Alkoxy-functionalized polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT) have become promising materials for a variety of applications including bioelectronic devices due to their high conductivity, relatively soft mechanical response, good chemical stability and excellent biocompatibility. However the long-term applications of PEDOT and PProDOT coatings are still limited by their relatively poor electrochemical stability on various inorganic substrates. Here, we report the synthesis of an octa-ProDOT-functionalized polyhedral oligomeric silsesquioxane (POSS) derivative (POSS-ProDOT) and its copolymerization with EDOT to improve the stability of PEDOT coatings. The POSS-ProDOT crosslinker was synthesized via thiol–ene “click” chemistry, and its structure was confirmed by both Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopies. PEDOT copolymer films were then electrochemically deposited with various concentrations of the crosslinker. The resulting PEDOT- co -POSS-ProDOT copolymer films were characterized by cyclic voltammetry, Electrochemical Impedance Spectroscopy, Ultraviolet-Visible spectroscopy and Scanning Electron Microscopy. The optical, morphological and electrochemical properties of the copolymer films could be systematically tuned with the incorporation of POSS-ProDOT. Significantly enhanced electrochemical stability of the copolymers was observed at intermediate levels of POSS-ProDOT content (3.1 wt%). It is expected that these highly stable PEDOT- co -POSS-ProDOT materials will be excellent candidates for use in bioelectronics devices such as neural electrodes.
more »
« less
Functionalized Polythiophene Copolymers for Electronic Biomedical Devices
ABSTRACT We continue to investigate the design, synthesis, and characterization of electrically and ionically active conjugated polythiophene copolymers for integrating a variety of biomedical devices with living tissue. This paper will describe some of our most recent results, including the development of several new monomers that can tailor the surface chemistry, adhesion, and biointegration of these materials with neural cells. Our efforts have focused on copolymers of 3,4 ethylenedioxythiophene (EDOT), functionalized variants of EDOT (including EDOT-acid and the trifunctional EPh), and dopamine (DOPA). The resulting PEDOT-based copolymers have electrical, optical, mechanical, and adhesive properties that can be precisely tailored by fine tuning the chemical composition and structure. Here we present results on EDOT-dopamine bifunctional monomers and their corresponding polymers. We discuss the design and synthesis of an EDOT-cholesterol that combines the thiophene with a biological moiety known to exhibit surface-active behaviour. We will also introduce EDOT-aldehyde and EDOT-maleimide monomers and show how they can be used as the starting point for a wide variety of functionalized monomers and polymers.
more »
« less
- Award ID(s):
- 1808048
- NSF-PAR ID:
- 10147100
- Date Published:
- Journal Name:
- MRS Advances
- ISSN:
- 2059-8521
- Page Range / eLocation ID:
- 1 to 14
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract A detailed investigation addressing the effects of functionalizing conjugated polymers with oligo(ethylene glycol) (EG
n ) sidechains on the performance and polymer‐electrolyte compatibility of electrochromic devices (ECDs) is reported. The electrochemistry for a series of donor‐acceptor copolymers having near‐infrared (NIR)‐optical absorption, where the donor fragment is 3,4‐ethylenedioxythiophene (EDOT) or an EGn functionalized bithiophene (g2T) and the acceptor fragment is diketopyrrolopyrrole (DPP) functionalized with branched alkyl or EGn sidechains, is extensively probed. ECDs are next fabricated and it is found that EGn sidechain incorporation must be finely balanced to promote polymer‐electrolyte compatibility and provide efficient ion exchange. Proper electrolyte‐cation pairing and polymer structural tuning affords a 2x increase in optical contrast (from 12% to 24%) and >60x reduction in switching time (from 20 to 0.3 s). Atomic force microscopy (AFM)/grazing incidence wide‐angle X‐ray scattering (GIWAXS) characterization of the polymer film morphology/microstructure reveals that an over‐abundance of EGn sidechains generates large polymer crystallites, which can suppress ion exchange. Lastly, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) indicates sidechain/electrolyte identity does not influence the electrolyte penetration depth into the films, and EGn sidechain inclusion increases electrolyte cation uptake. The material structural design insight and guidelines regarding the polymer‐electrolyte ion insertion/expulsion dynamics reported here should be of significant utility for developing next‐generation mixed ionic‐electronic conducting materials. -
more » « less
Abstract Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne‐containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1‐disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.
-
more » « less
Abstract Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne‐containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1‐disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.
-
Natural biological materials are formed by self-assembly processes and catalyze a myriad of reactions. Here, we report a programmable molecular assembly of designed synthetic polymers with engineered Bacillus subtilis spores. The bacterial spore-based materials possess modular mechanical and functional properties derived from the independent design and assembly of synthetic polymers and engineered spores . We discovered that phenylboronic acid (PBA) derivatives form tunable and reversible dynamic covalent bonds with the spore surface glycan. Spore labeling was performed using fluorescent PBA probes and monitored by fluorescence microscopy and spectroscopy. Binding affinities of PBA derivatives to spore surface glycan was controlled by aryl substituent effects. On the basis of this finding, PBA-functionalized statistical copolymers were synthesized and assembled with B. subtilis spores to afford macroscopic materials that exhibited programmable stiffness, self-healing, prolonged dry storage, and recyclability. These material properties could be examined using shear rheology, tensile testing, and NMR experiments. Integration of engineered spores with surface enzymes yielded reusable biocatalytic materials with exceptional operational simplicity and high benchtop stability. The reaction progress of the biocatalyses could be monitored with fluorescence specroscopy and absorption measurements, while spore leakage could be monitored by changes in solution turbidity (OD600). The use of bacterial spores as an active partner in dynamic covalent crosslinking sets our material apart from previous examples and grants control over biocontainment as well as the subsequent fate of the spores through stimuli-responsive reversal of the crosslink. All experimental methods are briefly described in the README.md file, and fully detailed in the Supporting Information file for the paper article "Catalytic materials enabled by a programmable assembly of synthetic polymers and engineered bacterial spores".more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1557/adv.2020.3
