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1.
Three pyrrolidinium-based ionic liquids-N-dodecyl-N-methylpyrrolidinium bromide, N-butyl-N-octylpyrrolidinium bromide, and N-butyl-N-dodecylpyrrolodinium bromide-were synthesized and characterized by their decomposition temperatures (T(d)) measured by thermogravimetric analysis, and by their melting point (T(m)), glass transition (T(g)) and crystallization temperatures (T(cryst)) determined by differential scanning calorimetry. Their self-aggregation properties in aqueous solution were studied and their behavior is compared with that of analogous conventional cationic surfactants, namely tetra-alkylammonium bromide salts. The critical micellar concentration, cmcs were obtained by isothermal titration calorimetry (ITC); which were further validated by measurements of interfacial tension, fluorescence and NMR spectroscopy. Enthalpies of micellization were measured at three different temperatures using ITC. The Taylor dispersion method and DOSY NMR were used to determine diffusion coefficients of the ionic liquid surfactants in aqueous solution at 298.15K. Several correlations between structural features of the surfactant species, such as the number and size of their alkyl chains, and the thermodynamic quantities of micellization-expressed by experimental values of cmc, counter-ion binding fraction, Δ(mic)G°, Δ(mic)°, and Δ(mic)S°-are established. We could interpret the different contributions of the two alkyl side chains to the aggregation properties in terms of the balance of interactions in homogeneous and micellar phases, contributing to understanding the aggregation behavior of ionic liquids in water and the parallel between these systems and traditional ionic surfactants.  相似文献   

2.
The micellization of a novel family of nonionic surfactants poly(oxyethylene) glycol alkyl ethers has been studied by microcalorimetry. One of the surfactants has adamantane, and the other nonionic surfactants have a benzene ring in their hydrophobic chains, which moves from the terminal of the hydrophobic chain toward the headgroup. Moreover, the alkyl chain of the nonionic surfactants is straight or branched. Both the critical micelle concentration (cmc) and the thermodynamic parameters associated with the micelle formation have been obtained. The cmc decreases and the enthalpy of micelle formation (deltaH(mic)) becomes less positive gradually as the length of hydrophobic chain increases, whereas the values of cmc and deltaH(mic) tend to increase for the surfactants with a longer ethylene oxide chain. However, the deltaH(mic) value of the surfactant with seven carbon atoms in a hydrophobic chain is more positive than that of the surfactant with six carbon atoms in a hydrophobic chain. Comparing with the nonionic surfactant with a methylene hydrophobic chain, the surfactants with benzene rings and adamantane groups have larger cmc values and the cmc values increase with the size of the groups. Furthermore, moving the phenyl group from the terminal of the hydrophobic chain to the neighbor of the hydrophilic headgroup leads to the decreased cmc. Both the variation of hydrophobic interaction from the movement of phenyl group and pi-pi interaction among adjacent phenyl groups affect deltaH(mic) values.  相似文献   

3.
A family of two-headed surfactants, the disodium 4-alkyl-3-sulfonatosuccinates, has been prepared by reacting maleic anhydride with the appropriate chain-length alcohol and subsequent addition of sodium bisulfite to the corresponding monoester. The properties of the micelles formed by these compounds in aqueous solution (aggregation numbers, degrees of counterion binding, and the cmc values) have been investigated as a function of temperature and surfactant chain length using viscosity, density, and conductance measurements. The critical micelle concentrations (cmc's) and the aggregation numbers appear to indicate that, in agreement with the earlier literature on other two-headed surfactants systems, these amphiphiles have higher cmc and lower aggregation numbers when compared to single-headed surfactants of comparable chain length. In addition, viscosity B coefficients and the thermodynamic parameters of activation of viscous flow have been determined. These results are interpreted in terms of the structure-making or -breaking properties of the surfactant amphiphiles below the cmc region. Finally, the thermodynamic properties of micelle formation have been estimated from the dependence of the cmc on the absolute temperature according to the charged pseudo-phase separation model of micelle formation. All these results are discussed in terms of how the addition of the second charged surfactant headgroup alters the micellar and solution properties of two-headed surfactants vs. their single-headed counterparts.  相似文献   

4.
A series of cationic gemini surfactants butanediyl-1,4-bis(dodecyldialkylammonium bromide), C(12)H(25)N(+)(C(m)H(2)(m)(+1))(2)C(4)H(8)N(+)(C(m)H(2)(m)(+1))(2)C(12)H(25)·2Br(-), where m=1, 2, 3, 4, referred to as C(12)C(4)C(12)(Me), C(12)C(4)C(12)(Et), C(12)C(4)C(12)(Pr), and C(12)C(4)C(12)(Bu), respectively, were synthesized, and their thermodynamic properties of micellization were studied by electrical conductivity measurements. There existed a minimum critical micelle concentration (cmc) in the curve of cmc versus temperature, and the temperature of the minimum of cmc (T(min)) increased with increasing the headgroup alkyl chain length. The values of log (cmc) depended linearly on carbon number of the alkyl chains, but that was not true for the carbon number of the headgroup substituents. The temperature dependence of cmc and degree of counterion association (β) were used to calculate the Gibbs free energy (Δ(mic)G°), enthalpies (Δ(mic)H°) and entropies (Δ(mic)S°) of micelle formation for these gemini surfactants, and well correlated enthalpy-entropy compensation was observed. The analyses showed C(12)C(4)C(12)(Me) and C(12)C(4)C(12)(Et) behaved similarly in terms of thermodynamics of micellization, but they behaved differently from C(12)C(4)C(12)(Pr) and C(12)C(4)C(12)(Bu), which could be ascribed to the hydrophobicity and the location of the headgroup alkyl chains in the aggregates. These initial results indicate the headgroup alkyl chain plays an important role in influencing the thermodynamic properties of gemini surfactants.  相似文献   

5.
The aggregation behavior of cationic gemini surfactants with respect to variation in head group polarity and spacer length is studied through conductance, surface tension, viscosity, and small-angle neutron-scattering (SANS) measurements. The critical micellar concentration (cmc), average degree of micelle ionization (beta(ave)), minimum area per molecule of surfactant at the air-water interface (A(min)), surface excess concentration (gamma(max)), and Gibb's free energy of micellization (delta G(mic)) of the surfactants were determined from conductance and surface tension data. The aggregation numbers (N), dimensions of micelles (b/a), effective fractional charge per monomer (alpha), and hydration of micelles (h(E)) were determined from SANS and viscosity data, respectively. The increasing head group polarity of gemini surfactant with spacer chain length of 4 methylene units promotes micellar growth, leading to a decrease in cmc, beta(ave), and delta G(mic) and an increase in N and b/a. This is well supported by the observed increase in hydration (h(E)) of micelles with increase in aggregation number (N) and dimension (b/a) of micelle.  相似文献   

6.
Surface tension and isothermal titration calorimetry (ITC) were used to determine the critical micelle concentration (cmc) of the zwitterionic amidosulfobetaine surfactants ASB-14 and ASB-16 (linear-alkylamidopropyldimethylammoniopropanosulfonates) at 25 °C. The cmc and the heat of micellization were determined from 15 to 75 °C by ITC for both surfactants. The increase in temperature caused significant changes in the enthalpy and in the entropy of micellization, with small changes in the standard Gibbs energy (ΔG(mic)), which is consistent to an enthalpy?entropy compensation with a compensatory temperature of 311 K (ASB-14) and 314 K (ASB-16). In the studied temperature range, the heat capacity of micellization (ΔC(p)(mic)) was essentially constant. The experimental ΔC(p)(mic) was lower than that expected if only hydrophobic interactions were considered, suggesting that polar interactions at the head groups are of significant importance in the thermodynamics of micelle formation by these surfactants. Indeed, a NMR NOESY spectrum showed NOEs that are improbable to occur within the same monomer, resulting from interactions at the polar head groups involving more than one monomer. The ITC and NMR results indicate a tilt in the polar headgroup favoring the polar interactions. We have also observed COSY correlations typical of dipolar interactions that could be recovered with the partial alignment of the molecule in solution, which results in an anisotropic tumbling. The anisotropy suggested an ellipsoidal shape of the micelles, which results in a positive magnetic susceptibility, and ultimately in orientation induced by the magnetic field. Such an ellipsoidal shape was confirmed from results obtained by SAXS experiments that revealed aggregation numbers of 108 and 168 for ASB-14 and ASB-16 micelles, respectively. This study characterizes an interesting micelle system that can be used in the study of membrane proteins by solution NMR spectroscopy.  相似文献   

7.
The energetics of micelle formation of three single-chain cationic surfactants bearing single (h = 1), double (h = 2), and triple (h = 3) trimethylammonium [(+)N(CH(3))(3)] headgroups have been investigated by microcalorimetry. The results were compared with the microcalorimetric data obtained from well-known cationic surfactant, cetyl trimethylammonium bromide (CTAB), bearing a single chain and single headgroup. The critical micellar concentrations (cmc's) and the degrees of counterion dissociation (alpha) of micelles of these surfactants were also determined by conductometry. The cmc and the alpha values increased with the increase in the number of headgroups of the surfactant. The relationship between the cmc of the surfactant in solution and its free energy of micellization (DeltaG(m)) was derived for each surfactant. Exothermic enthalpies of micellization (DeltaH(m)) and positive entropies of micellization (DeltaS(m)) were observed for all the surfactants. Negative DeltaH(m) values increased from CTAB to h = 1 to h = 2 and decreased for h = 3 whereas DeltaS(m) values decreased with increase in the number of headgroups. The DeltaG(m) values progressively became less negative with the increase in the number of headgroups. This implies that micelle formation becomes progressively less favorable as more headgroups are incorporated in the surfactant. From the steady-state fluorescence measurements using pyrene as a probe, the micropolarities sensed by the probe inside various micelles were determined. These studies suggest that the micelles are more hydrated with multiheaded surfactants and the micropolarity of micelles increases with the increase in the number of headgroups.  相似文献   

8.
The micellization behavior of MEGA 10 has been studied at nine different temperatures by isothermal titration calorimetry (ITC), and thermodynamics of the process have been evaluated and examined in detail. The aggregation number of the nonionic surfactant has been estimated from the ITC results by a simulation procedure based on the mass action principle of micellization of the surfactant. The cmc of MEGA 10 has shown a minimum in temperature dependence as observed for ionic surfactants. For a comparison, the cmc and related thermodynamic parameters of an ionic surfactant, tetradecyltriphenylphosphonium bromide (C(14)TPB) studied at several temperatures in aqueous medium has been considered. The contributions of the headgroups of both the surfactants to the free energies of their respective micellization have been deciphered and presented.  相似文献   

9.
本文通过等温滴定量热法(ITC)、电导法和浊度法研究了阴离子生物表面活性剂脱氧胆酸钠(NaDC)及其与相反电荷的十二烷基三甲基溴化铵(DTAB)在水溶液中的自组装热力学.ITC结果支持了NaDC在水溶液中先生成预胶束再形成稳定胶束的分步聚集模型,由此得到了NaDC的预胶束和胶束化过程的一系列热力学参数,并讨论了它们形成的热力学机理.进一步研究了具有头-尾链式和疏水-亲水刚性面式非对称结构的DTAB/NaDC混合体系的聚集热力学行为,得到了富NaDC临界混合胶束浓度(cmcmix)、富DTAB临界胶束浓度(CM)及对应过程的转变焓.结果表明,NaDC面式结构与DTAB链式结构的对称性差异以及相反电荷的相互作用,导致混合体系有别于单一表面活性剂或头-尾链式结构的混合体系的聚集行为.混合溶液的聚集行为受控于表面活性剂浓度和摩尔分数的变化.富NaDC胶束化过程为熵驱动,而富DTAB的两种胶束形态转变过程为熵焓共同驱动的热力学机理.这些结果对于从热力学角度认识胆汁酸盐的自组装机理以及与传统的头-尾链式结构的表面活性剂相互作用机理和相行为有重要的意义.  相似文献   

10.
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。  相似文献   

11.
12.
采用等温滴定量热法、静态荧光猝灭法和电导法系统研究了典型离子液体1-烷基-3-甲基咪唑四氟硼酸盐([Cnmim][BF4])在水溶液中的聚集行为, 获得了胶束形成的临界胶束浓度(cmc), 摩尔焓变(ΔHmic), 摩尔吉布斯自由能变(ΔGmic), 摩尔熵变(ΔSmic)以及不同浓度时[Cnmim][BF4]胶束的平均聚集数等基本参数. 发现这类离子液体的聚集为熵驱动, 阳离子的烷基链越长, ΔGmic越负, 聚集更容易发生. 此外, 结合[Cnmim]X (X=Cl-, Br-)的相关研究发现, 阳离子相同时, 体积越大和疏水性越强的阴离子与头基的结合能力越强, 能有效地降低头基之间的静电排斥, 降低cmc, 利于胶束的形成. 对于[C12mim][BF4], 添加剂β-环糊精(β-CD)的加入可使cmc增大, ΔHmic和ΔSmic减小, 而KBF4则可使cmc和ΔHmic减小, ΔSmic增大.  相似文献   

13.
Three amphiphilic poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) ethers triblock copolymers, denoted Pluronic L61 (PEO3PPO30PEO3), Pluronic L64 (PEO13PPO30PEO13), and Pluronic F68 (PEO79PPO30PEO79) were shown to aggregate and form micelles in ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). The surface tension measurements revealed that the dissolution of the copolymers in ILs depressed the surface tension in a manner analogous to aqueous solutions. The cmcs of three triblock copolymers increase following the order of L61, L64, F68, suggesting that micellar formation was driven by solvatophobic effect. cmc and gamma cmc decrease with increasing temperature because hydrogen bonds between ILs and hydrophilic group of copolymers decrease and accordingly enhance the solvatophobic interaction. Micellar droplets of irregular shape with average size of 50 nm were observed. The thermodynamic parameters DeltaGm0, DeltaHm0, DeltaSm0 of the micellization of block copolymers in bmimBF4 and bmimPF6 were also calculated. It was revealed that the micellization is a process of entropy driving, which was further confirmed by isothermal titration calorimetry (ITC) measurements.  相似文献   

14.
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.  相似文献   

15.
The effect of TbCl3 on the aggregation processes of the anionic surfactants sodium decyl sulfate (SDeS) and sodium dodecyl sulfate (SDS) has been investigated. Electrical conductivity data, combined with Tb(III) luminescence measurements suggest that the formation of micelles involving TbCl3 and SDS occurs at concentrations below the critical micelle concentration (cmc) of the pure surfactants; the formation of these mixed aggregates was also monitored by light scattering, which indicates that the addition of TbCl3 to surfactant concentration at values below the pure surfactant cmc results in a much greater light scattering than that found with pure sodium alkylsulfate surfactant micelles. This phenomenon is dependent upon the alkyl chain length of the surfactant. With Tb(III)/DS-, complexes are formed with a cation/anion binding ratio varying from 3 to 6, which depends upon the initial concentration of Tb(III). This suggests that the majority of the cation hydration water molecules can be exchanged by the anionic surfactant. When the carbon chain length decreases, interactions between surfactant and Tb(III) also decrease, alterations in conductivity and fluorescence data are not so significant and, consequently, no binding ratio can be detected even if existing. The surfactant micellization is dependent on the presence of electrolyte in solution with apparent cmc being lower than the corresponding cmc value of pure SDS.  相似文献   

16.
To develop structure-property relationships for surfactants that control their adsorption, solubilization, and micellization behavior in mixed systems and to develop predictive models based on such relationships, it is necessary to acquire quantitative information on various species present in these complex systems. The analytical ultracentrifugation technique is selected for the first time to characterize the species present in mixed micellar solutions due to its powerful ability to separate particles on the basis of their size and shape. Two nonionic surfactants, n-dodecyl-beta-D-maltoside (DM) and nonyl phenol ethoxylated decyl ether (NP-10), and their 1:1 molar ratio mixture were investigated in this study. Micelles of the nonionic surfactants and their mixture are asymmetrical in shape at the critical micelle concentration (cmc). Interestingly, unlike ionic surfactants, the micellar growths of the nonionic surfactants were found to occur at concentrations immediately above the cmc. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and in its mixture with n-dodecyl-beta-D-maltoside, while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions. Type 1 micelles were primary micelles at the cmc, while type 2 micelles were elongated micelles. The differences in the micellar shapes of n-dodecyl-beta-D-maltoside and nonyl phenol ethoxylated decyl ether are attributed to packing parameters detected by their molecular structures.  相似文献   

17.
In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.  相似文献   

18.
Isothermal titration calorimetry (ITC) was used to determine the critical micelle concentration (cmc) and the thermodynamic parameters associated with the demicellization of sodium oleate (NaO) and mixed micelles composed of the bile salt (BS) sodium cholate (NaC) or sodium deoxycholate (NaDC), respectively, and NaO at a molar ratio of 5:2. The influence of the ionic strength (pure water and 0.1 M NaCl at pH 7.5) as well as that of the temperature (10-70 degrees C) were analyzed. For NaO, two cmc's were detected, indicating a two-step aggregation process, whereas only one cmc was observed for the two BSs. A single aggregation mechanism is also evident for the demicellization of mixed micelles (BS/NaO 5:2). Increasing the ionic strength induces the well-known decrease of the cmc. The cmc shows a minimum at room temperature. The cmc(mix) of the mixed micelles was analyzed using models assuming an ideal or nonideal mixing behavior of both detergents. The thermodynamic parameters describing the enthalpy (deltaHdemic), entropy (deltaSdemic), and Gibbs energy change (deltaGdemic), as well as the change in heat capacity (deltaCp,demic) for demicellization, were obtained from one ITC experiment. From the temperature dependence of deltaHdemic, the change of the hydrophobic surface area of the detergents from the micellar into the aqueous phase was derived. In all cases, the deltaCp,demic values are positive. In addition, the temperature dependence of the size of the formed aggregates was studied by dynamic light scattering (DLS). DLS indicated two populations of aggregates in the mixed system, small primary micelles (0.5-2 nm), and larger aggregates with a hydrodynamic radius in the range of 50-150 nm.  相似文献   

19.
Amino acid-derived surfactants have increasingly become a viable biofriendly alternative to petrochemically based amphiphiles as speciality surfactants. Herein, the Krafft temperatures and critical micelle concentrations (cmc) of three series of novel amino acid-derived surfactants have been determined by differential scanning microcalorimetry and surface tension measurements, respectively. The compounds comprise cationic molecules based on serine and tyrosine headgroups and anionic ones based on 4-hydroxyproline headgroups, with varying chain lengths. A linear dependence of the logarithm of cmc on chain length is found for all series, and in comparison to conventional ionic surfactants of equal chain length, the new amphiphiles present lower cmc and lower surface tension at the cmc. These observations highlight their enhanced interfacial performance. For the 18-carbon serine-derived surfactant the effects of counterion change and of the presence of a cis-double bond in the alkyl chain have also been investigated. The overall results are discussed in terms of headgroup and alkyl chain effects on micellization, in the light of available data for conventional surfactants and other types of amino acid-based amphiphiles reported in the literature.  相似文献   

20.
N-酰基-L-丝氨酸钠表面活性剂的合成和胶束化热力学性质   总被引:1,自引:0,他引:1  
梁亚琴  胡志勇  曹端林 《应用化学》2013,30(9):1042-1047
以L-丝氨酸和长链酰氯为原料,合成了3种不同碳链长度(n=8,12,14)的N-酰基-L-丝氨酸。 并以1H NMR、ESI-MS和元素分析对3种目标产物进行了表征。 采用表面张力法研究了N-酰基-L-丝氨酸钠在298、308、318和328 K时水溶液中的聚集行为,确定了临界胶束浓度(cmc)、临界胶束浓度下的最低表面张力(γcmc)、表面饱和吸附量Γmax。 由cmc和温度的关系,应用相分离模型计算了胶束化热力学参数ΔGom、ΔHom和ΔSom。 结果表明,ΔGom<0,ΔHom的绝对值比-TΔSom绝对值小的多,说明胶束化过程为熵驱动过程,随着温度的升高,胶束化过程是熵-焓补偿的过程。  相似文献   

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