged alumina. Whereas the mixed surfactant system of SHDPDS/DPCI showed adsorption on alumina that was comparable to the of SHDPDS alone, the mixed surfactant system of SDS/PODD showed increased adsorption on silica as compared with PODD alone. The adsorption of the SDS/PODD mixture increased as the anionic and cationic system approached an equimolar ratio. Precipitation diagrams for mixtures of single- and twin-head surfactant systems showed smaller precipitation areas than for single-head-only surfactant mixtures. Thus, the combination of single- and double-head surfactants helps reduce the precipitation region and can increase the adsorption levels, although the magnitude of the effect is a function of the specific surfactants used.     

Influence of breakup and reformation of micelles on surfactant diffusion in pure and mixed micellar systems

Pulsed field gradient (PFG) NMR technique was used to study diffusion of surfactant ions in the following two micellar systems: (i) aqueous solution of an anionic surfactant sodium dodecyl sulfate (SDS), and (ii) aqueous solution of a mixture of SDS and a small amount of the cationic surfactant N-dodecyltrimethylammonium bromide (C₁₂TAB). PFG NMR measurements provided separate sets of data on diffusion of SDS and C₁₂TAB surfactant ions for a broad range of diffusion times. For each type of surfactants at least two components with different effective diffusivities were observed at sufficiently small diffusion times. The faster component was assigned to the surfactants that experience breakup or reformation of micelles during the diffusion time of the PFG NMR measurement, while the slower component was assigned to the surfactants that did not participate in such events during the diffusion time. The observed changes of the fractions and diffusivities of these components with increasing diffusion time were found to be in a qualitative agreement with such assignment. Fundamental understanding of surfactant diffusion in micellar system is important due to an increasing use of such systems for synthesis of porous materials where micelles are used as templates as well as for many other applications.     

A Comparative Study on the Aggregation and Thermodynamic Properties of Anionic Sodium Dodecylsulphate and Cationic Cetyltrimethylammonium Bromide in Aqueous Medium: Effect of the Co-solvent N-Methylacetamide

The effect of co‐solvent N‐methylacetamide (NMA) (0.035, 0.046, 0.127, and 0.258 mol kg^?1) on the micellization behaviour of anionic surfactant sodium dodecylsulphate (SDS) (3.21–10.35 mmol kg^?1) and cationic surfactant cetyltrimethylammonium bromide (CTAB) (0.19–3.72 mmol kg^?1) in aqueous solution was explored by employing conductivity measurements at different temperatures (298.15–313.15 K). The critical micelle concentration (CMC) values for SDS and CTAB in aqueous solutions of NMA were determined from the conductivity versus surfactant concentration plots. The variations in the CMC values of SDS with NMA concentration are in striking contrast to those observed in the case of CTAB. The various relevant thermodynamic parameters of micellization, viz. standard enthalpy change, ΔH_m^o, standard entropy change, ΔS_m^o, and standard Gibbs free energy change, ΔG_m^o, were determined using the temperature variation of the CMC values and counterion binding. The results not only relate these thermodynamic parameters to the consequences of intermolecular interactions but are also able to differentiate between SDS–water–NMA and CTAB–water–NMA systems in terms of contributions from head groups as well as alkyl chains of surfactants.     

Wettability of Polymeric Solids by Aqueous Solutions of Anionic and Nonionic Surfactant Mixtures

Measurements of the surface tension (γ _LV) and advancing contact angle () on poly(tetrafluoroethylene) (PTFE) and poly(methyl methacrylate) (PMMA) were carried out for aqueous solutions of sodium decyl sulfate (SDS) and p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol) (TX100) and their mixtures. The results obtained indicate that the values of the surface tension and contact angles of solutions of surfactants on PTFE and PMMA surfaces depend on the concentration and composition of the surfactant mixtures. Calculations based on the Lucassen-Reynders equation indicate that for single surfactants and their mixtures at a given concentration in the bulk phase the values of surface excess concentration of surfactants at water–air and PTFE–water interfaces are nearly the same, so the adsorption of the surfactants at water–air and PTFE–water interfaces should also be the same. However, the adsorption of TX100 and its mixtures with SDS at water–air interface is higher than that at PMMA–water interface, which is confirmed by the ratio of absolute values of molecular interaction parameters at these interfaces calculated on the basis of Rosen approach. If we take into account the hydration of the poly(ethylene oxide) chains of TX100 and acid and base parameters of the surface tension of water it appears that the PMMA surface is covered by the 'pure' water molecules from the solution or molecules connected with the chain of nonionic surfactant. On the other hand, the lack of SDS molecules at the PMMA–water interface may result from the formations of its micelles which are connected with the TX100 chain.     

Microemulsion Formation and Detergency with Oily Soil: IV. Effect of Rinse Cycle Design

The objective of this work was to apply a microemulsion-based formulation for the removal of motor oil in laundry detergency at low salinity. To produce the desired phase behavior, three surfactants were used: alkyl diphenyl oxide disulfonate (ADPODS), sodium dioctyl sulfosuccinate (AOT) and sorbitan monooleate (Span 80). The mixed surfactant system of 1.5% ADPODS, 5% AOT and 5% Span 80 (13 parts ADPODS, 43.5 parts AOT, and 43.5 parts Span 80 of the total actives) was found to form a middle phase microemulsion (Type III) at a relatively low salinity of 2.83% NaCl. When this formulation was diluted, detergency performance increased with increasing total surfactant concentration and leveled off above about 0.1% total actives on the three types of fabrics studied (pure cotton, 65/35 polyester/cotton blend, and pure polyester). Detergency was found to improve with increasing hydrophilicity of the fabric with cotton being cleanest after washing and polyester the most difficult to clean. To achieve a specified oil removal, less rinse water can be used if a higher number of lower-volume rinses are employed. An interesting characteristic of microemulsion-based formulations is that a substantial fraction of oil removal occurs during the rinse cycle. In this work, this removal is shown to be due to the low oil/water interfacial tension during initial rinsing and is therefore strongly correlated to residual surfactant concentration in the rinse steps. As a result, the number of rinses and the volume of water per rinse can profoundly affect detergency in these systems.

表面活性剂对孪尾缔合聚合物水溶液表观黏度的影响

用黏度法研究了孪尾疏水缔合水溶性聚合物聚（丙烯酰胺／丙烯酸钠／N,N-二己基丙烯酰胺）[P（AM／NaAA／DiC6AM）]与十二烷基硫酸钠（SDS）、十六烷基三甲基溴化铵（CRAB）、OP-10的相互作用。结果表明,水溶液的表观黏度随SDS、CTAB质量浓度的增加急剧上升,超过一定浓度后水溶液黏度又急剧下降;黏度上升的幅度随疏水单体用量的增加、表面活性剂与疏水单体的摩尔比率（SMR值）的减小而增大;随水解度的增加,黏度上升的幅度较小。P（AM／NaAA／DiC6AM）的临界缔合浓度cac约为30g/mL,当加入SDS、CTAB时,能显著地降低。随OP-10质量浓度的增加,水溶液表观黏度几乎不变。表明P（AM／NaAA／DRAM）与SDS、CTAB的疏水缔合作用较强,而与OP-10的疏水缔合作用较弱。     

表面活性剂对化学镀镍-磷体系热力学的影响

为确定表面活性剂对化学镀镍体系的影响程度,采用紫外-可见分光光度计研究了固定工艺条件下苯磺酸钠(SBS)、十二烷基磺酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、十二烷基羟基磺丙基甜菜碱(DHSB)、琥珀酸二(2-乙基己基)酯磺酸钠(AOT)等5种表面活性剂在铜基体上相对沉积量θ和吸附自由能ΔG的变化。结果表明,加入表面活性剂的ΔGS与未加表面活性剂的基础镀液的ΔGI差的绝对值小于3.5 kJ/mol;在含有表面活性剂的镀液体系中,固/液相界面所吸附的镍离子量存在一个限度;镀层沉积速率的高低与体系ΔG,ΔS,ΔH的值并不呈正相关性,影响该速率的能量基于化学能与镀层的结构及组成成分的差异所消耗的能量等方面。     

柴油微乳液的相图及稳定性研究

选用双(2-乙基己基)琥珀酸酯磺酸钠(AOT)和辛酸(OA)作为表面活性剂制备柴油微乳液。体系中加入的混合表面活性剂总浓度为0.22mol/L。通过绘制R0-T相变图、研究微乳液体系在不同温度、不同乳化剂配比及不同水与甲醇比例时的相变化。实验结果表明:当AOT和OA的物质的量比为1∶1时,柴油微乳液W/O单相区域的面积最大。当温度为30℃,R0值小于22.5时,得到澄清透明的柴油微乳液。对于含有甲醇的体系,当水与甲醇体积比为2∶1时,相图中单相区域的面积最大。R0值小于15.1时,体系能够达到均匀稳定状态。使用AOT和OA作为表面活性剂可以制备澄清透明的柴油微乳液,样品放置64d后未出现分层现象,且仍为澄清透明乳液。     

不同表面活性剂对单相微乳液特性的影响

表面活性剂是影响微乳液特性的关键因素之一。本文选取聚氧乙烯脱水山梨醇单油酸酯（Tween 80）、烷基糖苷1214（APG 1214）、十二烷基苯磺酸钠（SDBS）、脂肪醇聚氧乙烯醚硫酸钠（AES）、十二烷基硫酸钠（SDS）和95%纯度鼠李糖脂（R-95%）这6种表面活性剂,通过对其乳化性能和临界胶束浓度进行筛选,结合其形成微乳液的拟三元相图、粒径分布和界面张力分析其特性,并提出微乳液增溶油能力和增溶油成本。研究表明：APG 1214、SDBS、Tween 80乳化性能好、临界胶束浓度低具有更易形成微乳液的优势;5种表面活性剂（Tween 80、SDBS、APG 1214、SDS、AES）均可与正丁醇、水和3号白油自发形成单相微乳液,单相区面积大小为AES型>SDS型>APG 1214型>Tween 80型>SDBS型,最大增溶油能力大小为SDS型>AES型>APG 1214型>Tween 80型>SDBS型,最低增溶油成本大小为AES型相似文献