Preparation and Unimolecular-Micellization Behavior of Homopolymer of Surface-Active Monomer AMC14AB

(2-acrylamido) ethyl tetradecyl dimethylammonium bromide (AMC14AB) was polymerized in aqueous solution to form the homopolymer P(AMC14AB). The physicochemical properties of P(AMC14AB) in aqueous solution were mainly studied with fluorescent probe method, surface tension measurement and conductometry. The experimental results show that the aggregation morphology of P(AMC14AB) in aqueous solution is unimolecular micelle as expected. Being different from conventional multimolecular micelle systems, the unimolecular micelle system of P(AMC14AB) not only shows critical micellar concentration (CMC=0), (i.e.once added to pure water, the surface tension decreases immediately in spite how small the density is), but also the surface tension stays almost the same with the concentration increasing. That is to say, there is no mutational point on the relationship curve between surface tension and concentration. Furthermore, the unimolecular micelle system of P(AMC14AB) has no Krafft temperature, i.e. at any temperature, so long as it is dissolved in water, the unimolecular micelles will form. Besides this, for the solubilization of hydrophobic organic substances, the unimolecular micelle system of P(AMC14AB) is obviously different from the common multimolecular micelle system, having no turning point on the relationship curve between toluene solubilizaion amount and P(AMC14AB) concentration, and the solubilizing ability of the unimolecular-micelle system of P(AMC14AB) for hydrophobic organic substances is much higher than that of the conventional multimolecular micelle solutions of common surfactants, such as centyl trimethyl ammonium bromide.     

The Self-Association and Mixed Micellization of an Anionic Surfactant,Sodium Dodecyl Sulfate,and a Cationic Surfactant,Cetyltrimethylammonium Bromide: Conductometric,Dye Solubilization,and Surface Tension Studies

In the present study, we investigate the self-association and mixed micellization of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of SDS, CTAB, and mixed (SDS + CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C₂₀ (the surfactant concentration required to reduce the surface tension by 20 mN/m), Π_CMC (the surface pressure at the CMC), Γ_max (maximum surface excess concentration at the air/water interface), and A_min (the minimum area per surfactant molecule at the air/water interface)) of SDS, CTAB, and (SDS + CTAB) micellar/mixed micellar systems were evaluated. The thermodynamic parameters of the micellar (SDS and CTAB), and mixed micellar (SDS + CTAB) systems were evaluated.

A schematic representation of micelles and mixed micelles.     

两相催化1—十二烯氢甲酰化反应中混合胶束的作用研究

研究了RhCl(CO)(TPPTS)2催化-1-十二烯氢甲酰化反应中,十六烷基三甲基溴化铵（CTAB）与十二烷基硫酸钠（SDS）形成的混合胶束对反应的促进作用。研究结果表明,随SDS在混合表面活剂溶液中比例的增大,1-十二烯生成醛的转华率先增大后又降低,并从混合胶束的临界胶束浓度及混合胶束对底物增溶作用的变化对这一结果进行了讨论。     

THE EFFECT OF MIXED MICELLES OF SURFACTANTS ON THE ALKALINE HYDROLYSIS OF ESTERS

The alkaline hydrolysis of aromatic and normal aliphatic acid esters have been studied at 25°C In mixed micellar solution of surfactants (Brij35—SDS, Brij35 — DTAB, Brij35—TTAB.Brij35-CTAB. Triton X—100 —CTAB, Triton X— 100 —SDS) with UV spectrophotometry and the method of thermokinetics The critical mice liar concentrations of the corresponding systems have also been measured with UV spectrophotometry in this paper. K_jnln micellar pseudo-phase has been calculated- The ratios of ki.to ki.for all mixed micellar systems Investigated are less than 1. The results indicate that these reactions are inhibited by the mixed micelles and the mixed micelles exhibit a greater effect of Inhibition on the reactions than those do In corresponding single ones. The reason for this is that the micropolarity of the compact Stern layer of mixed micelle is lower, and the micro viscidity Is higher. The Inhibition effect! also depend on the hydrophobic chain length of the surfactants and the hydrophobicity of the substrate.     

单分子链胶束的胶束化行为与相关新概念的提出

采用水溶液均聚合方法,制备了阳离子型表面活性单体（2-丙烯酰胺基）乙基十四烷基二甲基溴化铵（AMC14AB）的均聚物,使用荧光探针法、表面张力测定及电导测定法,重点考察了均聚物P（AMC14AB）在水溶液中的胶束化行为与表面吸附现象．在水溶液中,均聚物P（AMC14AB）呈现单分子链胶束的聚集形态,具有零临界胶束浓度（CMC=0）,从开始加入P（AMC14AB）起,水溶液中随即产生单分子链胶束,不存在Krafft温度．P（AMC14AB）在溶液表面也发生表面吸附,使水的表面张力下降,即P（AMC14AB）也具有表面活性;随着浓度增大,表面吸附量增大,水的表面张力持续下降;当表面吸附达到饱和时,表面张力一浓度曲线上出现突变点,该点应该定义为饱和的表面吸附浓度（SSAC）,而不应该再称为临界胶束浓度．P（AMC14AB）单分子链胶束溶液对疏水有机物（甲苯）的增溶情况,明显不同于普通小分子表面活性剂十六烷基二甲基溴化铵（CTAB）的多分子胶束溶液,甲苯增溶量-P（AMC14AB）浓度的关系曲线上无突变点,而且对甲苯的增溶能力高于CTAB的多分子胶束溶液．     

Effects of a lysophosphatidylcholine and a phosphatidylcholine on the morphology of taurocholic acid-based mixed micelles as determined by small-angle X-ray scattering

We previously showed that Caco-2 cell absorption of β-carotene from taurocholic acid (TA)-based mixed micelles differed depending on the composition of the micelles. In this study, the shapes and sizes of TA-based mixed micelles, that is, mixed micelles of TA, 1-oleoyl-rac-glycerol (MG), oleic acid (OLA), and either 1-palmitoyl-sn-glycero-3-phosphocholine (MPPC; i.e., a lysophospholipid) or 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC; i.e., a phospholipid) (60:3:1:0.75–12) were determined by using small-angle X-ray scattering (SAXS). We found that increasing the ratio of MPPC in mixed micelles of TA, MG, OLA, and MPPC was responsible for the previously observed enhanced β-carotene absorption by Caco-2 cells and changed the micelle shape from core–shell spherical to core–shell ellipsoidal. In contrast, increasing the ratio of POPC in mixed micelles of TA, MG, OLA, and POPC was responsible for the suppressed β-carotene absorption by the cells, changed the micelle shape from core–shell spherical to core–shell ellipsoidal to core–shell cylindrical, and caused a rapid increase in micelle volume. These results will be useful for understanding the mechanisms that mediate β-carotene absorption by cells and for developing technologies to improve the intestinal absorption of lipophilic components of drugs and nutrients.     

Properties of polyethylene glycol (23) lauryl ether with cetyltrimethylammonium bromide in mixed aqueous solutions studied by self-diffusion coefficient NMR

NMR self-diffusion coefficient measurements have been used to study the properties of polyethylene glycol (23) lauryl ether (Brij-35) with cetyltrimethylammonium bromide (CTAB) in the mixed aqueous solutions with different mole fractions of CTAB. By fitting the self-diffusion coefficients to the two-state exchange model, the critical micelle concentrations of the two solutes in the mixed solutions (cmc*1 and cmc*2) were obtained. The critical mixed micelle concentrations (cmc*) were then evaluated by the sum of cmc*1 and cmc*2, which are in good agreement with the results measured by the surface tension method. The cmc* values are lower than those of the ideal case of mixing, which indicates that the behavior of the CTAB/Brij-35 system is nonideal. Moderate interactions between CTAB and Brij-35 in their mixtures can be deduced from the interaction parameters (betaM) based on the cmc* obtained by the NMR self-diffusion method. The compositions (x1) of the mixed micelles at different total surfactant concentrations were also evaluated. By using these results, a possible mechanism of mixed micellar formation and a picture of the formation of nonsimultaneous CTAB/Brij-35 binary mixed micelle were proposed. In contrast to the case of CTAB/TX-100 system, Brij-35 molecules have a tendency to form micelles first at any mole fraction of CTAB. The mixed micellar self-diffusion coefficients (Dm) increase slightly at lower CTAB molar ratios, and then speed up with increasing CTAB mole fraction.     

Aggregation behavior and catalytic activity of systems based on calix[4]resorcinarene derivatives and surfactants. 1. Mixed micellization of aminomethylated calix[4]resorcinarenes with cetyltrimethylammonium bromide in aqueous dimethylformamide

Mixed micellization of amphiphilic aminomethylated calix[4]resorcinarenes and phenols, which are their structural units, with the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous 10—70 vol % DMF decreases the critical micelle concentration; the resulting aggregates are larger than those in the CTAB—DMF—water systems. The micellization of CTAB with aminomethylated calix[4]resorcinarenes proceeds in two steps, while its micellization with phenols is a single-step process. The micellization characteristics depend on the structure and hydrophobicity of the amphiphilic compound and the concentration of DMF.     

苄泽类非离子表面活性剂与离子型表面活性剂复配性质研究

通过测定苄泽类非离子型表面活性剂Brij58、Brij76、Brij78与阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)复配体系的表面张力,研究了复配体系的形成胶束能力、降低表面张力效率、降低表面张力能力3种增效作用,并结合复配体系中表面活性剂分子间的相互作用参数进行了深入的讨论。研究结果表明,与阳离子表面活性剂复配时,Brij76/CTAB体系增效作用最强;与阴离子表面活性剂复配时,Brij58/SDS复配体系增效作用最强,而且苄泽类非离子型表面活性剂与阴离子表面活性剂复配增效作用更加显著。     

Model of cylindrical micelles with different endcaps

The system of alcohol (C₈OH) and hexadecyl trimethyl ammonium bromide (CTAB) was studied by molecular dynamics simulation, and the cylindrical (or rod-like) micelles with different endcaps were obtained. The simulation results presented the different terminal structures of the cylindrical (rod-like) micelles. According to the critical packing parameters of the micellar stability theory, the microscopic structures of cylindrical (or rod-like) micelles with different endcaps were analyzed. The shorter rod-like micelle was constituted by the cylindrical body and two swelling spherical endcaps, while the longer cylindrical (or rod-like) micelle had two spherical crown endcaps less than the hemisphere. The models of the cylindrical (rod-like) micelles were presented in detail based on the simulation results and the micellar stability theory.     

Distribution of emulsified monomers with different water solubility

The location and distribution of acrylic acid and styrene in emulsions made with a cationic surfactant, cetyltrimethylammonium bromide (CTAB), or an anionic surfactant, sodium dodecylsulfate (SDS), were determined with ultra-violet spectroscopy, conductivity, and potentiometry. In these systems, the acrylic acid remains in the aqueous phase near the micelle surface, whereas the styrene is located in the micelles or in emulsified droplets. In the absence of acrylic acid, some of the styrene is solubilized in the micelle interior and some is adsorbed at the micelle inner surface. Upon addition of acrylic acid, all the styrene is displaced to the center of the micelles. The interaction between acrylic acid and CTAB micelles is stronger than that between acrylic acid and SDS micelles. With CTAB, acrylic acid is adsorbed at the micelle surface, whereas with SDS, acrylic acid remains in the intermicellar solution. These differences can account for the differences reported in the emulsion copolymerization of acrylic acid and styrene using CTAB or SDS.     

Micellisation behaviour of mixtures of sodium dodecylsulphate and sodium lauroylsarcosinate in water

The critical micelle concentrations of binary mixtures of sodium dodecylsulphate (SDS) and sodium lauroylsarcosinate (SLAS) have been determined in water by conductivity measurements at different mole fractions for each of the components. The critical micelle concentrations were slightly lower than that predicted from ideal mixing theory indicating positive synergistic interactions in mixed micelle formation. The results of the mixed systems were analysed using the Regular Solution Theory and the approach based on the Gibbs–Duhem equation which allowed for the determination of the composition of the mixed micelle, the activity coefficients and the pair-wise molecular interaction parameter β. The β values were all negative at all mole fractions investigated, showing a slight deviation from ideality, with an average value of –0.27. The excess free energy of the mixed systems was also calculated and the values were all negative for the mixed systems studied, an indication that the mixed micelles are thermodynamically stable relative to the individual component. This thermodynamic parameter also exhibits symmetrical behaviour with respect to micellar composition suggestive of a regular solution behaviour of the mixed surfactant system.     

Mixed micelles of polyethylene glycol (23) lauryl ether with ionic surfactants studied by proton 1D and 2D NMR

(1)H NMR chemical shift, spin-lattice relaxation time, spin-spin relaxation time, self-diffusion coefficient, and two-dimensional nuclear Overhauser enhancement (2D NOESY) measurements have been used to study the nonionic-ionic surfactant mixed micelles. Cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) were used as the ionic surfactants and polyethylene glycol (23) lauryl ether (Brij-35) as the nonionic surfactant. The two systems are both with varying molar ratios of CTAB/Brij-35 (C/B) and SDS/Brij-35 (S/B) ranging from 0.5 to 2, respectively, at a constant concentration of 6 mM for Brij-35 in aqueous solutions. Results give information about the relative arrangement of the surfactant molecules in the mixed micelles. In the former system, the trimethyl groups attached to the polar heads of the CTAB molecules are located between the first oxy-ethylene groups next to the hydrophobic chains of Brij-35 molecules. These oxy-ethylene groups gradually move outward from the hydrophobic core of the mixed micelle with an increase in C/B in the mixed solution. In contrast to the case of the CTAB/Triton X-100 system, the long flexible hydrophilic poly oxy-ethylene chains, which are in the exterior part of the mixed micelles, remain coiled, but looser, surrounding the hydrophobic core. There is almost no variation in conformation of the hydrophilic chains of Brij-35 molecules in the mixed micelles of the SDS/Brij-35 system as the S/B increases. The hydrophobic chains of both CTAB and SDS are co-aggregated with Brij-35, respectively, in their mixed micellar cores.     

表面活性剂对纳米CaCO3形貌的调控

分别在AOT／异辛烷／水、CTAB／环己烷／水和OP-10／环己烷／水三种不同的反胶束体系中合成出具有不同形貌的纳米碳酸钙，讨论了表面活性剂的类型以及溶剂热过程对纳米碳酸钙的形貌及尺寸的影响．     

The interaction between morin and CTAB aggregates

Electronic absorption spectra, fluorescence emission spectra, ATR-FTIR spectra, cyclic voltammetric measurements, and ab initio quantum calculation are used to study the properties of morin in CTAB micelles with different microstructures and microenvironments and to gain information about the binding of morin with CTAB micelles. Morin can be located in the CTAB micelle with its phenyl group (deviating with 38.98 degrees from the planarity) only in the form of the monomer, which leads to increase of the planarity and extension of the pi conjugation of the whole molecule. The embedding of two hydroxyl groups on the phenyl into a more hydrophobic microenvironment makes the oxidation peak of morin move to a higher potential with a decreased peak current. The binding of morin with CTAB micelles is a spontaneous (DeltaG<0) and endothermic process (DeltaH>0), and the hydrophobic and electrostatic force is the main driving force for its solubilization.     

含金鸡钠碱的光活性聚合物：2.含辛可宁的两亲单体及其两亲聚合物

通过两亲单体２－丙烯酰胺基烷磺酸与辛可宁成盐后再聚合，或ＡＭＣｎＳ聚合成梳型两亲聚合物后再生ＣＮ成盐，可获得含辛可宁的两亲聚合物。ＡＭＣｎＳ－ＣＮ盐及其相应的两亲聚合物具有比ＣＮ好得多的溶解性，易溶于氯仿、ＴＨＦ、乙醇、ＤＭＦ和ＤＭＳ等极性不同的溶剂。ＡＭＣｓＳ－ＣＮ盐好得多的溶解性，易溶于氯仿、ＴＨＦ、乙醇、ＤＭＦ和ＤＭＳＯ等极性不同的溶剂。ＡＭＣｎＳ－ＣＮ盐在乙醇／氯仿（Ｖ／Ｖ＝１／２）中比旋     

助表面活性剂对介孔二氧化硅孔径的影响

在十六烷基三甲基溴化铵(CTAB)与硝酸形成的胶束体系中,分别加入正戊醇与正辛胺作助表面活性剂,合成出介孔二氧化硅.经小角XRD和N₂气体吸附与脱附实验证实,随着CTAB与正戊醇摩尔比的增加,介孔二氧化硅的孔径增加;而随CTAB与正辛胺摩尔比的增加,介孔二氧化硅的孔径减小.主要原因是正戊醇增大了CTAB胶束体积,从而导致介孔二氧化硅的孔径增加.而在CTAB与正辛胺的混合胶束中,正辛胺同硅酸盐作用力比CTAB强,导致介孔二氧化硅的孔径减小.     

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.     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

头孢唑酮对CTAB胶束结构特性的影响

应用电导法和荧光法测定了头孢唑酮对阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）胶束第一cmc1、第二cmc2、胶束聚集数及体系粘度的影响,测定了头孢唑酮在CTAB胶束中的分配系数.结果表明,头孢唑酮的加入使得CTAB胶束的第一cmc和第二cmc均上升,胶束的聚集数和体系的粘度降低.上述结果与头孢唑酮和CTAB分子的相互作用及其在CTAB胶束相和水连续相的分配有关.