ATR FTIR Study of the Interaction of TiO2 Nanoparticle Films with ß-Lactoglobulin and Bile Salts.

The technique of in situ particle film attenuated total reflection Fourier transform infrared spectroscopy (ATR FTIR) has been used to probe the adsorption and coadsorption (sequential) of a common food protein (ß-lactoglobulin, BLG) and two representative bile salts (taurocholic acid and glycocholic acid, abbreviated as TCA and GCA) onto the surface of titanium dioxide (TiO2) nanoparticles. Evaluating of binding interactions between commonly used (historically now, in some countries) food additives and food components, as well as the body's own digestion chemicals, is a critical step in understanding the role of colloidal phenomena in digestion and bioavailability. TCA is found to adsorb onto TiO2 but without any significant ability to be retained when it is not present in the aqueous phase. GCA is also found to adsorb via two distinct binding mechanisms, with one type of adsorbed species being resistant to removal. BLG adsorbs, is irreversibly bound, and has altered conformation when adsorbed at pH 2 (stomach conditions) to the conformation when adsorbed at pH 6.5 (small intestine conditions). This altered conformation is not interface-dependent and is mirrored in the solution spectra of BLG. Sequential coadsorption studies indicate that TCA and GCA adsorb onto TiO2 nanoparticle surfaces and display similar degrees of reversibility and binding in the presence or absence of preadsorbed BLG.

Dynamic wetting of imidazolium-based ionic liquids on gold and glass.

Many of the applications of ionic liquids rely on their bulk properties or their solvation abilities. However, it is their interactions with solid surfaces that underpin many of their potential applications in advanced technologies. Whether it is as lubricants for wind turbines or as electrolytes in supercapacitors, there are many areas where ionic liquids can provide an improvement in performance relative to more commonplace liquids. However, there are some barriers to their implementation in such applications. Foremost of these is the lack of systematic studies of their interactions with solid surfaces as well as neglecting the effect of the absorbed water on wetting. The present study explores the dynamic wetting of three ionic liquids (with a different length of hydrocarbon chain in the cation) on gold and glass substrates, both of which are relevant for nano- and micromechanical machine applications, under well-controlled environmental conditions. The form of data capture (Wilhelmy plate) allows for a direct analysis using analytical expressions for the two dominant approaches for dynamic wetting: the hydrodynamic and molecular kinetic models. All ionic liquids yield data that are described best by the molecular kinetic model. Substrate-ionic liquid and water-ionic liquid interactions contribute to the mechanisms involved in the wetting process.

In situ ATR FTIR studies of SO4 adsorption on goethite in the presence of copper ions.

Despite the existence of many single ion sorption studies on iron and aluminum oxides, fewer studies have been reported that describe cosorption reactions. In this work, we present an in situ ATR FTIR study of synergistic adsorption of sulfate (SO4) and copper (Cu) on goethite, which is representative of the minerals and ions present in mine wastes, acid sulfate soils, and other industrial and agricultural settings. Sulfate adsorption was studied as a function of varying pH, and as a function of increasing concentration in the absence and presence of Cu. The presence of Cu ions in solution had a complex effect on the ability of SO4 ions to be retained on the goethite surface with increasing pH, with complete desorption occurring near pH 7 and 9 in the absence and presence of Cu, respectively. In addition, Cu ions altered the balance of inner vs outer sphere adsorbed SO4. The solid phase partitioning of SO4 at pH 3 and pH 5 was elevated by the presence of Cu; in both cases Cu increased the affinity of SO4 for the goethite surface. Complementary ex situ sorption edge studies of Cu on goethite in the absence and presence of SO4 revealed that the Cu adsorption edge shifted to lower pH (6.3 --> 5.6) in the presence of SO4, consistent with a decrease of the electrostatic repulsion between the goethite surface and adsorbing Cu. Based on the ATR FTIR and bulk sorption data we surmise that the cosorption products of SO4 and Cu at the goethite-water interface were not in the nature of ternary complexes under the conditions studied here. This information is critical for the evaluation of the onset of surface precipitates of copper-hydroxy sulfates as a function of pH and solution concentration.