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Biomedical subjects

James Runt

Publications and source records attributed to James Runt.

7 recordsLinked to original sources

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes.

A novel method is presented whereby the parameters quantifying the conductivity of an ionomer can be extracted from the phenomenon of electrode polarization in the dielectric loss and tan delta planes. Mobile ion concentrations and ion mobilities were determined for a poly(ethylene oxide)-based sulfonated ionomer with Li(+), Na(+), and Cs(+) cations. The validity of the model was confirmed by examining the effects of sample thickness and temperature. The Vogel-Fulcher-Tammann (VFT)-type temperature dependence of conductivity was found to arise from the Arrhenius dependence of ion concentration and VFT behavior of mobility. The ion concentration activation energy was found to be 25.2, 23.4, and 22.3+/-0.5 kJmol for ionomers containing Li(+), Na(+), and Cs(+), respectively. The theoretical binding energies were also calculated and found to be approximately 5 kJmol larger than the experimental activation energies, due to stabilization by coordination with polyethylene glycol segments. Surprisingly, the fraction of mobile ions was found to be very small, <0.004% of the cations in the Li(+) ionomer at 20 degrees C.

Journal Article↗

Amylose crystallization from concentrated aqueous solution.

Maize amylose, separated from granular starch by means of an aqueous leaching process, was used to investigate spherulite formation from concentrated mixtures of starch in water. Amylose (10-20%, w/w) was found to form a spherulitic semicrystalline morphology over a wide range of cooling rates (1-250 degrees C/min), provided it was first heated to >170 degrees C. This is explained through the effect of temperature on chain conformation. A maximum quench temperature of approximately 70 degrees C was required to produce spherulitic morphology. Quench temperatures between 70 and 110 degrees C produced a gel-like morphology. This is explained on the basis of the relative kinetics of liquid-liquid phase separation vis-à-vis crystallization. The possibility of the presence of a liquid crystalline phase affecting the process of spherulite formation is discussed.

Amylose↗

Atomic force microscopy visualization of poly(urethane urea) microphase rearrangements under aqueous environment.

Polyurethane biomaterials are a critically important class of polymers used in a variety of medical devices. It has been suggested that the good blood compatibility of polyurethanes arises from nanoscale chemical heterogeneities at the surface as a consequence of the microphase separated morphology. In this study, we used tapping mode atomic force microscopy with phase imaging under aqueous conditions to visualize the distribution of the surface microphases for a series of poly(urethane urea) block co-polymers with varying hard segment content. The surfaces were prehydrated for 24 h under a flow of 1 mM phosphate buffer. Topographic images showed the formation of nanometer-sized raised features on the surface, having lateral dimensions of 50-70 nm and heights of 10-15 nm. Phase images, reflecting the local distribution of the mechanical properties under aqueous conditions, were quite different from those obtained in ambient conditions, consistent with water-induced structural reorientation. Images suggest that there is little soft phase material at the polymer surface in the presence of water, while images acquired after dehydration of the samples show that the surface layer remains rich in hard domains, indicating that the films do not return to their original states over the time period studied.

Microscopy, Atomic Force↗

Human foetal osteoblastic cell response to polymer-demixed nanotopographic interfaces.

Nanoscale cell-substratum interactions are of significant interest in various biomedical applications. We investigated human foetal osteoblastic cell response to randomly distributed nanoisland topography with varying heights (11, 38 and 85 nm) produced by a polystyrene (PS)/polybromostyrene polymer-demixing technique. Cells displayed island-conforming lamellipodia spreading, and filopodia projections appeared to play a role in sensing the nanotopography. Cells cultured on 11 nm high islands displayed significantly enhanced cell spreading and larger cell dimensions than cells on larger nanoislands or flat PS control, on which cells often displayed a stellate shape. Development of signal transmitting structures such as focal adhesive vinculin protein and cytoskeletal actin stress fibres was more pronounced, as was their colocalization, in cells cultured on smaller nanoisland surfaces. Cell adhesion and proliferation were greater with decreasing island height. Alkaline phosphatase (AP) activity, an early stage marker of bone cell differentiation, also exhibited nanotopography dependence, i.e. higher AP activity on 11 nm islands compared with that on larger islands or flat PS. Therefore, randomly distributed island topography with varying nanoscale heights not only affect adhesion-related cell behaviour but also bone cell phenotype. Our results suggest that modulation of nanoscale topography may be exploited to control cell function at cell-biomaterial interfaces.

Actins↗

Low permeability biomedical polyurethane nanocomposites.

In this article we describe our continuing research on a novel nanocomposite approach for reducing gas permeability through biomedical polyurethane membranes. Nanocomposites were prepared using commercially available poly(urethane urea)s (PUU) and two organically modified layered silicates (OLS). Wide-angle X-ray diffraction experiments showed that the silicate layer spacing in the nanocomposites increased significantly compared with the neat OLS, signifying the formation of intercalated PUU/OLS structures. The nanocomposite materials exhibit increased modulus with increasing OLS content, while maintaining polymer strength and ductility. Water vapor permeability was reduced by about fivefold at the highest OLS contents, as a result of PUU/inorganic composite formation.

Calorimetry, Differential Scanning↗

Solid-state microstructure of poly(l-lactide) and l-lactide/meso-lactide random copolymers by atomic force microscopy (AFM).

Tapping mode atomic force microscopy was used to investigate the lamellar morphology of poly(l-lactide) and two poly(l-lactide-co-meso-lactide) random copolymers containing 3% and 6% meso-lactide. Samples were isothermally crystallized at selected temperatures, and qualitative and quantitative analyses of lamellar structure were performed using height and phase images. This is the first study of the morphology of polylactide stereocopolymers using a real-space probe, and the important effects of scanning parameters on the acquired images are described. More open spherulites with an abundance of screw dislocations between edge-on lamellar stacks were observed in samples crystallized at higher temperatures. Mean lamellar thicknesses are lower for the random copolymers compared to PLLA, particularly at lower DeltaT, in agreement with the results of our previous small-angle X-ray scattering (SAXS) experiments. Mean lamellar thicknesses derived from the current real-space examination are in good agreement with those determined previously from SAXS. Internal surfaces-from microtomed specimens-were also studied to investigate the bulk crystal morphology. Although quantitative analysis was not feasible (for reasons discussed in the text), lamellar organization similar to that seen in the surface experiments is observed at high magnifications.

Biocompatible Materials↗

Spherulitic crystallization in starch as a model for starch granule initiation.

The influence of cooling rate and quench temperature on the formation of spherulitic morphology in heated mung bean starch is reported. Spherulites were obtained for a wide range of cooling rates (2.5-250 degrees C/min), provided the system was heated to 180 degrees C and then cooled below 65 degrees C. Branched crystalline structures were also observed, as was a gellike morphology. The dissolution temperature for spherulitic material ranged between 100 and 130 degrees C. A second dissolution endotherm was observed between 130 and 150 degrees C in systems containing gellike material. Spherulites revealed B-type X-ray diffraction patterns. Spherulitic crystallization of starch following phase separation is proposed as a model for starch granule initiation in vivo.

Carbohydrate Conformation↗