The effect of surfactants on adsorbed layers of a cationic polyelectrolyte

A comparative study of the influence of anionic (sodium dodecyl sulfate, SDS), cationic (tetradecyltrimethylammonium bromide, TTAB) and non-ionic (penta-ethyleneglycol mono n-dodecyl ether, C₁₂E₅) surfactants on the structure and composition of adsorbed layers of cationic hydrophobically modified hydroxyethylcellulose (Quatrisoft LM 200) on hydrophilic surfaces (mica and silica) was carried out using surface force apparatus andin situ null ellipsometry. It is shown that a complex interplay of electrostatic, hydrophobic, and steric effect govern polymer/surfactant/surface interactions and that the effect of surfactant addition strongly depends on its nature and concentration.Both anionic and non-ionic surfactants exhibit aggregation on the polymer hydrophobes. SDS has the most profound influence on Quatrisoft interfacial behavior due to the changes in electrostatics accompanying formation of the polymer/surfactant complex. In the case of C₁₂E₅, large surfactant clusters bound to the polymer affect the macromolecules' conformation in the adsorbed layer via steric effects. In contrast to SDS and C₁₂E₅, no evidence of interaction between the polycation and a like-charged surfactant, TTAB, was obtained. At the same time, TTAB adsorbs on the surface in competition with the polyelectrolyte. This results in partial displacement of the latter and its looser attachment to the surface.     

卵清蛋白与离子型表面活性剂的相互作用

本文通过荧光光谱法、紫外-可见吸收光谱法和透射电镜并结合电导率测定分别研究了水中卵清蛋白与阴离子表面活性剂十二烷基硫酸钠（SDS）和阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）之间的相互作用。研究结果表明卵清蛋白可以增加SDS和CTAB的临界胶束浓度,但对DTAB的临界胶束浓度没有影响。阴离子表面活性剂可以使卵清蛋白构象完全伸展,而阳离子表面活性剂却不具备此种作用。表面活性剂单体与卵清蛋白的相互作用强于表面活性剂胶束与卵清蛋白的相互作用。     

Effect of surfactant type on surfactant-maltodextrin interactions: isothermal titration calorimetry, surface tensiometry, and ultrasonic velocimetry study

Isothermal titration calorimetry (ITC), surface tensiometry, and ultrasonic velocimetry were used to characterize surfactant-maltodextrin interactions in buffer solutions (pH 7.0, 10 mM NaCl, 20 mM Trizma base, 30.0 degrees C). Experiments were carried out using three surfactants with similar nonpolar tail groups (C12) but different charged headgroups: anionic (sodium dodecyl sulfate, SDS), cationic (dodecyl trimethylammonium bromide, DTAB), and nonionic (polyoxyethylene 23 lauryl ether, Brij35). All three surfactants bound to maltodextrin, with the binding characteristics depending on whether the surfactant headgroup was ionic or nonionic. The amounts of surfactant bound to 0.5% w/v maltodextrin (DE 5) at saturation were < 0.3 mM Brij35, approximately 1-1.6 mM SDS, and approximately 1.5 mM DTAB. ITC measurements indicated that surfactant binding to maltodextrin was exothermic. Surface tension measurements indicated that the DTAB-maltodextrin complex was more surface active than DTAB alone but that SDS- and Brij35- maltodextrin complexes were less surface active than the surfactants alone.     

1H NMR relaxation of water: a probe for surfactant adsorption on kaolin

In this study, (1)H NMR is used to investigate properties of sodium dodecyl sulfate (SDS), tetradecyl trimethyl ammonium bromide (TTAB), and dodecyl trimethyl ammonium bromide (DTAB) adsorbed on kaolin by NMR T(1) and T(2) measurements of the water proton resonance. The results show that adsorbed surfactants form a barrier between sample water and the paramagnetic species present on the clay surface, thus significantly increasing the proton T(1) values of water. This effect is attributed to the amount of adsorbed surfactants and the arrangement of the surfactant aggregates. The total surface area covered by the cationic (DTAB and TTAB) and anionic (SDS) surfactants could be estimated from the water T(1) data and found to correspond to the fractions of negatively and positively charged surface area, respectively. For selected samples, the amount of paramagnetic species on the clay surface was reduced by treatment with hydrofluoric (HF) acid. For these samples, T(1) and T(2) measurements were taken in the temperature range 278-338 K, revealing detailed information on molecular mobility and nuclear exchange for the sample water that is related to surfactant behavior both on the surface and in the aqueous phase.     

Hydrophobic terminal group of surfactant initiating micellization as revealed by 1H NMR spectroscopy

The critical aggregation concentration (CAC) of four with three kinds of conventional surfactants, namely, two cationic surfactants [hexadecyltrimethyl ammonium bromide (CTAB) and tetradecyltrimethyl ammonium bromide (TTAB)], one anionic surfactant [sodium dodecyl sulfate (SDS)], and a nonionic surfactant [Triton X-100 (TX-100)], were determined by variation of ¹H chemical shifts with surfactant concentrations. Results show that the CAC values of protons at different positions of the same molecule are different, and those of the terminal methyl protons are the lowest, respectively, which suggests that the terminal groups of the alkyl chains aggregates first during micellization. Measurement of the transverse relaxation time (T₂) of different protons in SDS also show that the terminal methyl protons start to decrease with the increase in concentration first, which supports the above mentioned tendency.     

Polymer-Surfactant Interactions and the Effect of Tail Size Variation on Micellization Process of Cationic ATAB Surfactants in Aqueous Medium

The interactions between oppositely charged surfactant-polymer systems have been studied using surface tension and conductivity measurements and the dependence of aggregation phenomenon over the polyelectrolyte concentration and chain length of cationic ATAB surfactants, cetyltrimethyl ammonium bromide (CTAB), tetradecyltrimethyl ammonium bromide (TTAB), and dodecyltrimethyl ammonium bromide (DTAB) have been investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolyte at critical aggregation concentration (cac). The cac values of ATAB surfactants in the presence of anionic polyelectrolyte, sodium carboxy methyl cellulose (NaCMC), are considerably lower than their critical micelle concentration (cmc). After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in polyelectrolyte aqueous solution than in pure water. Among the cationic surfactants (i.e., CTAB, TTAB, and DTAB), DTAB was found to have least interaction with NaCMC. Surfactants with longer tail size strongly favor the interaction, indicating the dependence of aggregation phenomenon on the structure, morphology, and tail length of the surfactant.      

Encapsulation of curcumin in cationic micelles suppresses alkaline hydrolysis

The alkaline hydrolysis of curcumin was studied in three types of micelles composed of the cationic surfactants cetyl trimethylammonium bromide (CTAB) and dodecyl trimethylammonium bromide (DTAB) and the anionic surfactant sodium dodecyl sulfate (SDS). At pH 13, curcumin undergoes rapid degradation by alkaline hydrolysis in the SDS micellar solution. In contrast, alkaline hydrolysis of curcumin is greatly suppressed in the presence of either CTAB or DTAB micelles, with a yield of suppression close to 90%. The results from fluorescence spectroscopic studies reveal that while curcumin remains encapsulated in CTAB and DTAB micelles at pH 13, curcumin is dissociated from the SDS micelles to the aqueous phase at this pH. The absence of encapsulation and stabilization in the SDS micellar solution results in rapid hydrolysis of curcumin.     

Interactions between zwitterionic and conventional anionic and cationic surfactants

Critical micelle concentration (cmc) values have been determined for the mixed zwitterionic/anionic surfactant systems of N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-12)/sodium dodecyl sulfate (SDS), N-dodecyl-N,N-(dimethylammonio)butyrate (DDMAB)/SDS, N-octyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (ZW3-08)/sodium octyl sulfate (SOS), and the zwitterionic/cationic systems of ZW3-12/dodecyltrimethylammonium bromide (DTAB), DDMAB/DTAB. Conductivity studies and nuclear magnetic resonance (NMR) spectroscopy were the methods employed for cmc determinations. The degree of nonideality of the interaction in the micelle (beta(m)), for each system, was determined according to Rubingh's nonideal solution theory. Evidence was found for the existence of strong interactions between zwitterionic and anionic surfactants in each of the zwitterionic/anionic systems. The ZW3-08/SOS and DDMAB/SDS systems behaved synergistically at all mole fractions studied while the ZW3-12/SDS system exhibited synergistic behavior above mole fractions of 0.30. Greater negative deviations from ideal behavior were demonstrated in the DDMAB/SDS system than in the other two zwitterionic/anionic systems. The zwitterionic/cationic systems of ZW3-12/DTAB and ZW3-08/OTAB displayed only slight deviations from ideal behavior, therefore indicating near ideal mixing.     

Characterization and Aggregation Behaviors of Mixed DDAB/SDS Solution With and Without Poly(4-styrenesulfonic Acid-Co-Maleic Acid) Sodium

Synthetic vesicles are formed by cationic and anionic surfactants, didodecyldimethylammonium bromide (DDAB), and sodium dodecylsulfate (SDS). The morphology, size, and aqueous properties of cationic/anionic mixtures are investigated at various molar ratios between cationic and anionic surfactants. The charged vesicular dispersions made of DDAB/SDS are contacted or mixed with negatively charged polyelectrolyte, poly(4-styrenesulfonic acid-co-maleic acid) sodium (PSSAMA), to form complexes. Depending on DDAB/SDS molar ratio or PSSAMA/vesicle charge ratio, complexes flocculation or precipitation occur. Characterization of the cationic/anionic vesicles or complexes formed by the catanionic vesicles and polyelectrolytes is performed by transmission electron microscope (TEM), dynamic light scattering (DLS), conductivity, turbidity, and zeta potential measurements. The size, stability, and the surface charge on the mixed cationic/anionic vesicles or complexes are determined.     

Observations of the effect of anionic, cationic, neutral, and zwitterionic surfactants on the Belousov-Zhabotinsky reaction

In this paper we report the experimental observations of the effects of various surfactants on the oscillations of the ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction. The oscillations are followed by observing the change in absorbance at 510 nm due to ferroin in a well-stirred closed BZ reacting system. We have used sodium dodecyl sulfate (SDS) as the anionic surfactant, cetyl trimethylammonium bromide (CTAB) as the cationic surfactant, Triton X-100 as the neutral surfactant, and 3-[(3-cholamidopropyl)dimethylammonio)]-1-propanesulfonate (CHAPS) as the zwitterionic surfactant. In general, we observed that there is a change in the oscillation behavior in the presence of each of these surfactants above their critical micellar concentrations. For different surfactants, the time-dependent evolution of the oscillations is found to be characteristic of the surfactant. The results of our study suggest that the evolution of oscillations is most regular in the presence of micelles of SDS.     

Quenching of zinc phthalocyanine excited states by viologen surfactant assemblies——The influence of microenvironment

A series of functional surfactants of N-alkyl-N'-butyl viologens has been synthesized.The quenching of excited singlet and triplet states of zinc phthalocyanine was studied in DMSOand in mixed micelles containing the functional surfactant as one and cationic cetyl trimethylam-monium bromide(CTAB),anionic sodium dodecylsulfate(SDS)and neutral TX-100 surfactantas the other component.Fluorescence quenching and laser photolysis studies indicate that thefunctional surfactants are solubilized at different sites in micelles,the process depends on chainlength and exerts great influence on the quenching of zinc phthalocyanine excited states.     

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.     

表面活性剂与叶酸的相互作用及其对光氧化降解的影响

表面活性剂与有机小分子作用不仅能提高表面活性剂的聚集能力,还能提高小分子的溶解度、稳定性等应用性能,因此研究二者之间的相互作用机理对于促进表面活性剂的发展和实际应用具有重要意义。本工作提出了一种利用功能有机小分子调控表面活性剂聚集行为,进而提高不稳定小分子自身稳定性的新策略。利用表面张力、紫外可见吸收光谱、荧光光谱、动态光散射、等温滴定量热和核磁共振技术研究了在p H为7.0时,叶酸分别与十二烷基硫酸钠(SDS)、十二烷基三甲基溴化铵(DTAB)、季铵盐Gemini 12-6-12和季铵盐线性三聚12-3-12-3-12四种表面活性剂之间的相互作用及其导致的叶酸光氧化降解性能的变化,结果表明,阴离子表面活性剂SDS抑制叶酸光氧化降解的效率较低,而阳离子表面活性剂都能够显著抑制叶酸的光氧化降解,且随着表面活性剂寡聚度的增加,抑制效果增强,所需表面活性剂的浓度显著降低,寡聚表面活性剂12-3-12-3-12的抑制效率高达96%。     

A surfactant type fluorescence probe for detecting micellar growth

We report on the detection of micellar growth in anionic, cationic, and catanionic surfactant systems using a novel surfactant type fluorescence probe, sodium 12-(N-dansyl)amino-dodecanate (12-DAN-ADA). The fluorescent group was incorporated in the tail of the surfactant which tethers the fluorescent group deep inside the apolar micellar cores. The fluorescence anisotropy of 12-DAN-ADA was found to be very sensitive for directly detecting the micellar growth in micelles containing oppositely charged surfactants, including cationic CTAB systems and mixed systems of oppositely charged surfactants (DEAB/SDS); in regard to the like charged SDS micellar systems, the sensitivity can be greatly enhanced by addition of a water soluble quencher which quenches the background fluorescence from the equilibrium population of free 12-DAN-ADA.     

Surfactant polymer interactions between strongly interacting cationic surfactants and anionic polyelectrolytes from conductivity and turbidity measurements

The interactions between oppositely charged surfactant/polymer mixtures have been studied using conductivity and turbidity measurements. The dependence of aggregation phenomenon on the chain length and head group modifications of conventional cationic surfactants, i.e., hexadecyl- (HTAB), tetradecyl- (TTAB), and dodecyltrimethylammonium bromides (DTAB) and dimeric cationic surfactants, i.e., decyl- (DeDGB) and dodecyldimethylgemini bromides (DDGB), is investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolytes at critical aggregation concentration (cac). The cac values are considerably lower than the critical micelle concentration (cmc) values for the same surfactant. After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in aqueous polyelectrolyte than in pure water. Among the conventional and dimeric cationic surfactants, DTAB and DeDGB, respectively, have been found to have least interactions with oppositely charged polyelectrolytes.     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

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

Depletion flocculation of latex dispersion in ionic micellar systems

The flocculation behavior of anionic and cationic latex dispersions induced by addition of ionic surfactants with different polarities (SDS and cetyltrimethylammonium bromide (CTAB)) have been evaluated by rheological measurements. It was found that in identical polar surfactant systems with particle surfaces of SDS + anionic lattices and CTAB + cationic lattices, a weak and reversible flocculation has been observed in a limited concentration region of surfactant, which was analyzed as a repletion flocculation induced by the volume-restriction effect of the surfactant micelles. On the other hand, in oppositely charged surfactant systems (SDS + cationic lattices and CTAB + anionic lattices), the particles were flocculated strongly in a low surfactant concentration region, which will be based on the charge neutralization and hydrophobic effects from the adsorbed surfactant molecules. After the particles stabilized by the electrostatic repulsion of adsorbed surfactant layers, the system viscosity shows a weak maximum again in a limited concentration region. This weak maximum was influenced by the shear rate and has a complete reversible character, which means that this weak flocculation will be due to the depletion effect from the free micelles after saturated adsorption.     

表面胶团修饰电极电化学测定双酚A的增敏机理及抗污性能研究

分别以2种阴离子表面活性剂(SDS、SDBS)、3种季铵盐阳离子表面活性剂(CTAB、TTAB、DTAB)和2种季铵盐型双子表面活性剂(12-3-12、12-4-12)修饰碳糊电极。通过原子力显微镜、接触角以及分析物在电极表面的电化学行为探讨了不同表面活性剂在电极表面的吸附情况,推测在浓度大于临界胶束浓度(CMC)时,季铵盐型阳离子表面活性剂CTAB、TTAB、12-3-12和12-4-12在碳糊电极表面形成了圆柱形的表面胶团,而DTAB和SDS可能是饱和单分子层吸附。以BPA为分析物,研究了表面活性剂修饰电极对BPA的电化学增敏机理,结果表明修饰电极对双酚A(BPA)的电化学增敏作用主要是因为表面胶团对BPA的增溶作用,表面活性剂和BPA间的阳离子-π作用是表面胶团增溶BPA的主要原因。     

Manipulation of the adsorption of ionic surfactants onto hydrophilic silica using polyelectrolytes

This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.     

Rheological Study of Interactions between Anionic Guar and Oppositely Charged Surfactant

We have studied the interactions between anionic carboxymethyl guar (CMG) and oppositely charged surfactant: dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB), and gemini surfactants (16-4-16), using rheological measurements. In the present study, two competing forces, electrostatic interaction and hydrophobic interaction, have been identified as important factors. Various types of structure formed on the anionic CMG chains are qualitatively discussed in comparison. For example, C₁₂TAB and gemini surfactant tend to form polymer-bound aggregates, whereas the C₁₆TAB tend to form the polymer-associated architecture. Furthermore, possible mechanisms based on the experimental results to elucidate these interesting phenomena have been proposed and discussed.