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Competitive adsorption of two-component solutions containing fibronectin (Fn) and albumin (Ab) on hydroxyapatite (HAp) nanocrystals was analyzed in situ using the quartz crystal microbalance with dissipation (QCM-D) technique. Adsorption of the one-component protein (Fn or Ab) and the two-component proteins adjusted to different molar ratios of Fn to Ab at a fixed Fn concentration was investigated. The frequency shift (Δf; Hz) and the dissipation energy shift (ΔD) were measured with the QCM-D technique, and the viscoelastic changes of adlayers were evaluated by the saturated ΔD/Δf value and the Voigt-based viscoelastic model. For the adsorption of the one-component protein, the Fn adlayer showed a larger mass and higher viscoelasticity than the Ab adlayer, indicating the higher affinity of Fn on HAp. For the adsorption of the two-component proteins, the viscoelastic properties of the adlayers became elastic with increase in Ab concentration, whereas the adsorption mass was similar to that of Fn in the one-component solution regardless of the Ab concentration. The specific binding mass of the Ab antibody to the adlayers increased with increase in Ab concentration, whereas that of the Fn antibody decreased. Therefore, Fn preferentially adsorbs on HAp and Ab subsequently interacts with the adlayers, indicating that the interfacial viscoelasticity of the adlayers was dominated by the interaction between Fn and Ab.

The repeatability of the adsorption and removal of fibrinogen and fetal bovine serum on hydroxyapatite (HAp) nanocrystal sensors was investigated by Fourier transform infrared (FTIR) spectroscopy and quartz crystal microbalance with dissipation (QCM-D) monitoring technique. The HAp nanocrystals were coated on a gold-coated quartz sensor by electrophoretic deposition. Proteins adsorbed on the HAp sensors were removed by (i) ammonia/hydrogen peroxide mixture (APM), (ii) ultraviolet light (UV), (iii) UV/APM, (iv) APM/UV and (v) sodium dodecyl sulfate (SDS) treatments. FTIR spectra of the reused surfaces revealed that the APM and SDS treatments left peptide fragments or the proteins adsorbed on the surfaces, whereas the other methods successfully removed the proteins. The QCM-D measurements indicated that in the removal treatments, fibrinogen was slowly adsorbed in the first cycle because of the change in surface wettability revealed by contact angle measurements. The SDS treatment was not effective in removing proteins. The APM or UV treatment decreased the frequency shifts for the reused HAp sensors. The UV/APM treatment did not induce the frequency shifts but decreased the dissipation shifts. Therefore, we conclude that the APM/UV treatment is the most useful method for reproducing protein adsorption behavior on HAp sensors.

This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems.