Atherosclerosis is often described as a single disease entity; however, the morphology of each plaque is unique to the individual. The field currently lacks a technique that can discriminate stable from unstable plaques, to identify those at risk of a thromboembolic event. Small- and wide-angle X-ray scattering (SAXS/WAXS) holds the potential to be able to identify key materials present in a plaque, such as cholesterol species, collagen, low-density lipoproteins (LDLs), and hydroxyapatite.
View Article and Find Full Text PDFThe synthesis of a range of alkyl esters (methyl, n-butyl, and n-decyl) prepared via Steglich esterification of the thermodynamically controlled exo, exo Diels-Alder adduct of furfuryl alcohol and maleic anhydride is reported. Subsequent ring-opening metathesis polymerization of these bio-derivable tricyclic oxanorbornene analogs delivers polymers with targeted molar mass and low molar mass dispersity. The polymerizations are rapid with complete monomer conversion achieved within 15 min.
View Article and Find Full Text PDFCo-crystallization of polymers with different configurations/tacticities provides access to materials with enhanced performance. The stereocomplexation of isotactic poly(L-lactide) and poly(D-lactide) has led to improved properties compared with each homochiral material. Herein, we report the preparation of stereocomplex micelles from a mixture of poly(L-lactide)-b-poly(acrylic acid) and poly(D-lactide)-b-poly(acrylic acid) diblock copolymers in water via crystallization-driven self-assembly.
View Article and Find Full Text PDFUnderstanding the nature of mixed surfactant self-assembly on the surface of organoclays is an important step toward optimizing their performance in polymer nanocomposites and for other potential applications, where selective surface interactions are crucial. In segmented thermoplastic polyurethane nanocomposite systems, dual-modified organoclays have shown significantly better performance compared to their single-modified counterparts. Until now, we had not fully characterized the physical chemistry of these dual-modified layered silicates, but had hypothesized that the enhanced composite performance arises due to some degree of nanoscale phase separation on the nanofiller surface, which enables enhanced compatibilization and more specific and inclusive interactions with the nanoscale hard and soft domains in these thermoplastic elastomers.
View Article and Find Full Text PDFWe have prepared a number of silicone-based thermoplastic polyurethane (TPU) nanocomposites and demonstrated an enhancement of in vitro biostability against metal-ion-induced oxidation for potential use in long-term implantable medical devices. Organoclays based on both low-aspect-ratio hectorites and high-aspect-ratio fluoromicas were evaluated after being dual-modified with two quaternary alkyl ammonium salts with differing degrees of polarity. The resultant nanocomposites were tested for in vitro biostability using physiologically relevant oxidizing conditions.
View Article and Find Full Text PDFThe interactions of phenyldithioesters with gold nanoparticles (AuNPs) have been studied by monitoring changes in the surface plasmon resonance (SPR), depolarised light scattering, and surface enhanced Raman spectroscopy (SERS). Changes in the SPR indicated that an AuNP-phenyldithioester charge transfer complex forms in equilibrium with free AuNPs and phenyldithioester. Analysis of the Langmuir binding isotherms indicated that the equilibrium adsorption constant, K(ads), was 2.
View Article and Find Full Text PDFPolymer-stabilized gold nanoparticles (AuNPs) were prepared and encoded with a range of surface-enhanced Raman reporter molecules. A range of as-synthesized polymers produced by reversible addition fragmentation chain transfer (RAFT) polymerization were demonstrated to self-assemble at the surface of AuNPs dispersed in water. The method involved the coprecipitation of polymer-gold conjugates by the addition of polymer dissolved in a water-miscible solvent to gold AuNPs dispersed in water.
View Article and Find Full Text PDF