Acid-base interaction of probes at silica surface. Microcalorimetry and adsorption.

The interaction of four benzyl derivatives with silica surface sites in anhydrous cyclohexane is investigated. The strength and extent of adsorption is determined from the Langmuir adsorption isotherm. The enthalpy of immersion is determined microcalorimetrically, which is recalculated to the enthalpy of adsorption. The aim is to distinguish between the Lewis-type (electron exchange) and Brønsted-type (proton exchange) of interaction by selecting methanol-acetone and acetic acid-methylamine, respectively as acid-base substituent in benzene. Moreover, the experiments were performed in anhydrous cyclohexane in order to screen out hydrocarbon interactions from the energy balance. The monomolecular adsorption is also distinguished from the bulk wetting of solids. The results are evaluated in terms of possible proton exchange in anhydrous media.

Wettability of model fountain solutions: the influence on topo-chemical and -physical properties of offset paper.

The surface chemical and physical character of offset paper was studied before and after application of model fountain solutions based on isopropyl alcohol and an alcohol-free surfactant solution. The paper surface features were characterised with atomic force microscopy and the surface energies were determined by contact angle measurements. Changes in the surface chemical properties induced by the fountain solutions were investigated with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Coated papers wetted with the surfactant solution revealed a slight increase in the root mean square roughness, but the isopropyl alcohol solution led to no observable changes. The change in sub-micro roughness is ascribed not only to substrate swelling or migration of coating constituents but also to the presence of surfactant on the surface. A change in the surface energy and particularly the polar contribution was observed after application of the surfactant solution. The X-ray photoelectron spectroscopy showed an increase in the oxygen-to-carbon ratio, which confirms the presence of surfactant on the surface. Time-of-flight secondary ion mass spectroscopy showed that the isopropyl alcohol solution did not change the elemental composition of the surface whereas the surfactant solution clearly did so. The distribution of surfactant on the surface was confirmed by mapping the characteristic fragments of the molecule.

A critical evaluation of the binary and ternary solid-oil-water and solid-water-oil interaction.

When determining the surface energies of solids the most frequently utilised method is to measure contact angles for particular probe liquids. The measured contact angles (usually measured in air) are then combined with published values of surface- and interfacial tensions of the liquids to give the surface energy of the solid. It is, however, very seldom that sufficient attention is paid to the impurities, to the experimental (e.g. saturated vapour) conditions chosen and to the heterogeneities (chemical and structural) of the solid surface. In this study five typical probe liquids: octane, hexadecane, diiodomethane, alpha-bromonaphthalene and water have been used to establish the dispersion component of the surface energy of the solid and the hydrophobic interaction occurring at the interface of four solids: hydrophobic/hydrophilic SiO2 and hydrophobic/hydrophilic TiO2. Two (solid/liquid) and three (solid/liquid/liquid) component systems were investigated. The results are compared with previously published results when Alkenyl Succinic Anhydride (ASA) was brought into contact with SiO2 under water. The preferential surface vapour pressure and liquid spreading of the one liquid over the solids in the absence and presence of a saturated liquid vapour were evaluated as sources of errors.

Alternative models for determining the surface energy components in offset printing.

Different ways of calculating surface energy components for substrates used in offset printing are compared. The results of the very useful van Oss-Chaudhury-Good bi-bidentate model (vOCG) are simplified to mono-bidentate and mono-monodentate models. The unbalance in the acid-base values often obtained by the vOCG model is strongly reduced when applying the simple mono-monodentate model. Moreover, the frequently encountered problem of negative square roots of the acid and base components is removed. An attempt to describe the ink transfer during offset printing by calculating theoretical works of adhesion between ink/plate and ink/paper is also made. The effect of paper roughness on the wetting was studied with atomic force microscopy (AFM).

Surface properties of in vitro bioactive and non-bioactive sol-gel derived materials.

The acid-base properties of several in vitro bioactive (able to form bone mineral-like calcium phosphate on their surfaces) and non-bioactive sol-gel processed oxides are studied. The amount of Lewis acid sites was calculated from the pyridine adsorption using the Langmuir adsorption model. The Henry adsorption model was used in cases where no specific affinity between the adsorbent and the probe molecule was observed. The results were used to calculate the specific amounts of acidic and basic sites on SiO2- and TiO2-based materials. The zeta potential was measured for dip-coated TiO2 films, calcium- and phosphate-doped TiO2 films and for a non-bioactive Al2O3 film. Also, the calcium phosphate formation in simulated body fluid on in vitro bioactive TiO2 film was studied with zeta potential measurements. The results showed dependence on the negative surface charge and the important role of calcium adsorption in the beginning of the calcium phosphate formation. Surface topography of the films was investigated with atomic force microscopy, including a detailed analysis of the peak heights and distribution over cross sections. It was observed that in vitro bioactivity was strongly dependent on the nanoscale dimensions. Consequently, the in vitro calcium phosphate formation seems to be due to both the chemical interactions and the surface structure.

In vitro bioactivity of aerosol-gel deposited TiO(2) thin coatings.

Bioactive, pure, and Ca- or P-doped TiO(2) thin coatings on Ti metal and Si wafers were prepared by the aerosol-gel technique. The coatings were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy. Bioactivity was determined in vitro in a simulated body fluid and was shown to be fully comparable to sol gel-derived TiO(2) coatings prepared by dip-coating. However, the formation rate of carbonate containing apatite decreased with increasing dopant concentration, which was related to changes in chemical composition and topology of the coatings.

Calcium phosphate formation on porous sol-gel-derived SiO2 and CaO-P2O5-SiO2 substrates in vitro.

Sol-gel-derived SiO2 and CaO-P2O5-SiO2 have been shown to be bioactive and bone bonding. In this study bioactive sol-gel-derived SiO2 and CaO-P2O5-SiO2 systems were tested for in in vitro bioactivity. The calcined ceramic monoliths were immersed in a simulated body fluid and analyzed to follow the hydroxyapatite formation on the ceramic surface. Apatite-forming ability was investigated in terms of structural changes by changing the composition and the preparation method. The role of Ca and P dopants in the substrate structure is complicated, and careful characterization is needed. The composition and structure together determine the in vitro bioactivity. The pore structure was analyzed using N2-adsorption/desorption isotherms. The results indicate that a great mesopore volume and a wide mesopore size distribution favor hydroxycarbonate apatite nucleation and a great surface area is not needed. The performed preparation process for silica in a basic environment provides a convenient way to prepare a mesoporous material.

Application of zetametry to determine concentrations of acidic and basic impurities in analytical reagents.

The sign and magnitude of the ζ potential of mineral oxides in allegedly pure organic solvents (high-quality chemical reagents) depends on the concentration of acidic and basic impurities, chiefly organic acids and amines. "Zetametric titration" with HClO(4) makes it possible to estimate the concentration of basic impurities and offers an attractive alternative to other analytical methods. Titanium(IV) oxide has been chosen as the probe powder in view of its very low solubility and nearly neutral point of zero charge in aqueous systems. Some systems have a high buffer capacity and addition of acid and base has a minor effect on the ζ potential of titania. Specific adsorption of alkali metal cations on anatase can be also a significant problem.

Influence of sol and surface properties on in vitro bioactivity of sol-gel-derived TiO2 and TiO2-SiO2 films deposited by dip-coating method.

Different sol-gel-derived titania and titania-silica films were prepared and their properties related to in vitro bioactivity. The films were prepared by depositing the sols on the substrate surface using a dip-coating method. The sols were monitored carefully as a function of time, using rheological techniques and dynamic light scattering. The topography of the films was characterized using atomic force microscopy, and thicknesses and refractive indexes of the films were evaluated by fitting transmittance spectra measured in a wave length region of 370-1100 nm with a spectrophotometer. The in vitro bioactivity tests were performed in simulated body fluid. Surface topography was found to be of great importance with respect to the bioactivity of the studied films.

The distribution of oleic acid between salbutamol base drug and different propellant blends.

The distribution of oleic acid between Salbutamol base drug and the solvent in metered-dose inhalers (MDI's) has been investigated. The equilibrium surfactant concentration in the drug dispersions has been determined using a colorimetric method. The samples examined contained Salbutamol base drug particles and oleic acid dispersed in different propellant blends of freon 11 and 12. The maximum equilibrium concentration observed depended on the propellant blend used. The propellant blend and the distribution of the surfactant affected the dispersion stability. The effect of the surfactant is illustrated by the adsorption isotherm for oleic acid onto the Salbutamol particles. The results are correlated with zeta-potentials and particle size measurements made on similar systems in order to characterize the properties of surfactant stabilized MDI's.

Electrophoretic mobility of salbutamol drug powder in mixed propellant solvents.

The influence of lipids on the dispersion properties of micronized Salbutamol base drug in liquid fluorocarbons has been characterized by electrophoretic mobility measurements and by particle size measurements. A modified Malvern ps26 microelectrophoretic cell was employed, allowing pressurized samples to be analyzed. The measurements were carried out at 25 degrees C in 100:0, 50:50, 40:60, and 30:70 blends of trichlorofluoromethane (P11) and dichlorodifluoromethane (P12) as a function of oleic acid concentration. A limited number of measurements were also done with soybean lecithin or synthetic dipalmitoylphosphatidylcholine (DPPC). A solvent series based on the polarizability (alpha) and on the dipole moment (mu) of the solvent molecules is constructed in order to estimate the acid-base character of the propellants. The results indicate that the type and the amount of lipids and also the type of fluorocarbon mixture plays an important role in the formation of surface charge. The dispersion stability with respect to the measured particle size does not always correlate with the measured electrophoretic mobility, and hence, the surface charge cannot alone explain the dispersion stability. Instead, the wettability of the powders seems to be important as well. Positive surface charge is obtained with the oleic acid or with synthetic dipalmitoylphosphatidylcholine, but negative surface charge exists with soybean lecithin.

Enzyme-Catalyzed oxidation of cholesterol in physically characterized water-in-oil microemulsions.

The enzymatic conversion of cholesterol to cholestenone by cholesterol oxidase (Brevibacterium sp.)in reversed micelles in a system composed of AOT/isooctane/water/cholesterol has been examined. The catalytic activity of the enzyme was correlated with the physicochemical properties of water in water-in-oil (w/o) microemulsion systems. In a system consisting of 3 wt % AOT in isooctane, reversed micelles started to form as the [H(2)O]/[AOT] (e.g., the w(0)) ratio increased above 4-5. The formation of reversed micelles with a core of neat (bulk) water was verified from determinations of both the partial molar volume of water and the scissors vibration of water [with Fourier transform infrared (FTIR) spectroscopy] in the w/o microemulsion systems. A plot of enzyme activity vs. w(0) indicated that the hydration of enzyme molecules per se was not sufficient to give rise to catalytic activity. Instead, it appeared that the formation of an aqueous micellar core was necessary for full activation of the enzyme. Based on micelle size distribution analysis, it was estimated that about one micelle per one thousand contained an enzyme molecule. Since the apparent reaction rate could be markedly enhanced by increasing the enzyme/water ratio, we conclude that the number of enzyme-containing micelles was an important rate-limiting factor in the system.