Gemini Surfactants Foam Formation Ability and Foam Stability Depends on Spacer Length

A series of cationic gemini surfactants containing different spacer length were synthesized and analyzed structurally. It was shown that the surface tension (σ) and critical micelle concentration (CMC), which had a maximum for the n-C₄H₈ spacer depended on the spacer length. The foaming ability and foam stability are high for the gemini surfactants with short spacers (C₂H₄ to n-C₄H₈), while longer spacers lead to a distinct decrease of these foam parameters. Foaming properties are discussed in terms of configuration and conformation of a surfactant molecule and in relation to micellization state kinetic.     

阳离子双子表面活性剂的应用研究进展

介绍了阳离子双子表面活性剂近年来在新材料制备、抗腐蚀、杀菌、三次采油、织物染整、生物技术及造纸工业等方面的应用。     

新型Gemini阳离子表面活性剂的合成和性能（3）—在烷基链中引入易水解基团促进生物降解

概述了烷基链中含有酰受基和酯基的Gemini阳离子表面活性剂的合成,表面活性和生物降解性,含有酰胺基的Gemini阳离子具有优良的表面活性,但几乎不能生物降解,而含有酯基的Gemini阳离子不仅具有优良的表面活性,而且具有良好的生物降解性。     

新型Gemini阳离子表面活性剂的合成和性能（1）：从长链烷基二甲基胺及其盐酸盐和环氧氯丙烷合成双烷基双季铵盐阳离子

概述了从长链烷基二甲基叔胺及其盐酸盐和环氧氯丙烷或其他连接剂在温和条件下合成新型双烷基双季铵盐型阳离子表面活性剂的方法,产品的表面活性以及烷基链长、连接基团结构对产物表面活性的影响。     

非离子Gemini表面活性剂的合成进展

双子（Gemini）表面活性剂是近年来迅速发展的一类新型表面活性剂,它是指分子中具有双亲水基和双亲油基的由一个间隔基团连接的表面活性剂,与传统表面活性剂相比,Gemini表面活性剂具有许多优异性能。相对而言,近年来非离子Gemini表面活性剂研究远较阴离子和阳离子的Gemini表面活性剂研究少。本文对非离子Gemini表面活性剂的研究现状进行了概述,以期对非离子Gemini类表面活性剂的研究与应用开发有所裨益。     

Preparation,Characterization and Properties of Novel Cationic Gemini Surfactants with Rigid Amido Spacer Groups

A series of novel cationic gemini surfactants with rigid amido groups inserted as the spacers, named C ₁₂ ‐PPDA‐C ₁₂ , C ₁₄ ‐PPDA‐C ₁₄ and C ₁₆ ‐PPDA‐C ₁₆ , were synthesized by a two‐step reaction with dimethyl terephthalate, N,N‐dimethyl propylene diamine and alkyl bromide as raw materials. The chemical structures of the prepared compounds were confirmed by IR, ¹H and ¹³C NMR and element analysis. Surface activity properties of the synthesized compounds were investigated by surface tension, electrical conductivity and fluorescence. Increasing the number of carbon atoms in the hydrophobic alkyl chain, decreased the critical micelle concentration (CMC), surface tension at the CMC and the minimum surface area. Other relevant properties including foaming ability and emulsion stability were investigated. The results indicated that the synthesized gemini surfactants possess good surface properties, emulsifying properties and steady foam properties.     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

双子季铵盐的静态合成及表征

以1,5-二溴戊烷和三乙胺为原料、无水乙醇为溶剂,水浴回流(未使用搅拌)条件下合成阳离子型双子季铵盐(CH3CH2)3N(CH2)5N(CH2CH3)3·2Br。此种静态合成方法不仅氧化副反应少,而且避免了洗涤和重结晶操作中大量有毒有害溶剂的使用。同时,元素分析及液体核磁共振表征结果证明了静态合成法能够获得高纯度目的产物。该方法合成效率高、操作简单、环境友好,易于双子季铵盐应用领域的进一步拓宽。     

季铵盐双子表面活性剂的合成和表面活性

以吗啉和溴代烷为原料,合成了两种季铵盐双子表面活性剂(m-6-m,m=10,12),并用IR和1HNMR表征了其结构。测得28℃时,12-6-12和10-6-10的表面张力(γCMC)分别为26.45 mN/m和25.55 mN/m;临界胶束浓度(CMC)分别为1.0 mmol/L和3.1 mmol/L;pC20值分别为3.48和3.03;比表面过剩(Γmax)分别为2.72×10-6mol/m2和2.80×10-6mol/m2;分子最小截面积(Amin)分别为0.611 nm2和0.593 nm2。结果表明,该季铵盐双子表面活性剂与相同离子头基及烷基链的单季铵盐表面活性剂相比,CMC低一个数量级,γCMC相差不大。     

Interaction of Myoglobin with Cationic Gemini Surfactants in Phosphate Buffer at pH 7.4

The interactions between myoglobin, a monomeric water soluble heme protein, and cationic gemini surfactants 14‐3‐14, 14‐4‐14, 14‐5‐14 have been studied in phosphate buffer at pH 7.4 using different techniques such as surface tension, UV–visible spectroscopy, fluorescence spectroscopy and circular dichroism. Myoglobin is a surface active protein and it is bound with surfactant molecules. The spin states of the heme group of myoglobin change depending on the concentration of surfactant. The unfolding process of protein in the presence of surfactant is observed from fluorescence spectra. With increasing surfactant concentration, α‐helicity of myoglobin decreases with the appearance of β‐sheet and random coil. The extent of interaction of myoglobin with gemini surfactant increases with increasing spacer length.     

Salt Effect on the Solution Properties of Cationic Gemini/Conventional Surfactants in the Presence of the Nonionic Polymer Hydroxypropylmethyl Cellulose

In this article, we report the salt effect on interaction of a water-soluble polymer hydroxypropylmethyl cellulose (HPMC) with the cationic Gemini surfactant (ethane-1, 2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride, 16-E2-16), and also its monomeric counterpart cetyltrimethylammonium chloride (CTAC) using the tensiometric method. Surface tension of the amphiphiles diminished in the presence of the polymer as well as salts; eventually, the polymer gets saturated with the surfactant and there is no further change of surface tension of the solution. Interaction between the polymer and surfactant starts at the critical aggregation concentration (CAC) that is stronger for 16-E2-16 than CTAC. CAC and critical micelle concentration (CMC) values of the surfactant-polymer binary mixtures at various concentrations of the polymer were determined. CAC as well as CMC of 16-E2-16 are considerably lower than CTAC. The inorganic salts (KCl and KBr) have a considerable influence on the polymer–surfactant interaction.     

Aggregation and Thermodynamic Properties of Some Cationic Gemini Surfactants

In this study, the gemini surfactants of the alkanediyl-α-ω-bis(alkyl dimethyl ammonium) dibromide type, on the one hand, with different alkyl groups containing m carbon atoms and an ethanediyl spacer, referred to as “m-2-m” (m = 10, 12 and 16) and, on the other hand, with n-C₁₆ alkyl groups and different spacers containing s carbon atoms, referred to as “16-s-16” (s = 2, 6, 10 and Ar (8)) have been synthesized, purified and characterized. The critical micelle concentration (CMC), micelle ionization degree (α) and Gibbs free energy of micellization (∆G _mic) of these surfactants and the monomeric cationic surfactants DTAB and CTAB have been determined by means of electric conductivity measurements. In addition, the temperature dependence of the CMC was determined for the 10-2-10 gemini surfactant. The CMCs of the gemini surfactants are found to be much lower than those of the corresponding monomeric surfactants and the effect of the hydrophobic alkyl chain length is more important than that of the spacer. The CMC of 16-s-16 passes through a maximum of (or around) s = 6 and then decreases for s = 10. The presence of a maximum CMC is explained by the contribution of a change of conformation of the surfactant with increasing spacer chain length. The changes of α with s and m are found qualitatively similar to those found for CMC values. The values of ∆G _mic are more negative for the dimers than for the monomers and also change with an increasing spacer carbon number, as CMC values do. The thermodynamic parameters of micellization indicate that the micellization of 10-2-10 is enthalpy driven.     

Synthesis and Thermodynamic Properties of Rosin-Based Cationic Gemini Surfactants

A series of rosin-based cationic gemini surfactants with different spacer length (n = 2, 3, 4) were synthesized and characterized. Surface activity and micellization parameters including the critical micelle concentration, the degree of counterion dissociation, and thermodynamic functions of micellization in aqueous solutions have been investigated. Free energy perturbation was performed to study the enthalpy-entropy compensation of the synthesized gemini surfactants in aqueous solutions. The experimental results showed that the micellization of rosin-based gemini surfactants in aqueous solutions is a spontaneous and entropy-driven process. The micellization process was found to follow the entropy–enthalpy compensation phenomenon.     

Amido-Amine-Based Cationic Gemini Surfactants: Thermal and Interfacial Properties and Interactions with Cationic Polyacrylamide

Experimental studies were conducted to investigate thermal and interfacial properties of two in‐house synthesized amido‐amine‐based cationic gemini surfactants namely: dodecanoic acid [3‐({4‐[(3‐dodecanoylamino‐propyl)‐dimethyl‐amino]‐butyl}‐dimethyl‐amino)‐propyl]‐amide dibromide ( 12‐4‐12 ) and dodecanoic acid [3‐({6‐[(3‐dodecanoylamino‐propyl)‐dimethyl‐amino]‐hexyl}‐dimethyl‐amino)‐propyl]‐amide dibromide ( 12‐6‐12 ). Thermogravimetric analysis showed the excellent thermal stability of surfactants and no structural degradation was observed at temperatures up to 250 °C. The long‐term thermal stability of the surfactants was investigated with the aid of spectroscopic techniques such as nuclear magnetic resonance (NMR (¹H and ¹³C) and Fourier transform infrared (FTIR) spectroscopy. Both surfactants were found to be thermally stable, and no changes in structure were observed after aging for 10 days at 90 °C. The interfacial tension of the surfactants was measured at three different temperatures (30, 60, and 80 °C), and the results showed a decrease in interfacial tension with increasing temperature and increasing spacer length of the surfactants. Rheological measurements were used to assess the interactions between the cationic gemini surfactant and cationic polyacrylamide. The addition of cationic surfactant reduced the viscosity and storage modulus of the polymer at low shear rate and frequency due to surfactant–polymer interactions and charge screening. The investigated surfactant–polymer system has great potential in high‐temperature carbonate reservoirs, where conventional anionic surfactants are not recommended due to high adsorption.     

Counterion Effect of Cationic Surfactants Upon the Interaction with Poly(methacrylic acid)

This work investigates decylammonium salts, with inorganic (chloride and thiocyanate) and organic (acetate and butyrate) counterions, in interaction with poly(methacrylic acid) (PMA). The study is conducted by means of surface tension, relative viscosity and pH measurements. The role of the methyl group in PMA appears by comparison with analogous mixtures of poly(acrylic acid) (PAA). In aqueous solution, a non-cooperative interaction between the surfactant and the hydrophobic microdomains (HMD) of PMA starts first. With surfactant addition, micellar aggregates bound onto the polymer chain appear at a concentration T ₁, which is higher than for the analogous PAA systems, but lower than the respective CMC. T ₁ is lower for chloride than for thiocyanate and lower for acetate than for butyrate. Depending on the counterion, the HMD conceal or expose carboxyl groups, with influence upon the interaction strength and the bulk and surface behavior. Stronger interactions and maxima of surface tension and relative viscosity appear for the systems with organic counterions. An estimation of the interaction strength shows weaker surfactant interactions with PMA than with PAA, and that acetate induces the strongest interaction while thiocyanate the weakest.     

以金刚烷为联接链的Gemini表面活性剂的合成及性能

以1,3-金刚烷二甲酸为起始原料,合成了3种以金刚烷为联接链的具有不同疏水链长的Gemini表面活性剂(n P-Ad-Pn,n=12,14,16)。用FTIR、1HNMR、ESI-MS对目标化合物的结构进行了表征。采用表面张力法、电导率法和稳态荧光光谱法测定了金刚烷Gemini表面活性剂的表面活性、胶束化热力学参数和胶束微极性。结果显示:白金环法测得n P-Ad-Pn在25℃下的临界胶束浓度分别为6.0×10-4、1.0×10-4和2.5×10-5mol/L,ΔG0m和ΔH0m均为负值说明表面活性剂胶束形成是一个自发且放热的过程。化合物对金黄色葡萄球菌、枯草杆菌、大肠杆菌、绿脓杆菌、副溶血性弧菌抑菌活性的测定结果表明,12P-Ad-P12对5种菌株的MIC值在0.2~4.2mg/L,显示出很强的抑菌活性。     

Surface Activity and Cleavability of Gemini Surfactants Featuring Hydrophilic Spacer Groups

In this study we prepared and characterized a series of novel ester-linked gemini surfactants, featuring ester bonds in their structures, through the reactions of polyethylene glycol (PEG400) with various fatty acids (C8?CC18). These gemini surfactants exhibit excellent surface activities, as evidenced by their surface tension, wetting power, and low-foaming and buffer abilities. We examine the influence of the concentrations of the ester-linked gemini surfactants on the surface tension, from which we obtain the critical micelle concentrations. Under basic conditions, each of these cleavable surfactants decomposes into a water-insoluble fatty acid and two water-soluble products; in contrast, they are stable under neutral and acidic conditions.     

Interaction Between Cationic and Anionic Surfactants: Detergency and Foaming Properties of Mixed Systems

The micellar and interfacial behavior of mixtures of the anionic surfactant (alcohol ether sulfate, AES) with quaternary ammonium type cationic surfactants dodecyltrimethyl ammonium chloride (DTAC), dodecyl-(2-hydroxyethyl)-dimethyl ammonium chloride (DHDAC), dodecyl-di(2-hydroxyethyl)-methyl ammonium chloride (DHHAC) were investigated by means of surface tension measurements. Various physicochemical properties such as surface activity parameters (CMC, γ _CMC, Г _max, A _min), the micellar and interfacial compositions (x ₁ ^m , x ₁ ^σ ), interaction parameters (β ^m , β ^σ ), and activity coefficients ( \(f_{1}^{m}\) , \(f_{2}^{m}\) , \(f_{1}^{\sigma }\) , \(f_{2}^{\sigma }\) ) were evaluated. The influence of the hydroxyethyl groups of cationic surfactant component on the physicochemical properties of mixed systems has been analyzed. It is observed that the CMC values of the three mixed systems decrease with increases in the number of hydroxyethyl groups of the cationic surfactant component. From the results of β ^σ and β ^m values, the interactions between molecules for the three surfactant mixtures at the air/liquid interface increase in the following order DHHAC/AES < DHDAC/AES < DTAC/AES, but it is the opposite for the interactions in mixed micelles. The detergency and foaming properties of mixed systems were also studied. As expected, complex surfactant systems exhibit good detergency and foaming properties.     

Influence of Nature of Spacer and Hydrocarbon Chain Length on Micellar Encapsulation of Polynuclear Aromatic Hydrocarbons by Carbohydrate Derived Non-Ionic Gemini Surfactants in Aqueous Ethanol Medium

Gemini surfactants with rigid aromatic spacer -CH₂-Ar-CH₂-: 6,6′-(N,N′-di(alkyl)-1,4-phenylenedimethylamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) and Gemini surfactants with flexible aliphatic spacer -(CH₂)₆-: 6,6′-(N,N′-di(2-hydroxyalkyl)-1,6-hexanediamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) have been synthesized, and their micellar properties for encapsulation of polynuclear aromatic hydrocarbons (PAH) viz. fluorene, anthracene, triptycene, and pyrene in aqueous ethanol medium have been studied by means of electronic spectroscopy. The micellar study reveals that nature of spacer and length of hydrocarbon chain of the surfactant has profound effect on micellar encapsulation of PAH. The surfactants with rigid aromatic spacer show greater encapsulation as compared to surfactants with flexible aliphatic spacer. Moreover, the more hydrophobic surfactant, i.e. the surfactant with a longer hydrocarbon chain, shows greater encapsulation toward PAH which are encapsulated in the order of their smaller size.