ABSTRACT
The polysaccharides, as established previously (Yu.A. Shchipunov, J. Colloid Interface Sci. 268 (2003) 68; Yu.A. Shchipunov, T.Yu. Karpenko, Langmuir 20 (2004) 3882), can manipulate the formation of hybrid silica nanocomposites by sol-gel processes. Here atomic force microscopy was applied to show whether carbohydrate macromolecules serve as a template for silicate. Mica was used as a substrate to adsorb polysaccharide. It was found that its surface is not neutral to the sol-gel processes, providing the silica precipitation. To hinder it, the mica was protected by a monomolecular film of arachidic acid with the help of a Langmuir-Blodgett technique. Hydrophobically modified cationic hydrohyethylcellulose was adsorbed from a diluted aqueous solution. It was demonstrated that the carbohydrate macromolecules located on the hydrophobic surface did promote silica precipitation, serving as a template.
ABSTRACT
Moles of a surfactant (gamma2(1)) absorbed per unit area of the solid-liquid interface estimated analytically from the difference of the solute molality in the bulk phase before and after adsorption have been quantitatively related to the absolute compositions deltan1 and deltan2 of the solvent and solute forming the inhomogeneous surface phase in contact with the bulk phase of homogeneous composition. By use of isopiestic experiments, negative values of gamma2(1) for the adsorption of inorganic salts onto a solid-liquid interface have been calculated in the same manner. From the linear plot of gamma2(1) versus the ratio of the bulk mole fractions of the solute and solvent, values of deltan1 and deltan2 have been evaluated under a limited range of concentrations. For the adsorption of the surfactant and the inorganic salt respectively onto the fluid interface, gamma2(1) values have been evaluated from the surface tension concentration data using the Gibbs adsorption equation. Gamma2(1) based on the arbitrary placement of the Gibbs dividing plane near the fluid interface is quantitatively related to the composition of the inhomogeneous surface phase. Also, the Gibbs equation for multicomponent solutions has been appropriately expressed in terms of a suitably derived coefficient m. Integrating the Gibbs adsorption equation for a multicomponent system, the standard free energy change, deltaG degrees, per unit of surface area as a result of the maximum adsorption gamma2(m) of the surfactant at fluid interfaces due to the change of the activity alpha2 of the surfactant in the bulk from zero to unity have been calculated. A similar procedure has been followed for the calculation of deltaG degrees for the surfactant adsorption at solid-liquid interfaces using thermodynamically derived equations. deltaG degrees values for surfactant adsorption for all such systems are found to be negative. General expressions of deltaG degrees for negative adsorption of the salt on fluid and solid-liquid interfaces respectively have also been derived on thermodynamic grounds. deltaG degrees for all such systems are positive due to the excess spontaneous hydration of the interfacial phase in the presence of inorganic salt. Negative and positive values of deltaG degree for excess surfactant and salt adsorption respectively have been discussed in light of a generalized scale of free energy of adsorption.
ABSTRACT
The dependence of surface-enhanced infrared absorption (SEIRA) on structure and vibration modes of chemisorbates was studied in a reflection-absorption mode by employing self-assembled monolayers of 4-pyridinethiol and 4-nitrothiophenol formed on Au island films deposited on glass substrates. The present work shows that both the electromagnetic and chemical effects contribute to the total SEIRA enhancement, with the former playing a predominant role. Moreover, the bands due to different vibration modes give rise to distinctly different magnitudes of enhancement, suggesting the presence of a chemical origin in the enhanced IR absorption. Copyright 2001 Academic Press.
ABSTRACT
In this paper we report a versatile and effective strategy to attain strong surface-enhanced infrared absorption by employing a sandwich system consisting of metal island films and self-assembled monolayers (SAMs) of 4-pyridinethiol. The observed larger enhancement factor stems from coupling of the electric fields induced by excitation of the surface plasmon resonance of the overlayer and underlayer Au island films, and from enhanced chemical interactions of the Au island films and the pyridine molecule in the sandwiched structures, compared to the corresponding SAM-Au configuration. Copyright 2001 Academic Press.
ABSTRACT
Aggregation properties of sodium hyaluronate (NaHA) with alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants (referred to as dimeric surfactants) in aqueous sodium chloride solutions have been studied as a function of surfactant chemical structure. Surface tension measurements indicate the unusual parabolic dependence of surface tension vs log surfactant concentration with a surface tension minimum at concentration c(min). The increase of surface tension above c(min) may be related to the formation of clusters consisting of NaHA chain and dimeric surfactants at the air-water interface and in the bulk. From light scattering measurements, molecular weight, hydrodynamic radius, and second virial coefficient have been calculated. The simple calculation of the ratio of positive charge of dimeric surfactant unit per one negatively charged hyaluronate disaccharidic unit in NaHA-surfactant complex reveals that there is a slight excess of positive surfactant charges per one negatively charged disaccharidic unit in the region around c(min) and the NaHA-surfactant complex is not far from electroneutrality. The nonlinear behavior of viscosity vs surfactant concentration in the NaHA-dimeric surfactant system depends on surfactant chemical structure. The behavior is concerned with the size increase due to complex growth and with the size shrinkage above c(min). A model describing the behavior of NaHA-surfactant complex in the bulk and at the interface is suggested. Copyright 2000 Academic Press.
ABSTRACT
Forces have been measured for hexadecyltrimethylammonium salicylate (C(16)TASal) layers on glass beads. During the inward process, hydrophobic attraction occurred at lower adsorption of C(16)TASal and electrostatic repulsion interactions happened at higher adsorption. While the jump-in phenomenon was observed for solutions of concentrations below the critical micelle concentration (cmc = 0.15 mM), the step-in phenomenon was characteristic for solutions at the cmc and above the cmc, suggesting the push-out of adsorbed C(16)TASal layers and/or inserted micelles. The remarkable pull-off phenomenon on the outward process occurred for all solutions, indicating a strong interaction between C(16)TASal molecules. For aqueous 0.15 mM C(16)TASal solutions of various NaSal concentrations, on the inward process, the electrostatic repulsive interaction decreased with adding NaSal. This is due to the electrostatic shielding by salt excess. The height of the force wall on the inward process reached a maximum at 0.01 M NaSal, but the interlocking between molecules on two surfaces during the outward process was minimized at 0.1 M NaSal. These tendencies, which are different from that of the electrostatic repulsion interaction, imply the strong cohesion between adsorbed C(16)TASal layers.
ABSTRACT
Anionic glucophospholipids were recently reported as a new family of tubule-forming lipids. We report here investigations on the structure of nanotubules made from a glucophospholipid with a mixed fluorocarbon-hydrocarbon hydrophobe, using freeze fracture and cryo-transmission electron microscopy (TEM) and X-ray and neutron small angle scattering (SAXS, SANS). The hollow and regularly shaped tubules are very thin: they have an external radius of 140 Å and an internal radius of 35 Å on the average. Their 105 Å-thick wall appears to consist in three bilayers in which the glucophospholipid molecules are probably in a tilted and/or interdigitated configuration. Upon heating these nanotubes convert reversibly into vesicles; transformation is complete at 60 degrees C. Copyright 1999 Academic Press.
Subject(s)
Lipids/chemistry , Bile Acids and Salts , DNA , Molecular Structure , Stearic Acids , Surface-Active AgentsABSTRACT
The GH4C1 strain of hormone-producing rat pituitary cells has specific receptors for the tripeptide thyrotropin-releasing hormone (TRH). Membranes prepared from GH4C1 cells show intrinsic tryptophan fluorescence which was quenched by low concentrations (10--100 nM) of TRH and Ntau-methyl TRH but not by biologically inactive analogs of TRH. Membranes from GH4C1 cells were subjected to thermal denaturation. A conformational transition was noted above 40 degrees C and an irreversible denaturation was observed at 52 degrees C. TRH-induced quenching of intrinsic fluorescence was lost completely in membranes previously incubated for 10 min at 30 degrees C while loss of [3H]-TRH binding was only about 20% at this temperature. Collisional quenching by iodide revealed that about 38% of the tryptophanyl residues in GH4C1 membranes were exposed to solvent. Quenching by TRH occurred with a shift in wavelength maximum from 336 to 342 nm suggesting that few of the tryptophanyl residues quenched by the tripeptide are totally exposed. Membranes prepared from cells preincubated with 20 nM TRH for 48 h, in which TRH receptors were decreased to 30% of control values, showed no quenching of tryptophan fluorescence in response to freshly added TRH. We conclude that the TRH-receptor interaction in GH4C1 cells is associated with a change in membrane conformation that can be measured by differential spectrofluorometry of intrinsic tryptophan fluorescence.
