Effect of grafting architecture on the surfactant-like behavior of clay-poly(NiPAAm) nanohybrids

A new class of clay-polymer nanohybrids was synthesized by grafting poly(N-isopropylacrylamide) (PNiPAAm) on the edge of nanoscale silicate platelets (NSPs) through covalently bonded linkers to form various architectures. The inherent ionic character of NSPs and the organic moieties of isopropyl amide in PNiPAAms impart surface active properties to the nanohybrids. Surface tension and particle size measurements were used to determine the critical micelle concentrations (CMCs) of the nanohybrids. It was found that PNiPAAm brushes grafted onto NSPs with the single-headed linkers are loosely packed and can expand easily in water causing inter-hybrid interactions. In contrast, PNiPAAm brushes grafted onto NSPs with the double-headed linkers may alternatively exhibit intra-hybrid interactions and the hybrids tend to exist in a dispersed state. Consequently, the latter has a higher CMC than the former. In addition, the CMC can be tailored by adjusting the grafting density of the linkers on the NSP surfaces. The densely grafted nanohybrids exhibit close inter-hybrid contact resulting in a lower CMC than that for the sparsely grafted nanohybrids. Molecular simulations were also performed to study the effects of the polymer-grafted architecture and the density of the linkers on the micellar behavior of NSP-PNiPAAm hybrids. The simulation results were found to be in good agreement with the experimental observations. Thus, it is possible to control the surface active properties and aggregation of the clay-PNiPAAm hybrids by manipulating the organic grafting architectures of the silicate platelets.     

Obtaining surface tension from contact angle data by the individual representation approach

Young equation is the fundamental equation of wetting theory in which the connection among the surface tensions, \(\gamma _{{\varphi \psi }} \) and the contact angle, θ _L, are given. The surface tension of solid surfaces, however, cannot be obtained directly from the Young equation. In this paper, the application of the individual representation theory is demonstrated for the determination of surface tensions of solids (or any phase pair) using experimentally obtained contact angle data. According to this approach, the state of the interfacial layers depends upon, by definition, the properties of the bulk phases in every heterogeneous system, and thus, it complements the traditional capillary theory.     

Effect of molecular packing on adsorption and micelle formation of a homologous cationic surfactant mixture of hexadecyltrimethylammonium bromide and dodecyltrimethylammonium bromide

The surface tension of an aqueous solution of a hexadecyltrimethylammonium bromide (HTAB) and dodecyltrimethylammonium bromide (DTAB) mixture was measured as a function of the total molality and the composition of DTAB at 298.15 K under atmospheric pressure. The phase diagrams of adsorption and micelle formation were constructed and the excess Gibbs energy was evaluated by analyzing the phase diagrams thermodynamically. Both the excess Gibbs energy in the adsorbed film and the excess surface area are negative; therefore the mutual interaction between HTAB and DTAB is said to be stronger than that between the same species and is enhanced with increasing adsorption. By combining the results with those obtained in previous studies, we claimed that DTAB molecules can use effectively the space among the hydrocarbon chains of HTAB molecules and their polar head groups take a staggered arrangement at the surface so as to reduce the electrostatic repulsion. Consequently the dispersion force between hydrophobic chains becomes stronger. Furthermore, the comparison of the excess Gibbs energy in the adsorbed film with that in the micelle shows that the staggered arrangement of molecules is not necessary in the spherical micelle.     

Synthesis and surface properties of new semi-fluorinated sulfobetaines potentially usable for 2D-electrophoresis

New semi-fluorinated amidosulfobetaines, homologs of hydrocarbon amidosulfobetaines (ASB) commonly used in two-dimensional gel electrophoresis (2DE), were prepared in three steps from 2-F-alkylethyl iodide or F-alkyl iodide. Their synthesis was described and their air-water interface properties were investigated and compared with their perhydrogenated counterpart properties. The influence of the relative lengths of the perfluorinated and hydocarbonated moieties was discussed. 2DE of a rat testicular membrane fraction was performed comparatively using one of these fluorinated sulfobetaines and its hydrocarbon homolog; these preliminary results showed the great potential of the semi-fluorinated sulfobetaines in proteomic analysis.     

Prediction of surface tension and surface concentration of binary refrigerant system (R290/R600a) at various temperatures and pressures

The surface tension of a binary refrigerant mixture of R290(propane: C₃H₈) and R600a(isobutane:i-C₄H₁₀) has been calculated by using critical constants (P_c, V_c and T_c) and acentric factor (ω) at three isotherms of 278 K, 300 K and 320 K over the pressure range from 187.7 to 1540.2 kPa. In this paper, new formalism has been made by using simple mixing rule for modifying the predictive models: Brock–Bird, Pitzer, Hakim et al., Bolotin, Sastri–Rao and Zuo–Stenby. On comparing the computed values of surface tension with experimental data, satisfactory results have been observed. The average absolute deviation (AAD) obtained from the comparison of experimental and calculated surface tension values for six models is less than 1.9%. Finally, in a new approach, the extended Langmuir model (EL) was used to finding more information about the surface structure and surface concentration of binary refrigerant mixtures.     

The effect of counterions on the surface adsorption and micelle formation in mixed surfactant systems of dodecyl sulfates

 The surface tension of the aqueous solutions of sodium dodecyl sulfate (SDS) and tetramethylammonium dodecyl sulfate (TMADS) was measured as a function of total molality of the surfactants at fixed composition of TMADS at 298.15 K under atmospheric pressure. The phase diagrams of adsorption and of micelle formation, the activity coefficients, and the excess Gibbs energy were calculated to estimate the deviation from the ideal mixing quantitatively. The preferential adsorption and the micelle formation for TMA⁺ to Na⁺ is attributable to some extent to the hydrophobicity of the methyl groups of TMA⁺. The composition of TMA⁺ in the micelle is larger than that in the adsorbed film at equilibrium. That is, a larger hydrated counterion is more likely to exist in the micelle than in the adsorbed film owing to geometrical benefit. The negative values of the excess Gibbs energy of the adsorbed film and of the micelle arise from the positive ones of the excess entropy greater than that of excess enthalpy. The counterions of very similar size are mixed ideally in the micelle and the size effect appears sensitively in the adsorbed film. Received: 23 May 2001 Accepted: 16 July 2001     

Effect of solution viscosity on dynamic surface tension detection

A dynamic surface tension detector (DSTD) was used to examine the molecular diffusion and surface adsorption characteristics of surface-active analytes as a function of solution viscosity. Dynamic surface tension is determined by measuring the differential pressure across the air/liquid interface of repeatedly growing and detaching drops. Continuous surface tension measurement throughout the entire drop growth is achieved for each eluting drop (at a rate of 30 drops/min for 2 μl drops), providing insight into the kinetic behavior of molecular diffusion and orientation processes at the air/liquid interface. Three-dimensional data are obtained through a calibration procedure previously developed, but extended herein for viscous solutions, with surface tension first converted to surface pressure, which is plotted as a function of elution time axis versus drop time axis. Thus, an analyte that lowers the surface tension results in an increase in surface pressure. The calibration procedure derived for the pressure-based DSTD was successfully extended and implemented in this report to experimentally determine standard surface pressures in solutions of varied viscosity. Analysis of analytes in viscous solution was performed at low analyte concentration, where the observed analyte surface activity indicates that the surface concentration is at or near equilibrium when in a water mobile phase (viscosity of 1.0 Cp). Two surface-active analytes, sodium dodecyl sulfate (SDS) and polyethylene glycol (MW 1470 g/mol, PEG 1470), were analyzed in solutions ranging from 0 to 60% (v/v) glycerol in water, corresponding to a viscosity range of 1.0-15.0 Cp. Finally, the diffusion-limited surface activity of SDS and PEG 1470 were observed in viscous solution, whereby an increase in viscosity resulted in a decreased surface pressure early in drop growth. The dynamic surface pressure results reported for SDS and PEG 1470 are found to correlate with solution viscosity and analyte diffusion coefficient via the Stokes-Einstein equation.     

Effect of temperature on the surface tension of diluted aqueous solutions of 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol and 2,5-hexanediol

Surface tension of aqueous solutions of 1,2-hexanediol (1,2HD), 1,5-hexanediol (1,5HD), 1,6-hexanediol (1,6HD), and 2,5-hexanediol (2,5HD) was measured as a function of composition using the method of capillary rise at 283.15, 288.15, 293.15, 298.15, 303.15 and 308.15 K with emphasis in the very dilute region.     

Studies on solvophobic interactions and micelle formation in non aqueous solvents

Micelle formation of various surfactants, such as sodium caprylate, sodium laurate, sodium palmitate and sodium stearate has been studied in organic solvents of various dielectric constants and intermolecular H-bonding capability, viz. molten acetamide, N-methyl acetamide (NMA) and N,N-dimethyl acetamide (DMA), at different temperatures by electrical conductivity and surface tension methods. Both methods show that micelles are formed in acetamide, NMA and DMA. Gibbs energy changes, enthalpies and entropies of micelle formation, respectively, have been determined by studying the variation of critical micelle concentration (c.m.c.) with temperature. Micelle formation in these solvents has been explained on the basis of several factors such as dielectric constant of the medium, its intermolecular H-bonding capability including solvophobic interaction.     

Dependence of Surface Tension of Near-boiling Non-associated Liquids on Their Molar Volume and Some Critical Constants

Abstract

The equation proposed for near-boiling non-associated liquids describes a new functional dependence of their surface tension on such physico-chemical characteristics as: critical volume, critical temperature and molar volume at the temperatures which are near their normal boiling points. It is shown that, in the case of some low-boiling liquids, possessing small molecules, this equation can be used for the adequate calculation of surface tension at different temperatures in the liquid phase.     

Wetting, adsorption and surface critical phenomena

Our understanding of interfacial phenomena at the surfaces of critical systems, and in particular at the surfaces of critical binary liquid mixtures, has improved significantly in the past decade. There is now substantial agreement between theory and experiment. In this paper we review recent experimental progress, provide a conceptual framework within which the majority of these experiments can now be understood, and discuss critically any remaining unresolved discrepancies between experiments or with theory.     

Effect of copolymer structure on micellar behavior of acrylamide-octylphenylpoly (oxyethylene) acrylate surfactant

Acrylamide-octylphenylpoly (oxyethylene) acrylate copolymer (AM-C₈PhEO_nAc) surfactant is the copolymer of acrylamide (AM) and octylphenylpoly (oxyethylene) acrylate macromonomer (C₈PhEO_nAc). The effect of the copolymer structure on the micellar behavior in aqueous solution was studied using dynamic light scattering. It has been found that the length of ethylene oxide (EO) in the branch and the content of C₈PhEO_nAc in the copolymer surfactant have great effects on the size and distribution of the micelles. For AM-C₈PhEO₇Ac copolymer, at the concentration of 5 × 10⁻⁴ g/ml, the micellar size increases with the increase of C₈PhEO₇Ac content. However, for AM-C₈PhEO₁₀Ac copolymer, the result is the opposite; the micellar size decreases with the increase of C₈PhEO₁₀Ac content. Larger C₈PhEO_nAc content leads to narrower micellar distribution. For copolymer surfactants with equal C₈PhEO_nAc content, when the concentration of copolymer solution is the same, the copolymer with longer EO length forms smaller micelles. Received: 2 February 2000 Accepted: 6 October 2000     

Tensiometric study of surface activity and halothane impact on biosurfactant production of lung cells

Alveolar pneumocytes type II produce in vivo surface-active components, called lung surfactant (LS), which functions at the alveolar air/water interface are very important for the lung mechanics. LS exists in vivo as a colloid-dispersed phospholipid system and its deficiency or inactivation caused by inhalation toxins leads to severe respiratory problems, which are widely studied from the point of view of surface and colloid chemistry, biophysics, biochemistry and medicine.

In this work we investigated the biosurfactant (phospholipids) production by A 549 cells (which originate from the alveolar pneumocytes type II) by measuring the decrease of surface tension in the medium where the cells were grown. Also we studied the effects of halothane on the surfactant production, its accumulation in the cell culture medium and the cell adhesive properties.

Our results showed that there was significant increase of the phospholipid content in the cell culture medium and its surface activity during time of cell growth, detected by surface tension measurements. It was shown that the equilibrium surface tension values of the medium with cells decreased with ca. 4.5 mN/m at 24 h and with 12.0 mN/m at 48 h in comparison with the medium without cells. The effects of halothane on the surfactant production and cell adhesive properties were proved to be time- and concentration-dependent.

Our results demonstrate the opportunity of the interfacial tensiometry to monitor the production of biosurfactants in the field of cell culturing and in colloid systems where biosurfactants exist in vivo and that the tensiometric measurements have potential for use as diagnostic tools in medical applications.     

Protein surface area and retention in hydrophobic interaction chromatography

Summary Molecular surface areas accessible to a 4 ? diameter spherical probe were calculated from crystallographic data for five proteins: α-chymotrypsinogen A, lysozyme, trypsinogen, ribonuclease A and ribonuclease S. The retention factors of various proteins were measured on stationary phases having polyether- and phenylligates and with aqueous eluents containing (NH₄)₂SO₄, Na₂SO₄ or NaCl at pH 7.0. The logarithmic retention factors were plotted against the salt molality and the hydrophobic interaction parameters evaluated from the limiting slopes of the plots at high salt concentrations for the proteins in the chromatographic systems investigated. The hydrophobic interaction parameters thus obtained were linear in both the molecular surface areas of the proteins and the molal surface tension increments of the salts. The experimental results obtained with these relatively simple proteins of known molecular structure, which were available in high purity, support earlier theoretical predictions for the dependence of the hydrophobic interaction parameter on the surface area of the protein and the surface tension raising effect of the salt.     

Interfacial and aggregation properties of some anionic/cationic surfactant binary systems II. Mixed micelle formation and surface tension reduction effectiveness

Mixed micelle formation and surface tension reduction effectiveness (γ_cmc) were investigated for the following systems: triethanolammonium dodecylpoly(oxyethylene)sulfate (TADPS, containing about two ethylene oxide units)/dodecyltrimethylammonium bromide, TADPS/hexadecyltrimethylammonium bromide and TADPS/hexadecylpyridinium chloride. For all these anionic/cationic systems, the mixed critical micelle concentration (cmc) values reflect a strong synergism in mixed micelle formation, with β^M values ranging from −13.8 to −18.3. The mixed micelle composition is mixing-ratio dependent and, for equimolar mixtures, the mixed micelle is richer in the surfactant with the lower cmc. Precipitation is inhibited to a certain extent, thanks to the presence of ethylene oxide groups in the anionic species. The conditions for synergism in γ_cmc, differently expressed in the literature, can be derived from the surface tension equations established in our previous article. They can be conveniently described by a few characteristic constants: Γ _i ^∞ (saturated Gibbs excess), K _i (constant in the Szyszkowski equation), the cmc of the individual surfactants and the interaction parameters, β^S and β^M, of their mixtures. Excellent agreement between theoretically predicted and experimental results is obtained. With the increase in surfactant chain length, the β^M values decrease faster than the β^S ones and this can result in the loss of synergism in γ_cmc. Received: 11 June 2000 Accepted: 4 September 2000     

四硅氧烷Gemini咪唑表面活性剂的合成及表面性能

以三甲基氯硅烷、 γ-氯丙基三氯硅烷、 1,4-二氯丁烷和咪唑等为原料合成了一种新型的四硅氧烷Gemini咪唑表面活性剂([Si₄-4-Si₄im]Cl₂), 通过质谱(MS)和核磁共振氢谱(¹H NMR)证明所得产物为目标产物. 通过Wilhelmy板法测得其在25 ℃下的临界胶束浓度(cmc)为0.54 mmol/L, 水溶液的表面张力(γ_cmc)降至18.6 mN/m. 通过电导率法研究了其胶束形成热力学参数(Δ\begin{array}{c}{G}_m^{0—}\end{array},Δ\begin{array}{c}{H}_m^{0—}\end{array}和Δ\begin{array}{c}{S}_m^{0—}\end{array}), 表明在15~35 ℃下其胶束化过程是自发进行的, 且为熵驱动过程.     

Density and surface tension of binary mixtures of 1-ethyl-3-methylimdazolium nitrate with alcohols

New experimental data of densities and surface tensions are presented for the binary mixtures of the ionic liquid 1-ethyl-3- methyl imidazolium nitrate（[EMIM]NO₃） with methanol and ethanol.Measurements were performed at 298.15 K and atmospheric pressure,covering the whole composition range.Excess molar volumes V^E and the surface tension deviations Sy have been determined.For the excess molar volumes of binary mixture,there is a region of negative V^E at low IL mole fraction,passing through a minimum and then V^E increases and becomes positive,showing maximum at higher IL mole fraction.It is shown that the surface tension deviations Sy of[EMIM]NO₃ + methanol system are positive but those of[EMIM]NO₃ + ethanol system are negative over the entire mole fraction range.     

Capillary constant and surface tension of methane-nitrogen solutions: 1. Experiment

The differential version of the method of capillary rise has been used to measure the capillary constant and calculate the surface tension of methane-nitrogen solutions. Experiments have been conducted in the temperature range from 95 to 170 K at pressures up to 4 MPa. Experimental data on surface tension have been compared with the results of calculations by thermodynamic models. Equations are given which describe the dependence of the capillary constant of a solution on its temperature and composition.