Following Sharpless' visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol-ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol-ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Thiol–Ene Click Chemistry

The term photonic crystals appears because of the analogy between electron waves in crystals and the light waves in artificial periodic dielectric structures. During the recent years the investigation of one-, two-and three-dimensional periodic structures has attracted a widespread attention of the world optics community because of great potentiality of such structures in advanced applied optical fields. The interest in periodic structures has been stimulated by the fast development of semiconductor technology that now allows the fabrication of artificial structures, whose period is comparable with the wavelength of light in the visible and infrared ranges.

http://ieeexplore.ieee.org/iel5/6354/16969/00781867.pdf

Photonic crystals

Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

With the maturation of the information display field, liquid-crystal materials research is undergoing a modern-day renaissance. Devices and configurations based on liquid-crystal materials are being developed for spectroscopy, imaging and microscopy, leading to new techniques for optically probing biological systems. Biosensors fabricated with liquid-crystal materials can allow label-free observations of biological phenomena. Liquid-crystal polymers are starting to be used in biomimicking colour-producing structures, lenses and muscle-like actuators. New areas of application in the realms of biology and medicine are stimulating innovation in basic and applied research into these materials.

Liquid-crystal materials find a new order in biomedical applications.

Wide-band tunability, large coherence-area, and in some cases multidirectional emission have made liquid-crystal lasers an attractive light source for applications like miniature medical diagnostic tool and large-area holographic laser displays. This article discusses the scientific origins of the technology of liquid-crystal lasers and reviews the current cutting-edge research.

Liquid-crystal lasers

We have fabricated aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings by combining holographic interference patterning and APTES-functionalization of the pre-polymer syrup. The APTES facilitates the immobilization of biomolecules onto the polymeric grating surfaces. The successful detection of multiple biomolecules (biotin, steptavidin, biotinylated anti-rabbit IgG, and rabbit-IgG) indicates that the functionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays.

Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings: fabrication and application in biosensing

Holographic photopolymerization (H-P) is a simple, fast and attractive means to fabricate one-, two- and three-dimensional complex structures. Liquid crystals, nanoparticles and silicate nano-plates have been patterned into submicron periodical structures. In this article, we report fabrication of a one-dimensional reflection grating structure by patterning a semicrystalline polymer, polyethylene glycol (PEG), in Norland resin (thiol-ene based UV curable resin) matrix using the H-P technique. Sharp notches observed in the reflection grating of this Norland/PEG system indicate a finite Δn present in the system due to spatial segregation of the PEG and Norland resin. The notch position red shifts upon heating and the diffraction efficiency (ratio between diffraction and incident light intensity, DE) increases from ∼20% to 60% for the Norland 65/PEG 4600 grating. This dynamic behavior of the reflection grating is also fully reversible. The unique thermal switching behavior is attributed to the melting/formation of PEG crystals during heating/cooling. By employing different molecular weight PEGs which have different melting temperatures, a series of switching temperatures have been achieved. Since PEG can be easily coupled with a variety of functional groups, this research might shed light on fabricating multifunctional Bragg gratings using the H-P technique.

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Polymer crystallization/melting induced thermal switching in a series of holographically patterned Bragg reflectors

Holographic polymer dispersed liquid crystals (HPDLCs) are a polymer/liquid crystal (LC) composite with wavelength selective diffraction that can be switched in microseconds with electric field. As such, HPDLCs are widely applicable in optical and photonic devices. Recently, replacing acrylate polymer with thiol−ene polymer as host for HPDLCs has improved the stability and electrooptic performance of these materials. This work examines the electrooptic performance and morphology of thiol−ene-based HPDLC reflection gratings. To further understand the relationships between the formation and performance of thiol−ene HPDLCs, electrooptic performance was characterized as a function of polymerization rate, gel point conversion, and the presence of excess monomer (stoichiometry). To this end, HPDLC formulations were examined to isolate the contribution of ene monomer functionality, thiol monomer functionality, and thiol−ene stoichiometry. In all formulations, the performance of HPDLC reflection gratings is corre...

Pamela F. Lloyd

Papers

Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings: fabrication and application in biosensing

Polymer crystallization/melting induced thermal switching in a series of holographically patterned Bragg reflectors

Monomer Functionality Effects in the Formation of Thiol−Ene Holographic Polymer Dispersed Liquid Crystals

Holographic polymer dispersed liquid crystals (HPDLCs) containing triallyl isocyanurate monomer

Dynamic Lasing from All-Organic Two-Dimensional Photonic Crystals†