Development of a Biologically Relevant Calcium Phosphate Substrate for Sum Frequency Generation Vibrational Spectroscopy

Abstract

A novel biologically relevant composite substrate has been prepared consisting of a calcium phosphate (CaP) layer formed by magnetron sputter-coating from a hydroxyapatite (HA) target onto a gold-coated silicon substrate. The CaP layer is intended to mimic tooth and bone surfaces and allows polymers used in oral care to be deposited in a procedure analogous to that used for dental surfaces. The polymer cetyl dimethicone copolyol (CDC) was deposited onto the CaP surface of the substrate by Langmuir Blodgett deposition, and the structure of the adsorbed layer was investigated by the surface specific technique of sum frequency generation (SFG) vibrational spectroscopy. The gold sublayer provides enhancement of the SFG signal arising from the polymer but plays no part in the adsorption of the polymer. The surface morphology of the substrate was investigated using SEM and AFM. The surface roughness was commensurate with that of the thermally evaporated gold sublayer and uniform over areas of at least 36 mum(2). The chemical composition of the CaP-coated surface was determined by FTIR and TOF-SIMS. It was concluded that the surface is primarily calcium phosphate present as a mixture of amorphous, non-hydroxylated phases rather than solely stoichiometric hydroxyapatite. The SFG spectra from CDC on CaP were closely similar, both in resonance wavenumbers and in their relative intensities, with spectra of thin films of CDC recorded directly on gold. Application of previous analysis of the spectra of CDC on gold therefore enabled interpretation of the polymer orientation and conformation on the CaP substrate.

An SFG Study of Interfacial Amino Acids at the Hydrophilic SiO2 and Hydrophobic Deuterated Polystyrene Surfaces

“…In the past, there were few experimental techniques available to surface scientists to probe the chemistry and surface physics of biological interfaces under physiological conditions. However, several surface sensitive analysis techniques, particularly sum frequency generation vibrational spectroscopy (SFG), − second harmonic generation spectroscopy (SHG), − quartz crystal microbalance (QCM), and surface plasmon resonance (SPR), , have proven valuable to studying the interactions between surfaces and biomolecules in their native systems free from contributions from a bulk or surrounding environment.…”