Gemini表面活性剂的研究进展

Gemini型表面活性剂是一类双亲油基双亲水基的两亲物，因其特殊的二聚结构从而具有许多特殊的物化性质。综述了Gemini型表面活性剂的研究进展、合成方法、物化性质及其应用。     

不同电性Gemini表面活性剂界面扩张性质

利用Langmuir槽法研究了含聚氧乙烯醚链中间链的两性Gemini表面活性剂C8E4NC12、阳离子Gemini表面活性剂C12NE3NC12和阴离子Gemini表面活性剂C8E4C8在空气/水表面和癸烷/水界面上的扩张性质,考察浓度对3种Gemini表面活性剂溶液表、界面扩张性质的影响.结果表明,由于分子间存在库仑引力,两性Gemini分子表现出较高的扩张弹性和粘性,且界面扩张性质类似于表面.对于有相同电荷Gemini分子,C8E4C8分子中的刚性苯环导致其疏水长链在表面上的取向不同于C12NE3NC12分子,两者表现出不同的表面扩张性质;而油分子能改变同电荷Gemini分子中长链烷基的取向,造成其界面扩张弹性和粘性远低于表面.提出了不同电性Gemini分子在界面排布的示意图,并利用弛豫过程的特征参数进行了验证.     

电解质和乙醇对DNA与Gemini表面活性剂相互作用的影响

应用荧光探针和zeta电位方法研究了电解质NaBr、NaCl、KCl和有机溶剂乙醇对DNA与Gemini表面活性剂相互作用的影响. DNA诱导的表面活性剂类胶束在较低浓度即可生成, 这一浓度称为临界聚集浓度(CAC). Gemini表面活性剂比具有相同烷烃链长的单体表面活性剂更易聚集, 对应的CAC较低. 实验结果表明, 盐(NaBr)浓度对DNA/表面活性剂体系的CAC影响不大, 阴、阳离子的种类则对该体系有不同程度的影响. 阴离子(Br-、Cl-)对体系的CAC有显著的影响, 但阳离子(Na+、K+)的差异对CAC影响不大. 极性溶剂乙醇对DNA与表面活性剂相互作用的影响比较复杂. 乙醇浓度较低时有利于表面活性剂的聚集, 使得CAC减小; 而浓度较高时, 则不利于表面活性剂聚集,从而使CAC变大. 乙醇可显著改变DNA/表面活性剂复合物的zeta电位.     

季铵盐Gemini表面活性剂胶团水溶液的流变性质

用毛细管振荡剪切流动法研究联接基团为聚亚甲基链的季铵盐型Gemini表面活性剂C_12-s-C₁₂·2Br(s=2,4,8)的流变性质,并用动态光散射技术测定胶团生长过程中的胶团形状和大小的变化规律,探索联接基团长度对胶团形状、大小以及溶液流变性质的影响.实验结果表明,胶团形状和大小与联接基团长度有关,而溶液的流变性质主要由胶团的大小和形状所决定,球形和棒状(长椭球体)胶团溶液的流变性质以纯粘度为主,而线性胶团溶液则显示粘弹性质.此外,增加电解质浓度和降低温度均使溶液的粘度增大.     

混合极性溶剂乙二醇／水中正负离子表面活性剂SDS／CTAB的界面性质研究

正负离子混合表面活性剂由于其特异的自组织行为及良好的稳定性,已成为研究生物膜和用于生物活性物质分离分析的理想模型[1-2],近年来,该体系在界面化学性质中得到了广泛的研究,但是由于正负电性中和,其水溶液很不稳定,一旦超过临界胶束浓度(CMC),极易发生沉淀,从而失去表面活性,使其应用受到限制.     

阴离子Gemini表面活性剂在油/水界面行为的分子动力学模拟

采用分子动力学方法研究了磺酸盐型阴离子Gemini表面活性剂在油/水界面的吸附行为, 考察了不同长度的连接基(Spacer)对表面活性剂在界面的聚集形态及界面性质的影响. 密度分布和微观结构信息显示, Gemini表面活性剂能在油/水界面形成单层膜结构. Gemini表面活性剂能使油/水界面的厚度显著增大, 并使界面形成能降低. 当连接基为6个碳时, 此类磺酸盐型Gemini表面活性剂的界面厚度最大, 形成的界面最稳定. 连接基长度对Gemini表面活性剂单层膜周围的水分子和Na⁺的吸附结构影响不大, 但是能影响水分子的扩散行为.     

联接基长度对Gemini表面活性剂流变性质的影响

用毛细管振荡剪切流动法研究了联接基团为聚亚甲基链的阳离子Gemini表面活性剂的流变性质。实验结果表明,无论是普通单链单头基或Gemini表面活性剂,其流变性质主要由胶团的大小和形状所决定;随着联接基团长度的增加,胶团的轴比率变小,导致流动阻力减小,粘度降低。此外对于球形和棒状胶团溶液,其流变性质主要以粘性为主．弹性可忽略不计。在低剪切速率下,溶液属于牛顿型流体;而在高剪切速率下,则表现出准塑性流体性质。     

Gemini表面活性剂合成进展

系统总结了近百种Gemini表面活性剂的合成路线和方法,并且按照其结构特点分门别类地进行比较和归纳,对今后Gemini表面活性剂的合成发展方向提出了一些看法,这对促进此类新颖表面活性剂的工业化进程将具有指导意义。     

氨基酸基Gemini表面活性剂的研究进展

氨基酸基Gemini表面活性剂因具有高表面活性、独特的流变性能和优异的生物相容性等诸多优点受到科研工作者的青睐。本文按照氨基酸类型和亲水基种类对其进行归纳和总结,综述了氨基酸基Gemini表面活性剂的合成、性能和应用研究进展,指出开发简单合成步骤制备新型结构的高光学纯度的氨基酸基Gemini表面活性剂、探讨手性碳原子的立体构型对于其自组装行为的影响是今后的研究重点。     

甘氨酸在乙醇—水混合溶剂中离解常数的测定

本文利用电位滴定法测定了２５℃，ＫＣｌ离子强度Ｉ＝０．１ｍｏｌ．Ｌ＾－１时，甘氨酸在纯水及８个乙醇－水混合溶剂中的二级离解常数ｐＫａ，对应的碱离解常数ｐＫｂ和混合溶剂的质子自递常数ｐＫ。实验结果表明：在所研究的浓度范围内，随着混合溶剂中乙醇含量的增加，甘氨酸的酸离解常数及溶剂的质子自递常数逐渐减小，碱离解常数则逐渐增大。     

Synthesis and Surface Properties of Novel N-Alkyl Quinoline-Based Cationic Gemini Surfactants

Two series of cationic dimeric (gemini) surfactants are prepared with respect to key surfactants properties, such as surface activity and solubilization. The influence of both the dimerization and the spacer group is examined in order to establish structure-property relationships. The surface tension and critical micelle concentration can be markedly reduced compared to the monomeric surfactants in the pure state. The critical micelle concentration (cmc) of each series has been determined using equilibrium surface tension measurements. Furthermore, air/water interface parameters including effectiveness (π_cmc), efficiency (P_C20), maximum surface excess (Γ _max ), and minimum surface area (A _min ) have been also derived using Gibb's adsorption equation at 25°C. Standard free energies of micellization and adsorption were calculated. Solubilization behaviors of the synthesized surfactants were measured towards paraffin oil as solubilized material using light transmission technique.     

双子表面活性剂及其抗菌性能

Gemini surfactants contain two hydrophilic and two hydrophobic groups connected by a linkage close to the hydrophilic groups. Gemini surfactants have lower critical micelle concentration, higher surface activity, greater efficiency in decreasing the surface tension of water and the interfacial tension between water and oil, and better water solubility than conventional surfactants. Gemini surfactants are widely used as sterilizing, bacteriostatic, anti-foaming, and drug release agents in various enterprises including food production and industrial cleaning. They, therefore, play a very important social, economic, and industrial role. This paper briefly summarizes gemini surfactant development, structure, self-assembly, activity, classification, and characteristics, as well as focuses on the antibacterial mechanisms of these compounds. It is expected that the antibacterial properties of gemini surfactants may help slow the spread of the novel coronavirus (2019-nCoV).     

Synthesis and Evaluation of Surface Activity of Gemini Borate Surfactants Based on Glucose Moiety

A series of Gemini borate surfactants were synthesized based on glucose molecule. Their chemical structures were confirmed using ¹H-NMR,¹³C nuclear magnetic resonance (NMR), and mass spectroscopy. The surface activities of these Gemini amphiphiles were measured, including surface tension (γ), critical micelle concentration (CMC), effectiveness (II_cmc), efficiency (pC₂₀), maximum surface excess (Γ_max), and minimum surface area (A_min) at different temperatures 25, 35, and 45°C either in pure water or in water–ethanol mixture (10%). Also, thermodynamic data including free energy, entropy, and enthalpy changes (ΔS, TΔS, ΔH) for adsorption at the air–water interface and also for micellization in surfactant solutions were calculated.     

新型Gemini咪唑表面活性剂的合成及表面性能

以2,2-双(溴甲基)-1,3-丙二醇为连接基合成了新型的连接基为枝状的Gemini咪唑表面活性剂2,4-二(溴化-3-烷基咪唑)-1,3-丙二醇([Cn-P-Cnim]Br2,n=10,12,14).产物经核磁共振氢谱(1H NMR)、红外(IR)光谱和元素分析等进行了分析,证明所得产物即为目标产物.通过表面张力法和电导法测量其表面活性并计算胶束形成热力学参数(ΔG m—0,ΔH m—0,ΔS m—0).结果表明,25℃时3种表面活性剂均具有很高的表面活性,胶束的形成是自发的熵驱动过程.     

双子表面活性剂的粘度行为

对阳离子双子表面活性剂在溶液中的粘度行为进行了研究.发现联结基长度与双子表面活性剂在稀溶液中能否表现出粘度行为有很大关系，联结基数s = 2、3、4的双子表面活性剂稀溶液表现出显著的增粘性，但 s =4的某些双子表面活性剂的粘度具有时间依赖性，而s = 6的双子表面活性剂则没有明显的粘度行为.双子表面活性剂烷基链越长，其增粘能力也越强.联结基数s = 2或3的部分双子表面活性剂，其粘度随温度的变化有一最大值.双子表面活性剂与有机酸盐的复合物也表现出很强的增粘行为.     

新型脲基双子表面活性剂的合成及其性能

以N,N-二甲基-1,3-丙二胺、固体光气、溴代烷为原料合成了三种新型含脲基双子表面活性剂(LY-12、LY-14、LY-16),并通过1H NMR、ESI-MS和FT-IR表征了结构。测定了其Krafft点、乳化性能、起泡性能;通过测定表面张力γcmc以及不同温度下的临界胶束浓度(CMC)计算表面活性参数(Γmax、Amin、pc20)与热力学参数(ΔGmθ、ΔHmθ、ΔSmθ)。结果表明,LY-12、LY-14的Krafft点低于0℃,LY-16的Krafft点低于10℃;LY-12、LY-14、LY-16的乳化时间分别为173、275和338 s;LY-12的起泡性显著优于LY-14和LY-16;三种表面活性剂的表面张力γcmc分别为38. 77、37. 42和36. 59 m N/m;298. 15K条件下,其CMC值分别为0. 19、0. 15、0. 13 mmol/L。表面活性参数与热力学参数计算表明,三种表面活性剂均具有高的表面活性且胶束的形成是熵驱动的自发放热过程。     

乙醇—水混合溶剂中次氮基三乙酸离解平衡的研究

次氮基三乙酸(NTA)在非水或混合溶剂中离解常数的测定尚未见报道,本文用电位法测定了乙醇-水混合溶剂中溶解度较小的NTA的离解常数,用标准盐酸溶液返滴定其钾盐可增加NTA浓度,提高测定准确度,测量系统防止CO_2装置和数据处理方法也比文献简单。     

磺酸盐型Gemini表面活性剂合成研究进展

磺酸盐型Gimini表面活性剂是一类新型的阴离子表面活性剂,它由联结基团通过化学键将2个或多个单体磺酸盐型表面活性剂连接在一起,由此产生高表界面活性,低临界胶束浓度值,增强了洗涤能力,与传统的阴离子表面活性剂有较好的复配性,奇异的流变特性和良好的抗盐性等一系列的性质,从而具有广泛的应用前景。 本文以原料来源不同分类,综述了一系列磺酸盐型Gemini表面活性剂的合成方法,展望了合成磺酸盐型Gemini表面活性剂的研究方向。     

Interaction of Anionic Gemini Surfactants with Other Surfactants

The interaction of anionic gemini surfactants with other surfactants (such as anionic, cationic, nonionic) was systematically overviewed, paying attention to synergism observed in various properties. These mixed systems were found to show remarkable synergism in micelle formation. The critical micelle formation values being lower than the individual gemini surfactants indicate that the mixed micellization is due to attractive interaction between the two components. Almost all combinations were discussed in terms of respective surface tension reduction effectiveness and surface tension reduction efficiency and aggregation number for evaluation of synergism.     

Synthesis and Properties of Gemini Cationic Surfactants with Amide Spacers

Four gemini cationic surfactants {N,N‘-di[2-(lauryldimethylamino)acetyl]polymethylenediamine dichloride, LAA-s-LAA, s = 2,3,4,6 } were synthesized by using four bis (a-chloroacetamide)s and N, N-dimethyl-laurylamine, respectively. The molecular structures were characterized by means of IR, ^1H NMR. ^13C NMR and MS, and the behavior of their aqueous solutions was studied. The critical micell concentrations (CMC) of LAA-s-LAA were one order of magnitude lower than that of dodecyltrimethyl ammonium chloride (DTAC). With the change of the length of spacer chain(s), their CMC values change, and CMC reaches the top value at s=4.