pH-Sensitive Poly(histidine methacrylamide).

This research reports a synthetic amino acid based zwitterionic poly(histidine methacrylamide) (PHisMA), which possesses switchability among zwitterionic, anionic, and cationic states, pH-dependent antifouling properties, and chelation capability to multivalent metal ions. The PHisMA polymer brush surface shows good antifouling properties to resist protein adsorption and bacterial attachment in its zwitterionic state at pH 5. This study also demonstrates that the solution acidity significantly affects the mechanical properties of PHisMA hydrogels. PHisMA hydrogels show higher viscoelastic properties and lower swelling ratios in the zwitterionic state at pH 4 and pH 5, compared to higher or lower pH conditions. It was discovered that PHisMA can chelate multivalent metal ions, such as Ca(2+), Mg(2+), Cu(2+), Ni(2+) and Fe(3+). This study provides us a better understanding of structure-property relationships of switchable zwitterionic polymers. PHisMA can potentially be adapted for a broad range of applications including wound care, water treatment, bioseparation, coating, drug and gene delivery carriers, etc.

Structure-Function Relationships of a Tertiary Amine-Based Polycarboxybetaine.

Zwitterionic polycarboxybetaine (PCB) materials have attracted noticeable interest for biomedical applications, such as wound healing/tissue engineering, medical implants, and biosensors, due to their excellent antifouling properties and design flexibility. Antifouling materials with buffering capability are particularly useful for many biomedical applications. In this work, an integrated zwitterionic polymeric material, poly(2-((2-hydroxyethyl)(2-methacrylamidoethyl)ammonio)acetate) (PCBMAA-1T), was synthesized to carry desired properties (antifouling, switchability and buffering capability). A tertiary amine was used to replace quaternary ammonium as the cation to endow the materials with buffering capability under neutral pH. Through this study, a better understanding on the structure-property relationship of zwitterionic materials was obtained. The tertiary amine cation does not compromise antifouling properties of zwitterionic materials. The amount of adsorbed proteins on PCBMAA-1T polymer brushes is less than 0.8 ng/cm(2) for fibrinogen and 0.3 ng/cm(2) (detection limit of the surface plasmon resonance sensor) for both undiluted blood plasma and serum. It is found that the tertiary amine is favorable to obtain good lactone ring stability in switchable PCB materials. Titration study showed that PCBMAA-1T could resist pH changes under both acidic (pH 1-3) and neutral/basic (pH 7-9) conditions. To the best of our knowledge, such an all-in-one material has not been reported. We believe this material might be potentially used for a variety of applications, including tissue engineering, chronic wound healing and medical device coating.

Structure-function study of poly(sulfobetaine 3,4-ethylenedioxythiophene) (PSBEDOT) and its derivatives.

Poly(3,4-ethylenedioxythiophene) (PEDOT) has been widely studied in recent decades due to its high stability, biocompatibility, low redox potential, moderate band gap, and optical transparency in its conducting state. However, for its long-term in vivo applications, the biocompatibility of PEDOT still needs to be improved. To address this challenge, zwitterionic poly(sulfobetaine 3,4-ethylenedioxythiophene) (PSBEDOT) that contains EDOT backbone with sulfobetaine functional side chains was developed in our previous study. Although PSBEDOT showed great resistance to proteins, cells, and bacteria, it is still not clear how the zwitterionic sulfobetaine side chain affects the electrochemical properties of the polymer and reactivity of the monomer. To achieve better understanding of the structure-function relationships of zwitterionic conducting polymers, we synthesized two derivatives of PSBEDOT, PSBEDOT-4 and PSBEDOT-5, by introducing the alkoxyl spacer between PEDOT backbone and sulfobetaine side chain. The interfacial impedance of PSBEDOT-4 and PSBEDOT-5 was examined by electrochemical impedance spectroscopy and showed significant improvement which is about 20 times lower than PSBEDOT on both gold and indium tin oxide substrates at 1 Hz. In the protein adsorption study, PSBEDOT, PSBEDOT-4 and PSBEDOT-5 exhibited comparable resistance to the fibrinogen solution. All three polymers had low protein adsorption around 3-5% comparing to PEDOT. Additionally, the morphology of PSBEDOT, PSBEDOT-4 and PSBEDOT-5 have been investigated by scanning electron microscopy. We believe that these stable and biocompatible materials can be excellent candidates for developing long-term bioelectronic devices. STATEMENT OF SIGNIFICANCE: To address the challenges associated with existing conducting polymers for bioelectronics, we developed a versatile and high performance zwitterionic conducting material platform with excellent stability, electrochemical, antifouling and controllable antimicrobial/antifouling properties. In this work, we developed two high-performance conducting polymers and systematically investigated how the structure affects their properties. Our study shows we can accurately tune the molecular structure of the monomer to improve the performance of zwitterionic conducting polymer. This zwitterionic conducting polymer platform may dramatically increase the performance and service life of bio-electrochemical devices for many long-term applications, such as implantable biosensing, tissue engineering, wound healing, robotic prostheses, biofuel cell etc., which all require high performance conducting materials with excellent antifouling property/biocompatibility at complex biointerfaces.