基于胱氨酸的Gemini型表面活性剂的合成及其性质

合成了基于胱氨酸的两种Gemini表面活性剂, N,N’-二对丁氧基肉桂酰胺基胱氨酸钠(SDBCC)和N,N’-二癸酰胺基胱氨酸钠(SDDC). 利用表面张力、动态光散射(DLS)、透射电镜(TEM)等手段研究了体系的表面性质和聚集行为.     

Aggregation behavior of gemini surfactants and their interaction with macromolecules in aqueous solution

Gemini surfactants are constructed by two hydrophobic chains and two polar/ionic head groups covalently connected by a spacer group at the level of the head groups. Gemini surfactants possess unique structural variations and display special aggregate transitions. Their aggregation ability and aggregate structures can be more effectively adjusted through changing their molecular structures compared with the corresponding monomeric surfactants. Moreover, gemini surfactants exhibit special and useful properties while interacting with polymers and biomacromolecules. Their strong self-aggregation ability can be applied to effectively influence the aggregation behavior of both polymers and biomacromolecules. This short review is focused on the performances of gemini surfactants in aqueous solutions investigated in the last few years, and summarizes the effects of molecular structures on aggregation behavior of gemini surfactants in aqueous solution as well as the interaction of gemini surfactants with polymers and biomacromolecules respectively.     

Studies on SDLC (Sodium Dilauraminocystine) and SDMC (Sodium Dimyristaminocystine) Gemini Surfactants

The present work reports the synthesis and evaluation of surface active properties of amino acid-based gemini surfactants, namely, sodium dilauraminocystine (SDLC) and sodium dimyristaminocystine (SDMC) derived from L-cystine and fatty acids. The effect of reaction variables like molar ratio of raw materials and temperature has been studied for the synthesis of these gemini surfactants. In preparation of these gemini surfactants, fatty acids (lauric/myristic) were reacted with thionyl chloride to obtain respective acid chlorides (lauroyl/myristoyl). These acid chlorides were further reacted with L-cystine at different reaction conditions to get amino acid based-gemini surfactants. The study revealed that 1:2.5 molar ratio of reactants, namely, L-cystine and lauroyl/myristoyl chloride and 10–15° reaction temperature resulted in maximum yield of amino acid-based gemini surfactants (SDLC and SDMC). Surface active properties of synthesized gemini surfactants (SDLC and SDMC) were also compared with their corresponding monomeric units, namely, sodium lauroyl cysteine (SLC) and sodium myristoyl cysteine (SMC), respectively. The results demonstrated that gemini surfactants (SDLC and SDMC) had better surface active properties than their corresponding monomeric units. The structures of synthesized amino acid-based gemini surfactants were also confirmed by FTIR, ¹H NMR, ¹³C NMR, and ESI-MS spectral data.     

Gemini表面活性剂分子结构对其水溶液中聚集行为的影响

Gemini表面活性剂是通过联接基团将两个具有亲水亲油性质的两亲结构单元在其亲水头基上或靠近亲水头基处以共价键方式连接而成的一类表面活性剂。这类表面活性剂由于联接基团的引入具有比传统单链表面活性剂更高的表面活性,同时分子结构中更多的可调控因素使其在水溶液中表现出更为丰富的自聚集行为,而且分子不同部位结构的改变对分子内或分子间相互作用产生不同的影响,可实现通过分子结构的设计有效调控其自聚集能力和聚集体结构。本综述将从联接基团、烷基链、亲水头基、反离子和其它功能性基团这五个方面概述近些年Gemini表面活性剂水溶液中聚集行为方面的研究进展,总结人们对Gemini表面活性剂分子间相互作用规律的认识,期望对于进一步发展这类高效的表面活性剂体系提供有益的帮助。     

Oligoethyleneoxide spacer groups in polymerizable surfactants

Cationic and zwitterionic polymerizable surfactants bearing tri- and tetraethyleneglycol spacer groups between the polymerizable moiety and the surfactant structure were prepared and polymerized. Monomers and polymers were investigated with respect to their aggregation behavior in aqueous systems and compared to analogous monomers and polymers lacking spacer groups. In the case of the monomeric surfactants, the spacer groups depress both the Kraffttemperature and the critical micelle concentration. the area occupied per molecule at the air-water interface is substantially enlarged by the spacers, whereas the depression of surface tension is nearly constant. Although the monomers with and without spacers are true surfactants, all the polymers are water-insoluble, but form monomolecular layers at the air-water interface. In analogy to the monomer behavior, the incorporation of the spacer groups increases the area occupied per repeat unit at the air-water interface substantially, but hardly affects the surface activity.     

酰胺基团对Gemini表面活性剂表面活性和聚集行为的影响

本文合成了含酰胺基团和不含酰胺基团的两类Gemini阳离子表面活性剂,测定了其表面活性参数,研究了酰胺基团对表面活性剂的表面活性和聚集行为的影响。结果表明,酰胺基团提高了Gemini阳离子表面活性剂的临界胶团浓度,降低了胶团聚集数,增强了胶团微极性,增大了表面活性剂的饱和吸附量。     

Gemini表面活性剂烷烃尾链在吸附和聚集过程中的疏水协同效应(英文)

以表面张力法测定了系列Gemini表面活性剂m-6-m以及对应单体表面活性剂CmTABr的临界胶束浓度(cmc)和降低水表面张力20mN·m-1需要的浓度(pC20).比较这些参数表明m-6-m胶束化和在界面吸附的能力均强于CmTABr,这被归结为Gemini表面活性剂烷烃尾链间的疏水协同效应.与不对称Gemini表面活性剂12-6-m比较,对称的Gemini结构更有利于表面活性剂的聚集和吸附.     

Enantioselectivity of vesicle-forming chiral surfactants in capillary electrophoresis. Role of the surfactant headgroup structure

Two vesicle-forming single-tailed amino acid derivatized surfactants sodium N-[4-n-dodecyloxybenzoyl]-L-leucinate (SDLL) and sodium N-[4-n-dodecyloxybenzoyl]-L-isoleucinate (SDLIL) have been synthesized and used as pseudo-stationary phase in micellar electrokinetic chromatography to evaluate the role of steric factor of amino acid headgroup and hydrophobic/hydrophilic interactions for enantiomeric separations. The aggregation behavior of the surfactants has been studied in aqueous buffered solution using surface tension and fluorescence probe techniques. Results of these studies have suggested formation of vesicles in aqueous solutions. Microenvironment of the vesicle, which determines the depth of penetration of the analytes into vesicle was determined by fluorescence probe technique using pyrene, N-phenyl-1-naphthylamine (NPN), and 1,6-diphenyl-1,3,5-hexatriene (DPH) as probe molecules. Atropisomeric compounds (+/-)-1,1'-bi-2-naphthol (BOH), (+/-)-1,1'-binaphthyl-2,2'-diamine (BDA), (+/-)-1,1'-binaphthyl-2,2'-diylhydrogen phosphate (BNP) and Tr?ger's base (TB) and chiral compound benzoin (BZN) has been enantioseparated. The separations were optimized with respect to surfactant concentration, pH, and borate buffer concentration. SDLL was found to provide better resolution for BOH, BNP, and BZN. On the other hand, SDLIL offers better resolution for BDA. The chromatographic results have been discussed in the light of the aggregation behavior of the surfactants and the interaction of the solutes with the vesicles.     

Self-Assembly Behavior of Benzotriazole in Water

The self-assembly behavior of ¹H-benzotriazole (BTA) in aqueous solutions below its solubility limit has been revealed for the first time using NMR and light scattering techniques. Relaxation time, diffusion and chemical shift NMR techniques in addition to various light scattering techniques were used to study the aqueous behavior of ¹H-Benzotriazole (BTA). These studies have revealed the self assembly of BTA molecules in water. Results show that BTA molecules tend to aggregate in water to form nanoparticles with radius in the range of 5 nm. The critical aggregation concentration (CAC) is estimated based on NMR data to be ～16–20 mM. Such a critical aggregation concentration is comparable with the typical critical micelle concentration (CMC) for surfactants that have moderate aqueous solubility. The self-assembly behavior of BTA may not be limited to benzotriazole. It might be generally true for all poorly water soluble species to aggregate at concentrations below their solubility.     

Synthesis and properties of ionic liquid-type Gemini imidazolium surfactants

A series of ionic liquid-type Gemini imidazolium surfactants with four-methylene spacer groups were synthesized ([C(n)-4-C(n)im]Br(2), n=10, 12, 14). The surface activity and thermodynamic properties of micellization between the Gemini imidazolium surfactants and their corresponding monomers ([C(n)mim]Br, n=10, 12, 14) were compared by means of surface tension and electrical conductivity measurements. The values of cmc, gamma(cmc), pc(20), Gamma(max), and A(min) derived from surface tension measurement at 25 degrees C suggest that the surface activity of [C(n)-4-C(n)im]Br(2) is higher than that of [C(n)mim]Br. While the thermodynamic parameters of micellization (DeltaG(m)(o), DeltaH(m)(o), DeltaS(m)(o)) derived from electrical conductivity indicate that the micellization of [C(n)-4-C(n)im]Br(2) is entropy-driven, aggregation of [C(n)mim]Br is entropy-driven at low temperature but enthalpy-driven at high temperature. Finally, the activation energy of conductance (E(a)) that is associated with the effective charge is also obtained for [C(n)-4-C(n)im]Br(2) and it is constant below the cmc, but it increases above the cmc.     

含有酰胺基或酯基的可降解阳离子Gemini表面活性剂在水溶液中的聚集行为

In the last thirty years, Gemini surfactants with various structures have been designed, synthesized, and demonstrated to show superior physicochemical properties. However, the utilization of non-degradable surfactants, including these Gemini surfactants, poses a threat to the environment; hence, degradable Gemini surfactants are desirable. Herein, biodegradable cationic Gemini surfactants with amide or ester groups in the hydrophobic chains or the spacer were synthesized. A monomeric surfactant containing an amide group and a Gemini surfactant with amide groups both in the hydrophobic chains and the spacer were synthesized for comparison. The effects of amide group location on the aggregation behavior of Gemini surfactants were studied systematically. The differences between the Gemini surfactants with amide groups and Gemini surfactants with ester groups were evaluated by comparing their aggregation behavior and hydrogen bonding formation. The Gemini surfactants with amide groups (C₁₂A-C_n-AC₁₂) in the chains showed much larger exothermic ΔH_mic and more negative ΔG_mic values than those of the corresponding monomeric surfactant C₁₂A; besides, their critical micelle concentration (cmc) was more than one order of magnitude lower than that of C₁₂A. The amide groups located in the hydrophobic alkyl chains promoted hydrogen bonding formation and self-assembly of the Gemini surfactants C₁₂A-C_n-AC₁₂. Moreover, ¹H NMR spectra revealed that the co-effect of a short spacer and hydrogen bonding leads to slow exchange of the C₁₂A-C₂-AC₁₂ molecules between the monomer and the aggregate. For the Gemini surfactant series C₁₂-AC_nA-C₁₂, the amide groups notably increased the spacer length, and largest cmc value and smallest exothermic ΔH_mic value were observed for C₁₂-AC₂A-C₁₂ instead of C₁₂-AC₆A-C₁₂. In C₁₂-AC₁₂A-C₁₂, the spacer was long and sufficiently flexible to adopt a "U"-shaped conformation above the cmc, and it acted as the hydrophobic part of the surfactant, as confirmed by ¹H NMR spectra. Among the Gemini surfactant with amide groups in both the spacer and the hydrophobic alkyl chains, C₁₂A-AC₆A-AC₁₂ had a smaller cmc and I₁/I₃ ratio as well as more exothermic ΔH_mic values than those of C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂. ¹H NMR spectra indicated that an ester-alcohol structural equilibrium exists during aggregation for the Gemini surfactants with ester groups. In addition, the Gemini surfactants with ester groups formed water-mediated hydrogen bonds in the aggregates. This water-mediated hydrogen bonding between ester groups was weaker than the direct hydrogen bonding between amide groups. Therefore, the Gemini surfactants with ester groups, C₁₂E-C₆-EC₁₂ and C₁₂-EC₆E-C₁₂, exhibited lower surface activity, a larger micelle ionization degree, higher micropolarity, and smaller exothermic ΔH_mic and less negative ΔG_mic values than their counterparts with amide groups, C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂.     

荧光探针法研究连接基团对双子型阳离子表面活性剂聚集行为的影响

利用荧光探针法和表面张力法测定了新型双子型阳离子表面活性剂的临界胶团浓度(cmc)、最低表面张力(γ_cmc)、胶团微极性和胶团聚集数(N_agg),探讨了连接基团对此类表面活性剂在水溶液中聚集行为的影响.结果表明,当连接基团增长时,cmc和胶团微极性增加,γ_cmc增大,N_agg减少,表面活性降低,在溶液中自发形成胶团的能力减弱.     

pH-responsive surface activity and solubilization with novel pyrrolidone-based Gemini surfactants

A new series of pH-responsive Gemini surfactants with 2-pyrrolidone head groups, N,N'-dialkyl-N,N'-di(ethyl-2-pyrrolidone)ethylenediamine (Di-C(n)P, where n = 6, 8 10, 12), were synthesized and characterized by (1)H NMR, (13)C NMR, ESI-MS, and elemental analysis. The surface activity and micellization behavior at acidic, neutral, and basic conditions were characterized by equilibrium surface tension and fluorescence techniques. It was found that the surface activity of Di-C(n)P depends on the pH of aqueous solutions due to the protonation state of surfactant molecules when pH was varied. The new compounds have lower cmc and γ(cmc) in comparison with that of m-2-m type conventional cationic Gemini surfactants and gluconamide-type nonionic Gemini surfactants. Fluorescence data confirm that micelles are formed when the concentration is above the cmc. Since micellization is of fundamental importance in surfactant applications such as solubilization, microemulsion, and related technologies, the significant difference in cmc at different pH of this new Gemini surfactant is employed to solubilize cyclohexane. The preliminary result indeed shows that the solubilization capacity of Di-C(n)P can be tuned by pH.     

含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

采用电导法研究了不同温度下含酯基Gemini表面活性剂在纯水和在质量分数为10%的甲醇-水(MAWR),乙二醇-水(EG-WR),丙三醇-水(GL-WR)四种体系中的集聚行为和胶束热力学;聚集行为参数包括临界胶束浓度(cmc)和抗衡离子的解离程度(α)以及胶束的热力学参数,包括标准吉布斯自由能(ΔG_m~o)、吉布斯迁移自由能(ΔG_(trans)~o)、吉布斯烷基链胶束化自由能(ΔG_(tail)~o)、标准焓变(ΔH_m~o)和标准熵变(ΔS_m~o),均被计算和讨论。研究表明在所有的研究体系中,cmc值随着疏水链的增加而减小,随着加入的醇结构中羟基数目的增加而增大,随温度的升高先变小,后变大呈U字形;胶束化过程都是自发进行的,并且在293.15 K下,胶束化过程是吸热的,在293.15 K上,胶束化过程是放热的;通过稳态荧光光谱法研究了表面活性剂在纯水、有机醇-水混合溶液中的微极性,结果表明,在相同溶剂中,随着烷基链长度的增加,溶液微环境的疏水性越强;对于相同的Gemini表面活性剂,随着加入含羟基数目越多的醇,其微环境的疏水性越强。并研究了Gemini表面活性剂在混合体系中形成胶束过程的焓-熵补偿曲线。     

Aggregation behavior of silicone surfactants in ethylammonium nitrate ionic liquid

The aggregation behavior of two silicone surfactants (monomeric and Gemini) was studied by surface tension measurements in a room temperature ionic liquid, ethylammonium nitrate (EAN), at various temperatures. A series of parameters, including critical micelle concentration (CMC), surface tension at the CMC (γ _CMC), adsorption efficiency (pC ₂₀), and effectiveness of surface tension reduction (Π _CMC), were obtained. By comparing the silicone surfactants with traditional surfactants, we deduced that the surface activity of the silicone surfactants in EAN was superior to the activity of other surfactants. In addition, from the CMC values and their temperature dependence, we estimated the thermodynamic parameters of the micelle formation, $ \Delta G_m^0 $ , $ \Delta H_m^0 $ , and $ \Delta S_m^0 $ . It was revealed that the micellization of the silicone surfactants is entropy driven at low temperature and enthalpy driven at high temperature. Isothermal titration calorimetry measurements were also carried out to study the micellization of Gemini silicone surfactant. ¹H NMR was performed to study the silicone surfactant micelle formation mechanism in EAN.     

Gemini surfactants from natural amino acids

In this review, we report the most important contributions in the structure, synthesis, physicochemical (surface adsorption, aggregation and phase behaviour) and biological properties (toxicity, antimicrobial activity and biodegradation) of Gemini natural amino acid-based surfactants, and some potential applications, with an emphasis on the use of these surfactants as non-viral delivery system agents. Gemini surfactants derived from basic (Arg, Lys), neutral (Ser, Ala, Sar), acid (Asp) and sulphur containing amino acids (Cys) as polar head groups, and Geminis with amino acids/peptides in the spacer chain are reviewed.     

Effect of the headgroup structure on the aggregation behavior and stability of self-assemblies of sodium N-[4-(n-dodecyloxy)benzoyl]-l-aminoacidates in water

Three amino acid-derived chiral surfactants, sodium N-[4-(n-dodecyloxy)benzoyl]-L-leucinate (SDBL), sodium N-[4-(n-dodecyloxy)benzoyl]-L-isoleucinate (SDBIL), and sodium N-[4-(n-dodecyloxy)benzoyl]-L-threoninate (SDBT), were synthesized, and their aggregation behavior was studied in aqueous solution. Surface tension, fluorescence probe, dynamic light scattering, nuclear magnetic resonance (NMR), gel permeation chromatography, circular dichroism, and optical as well as transmission electron microscopic techniques were utilized to characterize the self-assemblies formed by the amphiphiles. Results of these studies reveal that the surfactants have a very low critical aggregation concentration (cac) and they form spherical vesicles spontaneously in dilute aqueous solution. The mean diameters of the vesicles were measured to be in the range of 130-190 nm. 1H NMR spectra indicated hydrogen bonding between the amide groups near the surfactant headgroup, which is one of the driving forces for vesicle formation. The vesicle formation is more favored at a pH of about 7.0. The amphiphiles also form chiral helical aggregates at relatively higher concentrations as indicated by circular dichroism spectra. The stability of the vesicles was also evaluated with respect to the surfactant concentration, pH, temperature, and aging. The vesicles have a tendency to transform into elongated vesicles (closed tubules) or rodlike micelles with an increase of the surfactant concentration and/or pH. On the basis of the results obtained from different studies, phase diagrams for all three water/amphiphile systems have been constructed. The studies have further shown that the stereogenic center at the amino acid side chain has a significant effect on the aggregation properties of the amphiphiles and on the stability of the self-assemblies.     

阴离子孪连表面活性剂的合成及其表/界面活性研究

合成了疏水链长度不同和连接基长度不同的7种系列阴离子孪连表面活性剂,研究了它们的表/界面活性。结果表明,它们有较低的表面张力和临界胶束浓度(CMC),有很好的表面活性。它们的CMC都在10-5~10-6mol/L之间,表面张力在26·5~34mN/m之间。它们有非常好的抗一价、二价盐的能力。除了C16-C2-C16在高于5%的NaCl溶液中会产生析出外,其余孪连表面活性剂都能耐盐20%以上。随着盐浓度的增加,孪连表面活性剂与烷烃间的界面张力逐渐降低,能达到10-3mN/m。与中原油田原油间的界面张力能降低到10-3~10-4mN/m,表明它们可应用于特高矿化度油藏提高采收率。     

Are hydrotropes distinct from surfactants?

The physicochemical properties of a homologous series of sodium p-n-alkylbenzoates have been investigated. The objective was to determine whether there is a clear transition point from hydrotropic to surfactant-like behavior with increasing alkyl chain length n, so as to shed clear light on the aggregation mechanism of so-called "hydrotropes". Electrical conductivity measurements were used for a first estimation of the critical aggregation concentrations (cac). As for classical surfactants, log(cac) depends on alkyl chain length n, but two branches of behavior were observed: one having a gradient typical of long chain fatty acid salts and the other with a more shallow dependence. Surface tension (γ) measurements of high purity aqueous solutions were used to generate limiting headgroup areas A(cac), which were in the range (40-50 ?(2)) being consistent with monolayer formation. Small-angle neutron scattering conclusively shows that the lower chain length homologues (classed as hydrotropes) exhibit sharp transitions in aggregation as a function of bulk concentration, typical of regular surfactants. As such, there is little to suggest from this study that hydrotropes differ in association behavior from regular surfactants.     

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.