Adsorption and mobility of a lipase at a hydrophobic surface in the presence of surfactants

With the aim of being able to manipulate the processes involved in interfacial catalysis, we have studied the effects of a mixture of nonionic/anionic surfactants, C12E6/LAS (1:2 mol %), on the adsorption and surface mobility of a lipase obtained from Thermomyces lanuginosus (TLL). Surface plasmon resonance (SPR) and ellipsometry were used to analyze the competitive adsorption process between surfactants and TLL onto hydrophobic model surfaces intended to mimic an oily substrate for the lipase. We obtained the surface diffusion coefficient of a fluorescently labeled TLL variant on silica silanized with octadecyltrichlorosilane (OTS) by fluorescence recovery after photobleaching (FRAP) on a confocal laser scanning microscope. By means of ellipsometry we calibrated the fluorescence intensity with the surface density of the lipase. The TLL diffusion was measured at different surface densities of the enzyme and at two time intervals after coadsorption with different concentrations of C12E6/LAS. The surfactant concentrations were chosen to represent concentrations below the critical micelle concentration (CMC), in the CMC region, and above the CMC. The apparent TLL surface diffusion was extrapolated to infinite surface dilution, D0. We found that the presence of surfactants strongly modulated the surface mobility of TLL: with D(0) = 0.8 x 10(-11) cm2/s without surfactants and D0 = 13.1 x 10(-11) cm2/s with surfactants above the CMC. The increase in lipase mobility on passing the CMC was also accompanied by a 2-fold increase in the mobile fraction of TLL. SPR analysis revealed that surface bound TLL was displaced by C12E6/LAS in a concentration-dependent manner, suggesting that the observed increase in surface mobility imparts bulk-mediated diffusion and so-called rebinding of TLL to the surface. Our combined results on lipase/surfactant competitive adsorption and lipase surface mobility show how surfactants may play an important role in regulating interfacial catalysis from physiological digestion to technical applications such as detergency.     

Adsorption and activity of Thermomyces lanuginosus lipase on hydrophobic and hydrophilic surfaces measured with dual polarization interferometry (DPI) and confocal microscopy

The adsorption and activity of Thermomyces lanuginosus lipase (TLL) was measured with dual polarization interferometry (DPI) and confocal microscopy at a hydrophilic and hydrophobic surface. In the adsorption isotherms, it was evident that TLL both had higher affinity for the hydrophobic surface and adsorbed to a higher adsorbed amount (1.90 mg/m²) compared to the hydrophilic surface (1.40–1.50 mg/m²). The thickness of the adsorbed layer was constant (3.5 nm) on both surfaces at an adsorbed amount >1.0 mg/m², but decreased on the hydrophilic surface at lower surface coverage, which might be explained by partially unfolding of the TLL structure. However, a linear dependence of the refractive index of the adsorbed layer on adsorbed amount of TLL on C18 surfaces indicated that the structure of TLL was similar at low and high surface coverage. The activity of adsorbed TLL was measured towards carboxyfluorescein diacetate (CFDA) in solution, which upon lipase activity formed a fluorescent product. The surface fluorescence intensity increase was measured in a confocal microscope as a function of time after lipase adsorption. It was evident that TLL was more active on the hydrophilic surface, which suggested that a larger fraction of adsorbed TLL molecules were oriented with the active site facing the solution compared to the hydrophobic surface. Moreover, most of the activity remained when the TLL surface coverage decreased. Earlier reports on TLL surface mobility on the same surfaces have found that the lateral diffusion was highest on hydrophilic surfaces and at low surface coverage of TLL. Hence, a high lateral mobility might lead to a longer exposure time of the active site towards solution, thereby increasing the activity against a water-soluble substrate.     

Forces between polyethylene surfaces in oxyethylene dodecyl ether solutions as influenced by the number of oxyethylene groups

The atomic force microscopy (AFM) colloidal probe technique was used to study the effect of oxyethylene dodecyl ethers, C12En (n = 1-7), on interactions between hydrophobic polyethylene (PE) surfaces in aqueous solutions. Long-range (colloidal) and contact (pull-off) forces were measured between 10 to 20 microm PE spheres and a flat PE surface at concentrations of surfactant of 1 x 10(-6) and 1 x 10(-4) M. The surface tension of the surfactant solutions and contact angles at PE surfaces were also studied. The influence of the number of oxyethylene groups in the surfactant molecule was examined. Initially, long-range attractive (hydrophobic) forces between the PE surfaces were observed that decreased in range and magnitude with an increase in the number of oxyethylene groups in 1 x 10(-4) M solutions. Above four oxyethylene groups per molecule, repulsive forces were observed. The measured pull-off force between PE surfaces decreased monotonically from approximately 500 mJ/m2 for C12E1 to 150 mJ/m2 for C12E7. The interfacial energy was calculated on the basis of the JKR model, taking into account long-range forces operating outside the contact area. The interfacial energies decreased from 43-47 mJ/m2 for PE-water and PE-C12E1 (1 x 10(-4) M) interfaces to approximately 18 mJ/m2 for PE-C12E7 (1 x 10(-4) M). The interfacial energy was also calculated from measured contact angles and surface tensions using Neumann's equation of state and Young's equation. A similar relationship between interfacial energy and the number of oxyethylene groups was observed on the basis of contact and surface tension measurements. However, interfacial energy values were smaller, within 15-20 mJ/m2, than those calculated from AFM pull-off force measurements.     

Interactions between nonpolar surfaces coated with the nonionic surfactant hexaoxyethylene dodecyl ether C12E6 and the origin of surface charges at the air/water interface

The interactions between nonpolar surfaces coated with the nonionic surfactant hexaoxyethylene dodecyl ether C12E6 were investigated using two techniques and three different types of surfaces. As nonpolar surfaces, the air/water interface, silanated negatively charged glass, and thiolated uncharged gold surfaces were chosen. The interactions between the air/water interfaces were measured with a thin film pressure balance in terms of disjoining pressure as a function of film thickness. The interactions between the solid/liquid interfaces were determined using a bimorph surface force apparatus. The influence of the nature of the surface on the interaction forces was investigated at surfactant concentrations below and above the cmc. The adsorption of the nonionic surfactant on the uncharged thiolated surface does not, as expected, lead to any buildup of a surface charge. On the other hand, adsorption of C12E6 on the charged silanated glass and the charged air/water interface results in a lowering of the surface charge density. The reduction of the surface charge density on the silanated glass surfaces is rationalized by changes in the dielectric permittivity around the charged silanol groups. The reason for the surface charge observed at the air/water interface as well as its decrease with increasing surfactant concentration is discussed and a new mechanism for generation of OH- ions at this particular interface is proposed.     

Interaction between bovine serum albumin and equimolarly mixed cationic-anionic surfactants decyltriethylammonium bromide-sodium decyl sulfonate

The interactions of bovine serum albumin (BSA) with the anionic surfactant sodium decylsulfonate (C10SO3), the cationic surfactant decyltriethylammonium bromide (C10NE) and equimolarly mixed cationic-anionic surfactants C10NE-C10SO3 were investigated by surface tension, viscosity, dynamic light scattering (DLS) and circular dichroism (CD). It was shown that the single ionic surfactant C10SO3 or C10NE has obvious interaction with BSA. The presence of C10SO3 or C10NE modified BSA structure. However, the equimolarly mixed cationic-anionic surfactants C10NE-C10SO3 showed very weak interactions with BSA. The surface tension-log concentration (gamma-logC) plot for the aqueous solutions of C10NE-C10SO3/BSA mixtures coincided with that of C10NE-C10SO3 solutions. Viscometry showed that there is no significant change in the rheological properties for the C10NE-C10SO3/BSA mixed solutions. DLS showed that BSA monomers and mixed aggregates of C10NE-C10SO3 existed in the C10NE-C10SO3/BSA mixed solutions. From CD spectra no obvious modification of BSA structure in the presence of C10NE-C10SO3 mixtures was observed. The weak interactions between BSA and C10NE-C10SO3 might be explained in terms of the very low critical micelle concentration (cmc) of C10NE-C10SO3 mixtures that made the concentration of ionic surfactant monomers much lower than that needed for inducing the modification of BSA structure. In other words, the very strong synergism between oppositely charged cationic and anionic surfactants makes the formation of cationic-anionic surfactant mixed aggregates in the bulk solution a more favorable process than binding to proteins.     

C_（12）C_6C_（12）Br_2/C_（12）E_（10）混合表面活性剂与DNA之间的相互作用

本文以构建有效的非病毒基因载体为目的,研究了C12C6C12Br2/C12E10混合表面活性剂组成对其与DNA之间相互作用的影响,并对混合表面活性剂与DNA形成的聚集体结构和形貌进行了表征。结果表明,当固定混合表面活性剂的总浓度为1.0 mmol/L时,混合表面活性剂组成的改变会引起混合体系浊度、聚集体表面电荷和聚集体...     

Mobility of Thermomyces lanuginosus lipase on a trimyristin substrate surface

We have studied the mobility of active and inactive Thermomyces lanuginosus lipase (TLL) on a spin-coated trimyristin substrate surface using fluorescence recovery after photobleaching (FRAP) in a confocal microscopy setup. By photobleaching a circular spot of fluorescently labeled TLL adsorbed on a smooth trimyristin surface, both the diffusion coefficient D and the mobile fraction f could be quantified. FRAP was performed on surfaces with different surface density of lipase and as a function of time after adsorption. The data showed that the mobility of TLL was significantly higher on the trimyristin substrate surfaces compared to our previous studies on hydrophobic model surfaces. For both lipase variants, the diffusion decreased to similar rates at high relative surface density of lipase, suggesting that crowding effects are dominant with higher adsorbed amount of lipase. However, the diffusion coefficient at extrapolated infinite surface dilution, D0, was higher for the active TLL compared to the inactive (D0 = 17.9 x 10(-11) cm2/s vs D0 = 4.1 x 10(-11) cm2/s, data for the first time interval after adsorption). Moreover, the diffusion decreased with time after adsorption, most evident for the active TLL. We explain the results by product inhibition, i.e., that the accumulation of negatively charged fatty acid products decreased the diffusion rate of active lipases with time. This was supported by sequential adsorption experiments, where the adsorbed amount under flow conditions was studied as a function of time after adsorption. A second injection of lipase led to a significantly lower increase in adsorbed amount when the trimyristin surface was pretreated with active TLL compared to pretreatment of inactive TLL.     

Physicochemical characterization of an anatase TiO2 surface and the adsorption of a nonionic surfactant: an atomic force microscopy study

Atomic force microscopy was used to characterize an anatase TiO2 surface, prepared by the helical vapor preparation method. The forces between two bare TiO2 surfaces were measured in the presence of water at various pH values. This TiO2 isoelectric point (iep) was characterized by the presence of only a van der Waals attraction and was measured at pH 5.8; this value is similar to that for a rutile TiO2 surface. The adsorption mechanism of a nonionic surfactant molecule to this anatase TiO2 surface was investigated by measuring the forces between two such TiO2 surfaces at their iep pH in the presence of linear dodecanol tetraethoxylate (C12E4), a poly(ethoxylene oxide) n-alkyl ether. C12E4 was seen by the presence of steric forces to adsorb to the uncharged TiO2 surface. For low surfactant concentrations, C12E4 adsorbed with its hydrophobic tail facing the TiO2 substrate, to reduce its entropically unfavorable contacts with water. Additional surfactant adsorption occurred at higher surfactant concentrations by the hydrophobic and hydrophilic interactions between the surfactant tails and heads, respectively, and gave sub-bilayers. A two-step adsorption isotherm was subsequently proposed with four regions: (1) submonolayer, (2) complete monolayer, (3) sub-bilayer, and (4) bilayer. The absence of a long-range repulsive force between the two TiO2 surfaces in the presence of the C12E4 surface aggregates indicated that a C12E4 nonionic surfactant aggregate did not possess charge.     

Analytical investigation of the self-desorption of the oligomers of mixtures of a polydisperse ethoxylated surfactant with sodium dodecylsulfate from a silica/water interface

The adsorption isotherms onto a hydrophilic silica of mixtures of sodium dodecylsulfate (SDS) and of all the oligomers of a polydisperse nonylethylene glycol n-dodecyl ether (C(12)E(9)) surfactant were determined using a high-performance liquid chromatography (HPLC) technique. Incorporation of the anionic surfactant to the negatively charged silica surface is favored by the adsorption of the nonionic surfactant. Comparison between the adsorption isotherms of mixtures of SDS with a monodisperse C(12)E(9) and a polydisperse C(12)E(9) shows that the adsorption of SDS at the silica/water interface is stronger with the latter material than with the former in a large surface coverage domain. The composition of the surface aggregates and the variation of the oligomer distribution in these aggregates were determined. The previously described phenomena called self-desorption which was observed for the global C(12)E(9) and SDS surfactant mixtures was confirmed: increasing the total concentration at a fixed surfactant ratio induces at high concentration a desorption of the anionic surfactant and all of the less polar oligomers from the solid/water interface. An interpretation scheme is proposed which assumes that the interaction of SDS is larger with the less polar oligomers than with the polar ones. The self-desorption effect could then be considered as the consequence of the polydispersity of the nonionic surfactant and to the net repulsion interaction between SDS and the silica surface as the mole fraction of SDS in the surfactant mixture increases.     

Dependence of Colloidal Forces Between Bitumen and Silica on the Chain Lengths of Ammonium Surfactants

Effects of ammonium surfactants with different hydrocarbon chain lengths (C8, C12, C16, and C18) on the colloidal forces between bitumen and silica were studied by atomic force microscopy. The results showed that the chain length of the ammonium surfactants had a significant impact on both the long-range interaction and adhesion forces. With the addition of surfactants with relative short chains of C8 and C12 in the solutions, the long-range repulsive force decreased or even became strong attractive force, while it became repulsive again in solutions of surfactants with long chains of C16 and C18. It was further observed that addition of Ca²⁺ in various surfactants solutions would either depress or enhance the colloidal interactions based on the surfactant chain lengths. It was believed that variation of the interaction behaviors resulted from the mono-layer or bilayer adsorption of various surfactant molecules on the negatively charged surfaces of bitumen and silica, which affected the surface wettability and the surface charge characteristics and then greatly changed the colloidal interactions. The findings indicated that, to have a high bitumen recovery and good froth quality, the surfactant type and concentration of the di-valent metal ions in the oil sand processing slurry must be well considered.     

Micellar Interactions in Nonionic/Ionic Mixed Surfactant Systems

To study the influence of the chemical nature of headgroups and the type of counterion on the process of micellization in mixed surfactant systems, the cmc's of several binary mixtures of surfactants with the same length of hydrocarbon tail but with different headgroups have been determined as a function of the monomer composition using surface tension measurements. Based on these results, the interaction parameter between the surfactant species in mixed micelles has been determined using the pseudophase separation model. Experiments were carried out with (a) the nonionic/anionic C(12)E(6)/SDS ((hexa(ethyleneglycol) mono-n-dodecyl ether)/(sodium dodecyl sulfate)), (b) amphoteric/anionic DDAO/SDS ((dodecyldimethylamine oxide)/(sodium dodecyl sulfate)), and (c) amphoteric/nonionic C(12)E(6)/DDAO mixed surfactant systems. In the case of the mixed surfactant systems containing DDAO, experiments were carried out at pH 2 and pH 8 where the surfactant was in the cationic and nonionic form, respectively. It was shown that the mixtures of the nonionic surfactants with different kinds of headgroups exhibit almost ideal behavior, whereas for the nonionic/ionic surfactant mixtures, significant deviations from ideal behavior (attractive interactions) have been found, suggesting binding between the head groups. Molecular orbital calculations confirmed the existence of the strong specific interaction between (1) SDS and nonionic and cationic forms of DDAO and between (2) C(12)E(6) and the cationic form of DDAO. In the case for the C(12)E(6)/SDS system, an alternative mechanism for the stabilization of mixed micelles was suggested, which involved the lowering in the free energy of the hydration layer. Copyright 2000 Academic Press.     

Molecular dynamics simulations of surfactants at the silica-water interface: anionic vs nonionic headgroups

Understanding surfactant adsorption on surfaces at the molecular level will provide us with the ability to design specific surfactants for surface modification. We conducted molecular dynamics simulations for sodium dodecyl sulfate (SDS) and hexaethylene glycol monododecyl ether (C(12)E(6)) adsorbed on silica substrates with varying degree of hydroxylation. Our results shed light on the effects of hydroxylation on the surfactant aggregate morphology. The discrete charge distribution on the substrate surface appears to dictate both surfactant adsorption and aggregate morphology. The differences in aggregate morphology observed for anionic SDS and non-ionic C(12)E(6) on silica substrates are discussed quantitatively and compared to available experimental data.     

In situ AFM studies on self-assembled monolayers of adsorbed surfactant molecules on well-defined H-terminated Si(111) surfaces in aqueous solutions

The formation of self-assembled monolayers (SAMs) of adsorbed cationic or anionic surfactant molecules on atomically flat H-terminated Si(111) surfaces in aqueous solutions was investigated by in situ AFM measurements, using octyl trimethylammonium chloride (C8TAC), dodecyl trimethylammonium chloride (C12TAC), octadecyl trimethylammonium chloride (C18TAC)) sodium dodecyl sulfate (STS), and sodium tetradecyl sulfate (SDS). The adsorbed surfactant layer with well-ordered molecular arrangement was formed when the Si(111) surface was in contact with 1.0x10(-4) M C18TAC, whereas a slightly roughened layer was formed for 1.0x10(-4) M C8TAC and C12TAC. On the other hand, the addition of alcohols to solutions of 1.0x10(-4) M C8TAC, C12TAC, or SDS improved the molecular arrangement in the adsorbed surfactant layer. Similarly, the addition of a salt, KCl, also improved the molecular arrangement for both the cationic and anionic surfactant layers. Moreover, the adsorbed surfactant layer with a well-ordered structure was formed in a solution of mixed cationic (C12TAC) and anionic (SDS) surfactants, though each surfactant alone did not form the well-ordered layer. These results were all explained by taking into account electrostatic repulsion between ionic head groups of adsorbed surfactant molecules as well as hydrophobic interaction between their alkyl chains, which increases with the increasing chain length, together with the increase in the hydrophobic interaction or the decrease in the electrostatic repulsion by incorporating alcohol molecules into the adsorbed surfactant layer, the decrease in the electrostatic repulsion by increasing the concentration of counterions, and the decrease in the electrostatic repulsion by alternate arrangement of cationic and anionic surfactant molecules. The present results have revealed various factors to form the well-ordered adsorbed surfactant layers on the H-Si(111) surface, which have a possibility of realizing the third generation surfaces with flexible structures and functions easily adaptable to circumstances.     

The role of electrolyte and polyelectrolyte on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, at the air-water interface

The role of the polyelectrolyte, poly(ethyleneimine), PEI, and the electrolytes NaCl and CaCl(2), on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, LAS, at the air-water interface have been investigated by neutron reflectivity and surface tension. The surface tension data for the PEI/LAS mixtures are substantially affected by pH and the addition of electrolyte, and are consistent with a strong adsorption of surface polymer/surfactant complexes down to relatively low surfactant concentrations. The effects are most pronounced at high pH, and this is confirmed by the adsorption data obtained directly from neutron reflectivity. However, the effects of the addition of PEI and electrolyte on the LAS adsorption are not as pronounced as previously reported for PEI/SDS mixtures. This is attributed primarily to the steric hindrance of the LAS phenyl group resulting in a reduction in the ion-dipole attraction between the LAS sulfonate and amine groups that dominates the interaction at high pH.     

The influence of polarization of the sorbent on sorption of albumin by carbon fibers

The sorption of bovine serum albumin (BSA) on non-charged and polarized surfaces of carbon fibers (ACF) and carbon fibers modified with titanium hydroxide (ACF-Ti) was studied. It was shown that cathodic polarization considerably influences the reversibility of the BSA sorption and decreases the BSA sorption by ACF and ACF-Ti to a larger extent than anodic polarization. A change in the surface charge mainly influences sorption of albumin by ACF-Ti, which is due to different surface properties of the initial and titaniumcontaining adsorbents. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1496–1498, August, 1998.     

Solubilization by different-sized surfactant mixtures

The solubilization phenomenon was investigated in mixed surfactant systems. The solubilization power of a mixed surfactant reaches its maximum at a particular temperature at each mixing ratio of surfactants. When the mole fraction of C4E1 in the total surfactant (w1 value) was varied in a water/C12E5/C4E1/decane system, the minimum mole fraction of total surfactant in the system necessary to obtain a single microemulsion phase (xi value) was almost unchanged for w1<0.3, whereas it increased remarkably for w1>0.8. The molar solubilization capacity (Cs=(1-xi)/xi) of the mixed surfactant decreased remarkably for w1<0.3, whereas it decreased gradually for w1>0.8. The result [Formula: see text] is due largely to the characteristic of the function xi(Cs)=1/(1+Cs), specifically, [Formula: see text] , where dxi/dw1=(dxi/dCs)(dCs/dw1). The partial molar solubilization capacity (Cs) of C4E1 was negative at almost all w1, but the Cs value of C12E5 went through a maximum on the addition of C4E1. Propanol (a cosurfactant) has the same effect on the solubilization phenomenon in the water/C12E6/propanol/heptane system. In the water/C12E5/C12E7/decane system, the Cs value of each surfactant did not vary greatly as the mixing ratio of surfactants was varied. The Cs and xi values were close to molar additivity for each mixing ratio.     

新型阴离子Gemini表面活性剂与非离子表面活性剂C10E6混合溶液的胶团化的研究

研究了烷基苯磺酸盐Gemini表面活性剂Ia与非离子表面活性剂C10E6溶液混合胶团中分子间的相互作用. 通过表面张力法测定了Ia 和C10E6不同比例不同温度下的临界胶束浓度(cmc). 结果表明, 两种表面活性剂以任何比例复配的cmc比单一表面活性剂的cmc都低, 表现出良好的协同效应. 传统型非离子表面活性剂C10E6、Gemini表面活性剂Ia及混合物的cmc都随着温度升高而降低. 而且, 任何配比的混合胶团中两种表面活性剂分子间的相互作用参数β都是负值, 这说明两种表面活性剂在混合胶团中产生了相互吸引的作用. 混合表面活性剂体系的胶团聚集数比单一Ia的大, 但比单一C10E6的小. 向Gemini表面活性剂Ia胶束中加入非离子表面活性剂C10E6会使胶束的微观极性变小.     

The influence of surfactant mixing ratio on nano-emulsion formation by the pit method

The formation of O/W nano-emulsions by the PIT emulsification method in water/mixed nonionic surfactant/oil systems has been studied. The hydrophilic-lipophilic properties of the surfactant were varied by mixing polyoxyethylene 4-lauryl ether (C12E4) and polyoxyethylene 6-lauryl ether (C12E6). Emulsification was performed in samples with constant oil concentration (20 wt%) by fast cooling from the corresponding HLB temperature to 25 degrees C. Nano-emulsions with droplet radius 60-70 nm and 25-30 nm were obtained at total surfactant concentrations of 4 and 8 wt%, respectively. Moreover, droplet size remained practically unchanged, independent of the surfactant mixing ratio, X(C12E6). At 4 wt% surfactant concentration, the polydispersity and instability of nano-emulsions increased with the increase in X(C12E6). However, at 8 wt% surfactant concentration, nano-emulsions with low polydispersity and high stability were obtained in a wide range of surfactant mixing ratios. Phase behavior studies showed that at 4 wt% surfactant concentration, three-liquid phases (W+D+O) coexist at the starting emulsification temperature. Furthermore, the excess oil phase with respect to the microemulsion D-phase increases with the increase in X(C12E6), which could explain the increase in instability. At 8 wt% surfactant concentration, a microemulsion D-phase is present when emulsification starts. The low droplet size and polydispersity and higher stability of these nano-emulsions have been attributed, in addition to the increase in the surface or interfacial activity, to the spontaneous emulsification produced in the microemulsion D-phase.     

Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the air-water interface

The adsorption of the surface-active protein hydrophobin, HFBII, and the competitive adsorption of HFBII with the cationic, anionic, and nonionic surfactants hexadecyltrimethylammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), has been studied using neutron reflectivity, NR. HFBII adsorbs strongly at the air-water interface to form a dense monolayer ～30 ? thick, with a mean area per molecule of ～400 ?(2) and a volume fraction of ～0.7, for concentrations greater than 0.01 g/L, and the adsorption is independent of the solution pH. In competition with the conventional surfactants CTAB, SDS, and C(12)E(6) at pH 7, the HFBII adsorption totally dominates the surface for surfactant concentrations less than the critical micellar concentration, cmc. Above the cmc of the conventional surfactants, HFBII is displaced by the surfactant (CTAB, SDS, or C(12)E(6)). For C(12)E(6) this displacement is only partial, and some HFBII remains at the surface for concentrations greater than the C(12)E(6) cmc. At low pH (pH 3) the patterns of adsorption for HFBII/SDS and HFBII/C(12)E(6) are different. At concentrations just below the surfactant cmc there is now mixed HFBII/surfactant adsorption for both SDS and C(12)E(6). For the HFBII/SDS mixture the structure of the adsorbed layer is more complex in the region immediately below the SDS cmc, resulting from the HFBII/SDS complex formation at the interface.     

Salt effect on the complex formation between cationic gemini surfactant and anionic polyelectrolyte in aqueous solution

Salt effect on the interaction of anionic polyelectrolyte sodium carboxymethylcellulose (NaCMC) with cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) [C12H25(CH3)2N(CH2)6N(CH3)2C12H25]Br2 (C12C6C12Br2) has been investigated using turbidimetric titration, steady-state fluorescence, and mobility measurement. It is found that the critical aggregation concentration(cac) for C12C6C12Br2/NaCMC complexes depends little on addition of sodium bromide (NaBr). However, in the presence of nonionic surfactant Triton X-100 (TX100), the critical ionic surfactant mole fraction for the onset of complex formation (Yc) increases markedly with increasing NaBr concentration. These salt effects are supposed as the overall result from competition between the increase of interaction and the screening of interaction. The increase of interaction is referred to as the effect that the larger micelle with higher surface charge density induced by salt has a stronger interaction with oppositely charged polyelectrolyte. The screening of interaction is referred to as the salt screening of electrostatic attraction between the polymer chain and the surfactant. For complex formation between C12C6C12Br2 and NaCMC, the increase of interaction probably compensates the screening of interaction, leading to constant cac values at different salt concentrations. For complex formation between the C12C6C12Br2/TX100 mixed micelle and NaCMC, the screening of interaction probably plays a dominant role, leading to higher suppression of electrostatic binding of micelles to polyelectrolyte.