阴离子蠕虫胶束

本文从分析蠕虫胶束形成的分子几何条件和自由能驱动因素入手,总结了传统阴离子表面活性剂蠕虫胶束的形成和性质,指出制约其构筑和产生优良黏弹性的原因。在此基础上,介绍了Gemini表面活性剂构筑蠕虫胶束的分子结构优势,以及由此构筑阴离子蠕虫胶束的研究进展,尤其是长刚性联接链Gemini表面活性剂形成的蠕虫胶束。最后特别指出,基于新颖分子结构优势,Gemini表面活性剂可望成为蠕虫胶束构筑的主要分子对象。     

智能型蠕虫状胶束体系

智能型蠕虫状胶束体系是指宏观性能随着外界环境条件的微小变化而发生明显改变的胶束体系,是智能型胶体材料和软物质的重要组成部分。本文按照“体系组成-微观结构-宏观性能”的思路分别介绍了具有温度、光、pH和氧化还原响应的智能型蠕虫状胶束体系的组成、性能及响应机理,并展望了其发展前景。     

Rheological Properties of Wormlike Micelles Formed by Cetyltrimethylammonium Bromide and Sodium Laurate

Aqueous solutions of mixed cationic and anionic surfactants, cetyltrimethylammonium bromide (CTAB) and sodium laurate (SL), have been studied by steady-state rheology and dynamic oscillatory technique. Wormlike micelles can form due to attractive interactions between the oppositely charged headgroups of CTAB and SL. The wormlike micelles formed by CTAB/SL have been compared with that of cetylpyridinium bromide (CPB)/SL by steady-state rheology method. Effects of additional components such as NaBr, 1-propanol, 1-butanol, polyvinylpyrrolidone (PVP) on the micelles formation process have also been investigated. Cole-Cole plot has been applied to study the dynamic viscoelasticity of the wormlike micelles.     

CO2-Responsive Wormlike Micelles Based on Pseudo-Tetrameric Surfactant

Wormlike micelles, which are linear aggregates created by the self-assembly of surfactants, may entangle to form dynamic three-dimensional network-like structures, endowing solutions with considerable macroscopic viscoelasticity. Recently, a pressing need has arisen to research a novel stimuli-responsive worm-like micelle that is efficient and environmentally friendly. CO₂ is an inexpensive, abundant, non-toxic, biocompatible, and non-combustible gas, and it is anticipated that CO₂ may serve as the trigger for stimuli-responsive worm-like micelles. In this paper, the formation of CO₂-switchable pseudo-tetrameric surfactants, which subsequently self-assemble into CO₂-switched wormlike micelles, is accomplished using a simple mixing of two commercial reagents, such as stearic acids and cyclen. The rheological characteristics switched by the use of CO₂ are cycled between that of a low-viscosity (1.2 mPa·s) fluid and a viscoelastic fluid (worm-like micelles, 3000 mPa·s). This article expands the field of study on stimuli-responsive worm-like micelles.     

长链阳离子表面活性剂蠕虫状胶束的剪切带转变行为研究

报道一种含有不饱和疏水尾链的超长链阳离子表面活性剂——N-芥酸酰胺丙基-N,N,N-三甲基碘化铵(EDAI)自组装所形成的蠕虫状胶束及其剪切带行为. EDAI浓溶液表现出了明显的剪切带转变特征, 即溶液的流动曲线被介于两个临界剪切速率之间的剪切应力平台分割为粘度不同的两部分. 在剪切带转变区域, 原本均质的流体表现出机械剪切不稳定性, 沿速度梯度方向被分割为剪切速率不同的两个宏观流体层.     

阴离子疏水缔合共聚物/阳离子蠕虫状胶束协同增粘自组装网络

将阴离子疏水缔合丙烯酰胺共聚物P(NaAMC14S-b-AM)与阳离子蠕虫状胶束十六烷基三甲基溴化铵/水杨酸钠(CTAB/NaSal)在水溶液中自组装制备了新型的缔合增粘体. 由稳态剪切和动态流变实验结果得出: 自组装体系在80 ℃下仍具有显著的协同增粘效应, 其流变行为符合Maxwell模型. 同蠕虫状胶束相比, 自组装体系的稳态模量G0、力学松弛时间τR和缠结点密度ν都有增加, 由此分析缔合体系中两组分间形成了相互缠结的网络结构, 在链缠结处共聚物主链上的疏水侧链嵌入到了蠕虫状胶束的内核.     

甘油单油酸脂/水立方液晶体系流变性质的研究

Monoglyceride (MO) can form various liquid crystalline phases spontaneously in the presence of various amount of water at room temperature. The appropriate compositions from binary phase diagram of MO/H2O were selected to form cubic phases. The selected systems were studied at different salt concentrations and pH value using rheological methods. There was a weak effect of salt on viscoelastic properties of cubic phases formed from MO/H2O system. Hexagonal phase was formed when pH value was decreased or increased. The viscoelasticity of cubic phases was different from that of hexagonal liquid crystals. Rheological properties of MO/H2O cubic phases were stable at pH and salt concentration similar to physiological condition.     

The release of cephanone in CTAB/n-C5H11OH/H2O system

Controlled release of cephanone from hexadecyltrimethylammonium bromide (CTAB) micelles and CTAB/n-C₅H₁₁OH/H₂O microemulsions was studied. The results showed that the release rate of cephanone was reduced in CTAB micelles and CTAB/n-C₅H₁₁OH/H₂O microemulsions, because of the solubilization of cephanone in micelles and microemulsions. The release of cephanone from CTAB micelles and CTAB/n-C₅H₁₁OH/H₂O microemulsions was characterized by Fickian diffusion and non-Fickian diffusion.     

Rheological Properties and Crosslinking Rheo-Kinetics of CMHEC/CTAB Synergistic Systems

Aiming at synergistic interaction between carboxymethyl hydroxyethyl cellulose (CMHEC) and cetyltrimethyl ammonium bromide (CTAB), mixtures of CMHEC and CTAB solutions were investigated, employing relative viscosity and rheological measurements. The effects of mass ratio of CMHEC and CTAB solutions, temperature, and polysaccharide concentration on relative viscosities of CMHEC/CTAB systems were studied. Rheological method was used to study rheo-kinetics of the isothermal crosslinking process for CMHEC/CTAB synergistic fracturing fluid, and the novel crosslinking rheo-kinetics equation was established. The results showed the strong synergism between CMHEC and CTAB, resulting in a higher relative viscosity, storage modulus G′, and loss modulus G″ than that of separate ones. CMHEC/CTAB systems behave as pseudoplastic fluids with considerable thixotropy and viscoelasticity, and the flow behavior can be well described by Carreau?Williamson model. The crosslinking rheo-kinetics equation can well describe the isothermal crosslinking process at different shear rates. The model parameters are well-defined and reasonable.     

Study on Synergistic Effect Between Wormlike Micelles and Hydrophobically Modified Poly(acrylic acid) in Salt Solution

The complex system of hydrophobically modified poly (acrylic acid) (HMPA) and wormlike micelles formed by sodium oleate in the presence of sodium acetate is investigated by apparent viscosity and rheological measurements. Addition of small amount of HMPA markedly enhances the viscosity of wormlike micelles, with further increase of HMPA concentration, a viscosity drop is observed. At high salinity, the complex system still remains strong viscoelastic and eliminates the limitation of susceptibility to salt for HMPA. DPD simulation results are in good agreement with experimental data, which provide theoretical confirmation for a synergistic mechanism between HMPA and wormlike micelles.      

SDS/CTAB/H2O体系特异性质研究

对SDS/CTAB/H2O系统的三元相行为,导电能力,粘度性质等进行了相关性研究,发现相图中存在两个规则的液晶区。当SDS/CTAB(摩尔比)接近1∶2或2∶1时,其混合水溶液中表面活性剂分子异种电荷间的静电引力作用和同种电荷间的静电斥力作用达到吻合状态,既不易形成以胶束为主的均相溶液体系,也不易形成沉淀,而是形成远程有序组合体-液晶结构。当表面活性剂总浓度一定时,具有液晶结构的SDS/CTAB混合水溶液体系,致使体系的导电能力及粘度均呈现极大值。     

由碳酸钠诱导形成的油酸钠蠕虫状胶束的流变学性质

当Na₂CO₃浓度逐渐增加时, 用流变学的方法研究了阴离子表面活性剂油酸钠(NaOA)在溶液中从胶束转变成蠕虫状胶束的过程. 首先测量体系剪切粘度(η)和剪切速率的关系得到零剪切粘度(η₀). 然后由动态振荡实验得到复合粘度(|η^*|)、动态模量(储能模量G'、损耗模量G"和结构松弛时间τ_s)等物理量. 应用Cox-Merz规则和Cole-Cole图, 证明NaOA (0.040～0.080 mol/L)/Na₂CO₃ (0.25～0.50 mol/L)体系形成蠕虫状胶束, 且蠕虫状胶束的动态粘弹性在NaOA (0.050～0.080 mol/L)/Na₂CO₃ (0.35～0.45 mol/L)范围是符合Maxwell模型的线性粘弹性流体.     

Viscoelastic Drag of Particles Settling in Wormlike Micellar Solutions of Varying Surfactant Concentration

Wormlike micellar octadecyl trimethyl ammonium chloride (OTAC) solution is a self-assembled fracturing fluid used to carry proppants into fractures in oil recovery. Slow settling velocity of proppant is desirably resulted from the viscoelastic drag with low viscosity of fracturing fluids for fracturing work. Steel spheres, as a substitute for proppants, fall into three semi-dilute OTAC solutions. The steady rheology demonstrates that OTAC solutions are divided into shear-thickening and shear-thinning regimes by the critical shear rate. The applied steel spheres always lie in the shear-thickening regime of the 2.8 wt% OTAC solution with aggregated micelles as their characteristic shear rates are less than the critical shear rate of the solution. Strong shear-thickening viscous drag results in lower settling velocity of steel spheres. Most of the applied steel spheres, on the other hand, lie in the shear-thinning regime of the 4 wt% OTAC solution with orientated micelles. Although the latter solution has small dissipation coefficient, high Weissenberg number, and consequently high elastic effect, the shear-thinning viscosity results in higher settling velocity of steel spheres.     

孔雀绿与CTAB胶束的相互作用

以CTAB胶束模拟生命体系,用UV-Vis和荧光光谱等技术研究了孔雀绿与CTAB胶束的相互作用.结果表明,孔雀绿自发地定位于CTAB胶束栅栏层,使得胶束聚集数增加,胶束的微环境极性I1/I3下降.孔雀绿与CTAB胶束之间的结合常数K和孔雀绿在胶束相与水连续相之间的分配系数KD均随孔雀绿浓度增加而降低,表明孔雀绿与CTAB胶束之间的相互作用随孔雀绿浓度增加而降低.     

Wormlike Micelle Formation and Rheological Behavior in the Aqueous Solutions of Mixed Sulfate Gemini Surfactant without Spacer Group and Dodecyltrimethylammonium Bromide

The rheological behavior of the aqueous solutions of mixed sulfate gemini surfactant with no spacer group, referred to as d‐C₁₂S, and dodecyltrimethylammonium bromide (C₁₂TABr) at a total concentration of 100 mmol·L⁻¹ but different molar ratios of C₁₂TABr to d‐C₁₂S (α₁) was investigated using steady rate and frequency sweep measurements. The wormlike micelles were formed over a narrow α₁ range of 0.20–0.27. The viscoelastic solutions exhibited Maxwell fluid behavior. At the optimum molar ratio of 0.25, the zero‐shear viscosity was as high as 600 Pa·s and the length of the mixed wormlike micelle was about 0.45–0.85 µm. The present result provides an example to construct long wormlike micelles by anionic gemini surfactant.     

pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants

Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(N-dodecyl-N-propanesulfonate sodium)-propane (C₁₂C₃C₁₂(SO₃)₂) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C₁₂C₃C₁₂(SO₃)₂ through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C₁₂C₃C₁₂(SO₃)₂ molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C₁₂C₃C₁₂(SO₃)₂ solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C₁₂C₃C₁₂(SO₃)₂, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.     

十六烷基三甲基溴化铵/油酸钠混合体系蠕虫状胶束流变性研究

阴、阳离子表面活性剂之间强烈的相互作用利于形成自由弯曲的蠕虫状胶束。本文利用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和阴离子表面活性剂油酸钠(Na OA)制备了CTAB/Na OA蠕虫状胶束,研究了两表面活性剂的混合比和表面活性剂总浓度的变化对蠕虫状胶束体系稳态流变性及动态粘弹性的影响。结果表明,蠕虫状胶束在剪切过程中的解缠、拟网状结构的破坏以及最终沿剪切速度方向取向等是蠕虫状胶束产生剪切稀释特性的原因。两表面活性剂的混合比和表面活性剂总浓度的变化导致表面活性剂之间的静电作用、疏水作用发生较大的变化,最终引起体系内部表面活性剂聚集体形态的差异。体系内蠕虫状胶束长度、体系结构复杂程度、蠕虫状胶束形成的网络结构的致密度等都影响着体系的流变行为。在混合比R=3.6、总浓度CT=0.24mol/L时,体系中蠕虫状胶束最长,网络结构最为紧密,体系的零剪切粘度达到最大值。表面活性剂浓度一定时,混合比的提高有助于蠕虫状胶束的定向生长,弛豫时间τR和储能模量高频区平台模量G0提高,R=3.6时两者皆达到极大值,此后由于蠕虫状胶束的分枝化及(或)胶束破裂导致τR及G0下降。在表面活性剂混合比一定(R=3.6)时,表面活性剂浓度的提高利于蠕虫状胶束的增长或者分枝化,增加了胶束网络结构缠绕(融合)点的密度,导致G0逐渐增大。Cole-Cole图证实本文研究的蠕虫状胶束体系是符合Maxwell模型的线性粘弹性流体。     

青霉素G钾盐在CTAB胶束中的水解及其抑制

以紫外光谱法研究了青霉素G钾盐(Pen-K)在十六烷基三甲基溴化铵（CTAB）胶束体系中的水解反应, 并探讨了水解反应机理.结果表明, CTAB胶束对Pen-K的水解具有抑制作用; Pen-K在CTAB胶束体系水解时,体系pH值的变化与在水中相似, 表明H＋浓度对这种抑制作用影响较小.红外光谱和微极性研究表明,部分Pen-K钾盐定位于CTAB胶束栅栏层中, 增加了其稳定性.     

Rheology and microstructure studies of SDS/CTAB/H2O system

Phase behavior of mixed sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) aqueous solution was studied. The rheological properties and microstructure were investigated using a rheostat and freeze-fracture technique and are shown to be closely related to the phase behavior. Experimental investigations reveal two symmetrical aqueous two-phase systems (ATPS) in the ternary phase diagram of SDS/CTAB/H₂O system. In the surfactant rich phase of ATPS or in the adjacent stoichiometric state of ATPS, the system has high viscosity because of its long range ordered structure. Lamellar phase was found in the high viscosity samples in which the cationic and anionic surfactant are in 1: 3 or 3: 1 stoichiometry. In addition, the viscosity has a tendency to increase when salt was added to the solution. The viscosity increase is due to the salt can screen the repulsion between different charged headgroups and thus reduces the effective size of surfactants and facilitates the spherical or rod likes micelles to be transformed to worm-like micelles which can form hexagonal or liquid crystal phases. Large-size salt ions like sodium sulfate (especially organic salt ions) have more significant effect on the surfactant solution viscosity. The text was submitted by the authors in English.     

水相胶束中锰卟啉体系的停流谱研究

对于以水溶性锰卟啉Mn^Ⅱ（TMPyP）为催化剂的氧化反应，体系所处的环境对反应的过程有着重要的影响，在CTAB阳离子表面活性剂胶束溶液中，Mn^Ⅱ（TMPyP）与H2O2和PhIO作用，均生成两种锰氧卟啉中间体Mn^Ⅴ（TMPyP）和Mn^Ⅳ（O）；但在AOT和SDS阴离子胶束中，Mn^Ⅱ（TMPyP）与PhIO反应，只生成四价锰氧中间体Mn^Ⅳ（TMPyP）；而在与H2O2的反应中，Mn^Ⅱ（TMPyP）被降解。