Properties of Electropolymerized Dopamine and Its Analogues.

This work reports a study of electropolymerization kinetics, film thickness, stability, and antifouling properties of polydopamine (PDA) and its three analogues: poly(3-(3,4-dihydroxyphenyl)-l-alanine) (PL-DOPA), poly(5-hydroxytryptophan) (PL-5-HTP), and poly(Adrenalin) (PAdrenalin). It was observed that the number of the hydroxyl groups on the benzene ring and the type (primary vs secondary) of amine group significantly affect the electropolymerization kinetics and thus the thickness of the obtained polymer films. Monomers with two hydroxyl groups (except Adrenalin) resulted in films that were thicker (∼10-15 nm) than the one with only one hydroxyl group (PL-5-HTP) (∼5-8 nm) under similar conditions. Adrenalin containing a secondary amino group could not be deposited onto the ITO substrate, while the other three compounds containing a primary amino group completely covered the ITO. The PDA films had better electrochemical stability than the other films. No film showed stable antifouling surfaces against protein.

Zwitterionic Polyurethanes with Tunable Surface and Bulk Properties.

To address the lack of blood compatibility and antifouling properties of polyurethanes (PUs), a novel zwitterionic poly(carboxybetaine urethane) (PCBHU) platform with excellent antifouling and tunable mechanical properties is presented. PCBHU was synthesized via the condensation polymerization of diisocyanate with carboxybetaine (CB)-based triols. Postpolymerization hydrolysis of triol segments at the interface generates zwitterionic CB functional groups that provide superior antifouling properties via the enhanced hydration capacities of CB groups. Thermogravimetric analysis and differential scanning calorimetry measurement show the high thermal stability of PCBHU with up to 305 °C degradation temperature. Tunable mechanical properties and water uptakes can be finely tuned by controlling the structure and ratio of CB-based triol cross-linkers. This study presents a new strategy to incorporate CB functional groups into PU without significantly changing the synthetic methods and conditions of PU. It also provides a deeper understanding on structure-property relationships of zwitterionic PUs. Because of its superior antifouling properties than existing PUs and similar cost, mechanical properties, stability, and processability, PCBHU has the great potential to replace current PUs and may open a new avenue to PUs for more challenging biomedical applications in which the existing PUs are limited by calcification and poor antifouling properties.

Hierarchical structures on nickel-titanium fabricated by ultrasonic nanocrystal surface modification.

Hierarchical structures on metallic implants can enhance the interaction between cells and implants and thus increase their biocompatibility. However, it is difficult to directly fabricate hierarchical structures on metallic implants. In this study, we used a simple one-step method, ultrasonic nanocrystal surface modification (UNSM), to fabricate hierarchical surface structures on a nickel-titanium (NiTi) alloy. During UNSM, a tungsten carbide ball hits metal surfaces at ultrasonic frequency. The overlapping of the ultrasonic strikes generates hierarchical structures with microscale grooves and embedded nanoscale wrinkles. Cell culture experiments showed that cells adhere better and grow more prolifically on the UNSM-treated samples. Compared with the untreated samples, the UNSM-treated samples have higher corrosion resistance. In addition, the surface hardness increased from 243 Hv to 296 Hv and the scratch hardness increased by 22%. Overall, the improved biocompatibility, higher corrosion resistance, and enhanced mechanical properties demonstrate that UNSM is a simple and effective method to process metallic implant materials.

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.

Highly sensitive and stable zwitterionic poly(sulfobetaine-3,4-ethylenedioxythiophene) (PSBEDOT) glucose biosensor.

A zwitterionic poly(sulfobetaine-3,4-ethylenedioxythiophene) (PSBEDOT)-based glucose biosensor was fabricated via encapsulating glucose oxidase (GOx) in a one-step electropolymerization method. Integrating conductivity and hydrophilic properties, PSBEDOT provides a great framework for GOx immobilization and stabilization. The anti-fouling, high-sensitivity, and long-term stability properties of PSBEDOT-GOx make it a promising platform for long-term and continuous glucose monitoring.

Ionic Conductivity of Polyelectrolyte Hydrogels.

Polyelectrolytes have many important functions in both living organisms and man-made applications. One key property of polyelectrolytes is the ionic conductivity due to their porous networks that allow the transport of water and small molecular solutes. Among polyelectrolytes, zwitterionic polymers have attracted huge attention for applications that involve ion transport in a polyelectrolyte matrix; however, it is still unclear how the functional groups of zwitterionic polymer side chains affect their ion transport and swelling properties. In this study, zwitterionic poly(carboxybetaine acrylamide), poly(2-methacryloyloxyethyl phosphorylcholine), and poly(sulfobetaine methacrylate) hydrogels were synthesized and their ionic conductivity was studied and compared to cationic, anionic, and nonionic hydrogels. The change of the ionic conductivity of zwitterionic and nonionic hydrogels in different saline solutions was investigated in detail. Zwitterionic hydrogels showed much higher ionic conductivity than that of the widely used nonionic poly(ethylene glycol) methyl ether methacrylate hydrogel in all tested solutions. For both cationic and anionic hydrogels, the presence of mobile counterions led to high ionic conductivity in low salt solutions; however, the ionic conductivity of zwitterionic hydrogels surpassed that of cationic and ionic hydrogels in high salt solutions. Cationic and anionic hydrogels showed much higher water content than that of zwitterionic hydrogels in deionized water; however, the cationic hydrogels shrank significantly with increasing saline concentration. This work provides insight into the effects of polyelectrolyte side chains on ion transport. This can guide us in choosing better polyelectrolytes for a broad spectrum of applications, including bioelectronics, neural implants, battery, and so on.

Intensification of Electrochemical Performance of AA7075 Aluminum Alloys Using Rare Earth Functionalized Water-Based Polymer Coatings.

This work reports the effect of different amounts of ceria nanoparticles on UV resistance and barrier properties of water-based polyurethane (WPU) on glass and AA7075 aluminum alloy substrates. Hybrid coatings were synthesized from an aliphatic WPU⁻HDI (1,6-hexamethylene di-isocyanate) and cerium oxide nanoparticles (CeO2) with an average particle size distribution of about 25 nm. Different nanoceria amounts (1, 3 and 5 wt %), mixing times (30, 60 and 120 min) and methods to disperse the nanostructures into the polymer matrix (magnetic stirring and sonication) were evaluated. Initially, the dispersion of CeO2 nanoparticles embedded in the polymer matrix and displacement in the corrosion potential (Ecorr) were analyzed by confocal scanning laser microscopy (CLSM) and open circuit potential (Eocp) measurements. According to this behavior, the dispersion and water ratio required during the polymerization process were established. Coated samples obtained after the second stage were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and optical light microscopy. In addition, optical measurements on glass substrates were evaluated with UV-vis spectroscopy. The effect of the synthesis parameters on the corrosion behavior of WPU⁻CeO2/AA7075 systems was investigated with Eocp and electrochemical impedance spectroscopy (EIS) in a 3 wt % NaCl solution. In addition, the films were subjected to 180 h of accelerated weathering. The results show that the combination of specific nanoceria addition with the optimal synthesis parameters enhances optical transparence of WPU as well as barrier properties. From these, the coated specimens prepared with 3 wt % of ceria content and sonicated for 30 min showed a highly dispersed system, which results in a high charge transfer resistance. The observed properties in clear coats deposited on metallic substrates suggested an improvement in the appearance and less deterioration in UV exposure in comparison with pure WPU, enhancing the protective properties of the AA7075 aluminum alloy when exposed to a corrosive medium.

Electroactive poly(sulfobetaine-3,4-ethylenedioxythiophene) (PSBEDOT) with controllable antifouling and antimicrobial properties.

This paper reports a multifunctional zwitterionic poly(sulfobetaine-3,4-ethylenedioxythiophene) (PSBEDOT), which could be facilely synthesized by electropolymerization in aqueous solution. The PSBEDOT surface exhibits excellent conductivity, stability and switchable antifouling/antimicrobial properties. It shows great promise for applications in organic bioelectronics. This new material may significantly increase the performance and service life, minimize the foreign body reaction, improve the biocompatibility and reduce the infection of bio-electronic devices.

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.