Thiol–enes: Chemistry of the past with promise for the future
TL;DR: The photopolymerization of mixtures of multifunctional thiols and enes is an efficient method for the rapid production of films and thermoset plastics with unprecedented physical and mechanical properties.
Abstract: The photopolymerization of mixtures of multifunctional thiols and enes is an efficient method for the rapid production of films and thermoset plastics with unprecedented physical and mechanical properties. One of the major obstacles in traditional free-radical photopolymerization is essentially eliminated in thiol–ene polymerizations because the polymerization occurs in air almost as rapidly as in an inert atmosphere. Virtually any type of ene will participate in a free-radical polymerization process with a multifunctional thiol. Hence, it is possible to tailor materials with virtually any combination of properties required for a particular application. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5301–5338, 2004
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TL;DR: The radical-mediated thiol-ene 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.
Abstract: 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.
3,229 citations
TL;DR: The current status and future perspectives in atom transfer radical polymerization (ATRP) are presented in this paper, with a special emphasis on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP.
Abstract: Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.
2,188 citations
TL;DR: This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms.
Abstract: The merits of thiol-click chemistry and its potential for making new forays into chemical synthesis and materials applications are described Since thiols react to high yields under benign conditions with a vast range of chemical species, their utility extends to a large number of applications in the chemical, biological, physical, materials and engineering fields This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms (81 references)
1,412 citations
TL;DR: This paper aims to demonstrate the efforts towards in-situ applicability of EMMARM, which aims to provide real-time information about the physical properties of EMTs and their applications in the treatment of cancer.
Abstract: Department of Chemistry, Department of Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130, Department of Chemistry, Texas A&M University, College Station, Texas 77842, Cancer Center Karolinska, Department of Oncology-Pathology CCK, R8:03 Karolinska Hospital and Institute, SE-171 76 Stockholm, Sweden, and Department of Chemistry and Biochemistry, Department of Materials, and Materials Research Laboratory, University of California, Santa Barbara, California 93106
1,323 citations
TL;DR: In this paper, a review highlights examples of recent applications of both the radical-mediated and base/nucleophile-initiated thiol-ene reactions in polymer and materials synthesis.
1,320 citations
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TL;DR: In this article, the preparation of two-layer stamps was adapted from a procedure originally developed by Schmid et al. (Macromolecules 2000, 33, 3042) for microcontact printing.
Abstract: Composite stamps composed of two layersa stiff layer supported by a flexible layerextend the capabilities of soft lithography to the generation of 50−100-nm features. The preparation of these stamps was adapted from a procedure originally developed by Schmid et al. (Macromolecules 2000, 33, 3042) for microcontact printing. This paper demonstrates how pattern transfer using other soft lithographic techniquesmicromolding in capillaries, microtransfer molding, and phase-shifting lithographycan be improved using two-layer stamps relative to stamps made of Sylgard 184 poly(dimethylsiloxane).
734 citations
Book•
01 Jan 1974
TL;DR: The chemistry of the thiol group is studied in detail in order to establish a clear picture of the chiral stationary phase and its role in the polyene-like structure.
Abstract: The chemistry of the thiol group. , The chemistry of the thiol group. , کتابخانه دیجیتال جندی شاپور اهواز
601 citations
TL;DR: In this article, the authors used real-time Fourier transform infrared to monitor the conversion of both thiol and ene functional groups independently during photoinduced thiol-ene photopolymerizations.
Abstract: We used real-time Fourier transform infrared to monitor the conversion of both thiol and ene (vinyl) functional groups independently during photoinduced thiol–ene photopolymerizations. From these results, the stoichiometry of various thiol–ene and thiol–acrylate polymerizations was determined. For thiol–ene polymerizations, the conversion of ene functional groups was up to 15% greater than the conversion of thiol functional groups. For stoichiometric thiol–acrylate polymerizations, the conversion of the acrylate functional groups was roughly twice that of the thiol functional groups. With kinetic expressions for thiol–acrylate polymerizations, the acrylate propagation kinetic constant was found to be 1.5 times greater than the rate constant for hydrogen abstraction from the thiol. Conversions of thiol–acrylate systems of various initial stoichiometries were successfully predicted with this ratio of propagation and chain-transfer kinetic constants. Thiol–acrylate systems with different initial stoichiometries exhibited diverse network properties. Thiol–ene systems were initiated with benzophenone and 2,2-dimethoxy-2-phenylacetophenone as initiators and were also polymerized without a photoinitiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3311–3319, 2001
462 citations
TL;DR: In this paper, a thiol monomer is shown to copolymerize with vinyl ether, allyl, acrylate, methacrylate and vinylbenzene monomers.
Abstract: A thiol monomer is shown to copolymerize with vinyl ether, allyl, acrylate, methacrylate, and vinylbenzene monomers. These thiol−ene polymerizations are photoinitiated without the use of photoinitiator molecules. It is seen that the polymerization proceeds more readily when initiatorless samples are irradiated with light centered around 254 nm as compared to 365 nm light. To demonstrate resistance to oxygen inhibition, thin polymer films of 3−15 μm are polymerized while exposed to ambient air. Without photoinitiator molecules present, light is attenuated only by the monomer and polymer. This feature leads to greater penetration of ultraviolet light and allows for the polymerization of extremely thick polymers. Thick cures of up to 25 in. are obtained using a thiol−vinyl ether system.
341 citations
TL;DR: In this paper, a method for the crystallization of mesoscale particles over areas as large as ∼1 cm2 was described, where an aqueous dispersion of spherical particles was injected into a cell formed by two glass substrates and a square frame of photoresist that had been patterned on the surface of one of the substrates.
Abstract: This paper describes a method for the crystallization of mesoscale particles over areas as large as ∼1 cm2. We injected an aqueous dispersion of spherical particles into a cell formed by two glass substrates and a square frame of photoresist that had been patterned on the surface of one of the substrates. One side of the frame had channels on its surface that could retain the particles while letting the solvent flow through. External gas pressure and sonication drove the particles into a cubic-close-packed (ccp) assembly with the (111) face parallel to the surfaces of the glass substrates. The smallest particles that have been crystallized by this method are polystyrene beads of ∼60 nm in diameter. The procedure presented here offers a number of attractive features: (i) It is relatively fast. For example, polystyrene beads of 0.48 μm in diameter can be crystallized into a 25 layer assembly over an area of ∼1 cm2 in ∼48 h. (ii) It has a tight control over the surface morphology and the number of layers of...
318 citations