Bioadhesive polymer semiconductors and transistors for intimate biointerfaces.

The use of bioelectronic devices relies on direct contact with soft biotissues. For transistor-type bioelectronic devices, the semiconductors that need to have direct interfacing with biotissues for effective signal transduction do not adhere well with wet tissues, thereby limiting the stability and conformability at the interface. We report a bioadhesive polymer semiconductor through a double-network structure formed by a bioadhesive brush polymer and a redox-active semiconducting polymer. The resulting semiconducting film can form rapid and strong adhesion with wet tissue surfaces together with high charge-carrier mobility of ~1 square centimeter per volt per second, high stretchability, and good biocompatibility. Further fabrication of a fully bioadhesive transistor sensor enabled us to produce high-quality and stable electrophysiological recordings on an isolated rat heart and in vivo rat muscles.

Odd-even effect on the thermal conductivity of liquid crystalline epoxy resins.

Rapid developments in high-performance computing and high-power electronics are driving needs for highly thermal conductive polymers and their composites for encapsulants and interface materials. However, polymers typically have low thermal conductivities of ∼0.2 W/(m K). We studied the thermal conductivity of a series of epoxy resins cured by one diamine hardener and seven diepoxide monomers with different precise ethylene linker lengths (x = 2-8). We found pronounced odd-even effects of the ethylene linker length on the liquid crystalline order, mass density, and thermal conductivity. Epoxy resins with even x have liquid crystalline structure with the highest density of 1.44 g/cm3 and highest thermal conductivity of 1.0 W/(m K). Epoxy resins with odd x are amorphous with the lowest density of 1.10 g/cm3 and lowest thermal conductivity of 0.17 W/(m K). These findings indicate that controlling precise linker length in dense networks is a powerful route to molecular design of thermally conductive polymers.

Effect of Linker Length and Temperature on the Thermal Conductivity of Ethylene Dynamic Networks.

Dynamic covalent networks are a class of polymers containing exchangeable bonds. The influence of the thermodynamics and kinetics of dynamic bond exchange on the thermal conductivity and mechanical properties of dynamic networks is important for understanding how they differ from thermoplastics and thermosets. In this work, a series of ethylene dynamic networks are synthesized from benzene diboronic acid and alkane diols with different precise ethylene linker lengths. The thermal conductivity of these ethylene dynamic networks at 40 °C decreases from 0.19 to 0.095 W/(m K) when the ethylene linker length increases from 4 to 12 carbons. The thermal conductivity also has a strong temperature dependence, decreasing by a factor of 3 over the temperature range from -80 °C to 100 °C. The minimum thermal conductivity model predicts these trends of the thermal conductivity with variations in ethylene linker length and temperature.

Critical Role of Ion Exchange Conditions on the Properties of Network Ionic Polymers.

Ionic polymers are important in a wide range of applications and can exhibit widely different properties depending on the ionic species. In the case of single ion conducting polymers, where one charge is attached to the backbone or as a side group, ion exchange is performed to control the mobile species. While the conditions are often specified, the final ion content is not always quantified, and there are no clear criteria for what concentration of salt is needed in the exchange. A series of ammonium network ionic polymers with different precise carbon spacers (C4-C7) between ionic junctions were synthesized as model systems to understand how the ion exchange conditions impact the resultant polymer properties. The initial networks with free bromide anions were exchanged with 1.5, 3, or 10 equiv of lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt in solution. For networks with seven carbons between cross-links, increasing the LiTFSI concentration led to an increase in ion exchange efficiency from 83.6 to 97.6 mol %. At the highest conversion, the C7 network showed a 4 °C decrease in glass transition temperature (Tg), a 50 °C increase in degradation temperature, 12-fold lower water uptake from air, and a greater than 10-fold increase in conductivity at 90 °C. These results illustrate that properties such as Tg are less sensitive to residual ion impurities, whereas the conductivity is highly dependent on the final exchange conversion.