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Robert S Ward

Publications and source records attributed to Robert S Ward.

4 recordsLinked to original sources

In situ adsorption studies of a 14-amino acid leucine-lysine peptide onto hydrophobic polystyrene and hydrophilic silica surfaces using quartz crystal microbalance, atomic force microscopy, and sum frequency generation vibrational spectroscopy.

The adsorption of a 14-amino acid amphiphilic peptide, LK14, which is composed of leucine (L, nonpolar) and lysine (K, charged), on hydrophobic polystyrene (PS) and hydrophilic silica (SiO2) was investigated in situ by quartz crystal microbalance (QCM), atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. The LK14 peptide, adsorbed from a pH 7.4 phosphate-buffered saline (PBS) solution, displayed very different coverage, surface roughness and friction, topography, and surface-induced orientation when adsorbed onto PS versus SiO2 surfaces. Real-time QCM adsorption data revealed that the peptide adsorbed onto hydrophobic PS through a fast (t < 2 min) process, while a much slower (t > 30 min) multistep adsorption and rearrangement occurred on the hydrophilic SiO2. AFM measurements showed different surface morphologies and friction coefficients for LK14 adsorbed on the two surfaces. Surface-specific SFG spectra indicate very different ordering of the adsorbed peptide on hydrophobic PS as compared to hydrophilic SiO2. At the LK14 solution/PS interface, CH resonances corresponding to the hydrophobic leucine side chains are evident. Conversely, only NH modes are observed at the peptide solution/SiO2 interface, indicating a different average molecular orientation on this hydrophilic surface. The surface-dependent difference in the molecular-scale peptide interaction at the solution/hydrophobic solid versus solution/hydrophilic solid interfaces (measured by SFG) is manifested as significantly different macromolecular-level adsorption properties on the two surfaces (determined via AFM and QCM experiments).

Adsorption↗

Macrophage behavior on surface-modified polyurethanes.

Adherent macrophages and foreign body giant cells (FBGCs) are known to release degradative molecules that can be detrimental to the long-term biostability of polyurethanes. The modification of polyurethanes using surface modifying endgroups (SMEs) and/or the incorporation of silicone into the polyurethane soft segments may alter macrophage adhesion, fusion and apoptosis resulting in improved long-term biostability. An in vitro study of macrophage adhesion, fusion and apoptosis was performed on polyurethanes modified with fluorocarbon SMEs, polyethylene oxide (PEO) SMEs, or poly(dimethylsiloxane) (PDMS) co-soft segment and SMEs. The fluorocarbon SME and PEO SME modifications were shown to have no effect on macrophage adhesion and activity, while silicone modification had varied effects. Macrophages were capable of adapting to the surface and adhering in a similar manner to the silicone-modified and unmodified polyurethanes. In the absence of IL-4, macrophage fusion was comparable on the modified and unmodified polyurethanes, while macrophage apoptosis was promoted on the silicone modified surfaces. In contrast, when exposed to IL-4, a cytokine known to induce FBGC formation, silicone modification resulted in more macrophage fusion to form foreign body giant cells. In conclusion, fluorocarbon SME and PEO SME modification does not affect macrophage adhesion, fusion and apoptosis, while silicone modification is capable of mediating macrophage fusion and apoptosis. Silicone modification may be utilized to direct the fate of adherent macrophages towards FBGC formation or cell death through apoptosis.

Apoptosis↗

Quantitative structure-activity relationship modeling of acute toxicity of quaternary alkylammonium sulfobetaines to Daphnia magna.

The logarithm of the octanol/water partition coefficient has been widely used as the sole physicochemical property to define various types of biological activity, such as aquatic toxicity. In the present study, we derive a quantitative structure-activity relationship (QSAR) equation for the prediction of acute aquatic toxicity (48-h median effective concentration) of quaternary alkylammonium sulfobetaines to the aquatic invertebrate Daphnia magna Straus. The single-parameter approach described is also based on the hydrophobicity parameter, log P. The 17 zwitterionic compounds were considered for QSAR development. They have the general formula RN+(CH3)2(CH2)nSO3-, where n = 2 to 4, and were synthesized by reacting the corresponding N,N-dimethylamines with either sodium-2-chloroethanesulfonate (n = 2), 1,3-propanesultone (n = 3), or 1,4-butanesultone (n = 4). The R group was either a C6 to C12 alkyl chain, a phenylalkyl unit bearing a C1 to C4 chain, or a phenylpropyl unit with a C4 to C6 para-substituted alkyl group. Octanol/water partition coefficients were experimentally determined via a conventional stir-flask procedure, which was quantified using a reverse-phase, high-performance liquid chromatographic technique coupled with either an ultraviolet or an electrospray ionization mass spectrometry detection system. Median effective concentration values were also determined experimentally via a standard acute immobilization test recommended by Organisation for Economic Cooperation and Development (Paris, France) Guideline 202. The established QSAR equation for such zwitterionic compounds is consistent with the standard equation that normally defines the polar narcosis mode of toxic action.

Animals↗

Applications of immobilised artificial membrane chromatography to quaternary alkylammonium sulfobetaines and comparison of chromatographic methods for estimating the octanol-water partition coefficient.

The chromatographic behaviour of a series of quaternary alkylammonium sulfobetaines of general formula RN-(CH3)2(CH2)nSO3-, where n = 2-4, has been examined using an immobilised artificial membrane column. The k values have been correlated both with experimentally determined values for the octanol-water partition coefficient (P) and with aquatic toxicity measurements. Other indirect chromatographic methods for measuring log P for these compounds using reversed-phase columns and octanol-coated columns have also been investigated.

Betaine↗