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

This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.

50th Anniversary Perspective: RAFT Polymerization—A User Guide

The use of light to mediate controlled radical polymerization has emerged as a powerful strategy for rational polymer synthesis and advanced materials fabrication. This review provides a comprehensive survey of photocontrolled, living radical polymerizations (photo-CRPs). From the perspective of mechanism, all known photo-CRPs are divided into either (1) intramolecular photochemical processes or (2) photoredox processes. Within these mechanistic regimes, a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved. To provide a clear understanding of each subcategory, reaction mechanisms are discussed. In addition, applications of photo-CRP reported so far, which include surface fabrication, particle preparation, photoresponsive gel design, and continuous flow technology, are summarized. We hope this review will not only provide informative knowledge to researchers in this field but also stimulate new ideas and applications to further advance photocontrolled reactions.

http://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.5b00671

Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications

Overcoming the challenge of metal contamination in traditional ATRP systems, a metal-free ATRP process, mediated by light and catalyzed by an organic-based photoredox catalyst, is reported. Polymerization of vinyl monomers are efficiently activated and deactivated with light leading to excellent control over the molecular weight, polydispersity, and chain ends of the resulting polymers. Significantly, block copolymer formation was facile and could be combined with other controlled radical processes leading to structural and synthetic versatility. We believe that these new organic-based photoredox catalysts will enable new applications for controlled radical polymerizations and also be of further value in both small molecule and polymer chemistry.

/pdf/metal-free-atom-transfer-radical-polymerization-48cu363rmk.pdf

Metal-Free Atom Transfer Radical Polymerization

The phase-shifting mask consists of a normal transmission mask that has been coated with a transparent layer patterned to ensure that the optical phases of nearest apertures are opposite. Destructive interference between waves from adjacent apertures cancels some diffraction effects and increases the spatial resolution with which such patterns can be projected. A simple theory predicts a near doubling of resolution for illumination with partial incoherence σ < 0.3, and substantial improvements in resolution for σ < 0.7. Initial results obtained with a phase-shifting mask patterned with typical device structures by electron-beam lithography and exposed using a Mann 4800 10× tool reveals a 40-percent increase in usuable resolution with some structures printed at a resolution of 1000 lines/mm. Phase-shifting mask structures can be used to facilitate proximity printing with larger gaps between mask and wafer. Theory indicates that the increase in resolution is accompanied by a minimal decrease in depth of focus. Thus the phase-shifting mask may be the most desirable device for enhancing optical lithography resolution in the VLSI/VHSIC era.

Improving resolution in photolithography with a phase-shifting mask

Controlled/living radical polymerization techniques have transformed polymer chemistry in the last few decades, affording the production of polymers with precise control over both molecular weights and architectures. It is now possible to synthesize almost an infinite variety of macromolecules using nonspecialized equipment, finding applications in high-tech industry. However, they have several shortcomings. Until recently, living radical polymerizations could not be controlled by an external stimulus, such as visible light, pH, mechanical, chemical, etc. Moreover, they are usually sensitive to trace amounts of oxygen in the system. In this Article, we report a photoinduced living polymerization technique, which is able to polymerize a large range of monomers, including conjugated and unconjugated monomers, using ultralow concentrations of an iridium-based photoredox catalyst (typically 1 ppm to monomers) and a low energy visible LED as the light source (1–4.8 W, λmax = 435 nm). The synthesis of homopolym...

A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance

Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications

Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications Cyrille Boyer,*,†,‡ Nathaniel Alan Corrigan,‡ Kenward Jung,‡ Diep Nguyen,‡ Thuy-Khanh Nguyen,‡ Nik Nik M. Adnan,†,‡ Susan Oliver,†,‡ Sivaprakash Shanmugam,‡ and Jonathan Yeow†,‡ †Australian Centre for Nanomedicine, and ‡Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia

Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications

This study reports a highly efficient photoredox catalyst, Ru(bpy)3Cl2, capable of controlling the polymerization of methacrylates, acrylates, and acrylamides in the presence of thiocarbonylthio compounds via a photoinduced electron transfer–reversible addition–fragmentation chain (PET-RAFT) process. This polymerization technique was performed in a closed vessel in the presence or absence of air. Online Fourier transform near-infrared spectroscopy (FTNIR) was employed to monitor the monomer conversions of methyl methacrylate, methyl acrylate, and N,N′-dimethylacrylamide in the presence or absence of air. Interestingly, after an induction period, the polymerization proceeded in the presence of air to yield well-defined polymers (PDI < 1.20). The polymers were characterized by 1H NMR, UV–vis spectroscopy, and gel permeation chromatography. Excellent end-group retention was also demonstrated by NMR, UV–vis, and successive chain extensions of the resulting homopolymers to yield diblock and multiblock copolyme...

Oxygen Tolerance Study of Photoinduced Electron Transfer–Reversible Addition–Fragmentation Chain Transfer (PET-RAFT) Polymerization Mediated by Ru(bpy)3Cl2

We report a photoinduced living polymerization technique able to polymerize a large range of monomers, including methacrylates, acrylates and acrylamides, in water and biological media as well as organic solvents. This polymerization technique employs ultra-low concentrations of a ruthenium-based photoredox catalyst (typically 1 ppm to monomers) and enables low energy visible LED light to afford well-defined polymers with narrow polydispersities (Mw/Mn < 1.3). In this paper, different parameters, including photocatalyst concentrations and solvent effects, were thoroughly investigated. In addition, successful polymerizations in biological media have been reported with good control of the molecular weights and molecular weight distributions (Mw/Mn < 1.4). Finally, protein–polymer bioconjugates using a “grafting from” approach were demonstrated using bovine serum albumin as a model biomacromolecule. The enzymatic bioactivity of the protein was demonstrated to be maintained using a standard assay.

Kenward Jung

Papers

A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance

Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications

Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications

Oxygen Tolerance Study of Photoinduced Electron Transfer–Reversible Addition–Fragmentation Chain Transfer (PET-RAFT) Polymerization Mediated by Ru(bpy)3Cl2

Aqueous photoinduced living/controlled polymerization: tailoring for bioconjugation