Interactions of beta-lactoglobulin with sodium decylsulfonate, decyltriethylammonium bromide, and their mixtures

The interactions of beta-lactoglobulin (BLG) with anionic surfactant sodium decylsulfonate (C10SO3), cationic surfactant decyltriethylammonium bromide (C10NE), and the mixtures of cationic-anionic surfactants (C10NE-C10SO3) were investigated by circular dichroism (CD) and fluorescence methods. At pH 7.0, C10NE and the C10NE-rich surfactant mixtures of C10NE-C10SO3 could form precipitates with BLG, while C10SO3, equimolar mixtures of C10NE-C10SO3, or C10SO3-rich mixtures of C10NE-C10SO3 form homogeneous solutions with BLG. CD observed that both C10NE and C10SO3 could change the BLG structure. The effects of the mixtures of C10NE-C10SO3 on BLG structure depended on the ratio of C10NE to C10SO3. The C10NE-rich or the C10SO3-rich mixtures of C10NE-C10SO3 could significantly affect BLG structure, while the equimolar mixtures of C10NE-C10SO3 exhibited weaker interaction with BLG. Fluorescence measurements showed that both C10NE and C10SO3 could induce the enhancement of fluorescence of BLG, and C10NE enhanced the BLG fluorescence more than C10SO3 did. The effect of the mixtures of C10NE-C10SO3 on the fluorescence of BLG became stronger with the increase of the molar fraction of C10NE in C10NE-C10SO3 mixtures.     

Interaction between lysozyme and mixtures of cationic-anionic surfactants decyltriethylammonium bromide-sodium decylsulfonate

The interaction of lysozyme with the mixtures of cationic-anionic surfactants decyltriethylammonium bromide-sodium decylsulfonate (C10NE-C10SO3) was investigated by turbidity, circular dichroism (CD) and lysozyme activity assay. At pH 3.0, the mixtures of C10NE-C10SO3 formed precipitates with lysozyme at a wide range around the equal molar ratio of C10NE to C10SO3. Homogeneous solutions were formed when the mixtures of C10NE-C10SO3 were far from equimolar. CD and lysozyme activity assay showed that lysozyme was in different state in the C10SO3-rich and C10NE-rich mixtures of C10NE-C10SO3. Lysozyme structure changed in C10SO3-rich C10NE-C10SO3 mixtures, while was almost kept in native state in C10NE-rich ones.     

聚氧乙烯与非等摩尔正负离子表面活性剂混合体系的相互作用

通过黏度、动态光散射和透射电镜方法研究了聚氧乙烯(PEO)对正负离子混合表面活性剂癸基磺酸钠(C₁₀SO₃)-癸基三乙基溴化铵(C₁₀NE)聚集体的影响. 实验结果表明, 加入PEO后, 非等摩尔C₁₀SO₃-C₁₀NE混合物的聚集体大小没有明显改变, 只有等摩尔混合物的聚集体发生了明显的长大, 且仍为囊泡, 说明PEO只对囊泡体系有显著的影响, 对胶团体系则没有明显的影响. 在接近等摩尔混合时, 混合体系中C₁₀SO₃与C₁₀NE过量程度相同的情况下, PEO对C₁₀NE过量的体系影响更大. PEO对囊泡体系的影响主要表现为PEO通过对囊泡的“空缺絮凝”作用(Depletion interaction)使囊泡长大, 而对于非等摩尔混合的胶团溶液, 由于胶团之间存在较强的静电排斥作用而无法发生聚集. PEO对C₁₀NE过量的体系影响更大, 主要是由于C10NE过量体系中的聚集体比C10SO3过量体系中的更接近于等摩尔组成.     

全氟丁基磺酸钠与辛基三乙基溴化铵的相互作用

通过测定辛基三乙基溴化铵(C8H17N(CH2CH3)3Br,C8NE)与全氟丁基磺酸钠(C4F9SO3Na,C4F)组成的不同混合比的碳氢-碳氟正负离子表面活性剂混合体系的表面张力,得到不同摩尔比时C8NEC4F体系的临界胶束浓度(cmc)、cmc处的表面张力(γcmc)、总饱和吸附量、不同表面张力时表面吸附层的组成,利用Gibbs-Duhem方程求得cmc处的胶团组成。 采用规则溶液理论计算了胶团中分子间相互作用参数(βm),并求得cmc以上的胶团组成。 实验表明,C8NEC4F复配体系的cmc远远小于单体系的cmc,这也体现在该体系的βm负值很大,胶团内分子相互作用很强。 但是C4F与C8NE复配后γcmc较C4F单体系的变化幅度不是特别大(γcmc降低2~4 mN/m),这是由于C8NEC4F碳链的不对称性导致部分C8NE的碳链在溶液表面弯曲而覆盖了C4F端基CF3基团。 表面吸附层中氟表面活性剂相对于本体溶液是富集的,即使对于C8NE大大过量的体系,表面吸附层组成也在等摩尔附近;对于C4F过量的体系,C4F在表面吸附层中的比例比溶液中的略高。 随着表面张力的降低,表面吸附层的组成相对更偏向于氟表面活性剂。 cmc处的胶团组成随着体系中C4F含量的增大偏向于形成显著富含C4F的胶团,对于C8NE大大过量的体系,胶团组成接近等摩尔。 cmc之后的胶团组成接近等摩尔,主要归因于此时静电相互作用占主导,这和溶液配制过程中发现复配体系超过cmc一定浓度后就易生成沉淀的现象是相符的。     

全氟壬烯氧基苯磺酸钠与烷基季铵盐的相互作用

通过六氟丙烯三聚体(全氟壬烯)氧基苯磺酸钠(C₉F₁₇OC₆H₄SO₃Na, OBS)与阳离子碳氢表面活性剂C_nNR[C_nH_2n+1N(CH₃)₃Br, C_nNM, n=8, 10和C_nH_2n+1N(CH₂CH₃)₃Br, C_nNE, n=8, 10, 12]复配, 研究了OBS与C_nNR的摩尔比、 C_nNR疏水链长及C_nNR亲水基团大小对此类阴、 阳离子碳氟-碳氢表面活性剂混合体系的临界胶束浓度(cmc)、 最低表面张力(γ_cmc)、 总饱和吸附量(Γ_tm)及极限分子面积(A_min)的影响. 结果表明, 通过与C_nNR复配, OBS的cmc和γ_cmc均大幅下降, 达到了全面增效的结果. 不同摩尔比的OBS-C₈NE混合体系中, 摩尔比为1:1时表面活性最好, cmc和γ_cmc均最小; 偏离等摩尔比时, OBS过量时混合体系的cmc小于C₈NE过量时混合体系的cmc, 但γ_cmc相差不大. 与单体系相比, OBS-C₈NE混合体系的Γ_tm明显增大、 A_min明显变小. OBS与不同疏水链长的C_nNE复配时, cmc的变化规律为C₈NE>C₁₀NE>C₁₂NE, 表明C_nNE疏水链长的增加能降低混合体系的cmc. 通过比较C_nNM和C_nNE(n=8, 10)的表面活性发现, 改变混合体系中C_nNR的亲水基团大小对混合体系的表面活性无明显影响.     

Aggregation behavior of p-n-alkylbenzamidinium chloride surfactants

The aggregation behavior of a novel class of surfactants, p-n-alkylbenzamidinium chlorides, has been investigated. The thermodynamics of aggregation of p-n-decylbenzamidinium chloride mixed with cationic and anionic cosurfactants has been studied using isothermal titration calorimetry. For mixtures of p-n-decylbenzamidinium chloride with n-alkyltrimethylammonium chlorides, the aggregation process is enthalpically more favorable than for the pure n-alkyltrimethylammonium chlorides, probably caused by diminished headgroup repulsion due to charge delocalization in the amidinium headgroup. A critical aggregation concentration between 3 and 4 mM has been extrapolated for p-n-decylbenzamidinium chloride at 40 degrees C, around two times lower than that of similar surfactants without charge delocalization in the headgroup and well comparable to that of similar surfactants with charge delocalization in the headgroup. In mixtures of p-n-decylbenzamidinium chloride with either sodium n-alkylsulfates or sodium dodecylbenzenesulfonate, evidence is found for the formation of bilayer aggregates by the pseudo-double-tailed catanionic surfactants composed of p-n-decylbenzamidinium and the anionic surfactant. These aggregates are solubilized to mixed micelles by excess free anionic surfactant at the measured critical aggregation concentration.     

表面活性剂双水相的性质及其应用 Ⅰ. 表面活性剂双水相的微环境性质

阴、阳离子表面活性剂混合体系, 在一定浓度及混合比范围内, 可以形成两个互不相溶、平衡共存的水相, 称为表面活性剂双水相。其中阳离子表面活性剂过量的双水相体系, 称为阳离子双水相。本文分别以芘和罗丹明B作为探针, 用荧光探针法研究了摩尔比为1.6:1的C12NE和SDS混合体系成形成的阳离子双水相,测定其上层和下层的胶束微环境的极性和微粘度, 取得了有意义的结果。     

Effect of addition of dendritic C60 amphiphiles on the structure of cationic surfactant solutions

The aggregation behavior of two water-soluble carboxylic C60 derivatives, dendritic methano[60] fullerene octadeca acid (1) and ennea acid (2), in aqueous solutions was investigated. Both 1 and 2 were highly soluble in pure water and buffer solutions with pH >or=7.0. Their spectral properties, especially those in the visible region, were found to be influenced greatly by solution parameters and additives. In pure water, dynamic laser light scattering (DLS) measurements revealed that both 1 and 2 could form aggregates. When 1 or 2 was added to micelle solution of a cationic surfactant, tetradecyltrimethylammonium hydroxide (TTAOH), unilamellar vesicles with diameters of several hundreds of nanometers were detected by freeze-fracture transmission electron microscope and DLS both below and above the critical micellar concentration of TTAOH. Vesicle formation was greatly suppressed when 1 or 2 was added to tetradecyltrimethylammonium bromide micelle solution and no vesicles were detected for 1 or 2 mixed with the aqueous solutions of tetrabutylammonium hydroxide or tetramethylammonium hydroxide, indicating that counterions and the hydrophobic chain length of the cationic surfactants played important roles in vesicle formation. At the same time, for mixtures of 1 and 2 with anionic surfactant sodium dodecyl sulfate, no vesicles were detected. In highly concentrated NaCl solutions, it was found that 1 and 2 could also form vesicles, which could be due to the shielding of the electrostatic interactions among hydrophilic parts of 1 and 2.     

Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge

Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.     

阴、阳离子表面活性剂混合体系在硅胶/水及硅胶/矿化水界面上的吸附

研究阴、阳离子表面活性剂混合体系(十二烷基氯代吡啶,辛基磺酸钠,辛基三乙基溴化铵/十二烷基苯磺酸钠)在硅胶,纯水和硅胶,矿化水界面上的吸附作用,探讨阴(阳)离子表面活性剂的存在对阳(阴)离子表面活性剂吸附作用的影响．结果表明,阴离子表面活性剂的存在基本不影响阳离子表面活性剂在带负电固体表面的吸附;而阳离子表面活性剂的存在却使本来吸附量就不大的阴离子表面活性剂在带负电的固体表面上不再吸附．在矿化水中阳离子表面活性剂的吸附量比在纯水中明显降低．从硅胶表面吸附机制解释了所得结果．     

Interaction of sodium N-lauroylsarcosinate with N-alkylpyridinium chloride surfactants: spontaneous formation of pH-responsive, stable vesicles in aqueous mixtures

The interaction of sodium N-lauroylsarcosinate (SLS) with N-cetylpyridinium chloride (CPC) and N-dodecylpyridinium chloride (DPC) was investigated in aqueous mixtures. A strong interaction between the anionic and cationic surfactants was observed. The interaction parameter, β was determined for a wide composition range and was found to be negative. The mixed systems were found to have much lower critical micelle concentration (cmc) and surface tension at cmc. The surfactant mixtures exhibit synergism in the range of molar fractions investigated. The self-assembly formation in the mixtures of different compositions and total concentrations were studied using a number of techniques, including surface tension, fluorescence spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), confocal fluorescence microscopy (CFM). Thermodynamically stable unilamellar vesicles were observed to form upon mixing of the anionic and cationic surfactants in a wide range of composition and concentrations in buffered aqueous media. TEM as well as DLS measurements were performed to obtain shape and size of the vesicular structures, respectively. These unilamellar vesicles are stable for periods as long as 3 months and appear to be the equilibrium form of aggregation. Effect of pH, and temperature on the stability was investigated. The vesicular structures were observed to be stable at pH as low as 2.0 and at biological temperature (37°C). In presence of 10 mol% of cholesterol the mixed surfactant vesicles exhibited leakage of the encapsulated calcein dye, showing potential application in pH-triggered drug release.     

Isothermal titration calorimetry and dynamic light scattering studies of interactions between gemini surfactants of different structure and Pluronic block copolymers

The interactions between triblock copolymers of poly(ethylene oxide) and poly(propylene oxide), P103 and F108, EO(n)PO(m)EO(n), m=56 and n=17 and 132, respectively, and m-s-m type gemini surfactants, m=8, 10, 12, and 18, and s = 3, 6, 12, and 16, have been studied in aqueous solution using isothermal titration calorimetry and dynamic light scattering techniques. The enthalpograms of F108 as a function of surfactant concentration show one broad peak at polymer concentrations C(p) < or = 0.50 wt%, below the cmc of the copolymer at 25 degrees C. It is attributed to interactions between the surfactant and the triblock copolymer monomer. DLS results show hydrodynamic radii (R(h)) initially consistent with copolymer monomers that change to values consistent with gemini surfactant micelles as the surfactant concentration is increased. In P103 solutions at C(p) > or = 0.05 wt%, two peaks appear in the enthalpograms, and they are attributed to the interactions between the gemini surfactant and the micelle or monomer forms of the copolymer. An origin-based nonlinear fitting program was employed to deconvolute the two peaks and to obtain estimates of peak properties. An estimate of the fraction of copolymer in aggregated form was also obtained. The enthalpy change due to interactions between the surfactants and P103 aggregates is very large compared to values obtained for traditional surfactants. This suggests that extensive reorganization of copolymer aggregates and surrounding solvent occurs during the interaction. DLS results for the P103 systems containing C(p) > or = 0.05% show evidence of very large aggregates in solution, likely P103 micelle clusters. The transitions observed in the hydrodynamic radii are consistent with a breakdown of micelle clusters with addition of gemini surfactant, followed by mixed micelle formation and/or deaggregation into monomer P103. This is followed by interactions similar to those typically observed in surfactant-nonionic polymer systems. Mechanisms for the interaction and the observed structural changes are discussed.     

Interaction between β‐Cyclodextrin and Mixed Cationic‐Anionic Surfactants (2): Aggregation Behavior

The interactions between β‐cyclodextrin (β‐CD) and the mixtures of cationic‐anionic surfactants in the aqueous solution were investigated by surface tension, rheology, and dynamic light scattering measurements. It was shown that the key‐lock interactions between β‐CD and mixed cationic‐anionic surfactants were stronger than the electrostatic/hydrophobic interactions between cationic and anionic surfactants. The inclusion of β‐CD to surfactants could destroy the ion‐pair and aggregates of cationic‐anionic surfactants, and even inhibited the precipitation of the mixed cationic‐anionic surfactants. Furthermore, the inclusion of β‐CD to surfactants could also destroy the hydrogen bond between β‐CD molecules, inducing the disassociation of the aggregation formed by β‐CD themselves.     

Interaction between β‐Cyclodextrin and Mixed Cationic‐Anionic Surfactants (1): Thermodynamic Study

The interactions between β‐cyclodextrin (β‐CD) and the mixtures of cationic‐anionic surfactants in aqueous solution were investigated by surface tension and ¹H NMR measurements. It was shown that the critical micelle concentration (cmc) increased linearly with the increase of β‐CD concentration. Furthermore, β‐CD formed 1∶1 inclusion complex with both cationic and anionic surfactants in the mixed surfactant systems, and no significant selective inclusion was observed. The thermodynamic parameters of the inclusion process of β‐CD to mixed cationic‐anionic surfactants were calculated by a numerical method based on the surface tension measurements, and it was found that the inclusion process was both enthalpy and entropy favorable.     

Interactions between nonpolar surfaces in mixed solutions of cationic and nonionic surfactants

The interaction energy between hydrophobic SiO₂ particles in aqueous solutions of a cationic surfactant (dodecylpyridinium bromide, DDPB), a nonionic surfactant (Triton X-100, TX-100), and their mixed solutions was measured as a function of concentration. Synergism has been observed in mixed surfactant solutions: the surfactant concentration required for achieving the set interaction energy in the mixed solutions was lower than in the solutions of the individual surfactants. The molecular interaction parameters in surfactant mixtures were calculated using the Rosen model. Chain-chain interactions between nonionic and cationic surfactants were suggested as the main reason for the synergism.     

Interaction between the water soluble poly{1,4-phenylene-[9,9-bis(4-phenoxy butylsulfonate)]fluorene-2,7-diyl} copolymer and ionic surfactants followed by spectroscopic and conductivity measurements

The interaction has been studied in aqueous solutions between a negatively charged conjugated polyelectrolyte poly{1,4-phenylene-[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl} copolymer (PBS-PFP) and several cationic tetraalkylammonium surfactants with different structures (alkyl chain length, counterion, or double alkyl chain), with tetramethylammonium cations and with the anionic surfactant sodium dodecyl sulfate (SDS) by electronic absorption and emission spectroscopy and by conductivity measurements. The results are compared with those previously obtained on the interaction of the same polymer with the nonionic surfactant C12E5. The nature of the electrostatic or hydrophobic polymer-surfactant interactions leads to very different behavior. The polymer induces the aggregation with the cationic surfactants at concentrations well below the critical micelle concentration, while this is inhibited with the anionic SDS, as demonstrated from conductivity measurements. The interaction with cationic surfactants only shows a small dependence on alkyl chain length or counterion and is suggested to be dominated by electrostatic interactions. In contrast to previous studies with the nonionic C12E5, both the cationic and the anionic surfactants quench the PBS-PFP emission intensity, leading also to a decrease in the polymer emission lifetime. However, the interaction with these cationic surfactants leads to the appearance of a new emission band (approximately 525 nm), which may be due to energy hopping to defect sites due to the increase of PBS-PFP interchain interaction favored by charge neutralization of the anionic polymer by cationic surfactant and by hydrophobic interactions involving the surfactant alkyl chains, since the same green band is not observed by adding either tetramethylammonium hydroxide or chloride. This effect suggests that the cationic surfactants are changing the nature of PBS-PFP aggregates. The nature of the polymer and surfactant interactions can, thus, be used to control the spectroscopic and conductivity properties of the polymer, which may have implications in its applications.     

Counterion binding on mixed anionic/cationic micelles

Measurements of counterion binding in mixtures of surfactant aqueous solutions have been performed to study the structure of the anionic/cationic mixed micelle/solution interface. The mixtures studied were SDS/DDAC and STS/TDPC. The binding of chloride and sodium ions to mixed anionic/cationic micelles was measured using ion-specific electrodes. Counterion binding was found to be strongly dependent on the molar ratio of surfactants present. The mixed micelle/solution interface includes the headgroups of both surfactants and counterions of surfactant in excess. The addition of oppositely charged surfactant caused an increasing dissociation of counterions.     

Vesicle formation of 1:1 cationic and anionic surfactant mixtures in nonaqueous polar solvents

The vesicle formations of 1:1 cationic-anionic surfactants in various nonaqueous polar solvents and their aqueous mixtures were investigated. Outstanding vesicle-forming capability and stability of cationic and anionic surfactants were found in nonaqueous polar solvents and their aqueous mixtures except for in formamide. A small amount of formamide destroys the vesicles formed by cationic-anionic surfactants in aqueous solutions. These results could be very well explained based on the effect of the medium dielectric constant. Received: 26 May 1998 Accepted in revised form: 24 November 1998     

Properties of binary surfactant systems of nonionic surfactants C12E10, C12E23, and C12E42 with a cationic gemini surfactant in aqueous solutions

Properties of binary surfactant systems of nonionic surfactants poly(ethylene oxide) (PEO) lauryl ethers (C(12)E(10), C(12)E(23), C(12)E(42)) with a cationic gemini surfactant, butanediyl-α,ω-bis(tetradecyldimethylammonium bromide) (14-4-14), have been investigated by Steady-state Fluorescence (FL), zeta potential, Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM), Cryogenic Transmission Electron Microscopy (CryoTEM), and X-ray Diffraction (XRD). Through FL measurements, critical micelle concentration (CMC) of the three binary systems for different mixing mole fractions is determined and the values fall between those of pure constituent surfactants. Ideal CMC (CMC(ideal)), mole fraction in aggregates (X), interaction parameter (β), activity coefficients (f(1) and f(2)), and excess free energy of mixing (ΔG(ex)) have been calculated. All these parameters indicate nonideal behavior and synergistic interactions between the constituent surfactants, which is explained in terms of electrostatic attraction between headgroups of constituent surfactants and reduction of electrostatic repulsion between headgroups of 14-4-14 due to the presence of nonionic surfactants. DLS, TEM and CryoTEM results show that nonionic surfactants facilitate the formation of larger aggregates. Micelles and vesicles in larger size compared with those of 14-4-14 coexist in the mixed solutions. Both surfactant composition and PEO chain length are found to play a strong effect on the properties of the binary systems.     

Synergism in the spreading of hydrocarbon-chain surfactants on polyethylene film-anionic and cationic mixtures by a two-step procedure

A study has been made of the adsorption, interaction, and spreading of mixtures of anionic and cationic surfactants at the aqueous solution/polyethylene (PE) interface. When a drop of an aqueous solution of an anionic or cationic hydrocarbon-chain surfactant is placed on a highly hydrophobic PE film (contact angle of water > 90 degrees ), it spreads to an area very little larger than that of a drop of water of the same volume. If the anionic and cationic hydrocarbon-chain surfactant solutions are mixed prior to being applied to PE film, synergism is small, if any, and the reproducibility of the experimental results is poor. However, when the cationic and anionic aqueous solutions are applied on the PE film in a sequential manner, a remarkable synergism in spreading is observed and the results are very reproducible. The area spread by an aqueous solution of the anionic-cationic mixture may be more than 400 times that of aqueous solutions of the same volume and surfactant concentration of the individual surfactant components. Previous work in this laboratory on surfactant systems showing synergism in spreading on PE film, but only weak interaction at the aqueous solution/air interface, showed that the synergy was due to changes at the aqueous solution/PE interface and not to the changes at the aqueous solution/air or PE/air interface. Investigation of the adsorption behavior at the aqueous solution/solid interface of two of the anionic-cationic mixtures studied here indicates the reason for differences in spreading behavior observed with different anionic-cationic mixtures. The more similar the adsorption tendencies at the solid/aqueous solution interface of the anionic and cationic surfactants, and the closer their adsorption to an equimolar monolayer there, the stronger their interaction there and the greater their enhancement of the spreading. A mechanism is proposed for the synergy in spreading observed, based upon the difference between the surface tension in the precursor film at the spreading interface and that at the top of the spreading drop.