Polymer composition and substrate influences on the adhesive bonding of a biomimetic, cross-linking polymer.

Hierarchical biological materials such as bone, sea shells, and marine bioadhesives are providing inspiration for the assembly of synthetic molecules into complex structures. The adhesive system of marine mussels has been the focus of much attention in recent years. Several catechol-containing polymers are being developed to mimic the cross-linking of proteins containing 3,4-dihydroxyphenylalanine (DOPA) used by shellfish for sticking to rocks. Many of these biomimetic polymer systems have been shown to form surface coatings or hydrogels; however, bulk adhesion is demonstrated less often. Developing adhesives requires addressing design issues including finding a good balance between cohesive and adhesive bonding interactions. Despite the growing number of mussel-mimicking polymers, there has been little effort to generate structure-property relations and gain insights on what chemical traits give rise to the best glues. In this report, we examine the simplest of these biomimetic polymers, poly[(3,4-dihydroxystyrene)-co-styrene]. Pendant catechol groups (i.e., 3,4-dihydroxystyrene) are distributed throughout a polystyrene backbone. Several polymer derivatives were prepared, each with a different 3,4-dihyroxystyrene content. Bulk adhesion testing showed where the optimal middle ground of cohesive and adhesive bonding resides. Adhesive performance was benchmarked against commercial glues as well as the genuine material produced by live mussels. In the best case, bonding was similar to that obtained with cyanoacrylate "Krazy Glue". Performance was also examined using low- (e.g., plastics) and high-energy (e.g., metals, wood) surfaces. The adhesive bonding of poly[(3,4-dihydroxystyrene)-co-styrene] may be the strongest of reported mussel protein mimics. These insights should help us to design future biomimetic systems, thereby bringing us closer to development of bone cements, dental composites, and surgical glues.

Ambivalent Adhesives: Combining Biomimetic Cross-Linking With Antiadhesive Oligo(ethylene glycol).

Oligo(ethylene glycol) (OEG) and poly(ethylene glycol) (PEG) exhibit several desirable properties including biocompatibility and resistance to fouling by protein adsorption. Still needed are surgical glues and orthopedic cements, among several other materials, that display similar traits. However the very lack of interactions with other molecules that prevents toxicity and fouling also makes adhesion elusive. In work described here the cross-linking chemistry of marine mussel adhesive is combined with OEG to make a family of terpolymers. The effect of polymer composition upon bulk adhesion was examined. High strength bonding was found with a subset of the polymers containing appreciable OEG content. These structure-property insights may help the design of new materials for which the properties of OEG and high strength adhesion are both being sought.

Highly extensible bio-nanocomposite fibers.

Here, we show that a poly(ethylene oxide) polymer can be physically cross-linked with silicate nanoparticles (Laponite) to yield highly extensible, bio-nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain-induced crystallization and high elongation. We explore the structural characteristics using X-ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.

Ab initio and in situ comparison of caffeine, triclosan, and triclocarban as indicators of sewage-derived microbes in surface waters.

Three organic wastewater compounds (OWCs) were evaluated in theory and practice for their potential to trace sewage-derived microbial contaminants in surface waters. The underlying hypothesis was that hydrophobic OWCs outperform caffeine as a chemical tracer, due to their sorptive association with suspended microorganisms representing particulate organic carbon (POC). Modeling from first principles (ab initio) of OWC sorption to POC under environmental conditions suggested an increasing predictive power: caffeine (0.2% sorbed) < triclosan (9-60%; pH 6-9) < triclocarban (76%). Empirical evidence was obtained via analysis of surface water from three watersheds in a rural-to-urban gradient in Baltimore, MD. Mass spectrometric OWC detections were correlated to microbial plate counts for 40 monitoring sites along 14 streams, including multiple chronic sewage release sites and the local wastewater treatment plant. Consistent with ab initio calculations, correlation analyses of 104 observations for fecal coliforms, enterococci, and Escherichia coli in natural surface waters showed that the particle-active antimicrobials triclosan and triclocarban (R2 range, 0.45-0.55) were indeed superior to caffeine (0.16-0.37) for tracking of microbial indicators. It is concluded that chemical monitoring of microbial risks is more effective when using hydrophobic OWCs such as triclosan and triclocarban in place of, or in conjunction with, the traditional marker caffeine.