Carboxylic acid-functionalized butyl rubber: Synthesis, characterization, and physical properties

© 2015 American Chemical Society. Polyisobutylene (PIB) and other PIB-based materials are of significant interest for a vast array of applications, but chemical modification is often required to obtain the desired properties. Described here are two new approaches for the preparation of carboxylic acid-functionalized PIB. The ring opening of cyclic anhydrides from an allylic alcohol derivative of butyl rubber and the atom transfer radical polymerization of tert-butyl methacrylate from a rubber derivative both ultimately afford carboxylated materials. These materials displayed significantly enhanced adhesion to stainless steel, as well as increased ultimate tensile strength and Young\u27s modulus in comparison to unmodified rubbers. Rheological studies suggested that they exhibit a greater degree of cross-linking-type behavior than the parent butyl rubber. Combined, these studies suggest that the properties of PIB can be readily tuned through synthetic modifications of the backbone, even at low mole percent, and that carboxylic acid moieties can impart desirable properties for various applications

Covalent Polyisobutylene-Paclitaxel Conjugates for Controlled Release from Potential Vascular Stent Coatings

© 2015 American Chemical Society. The development of covalent polyisobutylene (PIB)-paclitaxel (PTX) conjugates as a potential approach to controlling drug release from vascular stent coatings is described. PIB-PTX materials containing ∼24 and ∼48 wt % PTX, conjugated via ester linkages, were prepared. The PTX release profiles were compared with those of physical mixtures of PTX with carboxylic acid-functionalized PIB and with the triblock copolymer polystyrene-b-PIB-b-polystyrene (SIBS). Covalent conjugation led to significantly slower drug release. Atomic force microscopy imaging of coatings of the materials suggested that the physical mixtures exhibited multiple domains corresponding to phase separation, whereas the materials in which PTX was covalently conjugated appeared homogeneous. Coatings of the conjugated materials on stainless steel surfaces suffered less surface erosion than the physically mixed materials, remained intact, and adhered well to the surface throughout the thirty-five day study. Tensile testing and rheological studies suggested that the incorporation of PTX into the polymer introduces similar physical changes to the PIB as the incorporation of a glassy polystyrene block does in SIBS. Cytotoxicity assays showed that the coatings did not release toxic levels of PTX or other species into a cell culture medium over a 24 h period, yet the levels of PTX in the materials were sufficient to prevent C2C12 cells from adhering to and proliferating on them. Overall, these results indicate that covalent PIB-PTX conjugates have promise as coatings for vascular stents

Species delineation and global population structure of Critically Endangered sawfishes (Pristidae)

Sawfishes are among the most endangered of all elasmobranch species, a factor fostering considerable worldwide interest in the conservation of these animals. However, conservation efforts have been hampered by the confusing taxonomy of the group and the poor state of knowledge about the family's geographical population structure. Based on historical taxonomy, external morphology, and mitochondrial DNA sequences (NADH-2), we show here that, globally, the sawfish comprise five species in two genera: Pristis pristis (circumtropical), Pristis clavata (east Indo-West Pacific), Pristis pectinata (Atlantic), Pristis zijsron (Indo-West Pacific), and Anoxypristis cuspidata (Indo-West Pacific, except for East Africa and the Red Sea). This improved understanding will have implications for the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES), International Union for Conservation of Nature (IUCN) Red List assessments, and endangered species laws and regulations in several countries. Furthermore, based on both or either of NADH-2 and the number of rostral teeth per side, we show that populations of P. pristis, P. pectinata, P. zijsron, and A. cuspidata exhibit significant geographic structuring across their respective ranges, meaning that regional-level conservation will be required. Finally, the NADH-2 gene may serve as a marker for the identification of rostra and fins involved in illegal trade

An Analysis of Artificial Reef Fish Community Structure along the Northwestern Gulf of Mexico Shelf: Potential Impacts of “Rigs-to-Reefs” Programs

Artificial structures are the dominant complex marine habitat type along the northwestern Gulf of Mexico (GOM) shelf. These habitats can consist of a variety of materials, but in this region are primarily comprised of active and reefed oil and gas platforms. Despite being established for several decades, the fish communities inhabiting these structures remain poorly investigated. Between 2012 and 2013 we assessed fish communities at 15 sites using remotely operated vehicles (ROVs). Fish assemblages were quantified from standing platforms and an array of artificial reef types (Liberty Ships and partially removed or toppled platforms) distributed over the Texas continental shelf. The depth gradient covered by the surveys (30-84 m) and variability in structure density and relief also permitted analyses of the effects of these characteristics on fish richness, diversity, and assemblage composition. ROVs captured a variety of species inhabiting these reefs from large transient piscivores to small herbivorous reef fishes. While structure type and relief were shown to influence species richness and community structure, major trends in species composition were largely explained by the bottom depth where these structures occurred. We observed a shift in fish communities and relatively high diversity at approximately 60 m bottom depth, confirming trends observed in previous studies of standing platforms. This depth was also correlated with some of the largest Red Snapper captured on supplementary vertical longline surveys. Our work indicates that managers of artificial reefing programs (e.g., Rigs-to-Reefs) in the GOM should carefully consider the ambient environmental conditions when designing reef sites. For the Texas continental shelf, reefing materials at a 50-60 m bottom depth can serve a dual purpose of enhancing diving experiences and providing the best potential habitat for relatively large Red Snapper