Robust Thin Film Surface with a Selective Antibacterial Property Enabled via a Cross-Linked Ionic Polymer Coating for Infection-Resistant Medical Applications.

Fabrication of new antibacterial surfaces has become a primary strategy for preventing device-associated infections (DAIs). Although considerable progress has recently been made in reducing DAIs, current antibacterial coating methods are technically complex and do not allow selective bacterial killing. Here, we propose novel anti-infective surfaces made of a cross-linked ionic polymer film that achieve selective bacteria killing while simultaneously favoring the survival of mammalian cells. A one-step polymerization process known as initiated chemical vapor deposition was used to generate a cross-linked ionic polymer film from 4-vinylbenzyl chloride and 2-(dimethylamino) ethyl methacrylate monomers in the vapor phase. In particular, the deposition process produced a polymer network with quaternary ammonium cross-linking sites, which provided the surface with an ionic moiety with an excellent antibacterial contact-killing property. This method confers substrate compatibility, which enables various materials to be coated with ionic polymer films for use in medical implants. Moreover, the ionic polymer-deposited surfaces supported the healthy growth of mammalian cells while selectively inhibiting bacterial growth in coculture models without any detectable cytotoxicity. Thus, the cross-linked ionic polymer-based antibacterial surface developed in this study can serve as an ideal platform for biomedical applications that require a highly sterile environment.

Thermally Fast-Curable, "Sticky" Nanoadhesive for Strong Adhesion on Arbitrary Substrates.

Demand of adhesives that are strong but ultrathin with high flexibility, optical transparency, and long-term stability has been rapidly growing recently. Here, we suggest a thermally curable, "sticky" nanoadhesive with outstanding adhesion strength accomplished by single-side deposition of the nanoadhesive on arbitrary substrates. The sticky nanoadhesive is composed of an ionic copolymer film generated from two acrylate monomers with tertiary amine and alkyl halide functionalities, formed by a solvent-free method, initiated chemical vapor deposition (iCVD). Because of the low glass transition temperature (Tg) of the copolymer (-9 °C), the ionic copolymer shows a viscoelastic behavior that makes the adhesive attachable to various substrates, regardless of the substrate materials. Moreover, the copolymer film is thermally curable via a cross-linking reaction between the alkyl halide and tertiary amine functionalities, which substantially increased the adhesion strength of the 500 nm thick nanoadhesive greater than 25 N/25 mm within 5 min of curing at 120 °C. The adhesive thickness can further be reduced to 50 nm to achieve greater than 35 N/25 mm within 30 min at 120 °C. The nanoadhesive layer can form uniform adhesion in a large area substrate (up to 130 × 100 mm2) with the deposition of the adhesive only on one side of the substrates to be laminated. Because of its ultrathin nature, the nanoadhesive is also optically transparent as well as highly flexible, which will play a critical role in fabrication and the lamination of future flexible/wearable devices.

Flexible, Low-Power Thin-Film Transistors Made of Vapor-Phase Synthesized High-k, Ultrathin Polymer Gate Dielectrics.

A series of high-k, ultrathin copolymer gate dielectrics were synthesized from 2-cyanoethyl acrylate (CEA) and di(ethylene glycol) divinyl ether (DEGDVE) monomers by a free radical polymerization via a one-step, vapor-phase, initiated chemical vapor deposition (iCVD) method. The chemical composition of the copolymers was systematically optimized by tuning the input ratio of the vaporized CEA and DEGDVE monomers to achieve a high dielectric constant (k) as well as excellent dielectric strength. Interestingly, DEGDVE was nonhomopolymerizable but it was able to form a copolymer with other kinds of monomers. Utilizing this interesting property of the DEGDVE cross-linker, the dielectric constant of the copolymer film could be maximized with minimum incorporation of the cross-linker moiety. To our knowledge, this is the first report on the synthesis of a cyanide-containing polymer in the vapor phase, where a high-purity polymer film with a maximized dielectric constant was achieved. The dielectric film with the optimized composition showed a dielectric constant greater than 6 and extremely low leakage current densities (<3 × 10-8 A/cm2 in the range of ±2 MV/cm), with a thickness of only 20 nm, which is an outstanding thickness for down-scalable cyanide polymer dielectrics. With this high-k dielectric layer, organic thin-film transistors (OTFTs) and oxide TFTs were fabricated, which showed hysteresis-free transfer characteristics with an operating voltage of less than 3 V. Furthermore, the flexible OTFTs retained their low gate leakage current and ideal TFT characteristics even under 2% applied tensile strain, which makes them some of the most flexible OTFTs reported to date. We believe that these ultrathin, high-k organic dielectric films with excellent mechanical flexibility will play a crucial role in future soft electronics.

Facilitated embedding of silver nanowires into conformally-coated iCVD polymer films deposited on cloth for robust wearable electronics.

We propose that a silver nanowire (AgNW)-embedded conducting film can be monolithically applied onto an arbitrary cloth with strong adhesion and environmental stability. We employ a vapor-phase method, initiated chemical vapor deposition (iCVD), for conformal coating of a scaffold polymer film on the cloth. AgNWs are applied on the surface of iCVD polymer films, and the embedding of AgNWs is completed within only 20 s on heating the polymer-coated cloth to 70 °C. Crosslinking the copolymer at 120 °C renders the AgNW-embedded conducting films on the cloth not only thermally and chemically stable, but also mechanically robust. Moreover, when a hydrophobic encapsulating polymer layer is added on the AgNW-embedded film via iCVD, it substantially improves the stability of the cloth against thermal oxidation under hot and humid conditions, showing applicability of the technology to wearable electronics. With these robust conducting films, we demonstrate the fabrication of a waterproof cloth-based heater and circuit for a seven-segment display, thus, confirming the wide applicability of the technology developed in this study.

One-Step Synthesis of Cross-Linked Ionic Polymer Thin Films in Vapor Phase and Its Application to an Oil/Water Separation Membrane.

In spite of the huge research interest, ionic polymers could not have been synthesized in the vapor phase because the monomers of ionic polymers contain nonvolatile ionic salts, preventing the monomers from vaporization. Here, we suggest a new, one-step synthetic pathway to form a series of cross-linked ionic polymers (CIPs) in the vapor phase via initiated chemical vapor deposition (iCVD). 2-(Dimethylamino)ethyl methacrylate (DMAEMA) and 4-vinylbenzyl chloride (VBC) monomers are introduced into the iCVD reactor in the vapor phase to form a copolymer film. Simultaneously in the course of the deposition process, the tertiary amine in DMAEMA and benzylic chloride in VBC undergo a Menshutkin nucleophilic substitution reaction to form an ionic ammonium-chloride complex, forming a highly cross-linked ionic copolymer film of p(DMAEMA-co-VBC). To the best of our knowledge, this is the first report on the synthesis of CIP films in the vapor phase. The newly developed CIP thin film is further applied to the surface modification of the membrane for oil/water separation. With the hydrophilic and underwater oleophobic membrane whose surface is modified with the CIP film, excellent separation efficiency (>99%) and unprecedentedly high permeation flux (average 2.32 × 105 L m-2 h-1) are achieved.