Nicholas D. Spencer

A comparative study of protein adsorption on titanium oxide surfaces using in situ ellipsometry, optical waveguide lightmode spectroscopy, and quartz crystal microbalance/dissipation

Abstract The adsorption kinetics of three model proteins—human serum albumin, fibrinogen and hemoglobin—has been measured and compared using three different experimental techniques: optical waveguide lightmode spectroscopy (OWLS), ellipsometry (ELM) and quartz crystal microbalance (QCM-D). The studies were complemented by also monitoring the corresponding antibody interactions with the pre-adsorbed protein layer. All measurements were performed with identically prepared titanium oxide coated substrates. All three techniques are suitable to follow in-situ kinetics of protein–surface and protein–antibody interactions, and provide quantitative values of the adsorbed adlayer mass. The results have, however, different physical contents. The optical techniques OWLS and ELM provide in most cases consistent and comparable results, which can be straightforwardly converted to adsorbed protein molar (‘dry’) mass. QCM-D, on the other hand, produces measured values that are generally higher in terms of mass. This, in turn, provides valuable, complementary information in two respects: (i) the mass calculated from the resonance frequency shift includes both protein mass and water that binds or hydrodynamically couples to the protein adlayer; and (ii) analysis of the energy dissipation in the adlayer and its magnitude in relation to the frequency shift (c.f. adsorbed mass) provides insight about the mechanical/structural properties such as viscoelasticity.

Optical grating coupler biosensors.

By incorporating a grating in a planar optical waveguide one creates a device with which the spectrum of guided lightmodes can he measured. When the surface of the waveguide is exposed to different solutions, the peaks in the spectrum shift due to molecular interactions with the surface. Optical waveguide lightmode spectroscopy (OWLS) is a highly sensitive technique that is capable of real-time monitoring of these interactions. Since this integrated optical method is based on the measurement of the polarizability density (i.e., refractive index) in the vicinity of the waveguide surface, radioactive, fluorescent or other kinds of labeling are not required. In addition, measurement of at least two guided modes enables the absolute mass of adsorbed molecules to be determined. In this article, the technique will be described in some detail, and applications from different areas will be discussed. Selected examples will be presented to demonstrate how monitoring the modification of different metal oxides with polymers and the response of the coated oxides to biofluids help in the design of novel biomaterials; how OWLS is useful for accurate bioaffinity sensing, which is a key issue in the development of new drugs; and how the quantitative study of protein-DNA/RNA and cell surface interactions can enhance the understanding of processes in molecular and cellular biology.

Nanoparticle printing with single-particle resolution

Bulk syntheses of colloids efficiently produce nanoparticles with unique and useful properties. Their integration onto surfaces is a prerequisite for exploiting these properties in practice. Ideally, the integration would be compatible with a variety of surfaces and particles, while also enabling the fabrication of large areas and arbitrarily high-accuracy patterns. Whereas printing routinely meets these demands at larger length scales, we have developed a novel printing process that enables positioning of sub-100-nm particles individually with high placement accuracy. A colloidal suspension is inked directly onto printing plates, whose wetting properties and geometry ensure that the nanoparticles only fill predefined topographical features. The dry particle assembly is subsequently printed from the plate onto plain substrates through tailored adhesion. We demonstrate that the process can create a variety of particle arrangements including lines, arrays and bitmaps, while preserving the catalytic and optical activity of the individual nanoparticles.

Immobilization of the cell-adhesive peptide Arg-Gly-Asp-Cys (RGDC) on titanium surfaces by covalent chemical attachment

Surface modification of acid-pretreated titanium with 3-aminopropyltriethoxylsilane (APTES) in dry toluene resulted in covalently bonded siloxane films with surface coverage that was relatively controllable by regulating the reaction conditions. A hetero-bifunctional cross-linker, N-succinimidyl-3-maleimidopropionate (SMP), reacted with the terminal amino groups, forming the exposed maleimide groups. Finally, a model cell-binding peptide, Arg–Gly–Asp–Cys (RGDC), was immobilized on the surface through covalent addition of the cysteine thiol groups to the maleimide groups. X-ray photoelectron spectroscopy, radiolabelling techniques, and ellipsometry were used to quantify and characterize the modified surfaces.

Influence of epidermal hydration on the friction of human skin against textiles.

Friction and shear forces, as well as moisture between the human skin and textiles are critical factors in the formation of skin injuries such as blisters, abrasions and decubitus. This study investigated how epidermal hydration affects the friction between skin and textiles. The friction between the inner forearm and a hospital fabric was measured in the natural skin condition and in different hydration states using a force plate. Eleven males and eleven females rubbed their forearm against the textile on the force plate using defined normal loads and friction movements. Skin hydration and viscoelasticity were assessed by corneometry and the suction chamber method, respectively. In each individual, a highly positive linear correlation was found between skin moisture and friction coefficient (COF). No correlation was observed between moisture and elasticity, as well as between elasticity and friction. Skin viscoelasticity was comparable for women and men. The friction of female skin showed significantly higher moisture sensitivity. COFs increased typically by 43% (women) and 26% (men) when skin hydration varied between very dry and normally moist skin. The COFs between skin and completely wet fabric were more than twofold higher than the values for natural skin rubbed on a dry textile surface. Increasing skin hydration seems to cause gender-specific changes in the mechanical properties and/or surface topography of human skin, leading to skin softening and increased real contact area and adhesion.

Partial oxidation of methane to formaldehyde by means of molecular oxygen

The partial oxidation of methane to formaldehyde by molecular oxygen has been studied, with molybdenum(VI) oxide-silica and related catalysts. Although HCHO selectivities in excess of 85% could be obtained at very low conversions, sodium contamination as low as 300 ppm Na was found to lower both activity and selectivity to formaldehyde. On Na-free MoO/sub 3/-SiO/sub 2/ catalysts, methane was shown to be oxidized, in parallel, to HCHO and CO/sub 2/ via a common activation step. CO was produced via HCHO, and became the dominant oxidation product at high conversions. Methanol was detected in trace quantities, and is presumed to be an intermediate in formaldehyde formation. Reagent MoO/sub 3/, and MoO/sub 3/ in excess of approx. 0.1 monolayers on silica did not catalyze the oxidation of methane significantly. Molybdenum(VI) oxide appears to promote the catalytic activity already present on the bare silica.

Comparative investigation of the surface properties of commercial titanium dental implants. Part I: chemical composition.

The surfaces of five commercially available titanium implants (Brånemark Nobel Biocare, 3i ICE, 3i OSSEOTITE, ITI-TPS, and ITI-SLA) were compared by scanning electron microscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectroscopy. All five implant types were screw-shaped and fabricated from commercially pure (cp) titanium, but their surface properties differed both as regards surface morphology and surface chemical composition. The macro- and microstructure of the implant surfaces were investigated by scanning electron microscopy. The surfaces chemical composition was determined using the surface-sensitive analytical techniques of X-ray photoelectron spectroscopy and time-of-flight secondary ion spectrometry. Surface topographies were found to reflect the type of mechanical/chemical fabrication procedures applied by the manufacturers. The titanium oxide (passive) layer thickness was similar (5–6 nm) and typical for oxide films grown at or near room temperature. A variety of elements and chemical compounds not related to the metal composition were found on some implant types. They ranged from inorganic material such as sodium chloride to specific organic compounds believed to be due to contamination during fabrication or storage. The experimental findings are believed to make a contribution to a better understanding of the interplay between industrial fabrication procedure and physico-chemical implant surface properties.

CHARACTERIZATION OF ANODIC SPARK-CONVERTED TITANIUM SURFACES FOR BIOMEDICAL APPLICATIONS

The aim of the present study was to characterize the surface morphology, microstructure and the chemical composition of anodic spark-converted titanium surfaces. The coatings were prepared in an electrochemical cell by the anodic spark deposition technique in an aqueous solution of CaH2PO4)2. The coatings were characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and X-ray diffraction (XRD). The properties of the coatings are described in terms of morphology.

Surface-chemical and -morphological gradients

Surface gradients of chemistry or morphology represent powerful tools for the high-throughput investigation of interfacial phenomena in the areas of physics, chemistry, materials science and biology. A wide variety of methods for the fabrication of such gradients has been developed in recent years, relying on principles ranging from diffusion to time-dependent irradiation in order to achieve a gradual change of a particular parameter across a surface. In this review we have endeavoured to cover the principal fabrication approaches for surface-chemical and surface-morphological gradients that have been described in the literature, and to provide examples of their applications in a variety of different fields.

Sweet, Hairy, Soft, and Slippery

Synthetic polymer lubricants inspired by biological systems may be the key to water-based lubrication.