On the Behavior of Nonionic Surfactants at the N-Heptane/Silica Gel Interface: Influence of the Presence of Interfacial Water Inferred from Adsorption Isotherms and Calorimetric Data

The behavior of two polydisperse nonionic surfactants, poly (oxyethylene) glycol alkylphenyl ether TX-35 and TX-100, at the prewetted silica gel/n-heptane and dried silica gel/n-heptane interfaces has been compared by the determination of the average adsorption isotherms of the polydisperse surfactants and of displacement enthalpies. From HPLC experiments, we could also separately quantify the adsorption of each ethyleneoxide (EO) fractions for silica gel from the polydisperse surfactant solution. The adsorption isotherms clearly indicate an incomplete preferential adsorption of the large (EO) chains over the small ones, as well on dried silica gel as on a prehydrated sample. This preferential adsorption and its driving force follow the solubility rules of the poly(oxyethylene) glycol alkylphenyl ether in an apolar solvent and support the idea of a solubility-limited adsorption: solubility in organic solvents of the smaller (EO) chains is much more significant than that of the longer ones and hence prevents adsorption of the smaller species. Consequently, it is observed that the presence of interfacial water decreases the affinity of TX-35 molecules for the hydrophilic silica surface due to the hydration of (EO) chains. In contrast, for TX-100 adsorption after the prewetting treatment the clearest trend is a drastic increase of the adsorption ascribed to the additional solubilization (and micellization) of the TX-100 molecules in the interfacial aqueous phase. The differential molar enthalpies of displacement show a change in the adsorption mechanism, depending on the presence of molecular water on the surface. In the initial part of the adsorption isotherm, a prevailing exothermic process is obtained with prehydrated silica and suggests that hydration of the polar heads of TX-35 and the solubilization of the TX-35 in interfacial water are occurring. For higher equilibrium concentrations, the enthalpies of displacement observed with the prehydrated adsorbent become slightly lower than those obtained with dry silica gel. It may be that this difference is due to the micellization phenomenon of the surfactant species with longer EO chains in interfacial water. These features emphasize the influence of interfacial water on the adsorption of EO fractions from organic solvent. Copyright 2000 Academic Press.     

Adsorption of A Multifunctional Additive (ZnDTC) Onto Iron and Iron(III) Oxide from n-Decane

The adsorption of zinc diisooctylodithiocarbamate (ZnDTC) onto iron and iron(III) oxide from n-decane solution was studied. The adsorption isotherms were determined together with the variation of the apparent differential molar enthalpy of displacement for ZnDTC on both adsorbents at 298 K. The shapes of the iostherms for the adsorption of dithiocarbamate on iron and iron(III) oxide are quite different, especially in the low coverage ratio. The corresponding differential molar enthalpies of displacement for the two studied systems are exothermic. On iron, the very high exothermic values indicate a process of ZnDTC chemisorption, while on iron(III) oxide, the much lower enthalpic effects are characteristic of physisorption.     

Aspects on the interaction between sodium carboxymethylcellulose and calcium carbonate and the relationship to specific site adsorption

The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.     

Adsorption of benzoic acid from organic solvents on calcite and dolomite: Influence of water

A study has been carried out of the adsorption of benzoic acid from cyclohexane solution onto the hydrophilic surface of calcite.

We determined initially the chemical and mineral composition of the solid, its specific surface area and its granulometry. This was followed by the determination of the enthalpies of immersion of calcite in different solvents. These thermodynamic properties gave information on the energetics of calcite—solvent interactions. In this way, we could construct a scale of affinities of the different organic molecules and water for the calcite surface. It was noted that the enthalpies were higher in unsaturated than in saturated organic solvents, and higher in water than in the organic solvents.

The adsorption isotherms and the differential molar enthalpies of displacement were determined in the presence and the absence of water. The role played by water in the adsorption of polar organic molecules from the oil phase has not been clearly explained previously. In this paper, we indicate how the presence of water can modify the adsorption of aromatic compounds on the surface of calcite. As regards the adsorption isotherms, the presence of water essentially increases the amount of adsorption. The results of the calorimetric studies were found to be surprising; we observed that the differential molar enthalpies of displacement were endothermic.

Similar experiments were carried out with dolomite and n-heptane solution and the results compared with those obtained with calcite and cyclohexane, leading to the formulation of a general model concerning the adsorption of small polar organic molecules from organic solvents onto the surfaces of the carbonates.     

A study of the adsorption of bile salts onto model lecithin membranes

Bile salts play a central role in the promotion of cytotoxicity or cytoprotection. In this study, we examined the interaction of different bile salts with egg lecithin vesicles using 31P NMR spectroscopy. The effects of taurochenodeoxycholate (TCDC or 3alpha,7alpha,-dihydroxy-5beta-cholanoyl taurine, of tauroursodeoxycholate (TUDC) or 3alpha,7beta,-dihydroxy-5beta-cholanoyl taurine) and of taurobetamuricholate (TbetaMC or 3alpha,6beta,7beta,-trihydroxy-5beta-cholanoyl taurine), at various bile salt/lecithin ratios, were evaluated. From the percent 31P present in vesicles, the micellar capacity of bile salts to dissolve lecithin was determined. TCDC was incorporated into vesicles for bile salt/lecithin molar ratios lower than 0.62 while for TUDC and TbetaMC, the critical ratios were 0.94 and 1.1, respectively. The 31P chemical shift change was markedly larger with TCDC than that found with TUDC and TbetaMC. In order to specify the low interactions observed between hydrophilic bile salts and lecithin, we determined the intermixed micellar/vesicular bile salt concentrations (IMVC) of bile salt/lecithin solutions using rapid ultrafiltration-centrifugation for TUDC and lecithin solubility measurements for TUDC, TbetaMC and TCDC. The low IMVC obtained indicate that even hydrophilic bile salts were bound mostly to the mixed aggregates. In conclusion, the low disturbance in the arrangement of lecithin induced by TUDC and TbetaMC appears to be due to the interfacial location of these bile salts. TCDC (7alpha OH) penetrates more deeply in the membrane than the 7beta hydroxylated bile salts that may partly explain the distinct damaging effects of these bile salts.     

Studies of the association of chitosan and alkylated chitosan with oppositely charged sodium dodecyl sulfate

Cationic biopolymer chitosan has many applications in food, cosmetic and pharmaceutical industries. Grafting alkylated chains on its backbone can hydrophobically modify this water-soluble polymer.This paper concerns unmodified chitosan, alkylated chitosan and their interactions with a model anionic surfactant, sodium dodecyl sulfate (SDS). The solvent is pH 4 acetic acid solution. The purpose of this study is to highlight the hydrophobicity brought by the alkylated chains by comparing surface tension measurements and rheological properties of hydrophobically modified polymer (HMP) and chitosan solutions at 25 °C.Interactions of chitosan and HMP with surfactant have also been investigated giving information about surface activity and electrical conductivity of such systems. It results that alkylated chitosan/SDS system is more surface active than chitosan/SDS and it offers new potential applications in pharmaceutical and cosmetic fields because of the formation of amphiphilic complexes.     

Assessment of the Surface Heterogeneity of Talc Materials

The hydrophobic and hydrophilic components of the surface of talc materials in aqueous solution were determined using ionic surfactants and their polar headgroup adsorption isotherms. The hydrophilic and hydrophobic surface areas are inferred from the amount of probe molecule adsorbed and the structure of the adsorbed layer. Natural dispersion of talc shows at 298 K a pH of 9.4 and the electrophoretic measurements indicate that the particles are negatively charged. The hydrophilic surface area is estimated from the adsorption of benzyltrimethylammonium ions (BTMA(+)) through electrostatic interactions as supported by the increase of divalent ions in the bulk phase and the decrease in the exothermic displacement enthalpy. It was also observed from the adsorption isotherm of benzene sulfonate anions that the density of positive surface sites is very low and is thus neglected. The adsorption of an anionic surfactant essentially occurs through dispersive interactions between the nonpolar organic tail of the molecule and the hydrophobic surface. Furthermore, some assumptions on the structure of dodecyl sulfate surfactant aggregates at the interface allow the hydrophobic part of the talc particles to be estimated. The cationic surfactant adsorption has been investigated and found to corroborate the hydrophilic and hydrophobic area values first obtained. Copyright 2001 Academic Press.     

Micellar solubilization of tributylphosphate in aqueous solutions of Pluronic block copolymers. Part I. Effect of the copolymer structure and temperature on the phase behavior

Solubilization of tributylphosphate (TBP), a polar oil, in various micellar solutions of Pluronic has been investigated by turbidimetry emphasizing the effect of temperature and the role of the PPO and PEO blocks on the phase behavior of the three components systems (Pluronic-TBP-water). [Temperature-composition] diagrams allow monophasic and diphasic domains to be delimited. Two temperatures are shown to have a determining effect on the phase behavior (TBP solubilization); the well known cloud point temperature (CPT, here defined for the three components system) and the solubilization minimum temperature (SMT) which is defined as the lowest temperature allowing solubilization of TBP in the system. Both temperature depend on the copolymer structure and, interestingly, are directly related to the TBP concentration in the medium. Monophasic microemulsions are observed when the temperature ranges between the SMT and the CPT. When TCPT the system separates in two phase due to the co-precipitation of TBP and Pluronic. Moreover an unexpected evolution of the CPT with the TBP content clearly indicates the occurrence of a structural change of the microemulsions which allows higher quantities of TBP to be solubilized. But the structural change does not allow alone higher quantities of TBP to be solubilized. A well compromise between the SMT and the CPT must be also observed so as to obtain a large extent of monophasic domain after the restructuration. The best compromise is obtained with Pluronics with intermediate hydrophobic character. Reversely, hydrophobic and hydrophilic Pluronics exhibit a very small extent of monophasic domain after the restructuration which does not allow benefit by the structural change.     

Micellar solubilization of tributylphosphate in aqueous solutions of Pluronic block copolymers. Part II. Structural characterization inferred by 1H NMR

The solubilization of tributylphosphate (TBP), a polar oil, in various micellar solutions of Pluronic has been investigated by (1)H NMR spectroscopy. Partial phase diagrams of the three components systems (Pluronic-TBP-water) have shown two characteristic temperatures, called CPT and SMT, which control the phase behavior (see Part I); Both temperature depend on the copolymer structure and, interestingly, are directly related to the TBP concentration in the medium. Monophasic microemulsions are observed only when the temperature ranges between the SMT and the CPT. Moreover, the evolution of the CPT with the TBP content clearly indicated the occurrence of a structural change of the microemulsions which allows higher quantities of TBP to be solubilized. In this second part, (1)H NMR studies of TPB/micellar systems have essentially focused on elucidating the nature of the interactions between TBP and micelle, or on the location of the solubilized species, mainly from the dependence of chemical shifts or linewidths on TBP concentration. Especially, the NMR spectra of the microemulsions before and after the structural change have been compared with those obtained for pure solution of Pluronic in D(2)O at different temperatures and in CDCl(3). The analysis of the (1)H NMR chemical shifts suggests a structural transformation of the TBP-Pluronic micelles in the sense of an hydrophobic TBP-PPO core becoming more and more dense as the TBP concentration increases. Especially, (1)H NMR data evidence an evolution of the hydration state of the hydrophobic core following addition of TBP in the micellar solutions. During the addition of TBP, the microemulsion structure turns from spherical swelled micelles to nanodroplets of pure TBP stabilized by the Pluronic (pure nanophase of TBP stabilized by the copolymer). It is shown that the structural change strongly depends on the temperatures (CPT and SMT, see Part I) and on the copolymer structure.     

Native and hydrophobized human IGG: Enthalpies of heat-induced structural changes and adsorption onto silica

Differential scanning calorimetry (DSC) and isothermal calorimetric batch technique were used to monitor the heat-induced structural changes and adsorption properties of human immunoglobulin G (IgG), in native and hydrophobized states. The transition temperature (T _max) and enthalpy of heat-induced conformational changes (_cal H) of IgG in solution as well as the enthalpy change accompanying the adsorption of IgG onto hydrophilic silica (_ads H), were shown to depend on the degree of the protein hydrophobicity (number of covalently attached alkyl chains). The adsorption enthalpy for all forms of IgG at all surface concentrations was found to be endothermic, that is the process is entropy driven. Factors affecting the IgG adsorption onto silica are discussed.This revised version was published online in November 2005 with corrections to the Cover Date.