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Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy was used to study the nature of the dipalmitoylphosphatidylcholine (DPPC) aggregated structures adsorbed on TiO(2). DPPC molecules were assembled on TiO(2) using Langmuir-Blodgett (LB) deposition methods or by directly flowing the DPPC liposome solution across the TiO(2)-coated ATR crystal. We found that there is a direct correlation between the intensity and frequency position of the zwitterionic headgroup IR bands and the nature of LB films. Specifically, we have shown that the bands due to PO(2)(-) modes are sensitive to changes in the degree of hydration of the LB films and that the symmetric deformation vibrational mode (delta(s) (+)N-CH(3)) is sensitive to interaction with oppositely charged surface sites. Using this information, we found that the liposomes adsorbed on TiO(2) remain intact as vesicles and that the vesicles are stable and not removed in flowing water. We have also shown that the antisymmetric deformation vibrational (delta(as) (+)N-CH(3)) modes are sensitive to changes in lateral-lateral DPPC interactions. This information was used to show that there is a lateral interaction between each positively charged (+)N(CH(3))(3) headgroup and negatively charged PO(2)(-) headgroup of the adjacent DPPC molecule in the adsorbed vesicles and LB films. This study provides a framework for the use of this IR technique in studies of adsorption and transport of molecules across membrane interfaces.

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Iron is a bioactive trace element in seawater that regulates photosynthetic carbon dioxide drawdown and export from surface waters by phytoplankton in upward of 40% of the world's oceans. While autonomous sensor arrays are beginning to provide high-resolution data on temporal and spatial scales for some key oceanographic parameters, current analytical methods for iron are not amenable to autonomous platforms because of the need for user involvement and wet chemistry-based approaches. As a result, very large gaps remain in our understanding of iron distribution and chemistry in seawater. Here we present a straightforward nanostructure-based method to measure dissolved iron in natural seawater. The device comprises an iron-specific chelating biomolecule, desferrioxamine B (DFB), covalently immobilized on a mesoporous silica film. Changes in infrared spectral signatures of the immobilized DFB upon Fe(III) complexation provide an accurate and precise measure of iron on the surface of a chip exposed to seawater. The current system has a detection limit of approximately 50 pM for a 1-L sample at pH 1.7 and was used to measure dissolved iron in subarctic Pacific waters without interference from other elements in seawater. This technology provides a major step toward obtaining accurate iron measurements on autonomous research platforms.

A series of novel polymer-clay nanocomposites, that is, liquid-crystalline copolyester/montmorillonite (MMT) nanocomposites, were synthesized by the intercalation polycondensation of terephthalic acid, p-acetoxy benzoic acid, and 1,2-diacetoxy benzene in the presence of different organically modified montmorillonites (OMt's). The OMt's were prepared by the ion exchange of MMT with octadecylamine hydrochloride, p-aminobenzoic acid hydrochloride, or lysine hydrochloride. X-ray diffraction and transmission electron microscopy studies indicated that the inorganic cations in the MMT interlayers were already exchanged by organic onium ions and that the OMt intercalated with p-aminobenzoic acid or lysine was good for obtaining more delaminated clay nanocomposites. The glasstransition temperature and modulus of the nanocomposites increased compared with those of the pure polymer, whereas the isotropic temperature decreased.