Aggregation properties of cationic gemini surfactants with partially fluorinated spacers in aqueous solution

The aggregation properties of cationic gemini surfactants alkanediyl-alpha,omega-bis(dodecyldimethylammonium bromide), [C(12)H(25)(CH(3))(2)N(CH(2))(m)(CF(2))(n)(CH(2))(m))N(CH(3))(2)C(12)H(25)]Br(2) [where 2m + n = 12 and n = 0, 4, and 6; designated as 12-12-12, 12-12(C(4)(F))-12, and 12-12(C(6)(F))-12, respectively] have been studied by microcalorimetry, time-resolved fluorescence quenching, and electrical conductivity. Compared with a fully hydrocarbon spacer of 12-12-12, the fluorinated spacer with a lower ratio of CF(2) to CH(2) in 12-12(C(4)(F))-12 tends to disfavor the aggregation, leading to larger critical micelle concentration (cmc), lower micelle aggregation number (N), and less negative Gibbs free energy of micellization (DeltaG(mic)). However, the fluorinated spacer with a higher ratio of CF(2) to CH(2) in 12-12(C(6)(F))-12 may prompt the aggregation, resulting in lower cmc, higher N, and more negative DeltaG(mic). It is also noted that enthalpy change of micellization (DeltaH(mic)) for 12-12(C(4)(F))-12 is the most exothermic, but the values of DeltaH(mic) for 12-12-12 and 12-12(C(6)(F))-12 are almost the same. These results are rationalized in terms of competition among the enhanced hydrophobicity and the rigidity of the fluorinated spacer, and the variation of immiscibility of the fluorinated spacer with the hydrocarbon side chains.     

Effect of head group polarity and spacer chain length on the aggregation properties of gemini surfactants in an aquatic environment

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.     

Analysis of interfacial and micellar behavior of sodium dioctyl sulphosuccinate salt (AOT) with zwitterionic surfactants in aqueous media

The interfacial and bulk properties of mixtures of the anionic surfactant (dioctyl sulphosuccinate sodium salt, AOT) with zwitterionic surfactants 3-(N,N-dimethyldodecylammonio) propane sulfonate (DPS), 3-(N,N-dimethyltetradecylammonio) propane sulfonate (TPS), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HPS) have been studied employing surface tension, fluorescence, and viscometric techniques in aqueous media at 25 °C. It is observed that these mixtures exhibit synergism and these synergistic interactions increase with the enhancement of the hydrocarbon chain of the zwitterionic surfactant. The various physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Г(max)), minimum area per molecule (A(min)), aggregation number (N(agg)), interaction parameters (β(σ), β(m)), and thermodynamic parameters such as standard Gibbs free energy of adsorption (ΔG(ads)(o)), excess free energy of micellization (ΔG(ex)), and standard Gibbs free energy of micellization (ΔG(m)(o)) have been evaluated. The negative values of ΔG(m)(o) and ΔG(ads)(o) show that the micelle formation and adsorption of surfactant at the air/solution interface is energetically favorable, while a negative value of ΔG(ex) ensures stability of the mixed micelles formed. The Regular Solution Approximation, Motomura and Rosen's approaches have been used to explain and compare the results. The packing parameter (p) ensures the formation of vesicles or bilayers for AOT+DPS/TPS mixtures, which can potentially be used as delivery agents for industrial applications.     

Effect of the nature of the spacer on the aggregation properties of gemini surfactants in an aqueous solution

The aggregation properties of three dicationic quaternary ammonium gemini surfactants with the same structure, except the spacer group, diethyl ether, six methylene, and p-xylyl, have been studied using electrical conductivity and fluorescence. The critical micelle concentration (cmc) and the micelle aggregation number (N) were determined, and the micropolarity and the microviscosity of the micelle were characterized. The micelle ionization degree (alpha) was obtained by a combination of the electrical conductivity data and the micelle aggregation number. Furthermore, the Gibbs free energy of micellization (deltaGmic) was studied. These results have shown that the nature of the spacer has an important effect on the aggregation properties of gemini surfactants in an aqueous solution. A hydrophilic, flexible spacer prompts micelle formation, which leads to a smaller cmc, smaller alpha, larger N, and more negative deltaGmic. Meanwhile, the microviscosity study indicates that the gemini surfactant with a hydrophilic, flexible spacer forms a more closely packed micelle structure than the one with a hydrophobic, rigid spacer.     

Alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants 9. Effect of the spacer carbon number and temperature on the enthalpy of micellization

The enthalpies of dilution of micellar solutions of several 12-s-12 dimeric surfactants of the alkanediyl-alpha,omega-bis(dodecyldi-methylammonium bromide) type, differing by the carbon number s of the alkanediyl spacer, and of dodecyltrimethylammonium bromide (DTAB) have been measured calorimetrically, in a range of concentrations extending from well below to well above the critical micelle concentration (cmc). The results permitted the determination of the enthalpy of micellization, DeltaH degrees (M), of the investigated surfactants at 25 and 35 degrees C. The values of DeltaH degrees (M) were always negative and became more negative as the temperature was increased. The plot of -DeltaH degrees (M) against s showed a shallow minimum at about s=5 and a large decrease of -DeltaH degrees (M) going from 12-2-12 to 12- 4-12. This effect has been attributed to the contribution to DeltaH degrees (M) of the hindered rotation of the dodecyl chains around the spacer C-C bond for 12-2-12. This hindrance is shown to rapidly disappear when s is increased from 2 to above 4. The specific heats of micellization, the free energies of micellization, and the entropies of micellization (DeltaS degrees (M)) have been calculated using the DeltaH degrees (M) values and the reported cmc and micelle ionization degree data for 12-s-12 surfactants and DTAB. For all surfactants the results show that TDeltaS degrees (M)>-DeltaH degrees (M), indicating an entropy-driven micellization.     

Effect of hydrocarbon structure of the headgroup on the thermodynamic properties of micellization of cationic gemini surfactants: an electrical conductivity study

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.     

Synthesis and dilute aqueous solution properties of ester functionalized cationic gemini surfactants having different ethylene oxide units as spacer

New series of ester functionalized quaternary ammonium gemini surfactants having different ethylene oxide units as spacer have been synthesized and investigated for their aggregation behavior and thermodynamic properties of micellization by surface tension, conductivity, and fluorescence methods. The critical micelle concentration (cmc) of these gemini surfactants increases with the increase in the length of polar hydrophilic ethylene oxide spacer. The micellization process has been found to be entropy-driven and dependent on both the tendency of the hydrophobic group of the surfactants to transfer from aqueous environment to interior of micelle as well as the rearrangement of flexible ester-linked ethylene oxide units (hydrophilic spacer) into aqueous phase. The polar ester functional groups and pairs of nonbonding electrons on oxygen atom of ethylene oxide spacer form hydrogen bonding with water molecules enhancing their solubility in aqueous system.     

Micelle formation by N-alkyl-N-methylpyrrolidinium bromide in aqueous solution

The micellization of the ionic liquid N-alkyl-N-methylpyrrolidinium bromide (C(n)MPB, n = 12, 14 and 16) in aqueous solutions was investigated by surface tension measurements, electrical conductivity and static luminescence quenching. The effectiveness of the surface tension reduction (Π(cmc)), maximum surface excess concentration (Γ(max)) and the minimum area (A(min)) occupied per surfactant molecule at the air/water interface can be obtained from the surface tension measurements at 25 °C. The critical micelle concentration (cmc) at different temperatures and a series of thermodynamic parameters (ΔG, ΔH and ΔS) of micellization were evaluated from electrical conductivity measurements in the temperature range of 25-45 °C. The thermodynamic parameters show that the micelle formation is entropy-driven at low temperature and enthalpy-driven at high temperature. Furthermore, the micelle aggregation number (N(agg)) of C(n)MPB was calculated according to the Turro-Yekta method through static luminescence quenching and found that N(agg) (49, 55, and 59) increased with the hydrophobic chain length of C(n)MPB.     

Micelle formation of nonionic surfactants in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: surfactant chain length dependence of the critical micelle concentration

Micellization behavior was investigated for polyoxyethylene-type nonionic surfactants with varying chain length (C(n)E(m)) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)). Critical micelle concentration (cmc) was determined from the variation of (1)H NMR chemical shift with the surfactant concentration. The logarithmic value of cmc decreased linearly with the number of carbon atoms in the surfactant hydrocarbon chain, similarly to the case observed in aqueous surfactant solutions. However, the slope of the straight line is much smaller in bmimBF(4) than in aqueous solution. Thermodynamic parameters for micelle formation estimated from the temperature dependence of cmc showed that the micellization in bmimBF(4) is an entropy-driven process around room temperature. This behavior is also similar to the case in aqueous solution. However, the magnitude of the entropic contribution to the overall micellization free energy in bmimBF(4) is much smaller compared with that in aqueous solution. These results suggest that the micellization in bmimBF(4) proceeds through a mechanism similar to the hydrophobic interaction in aqueous surfactant solutions, although the solvophobic effect in bmimBF(4) is much weaker than the hydrophobic effect.     

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.     

氧乙烯基对胶团化过程热力学函数的影响

利用表面张力法测定了各种条件下C_8H_(17)(OC_2H_4)_n-SO_4Na(C_8E_nS; n=0,1,3)的cmc, 并计算了胶团的反离子结合度、胶团化过程中的自由能(ΔG°)和熵变(ΔS°)。结果发现: C_8E_nS的cmc随n的增加而下降, 并且下降的幅度逐渐变小; 胶团的反离子结合度也随n的增加而减小; ΔS°随n的增加而增加, 但增加的幅度逐渐变小, 对于离子和非离子表面活性剂都是如此。人们认为这是由于氧乙烯基(EO)具有亲水和疏水二重性, 随着EO数的增加, EO的疏水性相对减弱而亲水能力将相对增加所致。EO的这个特点, 是它在表面活性剂分子中具有特殊表现的根本原因。     

Structural effects on surface and micellar properties of alkanediyl-alpha, omega-bis(sodium N-acyl-beta-alaninate) gemini surfactants

A study of the equilibrium surface properties (in water and in the presence of 0.01 M NaCl) of a novel series of anionic gemini surfactants, alkanediyl-alpha,omega-bis(sodium N-acyl-beta-alaninates), is described. Parameters studied include cmc (critical micelle concentration), C20 (required to reduce the surface tension of the solvent by 20 mN/m), gamma(cmc) (the surface tension at the cmc), Gamma(max) (the maximum surface excess concentration at the air/aqueous solution interface), Amin (the minimum area per surfactant molecule at the air/water interface), and the cmc/C20 ratio (a measure of the tendency to form micelles relative to adsorb at the air/water interface). The geminis with a spacer consisting of two methylene groups show premicellar self-aggregation, both in water and in 0.01 M NaCl, when the N-acyl group contains more than 12 carbon atoms; geminis with a spacer consisting of four methylene groups show no premicellar aggregation even when the N-acyl group contains 16 carbon atoms. For the acyl chain lengths where premicellar aggregation does not occur, the values of the cmc of the geminis with a two-methylene spacer are lower than those for the corresponding analogous geminis with a four-methylene spacer. The premicellar formation for the geminis with a two-methylene spacer is due to the short-chain linkage. The geminis show little or no break in their specific conductance-surfactant molar concentration plots and an increase in the pH at the cmc. This is attributed to protonation of the carboxylate group and strong Na+ release during micellization.     

Thermodynamic and structural characterization of zwitterionic micelles of the membrane protein solubilizing amidosulfobetaine surfactants ASB-14 and ASB-16

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.     

Gemini阳离子表面活性剂在水溶液中胶团化行为的温度效 应与焓、熵补偿

测定了Cemini阳离子表面活性剂C~m-----s-----C~m·2Br(m=8,10,12,;s=2,6及m=12;s=3,4)水溶液的电导,从电导(k)～表面活性剂浓度(c)曲线的转折点可求得临界胶团浓度cmc.实验发现,Gemini阳离子表面活性剂的胶团化倾向明显强于其“单体分子”)即单离子头基单烷烃链表面活性剂)。根据质量作用模型计算了胶经过程的吉布氏能、焓和熵的改变。结果表明Gemini表面活性剂聚集机理和其对应的“单体分子”类似,主要来自熵驱动。所有的焓/熵补偿图均呈现良好的线性关系,补偿直线在γ轴的截距随s减小而变小,这意味着具有较小s的Gemini表面活性剂倾向于生成稳定的胶团。     

Thermodynamics of micellization for partially fluorinated cationic gemini surfactants and related single-chain surfactants in aqueous solution

A series of partially fluorinated cationic gemini surfactants and their corresponding monomeric surfactants have been studied by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaH(mic)) were obtained from calorimetric curves. The CMCs of the gemini surfactants are much lower than those of the corresponding monomeric surfactants and decrease with an increase in the number of fluorine atoms on the hydrophobic chain. The micellization of partially fluorinated cationic gemini surfactants is much more exothermic than that of the corresponding monomeric surfactants. Because of the incompatibility of hydrocarbon spacer and partially fluorinated chain, DeltaH(mic) values of the surfactants with a C6 spacer are more negative than those of the surfactants with a C12 spacer. The variations in the architecture of the fluorocarbon chain segments may be the reason of the irregularities in the change of DeltaH(mic) for the gemini surfactants. Moreover, the contribution of the enthalpy generally increases with an increase in the number of fluorine atoms.     

Thermodynamics of micellization of multiheaded single-chain cationic surfactants

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.     

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。     

新型Gemini咪唑表面活性剂的合成及表面性能

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.