Microcalorimetric determination of effect of the antioxidant (Quercetin) on polymer/surfactant interactions

Isothermal titration calorimetry (ITC) and batch calorimetry techniques have been used to evaluate the effect of added antioxidant (Quercetin, QN) on the binding between a polymer/surfactant complex, namely the sodium salt of polystyrene sulfonate (PSS) and typical anionic surfactant sodium dodecylsulfate (SDS). An indirect isotherm approximation method and the Satake–Yang model have been used to evaluate the binding parameter (Ku), adsorption cooperativity (u), and the Gibbs free energy of cooperative and non-cooperative binding (ΔG _C and ΔG _N) from the ITC data. The enthalpy of dissolution of QN into various PSS/water and PSS/SDS/water solutions has been evaluated from batch calorimetry to study the energetics of the polymer/surfactant binding in the presence of QN.     

Formation of surfactant and polyelectrolyte gel particles in aqueous solutions

Mixing of oppositely charged surfactants and polyelectrolytes in aqueous solutions can lead to associative phase separation, where the concentrated phase assumes the form of a viscous liquid, gel, or precipitate. This phenomenon can lead to the formation of gel-like particles whose size and polydispersity can be controlled. Here we present phase behavior and structural studies of gel-like particles formed by mixing drops of N,N,N-trimethylammonium derivatized hydroxyethyl cellulose (JR-400) polyelectrolyte solution with oppositely charged anionic and catanionic surfactant solutions composed of sodium perfluorooctanoate (FC₇) and cetyltrimethylammonium bromide (CTAB). Gel formation apparently occurs due to the collapse of the polyelectrolyte chains upon the adsorption of surfactant. This process results in the release of simple ions and water, and yields dense gel-like beads. The diameter of these beads ranges approximately from 200 to 4000 μm. Both the effects of solution composition and the method of preparation are studied by optical and confocal microscopy, and are linked to the structure and stability of the bead. Our observations suggest that the structure of the resulting particles is governed by the solution composition and the method of preparation, while the particle stability is governed by phase behavior alone.     

Adsorption of cationic cellulose derivative/anionic surfactant complexes onto solid surfaces. II. Hydrophobized silica surfaces

The effect of the anionic surfactant SDS (sodium dodecyl sulfate) on the adsorption behavior of cationic hydroxyethyl cellulose (Polymer JR-400) and hydrophobically modified cationic cellulose (Quatrisoft LM-200) at hydrophobized silica has been investigated by null ellipsometry and compared with the previous data for adsorption onto hydrophilic silica surfaces. The adsorbed amount of LM-200 is found to be considerably larger than the adsorbed amount of JR-400 at both surfaces. Both polymers had higher affinity toward hydrophobized silica than to silica. The effect of SDS on polymer adsorption was studied under two different conditions: adsorption of polymer/SDS complexes from premixed solutions and addition of SDS to preadsorbed polymer layers. Association of the surfactant to the polymer seems to control the interfacial behavior, which depends on the surfactant concentration. For the JR-400/SDS complex, the adsorbed amount on hydrophobized silica started to increase progressively from much lower SDS concentrations, while the adsorbed amount on silica increased sharply only slightly below the phase separation region. For the LM-200/SDS complex, the adsorbed amounts increased progressively from very low SDS concentrations at both surfaces, and no large difference in the adsorption behavior was observed between two surfaces below the phase separation region. The complex desorbed from the surface at high SDS concentrations above the critical micelle concentration. The reversibility of the adsorption of polymer/SDS complexes upon rinsing was also investigated. When the premixed polymer/SDS solutions at high SDS concentrations (>5 mM) were diluted by adding water, the adsorbed amount increased due to the precipitation of the complex. The effect of the rinsing process on the adsorbed layer was determined by the hydrophobicity of the polymer and the surface.     

Heat of adsorption of surfactants and its role on nanoparticle stabilization

In this work, the binding between sodium oleate (SO), sodium laurate (SL), sodium dodecyl sulfate (SDS), and sodium dodecylphosphonate (SDP) and iron oxide nanoparticles was systematically investigated using isothermal titration calorimetry (ITC). Comparing the heat exchanged during the isothermal titration with the corresponding surfactant adsorption isotherm, in the cases of SO and SDP, a strong binding takes place at low surfactant concentrations. The binding enthalpy at this low surfactant concentrations depends on the type of surfactant anionic head group. For C12 surfactants, the phosphonate group produced the strongest endothermic binding, followed by the exothermic binding with the carboxylate group, followed by weak exothermic interaction with the sulfate group. For carboxylate surfactants, longer surfactant tails result in larger exothermic binding. Surfactants that exhibited large binding enthalpies also produced more stable suspensions. The Langmuir (L), Freundlich (F), and Langmuir–Freundlich (L–F) adsorption models were used to interpret the adsorption isotherms during the titration with sodium oleate. The L–F adsorption isotherm model was selected to calculate the heat of the formation of the SO monolayer and bilayer on the iron oxide nanoparticles. The L–F model reflects the finite or limited adsorption of the Langmuir model, but accounts for non-homogeneous adsorption of the Freundlich model that help account for surfactant self-assembly before and after adsorption. Coupling the adsorption model with the titration data is possible to calculate the real heat of adsorption of the surfactants on the metal oxide.     

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.     

Co-adsorption of carboxymethyl-cellulose and cationic surfactants at the air-water interface

We investigated the interaction between an anionic polyelectrolyte (carboxymethylcellulose) and cationic surfactants (DTAB, TTAB, and CTAB) at the air/water interface, using surface tension, ellipsometry, and Brewster angle microscopy techniques. At low surfactant concentration, a synergistic phenomenon is observed due to the co-adsorption of polyelectrolyte/surfactant complexes at the interface, which decreases the surface tension. When the surfactant critical aggregation concentration (cac) is reached, the adsorption saturates and the thickness of the adsorbed monolayer remains constant until another characteristic surfactant concentration, C0, is reached, at which all the polymer charges are bound to surfactant in bulk. Above C0, the absorbed monolayer becomes much thicker, suggesting adsorption of bulk aggregates, which have become more hydrophobic due to charge neutralization.     

Salt effect on the complex formation between polyelectrolyte and oppositely charged surfactant in aqueous solution

The complex formation between sodium carboxymethylcellulose (NaCMC) and dodecyltrimethylammonium bromide (DTAB) at various sodium bromide concentrations (C(NaBr)) has been studied by microcalorimetry, turbidimetric titration, steady-state fluorescence measurements, and the fluorescence polarization technique. The addition of salt is found to influence the formation of NaCMC/DTAB complexes markedly. At C(NaBr) = 0.00, 0.01, 0.02, 0.10, and 0.20 M, DTAB monomers form micelle-like aggregates on NaCMC chains to form NaCMC/DTAB complexes above the critical surfactant concentration (C1). At C(NaBr) = 0.23 M, DTAB molecules first form micelles above a 2.46 mM DTAB concentration prompted by the added salt, and then, above C1 = 4.40 mM, these micelles can aggregate with NaCMC chains to form NaCMC/DTAB complexes. However, at C(NaBr) = 0.25 M, there is no NaCMC/DTAB complex formation because of the complete salt screening of the electrostatic attraction between DTAB micelles and NaCMC chains. It is also surprisingly found that the addition of NaBr can bring out a decrease in C1 at C(NaBr) < 0.20 M. Moreover, the addition of NaBr to a mixture of 0.01 g/L NaCMC and 3.6 mM DTAB can directly induce the formation of NaCMC/DTAB complexes. This salt-enhancing effect on the complex formation is explained as the result of competition between the screening of interaction of polyelectrolyte with surfactant and the increasing of polyelectrolyte/surfactant interaction owing to the growth of micelles by added salt. When the increasing of polyelectrolyte/surfactant interaction exceeds the screening of interaction, the complex formation can be enhanced.     

Phase behavior and molecular thermodynamics of coacervation in oppositely charged polyelectrolyte/surfactant systems: a cationic polymer JR 400 and anionic surfactant SDS mixture

Coacervation in mixtures of polyelectrolytes and surfactants with opposite charge is common in nature and is also technologically important to consumer health care products. To understand the complexation behavior of these systems better, we combine multiple experimental techniques to systematically study the polymer/surfactant binding interactions and the phase behavior of anionic sodium dodecyl sulfate (SDS) surfactant in cationic JR 400 polymer aqueous solutions. The phase-behavior study resolves a discrepancy in the literature by identifying a metastable phase between the differing redissolution phase boundaries reported in the literature for the surfactant-rich regime. Isothermal titration calorimetry analyzed within the framework of the simple Satake-Yang model identifies binding parameters for the surfactant-lean phase, whereas a calculation for polymer-bound micelles coexisting with free micelles is analyzed in the surfactant-rich redissolution regime. This analysis provides a preliminary understanding of the interactions governing the observed phase behavior. The resulting thermodynamic properties, including binding constants and the molar Gibbs free energies, enthalpies, and entropies, identify the relative importance of both hydrophobic and electrostatic interactions and provide a first approximation for the corresponding microstructures in the different phases. Our study also addresses the stability and metastability of oppositely charged polyelectrolytes and surfactant mixtures.     

Surfactant and polyelectrolyte gel particles that swell reversibly

Mixing of oppositely charged surfactants and polyelectrolytes in aqueous solutions can lead to associative phase separation, where the concentrated phase is a viscous liquid, gel, or precipitate. In recent years, this phenomenon has been exploited to form gel-like particles, ranging from approximately 100 to 4000 microm in diameter, whose stability depends on equilibrium phase behavior. As the sample composition is varied, these particles either remain stable (in a two-phase mixture) or dissolve over time. Here, we present the formation of reversibly swelling gel particles from mixtures of N,N,N-trimethylammonium-derivatized hydroxyethyl cellulose (JR-400) and sodium dodecyl sulfate (SDS), whose swelling is controlled by the ambient solution conditions. The effects of cross-linking density and surfactant concentration are investigated by gravimetry and confocal microscopy. The resulting particles have a core/shell morphology and undergo reversible swelling/collapse transitions which, depending on the cross-link density, can be either gradual or abrupt with changing SDS concentration.     

Water-soluble complexes between cationic surfactants and comb-type copolymers consisting of an anionic backbone and hydrophilic nonionic poly(N,N-dimethylacrylamide) side chains

The formation of complexes between the cationic surfactant dodecyl trimethylammonium bromide (DTAB) and the comb-type anionic polyelectrolytes poly(sodium acrylate-co-sodium 2-acrylamido-2-methylpropane sulfonate)-g-poly(N,N-dimethylacrylamide) (P(NaA-co-NaAMPS)-g-PDMAMx) was investigated in dilute aqueous solutions by means of turbidimetry, pyrene fluorescence probing, viscometry, z-potential measurements, and dynamic light scattering. The comb-type copolymers consist of an anionic copolymer backbone, P(NaA-co-NaAMPS), containing 84 mol % NaAMPS units, while the weight percentage, x, of the PDMAM side chains varies from x = 12% (w:w) up to x = 58% (w:w). It was found that, contrary to the water-insoluble complexes formed between the linear polyelectrolyte P(NaA-co-NaAMPS) and DTAB, the solubility in water of the complexes formed between the comb-type copolymers and DTAB is significantly improved with increasing x. The complexation process starts at the same critical aggregation concentration (about 2 orders of magnitude lower than the critical micelle concentration of DTAB), regardless of x, and it is accompanied by charge neutralization and appearance of hydrophobic microdomains. Both effects lead to the substantial collapse of the polyelectrolyte chain upon addition of DTAB. However, the complexes of the comb-type copolymers with DTAB are stabilized in water as nanoparticles, and probably consisted of a water-insoluble core (the polyelectrolyte/surfactant complex), protected by a hydrophilic nonionic PDMAM corona. The size of the nanoparticles varies from approximately 35 nm up to approximately 120 nm, depending on x.     

The Adsorption of Dodecyltrimethylammonium Bromide on Mica in Aqueous Solution Studied by X-Ray Diffraction and Atomic Force Microscopy

The adsorption of dodecyltrimethylammonium bromide (DTAB) onto natural muscovite mica and a synthetic expandable mica (EM) in aqueous solution has been investigated using both microscopic and macroscopic surface characterization techniques. The electrokinetic properties of the surfaces were monitored as a function of the concentration of DTAB using atomic force microscopy and microelectrophoresis. The adsorption isotherm of DTAB on EM was measured up to a solution concentration just below the critical micelle concentration of the surfactant. The thickness of the adsorbed layer on EM was determined using X-ray diffraction. Results indicate that the adsorbed layer consists of molecules lying quite flat on the mica surface at low concentrations and adsorbed in interleaved aggregate structures at concentrations approaching the critical micelle concentration of the surfactant in solution. Copyright 2001 Academic Press.     

Hydration and Lyotropic Melting of Amphiphilic Molecules: A Thermodynamic Study Using Humidity Titration Calorimetry

The hydration of the lipid 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) and of the cationic detergent dodecyltrimethylammonium bromide (DTAB) has been studied by means of isothermal titration calorimetry (ITC), gravimetry, and infrared (IR) spectroscopy. During the experiments films of the amphiphiles are perfused by an inert gas of variable relative humidity. The measurement of adsorption heats using ITC represents a new adaptation of adsorption calorimetry which has been called the humidity titration technique. This method yields the partial molar enthalpy of water upon adsorption. It is found to be endothermic with respect to the molar enthalpy of water on condensation for the water molecules which interact directly with the headgroups of POPC and DTAB. Consequently, the spontaneous hydration of the amphiphiles is entropy driven in an aqueous environment. IR spectroscopy shows that hydration is accompanied by the increase in the conformational and/or motional freedom of the amphiphilic molecules upon water binding. In particular, a lyotropic chain melting transition is induced at a certain characteristic relative humidity. This event is paralleled by the adsorption of water. The corresponding exothermic adsorption heat is consumed completely (POPC) or partially (DTAB) by the hydrocarbon chains upon melting. Differential scanning calorimetry was used as an independent method to determine transition enthalpies of the amphiphiles at a definite hydration degree. Water binding onto the headgroups is discussed in terms of hydrogen bonding and polar interactions. The adsorption isotherms yield a number of 2.6 tightly bound water molecules per POPC and DTAB molecule.     

Thermosensitive poly(N-isopropylacrylamide-co-acrylamide) hydrogels: Synthesis, swelling and interaction with ionic surfactants

Thermosensitive hydrogels were prepared by free-radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N-Methylenebis(acrylamide) (MBAAm) was used as a crosslinker. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(NIPA-co-AAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(NIPA-co-AAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In SDS and DTAB solutions, the equilibrium swelling ratio of the hydrogels increased, this is ascribed to the conversion of non-ionic P(NIPA-co-AAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(NIPA-co-AAm)—surfactant systems depended strongly on both the type and concentration of surfactant solutions.     

Interactions of polyelectrolyte brushes with oppositely charged surfactants

Using Brownian dynamics simulations, we study the effect of the charge ratio, the surfactant length, and the grafting density on the conformational behavior of the complex formed by the polyelectrolyte brush with oppositely charged surfactants. In our simulations, the polyelectrolyte chains and surfactants are represented by a coarse-grained bead-spring model, and the solvent is treated implicitly. It is found that varying the charge ratio induces different morphologies of surfactant aggregates adsorbed onto the brush. At high charge ratios, the density profiles of surfactant monomers indicate that surfactant aggregates exhibit a layer-by-layer arrangement. The surfactant length has a strong effect on the adsorption behavior of surfactants. The lengthening of surfactant leads to a collapsed brush configuration, but a reswelling of the brush with further increasing the surfactant length is observed. The collapse of the brush is attributed to the enhancement of surfactants binding to polyelectrolyte chains. The reswelling is due to an increase in the volume of adsorbed surfactant aggregates. At the largest grafting density investigated, enhanced excluded volume interactions limit the adsorption of surfactant within the polyelectrolyte brush. We also find that end monomers in polyelectrolyte chains exhibit a bimodal distribution in cases of large surfactant lengths and high charge ratios.     

链式与面式两种不对称疏水结构表面活性剂之间的相互作用热力学

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

A new method for simultaneous estimation of micellization parameters from conductometric data

A simple method for determination of the counterion binding parameter (alpha) and aggregation number (N) from conductivity data is proposed. The method is based on fitting the values of the first derivative of conductivity (kappa) versus total surfactant concentration (c(t)) function according to the equation derived from the mass action model (MAM) by using different conductivity models. Sodium dodecylsulphate (SDS) and dodecyltrimethylammonium bromide (DTAB) were chosen for validation of the proposed method. It was shown that the method gives a fairly accurate values for micellisation parameters of SDS (N=51-64, alpha=0.74-0.75) and DTAB (N=56-62, alpha=0.77-0.79), both in good agreement with the literature data. In addition, application of the proposed method does not require the value of the critical micelle concentration (cmc).     

Novel method for the estimation of the binding isotherms of ionic surfactants on oppositely charged polyelectrolytes

One of the most important characteristics of the polyelectrolyte/surfactant interaction is the binding isotherm of the surfactant because it provides basic thermodynamic information about the binding mechanism. However, the amount of the surfactant bound to the polymer may crucially affect the surface properties of these systems via changing the thermodynamic activity of the components. Therefore, a knowledge of the binding isotherms can also be useful in tuning the efficiency of commercial products. However, the determination of these isotherms is still subject to significant experimental difficulties. In this letter, we offer a novel method for the estimation of binding isotherms based on electrokinetic measurements. The technique provides a simple and quick way to estimate the bound amount of surfactant that might be useful in both fundamental and industrial research. In principle, the proposed method could also be extended to the determination of the binding isotherms of small ligands on biomacromolecules.     

Effect of type and concentration of surfactants on swelling behavior of poly[<Emphasis Type="Italic">N</Emphasis>-[3-(dimethylamino)propyl]methacrylamide-co- <Emphasis Type="Italic">N,N</Emphasis>-methylenebis(acrylamide)] hydrogels

A series of thermosensitive hydrogels were prepared from N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) monomer by using 11.6–17.8% (m/m) N,N-methylenebis(acrylamide) (MBAAm) as the crosslinker and comonomer in water. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(DMAPMA-co-MBAAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(DMAPMA-co-MBAAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In pure water, irrespective of the amount of MBAAm, the P(DMAPMA-co-MBAAm) hydrogels showed a discontinuous phase transition between 30 and 40 °C. However, the transition changed from discontinuous to continuous with the addition of surfactants, this is ascribed to the conversion of non-ionic P(DMAPMA-co-MBAAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactants through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(DMAPMA-co-MBAAm) – surfactant systems depended strongly on both the type and concentration of surfactant solutions.     

Interaction of Fluorocarbon Containing Hydrophobically Mdified Polyelectrolyte with Nonionic Surfactants

The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte(FMPAANa) with two kinds of nonionic surfactants(hydrogenated and fluorinated)in a semidilute (0.5wt%) aqueous solution had been studied by rheological measurements,Association behavior was found in both systems.The hydrophobic interaction of FMPAANa with fluorinated surfactant(FC171) is much stronger than that with hydrogenated surfactant(NP7.5) at low surfactoant concentrations.The interaction is strengthened by surfactants being added for the density of active junctions increased.Whereas distinct phenomena for FC171 and NP7.5 start to be found as the surfactants added over their respective certain concentration.The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases.     

Interaction of Fluorocarbon Containing Hydrophobically Modified Polyelectrolyte with Nonionic Surfactants

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