Surface grafting thermoresponsive PEO-PPO-PEO chains.

The objective of this study was to engineer surfaces comprising covalently bound polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) chains, able to coil and uncoil in aqueous media, as a function of temperature. Thermoresponsive surfaces can be used in diverse areas, such as tissue engineering and 'on-command' drug delivery. The grafting scheme was exemplified using a poly(ethylene terephthalate) (PET) film and started with the exposure of the substrate to plasma of ammonia, whereby amine groups were formed on the film. In the next stage, the amine moieties reacted with the hydroxyterminated thermoresponsive PEO-PPO-PEO triblocks via the hexamethylene diisocyanate (HDI) coupling agent. XPS analysis of the PET film after being exposed to plasma of ammonia revealed substantial amounts of nitrogen, as revealed by the sizeable N1s peak observed at 400.2 eV. A large increase in the C1s ether peak at 286.5 eV was apparent after binding the PEO-PPO-PEO triblocks to the substrate. These findings were confirmed by FTIR spectroscopy and supported by water contact angle measurements. PEO-PPO-PEO triblocks were chain extended by reacting them with HDI, whereby longer polyether urethane chains were formed. The long thermoresponsive chains produced (P-F127) were then tethered to the PET surface, following the procedure used to graft the shorter F127 triblocks. The thermoresponsiveness of the surface was demonstrated by measuring the water contact angle of the P-F127-containing surfaces as a function of temperature.

Engineering of bio-hybrid materials by electrospinning polymer-microbe fibers.

Although microbes have been used in industrial and niche applications for several decades, successful immobilization of microbes while maintaining their usefulness for any desired application has been elusive. Such a functionally bioactive system has distinct advantages over conventional batch and continuous-flow microbial reactor systems that are used in various biotechnological processes. This article describes the use of polyethylene oxide(99)-polypropylene oxide(67)-polyethylene oxide(99) triblock polymer fibers, created via electrospinning, to encapsulate microbes of 3 industrially relevant genera, namely, Pseudomonas, Zymomonas, and Escherichia. The presence of bacteria inside the fibers was confirmed by fluorescence microscopy and SEM. Although the electrospinning process typically uses harsh organic solvents and extreme conditions that generally are harmful to bacteria, we describe techniques that overcome these limitations. The encapsulated microbes were viable for several months, and their metabolic activity was not affected by immobilization; thus they could be used in various applications. Furthermore, we have engineered a microbe-encapsulated cross-linked fibrous polymeric material that is insoluble. Also, the microbe-encapsulated active matrix permits efficient exchange of nutrients and metabolic products between the microorganism and the environment. The present results demonstrate the potential of the electrospinning technique for the encapsulation and immobilization of bacteria in the form of a synthetic biofilm, while retaining their metabolic activity. This study has wide-ranging implications in the engineering and use of novel bio-hybrid materials or biological thin-film catalysts.