Oligoether-functionalized dioxythiophene polymers are a promising class of materials for electrochemical applications requiring aqueous electrolytes with rapid, reversible redox behavior, high pseudocapacitance, and strong electrochromic contrast. By copolymerizing different monomers (EDOT, DMP, and PheDOT) with an oligoether-functionalized propylenedioxythiophene unit, we tune the redox properties, modulating the onsets of oxidation, redox kinetics, and conductance properties in an aqueous electrolyte (NaCl/H 2 O). Density functional theory calculations are subsequently employed to establish a theoretical basis for the observed differences in energy levels of the polymers. Polymer films demonstrate <1 s discharge rates, <1.5 s electrochromic switching times, and 90% charge retention after 1000 cycles. As these materials demonstrate rapid and reversible redox behavior, we test the utility of these materials as electrochromes and as active layers in type I aqueous supercapacitors. In both aqueous and organic electrolytes, these materials demonstrate high electrochromic contrasts, with comonomer selection altering the colors of the resultant polymers. As active layers in supercapacitors, all polymers show relatively constant current response as a function of cell voltage, and P(OE3)-E, in a test device, demonstrates high current retention after 15,000 charge/discharge cycles. This work demonstrates the broad utility of oligoether-functionalized dioxythiophenes for aqueous redox applications while detailing the tuning of optical, electrochemical, and conductance properties through comonomer selection.

Antifouling surfaces are important for biomedical devices to prevent secondary infections and mitigate the effects of the foreign body response. Herein, we describe melt-coextruded poly(ε-caprolactone) (PCL) nanofiber mats grafted with antifouling polymers. Nonwoven PCL fiber mats are produced using a multilayered melt coextrusion process followed by high-pressure hydroentanglement to yield porous patches. The resulting fiber mats show submicrometer cross-sectional fiber dimensions and yield pore sizes that were nearly uniform, with a mean pore size of 1.6 ± 0.9 μm. Several antifouling polymers, including hydrophilic, zwitterionic, and amphipathic molecules, are grafted to the surface of the mats using a two-step procedure that includes photochemistry followed by the copper-catalyzed azide-alkyne cycloaddition reaction. Fiber mats are evaluated using separate adsorption tests for serum proteins and E. coli. The results indicate that poly(oligo(ethylene glycol) methyl ether methacrylate)-co-(trifluoroethyl methacrylate) (poly(OEGMEMA-co-TFEMA)) grafted mats exhibit approximately 85% less protein adhesion and 97% less E. coli adsorption when compared to unmodified PCL fibermats. In dynamic antifouling testing, the amphiphilic fluorous polymer surface shows the highest flux and highest rejection value of foulants. The work presented within has implications on the high-throughput production of antifouling microporous patches for medical applications.

In this paper, covalently linked graphene oxide–poly(ethylene glycol) methyl ether methacrylate–reversible addition‐fragmentation chain transfer (GO–PEGMEMA–RAFT) and physically mixed GO–PEGMEMA hydrogel nanocomposites are synthesized. Spectroscopic and imaging techniques such as UV–vis, Fourier transform infrared, Raman spectroscopy, and transmission electron microscopy show that the PEGMEMA is successfully grafted on GO sheets. The rheology of the nanocomposites is studied by small angle oscillatory shear, which shows a competition between reinforcement and lubrication behavior of GO. In the case where lubrication effect dominates reinforcement, the covalently linked GO–PEGMEMA–RAFT has higher G′ compared to the physically mixed GO‐PEGMEMA. Hence, in the covalently linked system, the grafted polymer chains appear to minimize the lubrication effect.

Polymeric fibers have drawn recent interest for uses in biomedical technologies that span drug delivery, regenerative medicine, and wound-healing patches, amongst others. We have recently reported a new class of fibrous biomaterials fabricated using coextrusion and a photochemical modification procedure to introduce functional groups onto the fibers. In this report, we extend our methodology to control surface modification density, describe methods to synthesize multifunctional fibers, and provide methods to spatially control functional group modification. Several different functional fibers are reported for bioconjugation, including propargyl, alkene, alkoxyamine, and ketone modified fibers. The modification scheme allows for control over surface density and provides a handle for downstream functionalization with appropriate bioconjugation chemistries. Through the use of multiple orthogonal chemistries, fiber chemistry could be differentially controlled to append multiple modifications. Spatial control on the fiber surface was also realized, leading to reverse gradients of small molecule dyes. One application is demonstrated for pH-responsive drug delivery of an anti-cancer therapeutics. Finally, the introduction of orthogonal chemical modifications onto these fibers allowed for modification with multiple cell-responsive peptides providing a substrate for osteoblast differentiation.

Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4‐ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal‐like charge transport properties using a fully solution processable precursor polymer is reported. This is achieved via an ester‐functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film‐forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm−1 and hopping‐like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos3). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm−1 and demonstrate metal‐like (i.e., thermally deactivated and band‐like) transport properties and high stability at comparable doping levels.