Light-Emitting Plasmonic Tunneling Junctions: Current Status and Perspectives.

Quantum tunneling, in which electrons can tunnel through a finite potential barrier while simultaneously interacting with other matter excitation, is one of the most fascinating phenomena without classical correspondence. In an extremely thin metallic nanogap, the deep-subwavelength-confined plasmon modes can be directly excited by the inelastically tunneling electrons driven by an externally applied voltage. Light emission via inelastic tunneling possesses a great potential application for next-generation light sources, with great superiority of ultracompact integration, large bandwidth, and ultrafast response. In this Perspective, we first briefly introduce the mechanism of plasmon generation in the inelastic electron tunneling process. Then the state of the art in plasmonic tunneling junctions will be reviewed, particularly emphasizing efficiency improvement, precise construction, active control, and electrically driven optical antenna integration. Ultimately, we forecast some promising and critical prospects that require further investigation.

Antifouling Silicone Hydrogel Contact Lenses with a Bioinspired 2-Methacryloyloxyethyl Phosphorylcholine Polymer Surface.

Inspired by the cell membrane surface as well as the ocular tissue, a novel and clinically applicable antifouling silicone hydrogel contact lens material was developed. The unique chemical and biological features on the surface on a silicone hydrogel base substrate were achieved by a cross-linked polymer layer composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), which was considered important for optimal on-eye performance. The effects of the polymer layer on adsorption of biomolecules, such as lipid and proteins, and adhesion of cells and bacteria were evaluated and compared with several conventional silicone hydrogel contact lens materials. The MPC polymer layer provided significant resistance to lipid deposition as visually demonstrated by the three-dimensional confocal images of whole contact lenses. Also, fibroblast cell adhesion was decreased to a 1% level compared with that on the conventional silicone hydrogel contact lenses. The movement of the cells on the surface of the MPC polymer-modified lens material was greater compared with other silicone hydrogel contact lenses indicating that lubrication of the contact lenses on ocular tissue might be improved. The superior hydrophilic nature of the MPC polymer layer provides improved surface properties compared to the underlying silicone hydrogel base substrate.

Dental resins based on dimer acid dimethacrylates: a route to high conversion with low polymerization shrinkage.

Incomplete polymerization, volumetric shrinkage, and shrinkage stress are among the primary disadvantages of current resin-based dental composites. Generally, any attempt to increase final double bond conversion only exacerbates polymerization shrinkage and stress. The use of dimer acid-derived dimethacrylate (DADMA) monomers in novel dental resin formulations is examined in this article as a potential means to address these disparate goals. A series of high molecular weight DADMA monomers with different functional groups used to connect the C36 dimer acid core and the methacrylates were formulated with urethane dimethacrylate (UDMA) and/or ethoxylated bisphenol A dimethacrylate (Bis-EMA) at various compositions to manipulate comonomer compatibility and polymeric mechanical properties. Along with reaction kinetics, dynamic polymerization shrinkage and shrinkage stress were assessed. Specific DADMA monomers demonstrated limited miscibility with either Bis-EMA or UDMA. Appropriate ternary resin formulations produced homogeneous monomeric mixtures capable of controlled polymerization-induced phase separation (PIPS) to yield heterogeneous final polymers. Reduced polymerization shrinkage and stress along with higher conversion was observed for DADMA ternary systems compared with a bisphenol A glycidyl methacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) resin control. The PIPS process resulted in a modest volume recovery and stress relaxation in the later stages of polymerization. These results indicate that certain dimer acid-derived dimethacrylates possess the potential to replace TEGDMA as a reactive diluent in dental resins that display a favorable and unique combination of properties.

A Mechanistic and Kinetic Study of the Photoinitiated Cationic Double Ring-opening Polymerization of 2-Methylene-7-phenyl-1,4,6,9-tetraoxa-spiro[4.4]nonane.

Efficient photopolymerization of a potentially expandable monomer is of practical importance for a variety of polymeric applications demanding dimensional stability, particularly if the polymerization process is well controlled based on a detailed investigation of the reaction. In the current study, photoinitiated polymerization kinetics of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro[4.4]nonane (MPN) either with cationic initiation alone or with combined cationic/free radical initiation was examined using real-time FT-IR. A proposed mechanism based on the simplified propagation steps of the cationic double ring-opening polymerization of MPN was confirmed by both computer modeling and NMR spectroscopic analysis of resulting polymers as well as the experimentally observed apparent activation energy. According to this mechanism, alpha-position attack is the predominant mode for the second ring opening during cationic polymerization of MPN. Further, cationic photopolymerization was performed along with a free radical co-initiator or with exposure to moisture to get an improved understanding of the complex cationic double ring-opening polymerization. As a result, free radical-promoted cationic polymerization helps increase the polymerization rate of MPN while even a trace amount of moisture was found to significantly impact both the reaction kinetics and the polymerization course.

Synthesis and photopolymerization of low shrinkage methacrylate monomers containing bulky substituent groups.

OBJECTIVES: This study was conducted to determine whether novel photopolymerizable formulations based on dimethacrylate monomers with bulky substituent groups could provide low polymerization shrinkage without sacrifice to degree of conversion, and mechanical properties of the polymers. METHODS: Relatively high molecular weight dimethacrylate monomers were prepared from rigid bisphenol A core groups. Photopolymerization kinetics and shrinkage as well as flexural strength and glass transition temperatures were evaluated for various comonomer compositions. RESULTS: Copolymerization of the bulky monomers with TEGDMA show higher conversion but similar shrinkage compared with Bis-GMA/TEGDMA controls. The resulting polymers have suitable mechanical strength properties for potential dental restorative materials applications. When copolymerized with PEGDMA, the bulky monomers show lower shrinkage, comparable conversion, and more homogeneous polymeric network structures compared with Bis-EMA/PEGDMA systems. SIGNIFICANCE: The novel dimethacrylate monomers with reduced reactive group densities can decrease the polymerization shrinkage as anticipated, but there is no significant evidence that the bulky substituent groups have any additional effect on reducing shrinkage based on the physical interactions as polymer side chains. The bulky groups improve the double bond conversion and help maintain the mechanical properties of the resulting polymer, which would otherwise decrease rapidly due to the reduced crosslinking density. Further, it was found that bulky monomers help produce more homogeneous copolymer networks.

Conversion-dependent shrinkage stress and strain in dental resins and composites.

The placement of dental composites is complicated by the contraction that accompanies polymerization of these materials. The resulting shrinkage stress that develops during cure of a bonded restoration can induce defects within the composite, the tooth or at the interface resulting in compromised clinical performance and/or esthetics. In light of the substantial efforts devoted to understanding and attempting to control shrinkage stress and strain in dental composite restoratives, this paper offers a perspective on the conversion dependent development of shrinkage and stress. The relationships between polymer property development and the physical evolution of the network structures associated with dental polymers as well as the interrelated kinetics of the photopolymerization reaction process are examined here. Some of the methods used to assess conversion in dental resins and composites are considered. In particular, newly introduced techniques that allow real time analysis of conversion by near-infrared spectroscopy to be coupled directly to simultaneous dynamic measurements of either shrinkage stress or strain are described. The results are compared with reports from the dental materials literature as well as complementary studies in other related fields of polymer science. The complex, nonlinear correlation between conversion, shrinkage and stress are highlighted. A brief review of some of the materials-based approaches designed to minimize polymerization shrinkage and stress is also provided.