Micellar effects of a triazole-based cationic gemini surfactant on the rate of a nucleophilic aromatic substitution reaction

The reaction between 2,4-dinitrochlorobenzene (DNCB) and hydroxide ion was studied spectrophotometrically at 25 °C in micelles of a triazole-based cationic gemini surfactant 18-triazole-18 or micelles of the conventional cationic surfactant CTAB. Both CTAB and 18-triazole-18 accelerated this nucleophilic aromatic substitution reaction. The binding constant of the substrate to the micelle, K _S, for 18-triazole-18 (K _S=335 M⁻¹) was found to be much larger than that for CTAB (85 M⁻¹) by fitting the kinetic results with pseudophase ion-exchange (PIE) model, which suggests that DNCB binds with gemini micelles more easily than it does with CTAB micelles. It was also found that 18-triazole-18 catalytic system was in accordance with PIE model at surfactant concentrations below ca. 0.5 mM, above which the increase of viscosity and the change of micelle size with increased surfactant concentration may remarkably influence the reaction. This was quite different from the reaction catalyzed by micelles of the conventional surfactant CTAB.     

Rheology of novel self-thickening cationic gemini surfactant solutions

A new cationic Gemini surfactant (25-HP-25) was synthesized with eruamidopropyl dimethylamine and epichlorohydrin, and its solution is self-thickening. The rheological properties of 25-HP-25 and 3-chloro-2-hydroxypropyl eruamidopropyl dimethyl ammonium acetate (EDAA) solutions were compared. The solution of EDAA behaves as Newtonian fluid (1?s^?1??1). Whereas the 25-HP-25 micelle solution (2?wt%) exhibits higher viscosity, which is about three hundred times than that of EDAA solution at low shear rate (γ??1). Especially, the 25-HP-25 solution shows obvious thixotropy, and with the increase of concentration, the viscoelasticity becomes better. Furthermore, the compaction of network structures has been confirmed by cryo-field emission scanning electron microscopy (cryo-FESEM) micrographs. This work is expected to enrich the research field of self-thickening surfactant.     

Small-angle neutron-scattering study and micellar model of the gemini (phenylenedimethylene)bis(n-octylammonium)dibromide surfactant micelles in water

The microstructure of the micelles formed in aqueous solution by gemini surfactants with aromatic spacers, [Br(CH₃)₂N⁺(C _m H_{2 m +1})-(Ph)-(C _m H_{2 m +1})N⁺(CH₃)₂Br, m=8 and Ph = o-, m- or p-phenylenedimethylene] has been examined by small-angle neutron scattering. Aggregation of the gemini surfactants with an o-phenylenedimethylene spacer brings about formation of premicelles and small micelles at concentrations below the second critical micelle concentration, while above this concentration marked micellar growth and variation in shape occurs. It is suggested that the minimum aggregate formed at this critical micelle concentration may be the trimer or tetramer and that this result supports the mechanism of “gemini → submicelle → assembly” for micellar growth. Received: 8 September 1998 Accepted in revised form: 27 November 1998     

Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for nucleophilic substitution reaction

A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups（（diethylhexanedioate） diyl-a,v-bis（dimethyl dodecyl ammonium bromide） referred to as 12-10-12）was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and1 HNMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.     

Effect of cationic gemini surfactants on the hydrolysis of carboxylate and phosphate esters using hydroxamate ions

The kinetics of the hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl diphenyl phosphate (PNPDPP) by hydroxamate ions mediated by gemini surfactants with quaternary ammonium bromide (16-n-16,2Br⁻, n = 3, 4, 6, 12) and pyridinium chloride (12py-n-py12,2Cl⁻, n = 3, 4) head group have been investigated at 27 °C. The gemini surfactant with the pyridinium head group, 12-py-4-py12,2Cl⁻ (tetramethylene-1,4 bis dodecylpyridinium chloride) shows a large rate acceleration effect than that with an ammonium head group, 16-12-16,2Br⁻, relative to those in water. The apparent pK _a of the hydroxamic acids have been determined in the presence of gemini surfactants. Catalytic system N-phenylbenzohydroxamate/12py-4-py12,2Cl⁻ demonstrated over ~1,590-fold and ~255-fold rate enhancement in the hydrolysis of PNPA and PNPDPP, respectively, for the identical reaction performed in buffer aqueous media at 27 °C. The second order rate constant and binding constants for reactions were determined employing pseudophase model for micellar catalysis.     

Aqueous two-phase system of an anionic gemini surfactant and a cationic conventional surfactant mixture

The aqueous two-phase system formed by the mixture of dodecyltrimethylammonium bromide (DTAB) with a gemini surfactant O,O′-bis(sodium 2-lauricate)-p-benzenediol (C₁₁pPHCNa) has been studied. Two two-phase regions were observed, one was a wide region in the cationic surfactant-rich side and the other in the vicinity of R = 1:1, where R is the mixing mole ratio of DTAB to C₁₁pPHCNa in global solution. Multi-lamellar vesicles are formed in the concentrated upper phase of cationic surfactant-rich systems and spherical aggregates in the concentrated bottom phase at R = 1:1. The microstructure of the solution and the phase behavior of the aqueous two-phase system strongly depended on the total concentration and the composition of the system.     

小分子有机添加物对胶团催化的影响

表面活性剂胶团对化学反应的催化作用具有重要的理论和实际意义^[1-2],在影响胶团催化的诸因素中,有机添加物的影响很受重视,这是因为有机物的加入既可能改变介质的性质,也可能对胶团的结构,大小,电性质产生影响,至今对添加有机物影响的研究大多为定性描述,缺少定量处理的结果,本文初步研究了小分子有机添加物异丙醇（i-PrOH),叔丁醇（t-BuOH),异戊醇（i-PeoH)和苯甲醛（PhCHO)对2－4－二硝基氯苯（DNCB）在溴代十六烷基三甲铵（CTAB）阳离子胶团训与NaOH反应的准一级反应速率常数k1 的影响,应用假相离子交换（PIE）模型的基本公式对实验结果进行了定量处理,并用胶团结构的变化对实验结果进行了解释。     

Membrane electrodes sensitive to doubly charged surfactants. Application to a cationic gemini surfactant

The response of a membrane electrode is not always identical to that of a redox electrode. Indeed, in the case of membrane electrode the response is not due to a redox equilibrium but to a cross-membrane potential. So, the membrane electrode's response depends mainly on the carrier system and the nature of the membrane. The properties of the membrane can favour several reactions giving rise to different ionic species diffusing in the membrane. The expression of the cross-membrane potential thus depends on the number and quantities of these ionic species. To illustrate this, we established the equations for the case of a two-charge cation detected by a univalent charged carrier. We show that the Nernstian response is not applicable to membrane electrodes. This approach allowed us to interpret results obtained with a cationic gemini surfactant-selective electrode prepared in the laboratory. To prove the well working of this electrode, we determined the critical micelle concentration in water and several NaBr solutions (0.004, 0.006, 0.01 and 0.02 M) from which the counterion binding has been determined.     

Applications of cationic gemini surfactant in preparing multi-walled carbon nanotube contained nanofluids

Stable homogeneous nanofluids of multi-walled carbon nanotubes (MWNTs) were prepared by using gemini cationic surfactant trimethylene-1,3-bis (dodecyldimethyl ammonium bromide), abbreviated as 12-3-12,2Br⁻¹, as dispersing agents. Zeta potential and FT-IR measurements were employed to investigate the adsorption mechanism of 12-3-12,2Br⁻¹ on MWNTs. The interactions between MWNTs and 12-3-12,2Br⁻¹ through hydrophobic segments cause hydrophilic MWNT-suspended medium interfaces with high positive charges, which enables the nanofluids to be stable for long periods. At relatively low temperatures the superfluous surfactant molecules form stable layer or column micelles, making an increase in the viscosity of nanofluids. Only 0.6 wt% gemini surfactant was used to obtain 0.5 wt% MWNT dispersions. The dispersions show no MWNTs precipitation for at least 5 weeks.     

2,4-二硝基氯苯衍生高效液相色谱法测定饮品中牛磺酸含量

建立了饮品中牛磺酸的高效液相色谱(HPLC)测定方法。采用2,4-二硝基氯苯90℃下衍生30 min,冷至室温后离心,取上清液10μL进样分析。以甲醇-KH2PO4为流动相梯度洗脱,360nm紫外检测,柱温20℃,流速1 mL/min。结果显示牛磺酸至少在0.02～200 mg/L范围内线性良好(r=0.999),回收率在97.5%～114.0%之间,保留时间和峰面积的相对标准偏差(RSD)(n=6)分别为0.40%和5.8%,方法已用于饮品中牛磺酸含量的测定。     

新型腰果酚双子表面活性剂的合成及表面活性

以天然生物质腰果酚、1,3-二溴丙烷及氯磺酸为原料,通过醚化、磺化及中和三步反应合成了一类新型的腰果酚基磺酸盐双子(Gemini)表面活性剂.采用傅立叶转换红外光谱仪和核磁共振谱仪表征了产物的结构;采用滴体积法测定了腰果酚Gemini表面活性剂的表面张力,研究了水溶液的表面性质,并与相应的单基腰果酚基磺酸盐表面活性剂进行了对比.结果表明:腰果酚Gemini表面活性剂水溶液的临界胶束浓度(cmc)为6.20×10-2 mmol.L-1,远小于相应的单基腰果酚表面活性剂水溶液的cmc(8.40mmol.L-1);其临界表面张力γcmc为36.92mN.m-1,与单基腰果酚表面活性剂水溶液的相近(γcmc为38.41mN.m-1).与此同时,腰果酚Gemini表面活性剂水溶液的最小分子截面积Amin为0.27nm2,比相应的单基表面活性剂水溶液的小得多.     

Rheological and thermo-responsive characteristics of the mixed aqueous solution of gemini cationic surfactant and hydroxyl naphthalene carboxylic acid sodium

The new thermo-switchable wormlike micellar systems were developed by mixing the gemini cationic surfactant, 2-hydroxypropyl-1,3-bis (dimethylmyristylammonium chloride) (14-3(OH)-14(2Cl) and sodium 1-hydroxynaphthalene-2-carboxylate (1SHNC) and sodium 2-hydroxynaphthalene- 3-carboxylate (2SHNC) in a certain concentration range. Their viscoelastic and thermos-responsive behaviors as a function of the salts concentration or temperature were investigated via rheological and cryo-TEM investigations. The results demonstrated that the zero-shear viscosity (η₀) significantly increased while raising salt concentrations above a threshold concentration (C_S*) until reaching maximum and then decreased. For the mixed solutions before the maximum, the zero-shear viscosity linearly decreased with increasing temperature and conformed to the Arrhenius law. However, for those mixed systems displaying thermo-responsive characteristic after the summit, the curve of η₀ as a function of temperature exhibited a maximum over the whole temperature range, namely, the systems showed thermo-thickening and thermo-thinning behaviors at low and high temperatures. The abovementioned phenomena were explained by the formation of hydrogen bond in 14-3(OH)-14(2Cl) molecules and the different solubility of SHNC under different temperatures, and the transition mechanisms of the aggregates were analyzed accordingly.     

Synthesis of conducting polyaniline using novel anionic Gemini surfactant as micellar stabilizer

The Gemini surfactant 9B-4-9B containing sodium sulfonate as hydrophilic head group was synthesized based on nonylphenol and characterized by FTIR, ¹H NMR spectroscopy and the surface tension measurement. The CMC and C₂₀ of the 9B-4-9B were smaller than that of sodium dodecylbenzene sulfonate and sodium dodecylsulfate, respectively, indicating excellent efficiency of micelle formation and reduced surface tension. Conducting polyaniline salts were synthesized by chemical oxidative micellar polymerization of aniline in water firstly using Gemini surfactant 9B-4-9B as the micelle stabilizer and ammonium peroxydisulfate as the oxidant at 0 °C. The stable polyaniline dispersions have been obtained when the molar ratio of the 9B-4-9B to aniline was equal to or above 0.5 used in the polymerization system. The obtained granular polyaniline particles with the size of 1-2 μm were characterized by FTIR, UV-Vis, SEM, WAXD and conductivity measurement.     

pH reversible micelle transition of a tertiary amine-based gemini surfactant in aqueous solution

In this work, we prepared a tertiary amide-based gemini surfactant (DSTAPA), which contained two pH-sensitive tertiary amide head groups. Then the molecule state distribution and self-assembly transition of the surfactant in aqueous solution were investigated under different pH conditions. The DSTAPA molecules were on the states of double cationic (DSTAPAH²⁺), single cationic (DSTAPAH⁺), and double tertiary amine groups (DSTAPA) under acidic, neutral, and basic conditions, respectively. With the variation of the molecule states, the sample was water-like below pH of 6.8 and immediately transformed to gel-like fluid between pH of 6.8 and 7.8, then changed to white precipitate with the further increase of pH value. Furthermore, the microstructure and regulation mechanism were investigated by rheological measurements, dynamic light scattering, and cryogenic transmission electron microscopy. The appearance and micelle transitions of the DSTAPA aqueous solution are actually owing to the spherical–worm-like micelle transition, leading to dramatic viscosity increase and hydrogel formation. This transition was completely reversible and repeated for at least three cycles. Finally, a reasonable mechanism of the transition was proposed based on the viewpoints of the molecular states and micelle structures. The DSTAPA aqueous system with pH-reversible property has a great potential application in oil and gas production.     

Synthesis and surface properties of PDMS–acrylate emulsion with gemini surfactant as co-emulsifier

Composite latex particles of acrylate and polydimethylsiloxane (PDMS) with high PDMS content was prepared by emulsion copolymerization and characterized by particle size analyzer, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). With gemini surfactant as the co-emulsifier in the system, the PDMS content in the system reached 50%, which was far higher than the other reported values. Through the characterization of the particle size analyzer, the particle size augmented with the increase of the amount of PDMS, which could be said that the polysiloxane had participated into the reaction and had been introduced into the colloid particle. The results of FTIR indicated that almost all the monomer had been exhausted in the reaction because there was no C=C and D₄ characteristic peaks in the spectrum. Besides the surface properties also were measured by surface tension analysis, water absorption, and the static contact angle, it could be found that with the increase of polysiloxane content, the excellent properties acquired by PDMS were clearly revealed by the findings, such as the decrease of surface tension and water absorption, and the increase of static contact angle. All the measurements were consistent with the conclusion that the composite latex particles of polysiloxane and acrylate with high siloxane content had been prepared successfully.     

16-n-16型双子表面活性剂稳定纳米金的制备及其催化性能

双子表面活性剂由于其特殊的两亲结构可以作为纳米金颗粒(AuNPs)的表面稳定剂,但双子表面活性剂结构中的连接基团对AuNPs的粒径大小及稳定性有显著影响。本文制备了16-n-16(n=2,3,4和6)型双子表面活性剂稳定的金纳米溶胶,考察了体系pH对AuNPs稳定性的影响,并测试了其对4-硝基苯酚加氢还原体系的催化效果。结果表明,16-4-16和16-3-16对AuNPs的稳定性效果较好,所制备的AuNPs中,16-3-16-AuNPs在不同pH的环境中稳定性最好,而16-4-16-AuNPs在4-硝基苯酚加氢还原反应中的催化活性最佳。     

Micellization behavior of [C16-12-C16], 2Br gemini surfactant in binary aqueous-solvent mixtures

The micellization behavior of bis cationic gemini surfactant, N,N′-dihexadecyl-N,N,N′,N′-tetramethyl-1,12-dodecanediammonium dibromide [C₁₆H₃₃N⁺(CH₃)₂-(CH₂)₁₂-N⁺(CH₃)₂C₁₆H₃₃, 2Br⁻] has been studied in binary aqueous mixtures of dimethyl sulfoxide, methanol, 1,4-dioxane, glycerol and ethylene glycol by conductivity and surface tension measurements at 300 K. The critical micellar concentration, degree of micelle ionization (α), surface excess concentration (Г_max), minimum surface area per molecule of surfactant (A_min), Gibbs free energy of micellization (ΔG_m°), the surface pressure at cmc (π_cmc), and the Gibbs energy of adsorption (ΔG_ad°) of the gemini surfactant have also been determined. The cmc, α, A_min increases where as (ΔG_m°), Г_max, and π_cmc decreases with increasing volume percentage of the solvents in the solvent–water binary mixture. The interfacial properties of the gemini surfactant, solute–solute, solvent–solute interactions and the effectiveness of a surface-active molecule in binary solvent systems have been discussed.     

以一种新型Gemini表面活性剂作为介孔模板剂通过转晶过程合成介孔ZSM-5分子筛

将一种新型Gemini表面活性剂,丙撑基双(十八烷基二甲基氯化铵)[C18H37(CH3)2–N+–(CH2)3–N+–(CH3)2C18H37]Cl2(C18-3-18),作为介孔模板剂用于水热法合成介孔ZSM-5分子筛.结果表明,在130 oC低温晶化即可高效合成介孔ZSM-5分子刷.C18-3-18的加入量可影响到所合成介孔ZSM-5分子筛的相对结晶度和织构性质,它的形成遵从一个转晶过程.在合成初期,凝胶中介孔模板剂C18-3-18的使用导向了介孔材料的生成;随后在TPABr的模板作用下,介孔材料慢慢转晶生成具有MFI结构的介孔ZSM-5;然后所合成的介孔ZSM-5晶粒进一步长大并聚集形成块状颗粒,同时产生晶间介孔.C18-3-18作为介孔导向剂不仅可用于合成介孔ZSM-5分子筛,也可用于其它介孔分子筛的合成中.     

Spontaneous aggregate transition in mixtures of a cationic gemini surfactant with a double-chain cationic surfactant

Controllable aggregate transitions were realized by mixing two kinds of cationic surfactants, hexylene-1,6-bis(dodecyldimethylammonium bromide) (C(12)C(6)C(12)Br(2)) and didodecyldimethylammonium bromide (DDAB). It was found that two parameters are the main factors determining the aggregation behavior of the mixed system, the total concentration of DDAB and C(12)C(6)C(12)Br(2) (C(T)), and the mole fraction of DDAB in the mixtures of DDAB and C(12)C(6)C(12)Br(2) (X(DDAB)). How these two parameters act on the aggregate transitions was studied in detail by various measurements including surface tension, turbidity, electrical conductivity, ζ potential, isothermal titration microcalorimetry, dynamic light scattering, cryogenic transmission electron microscopy, and (1)H NMR. When C(T) was constant, spontaneous vesicle-to-micelle transitions were found with decreasing X(DDAB) at high C(T). When X(DDAB) was constant, aggregate transitions were generated by gradually increasing C(T), depending on different X(DDAB) ranges. At X(DDAB) < 0.6, small spherical aggregates formed first and then transferred to vesicles, and finally the vesicles transitioned to micelles. At X(DDAB) ≥ 0.6, the progressive increase in C(T) led to aggregate transitions on the order of the arising of vesicles, the continuous growth of vesicles, the disruption of vesicles into micelles, and the final coexistence of vesicles and micelles. The hydrophobic interaction and electrostatic repulsion between DDAB and C(12)C(6)C(12)Br(2) together with the related degree of ionization and hydration of the surfactants were gradually adjusted by changing the ratio and the total concentration of these two surfactants, which should be responsible for the complicated aggregation behavior.