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

The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ev...

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

Surface-initiated polymer brushes in the biomedical field : applications in membrane science, biosensing, cell culture, regenerative medicine and antibacterial coatings

Surface-Initiated Polymer Brushes in the Biomedical Field: Applications in Membrane Science, Biosensing, Cell Culture, Regenerative Medicine and Antibacterial Coatings

The Langmuir-Blodgett (LB) technique is known as an elegant method for fabrication of well-defined layered structures with molecular level precision. Since its discovery the LB method has made an indispensable contribution to surface science, physical chemistry, materials chemistry and nanotechnology. However, recent trends in research might suggest the decline of the LB method as alternate methods for film fabrication such as layer-by-layer (LbL) assembly have emerged. Is LB film technology obsolete? This review is presented in order to challenge this preposterous question. In this review, we summarize recent research on LB and related methods including (i) advanced design for LB films, (ii) LB film as a medium for supramolecular chemistry, (iii) LB technique for nanofabrication and (iv) LB involving advanced nanomaterials. Finally, a comparison between LB and LbL techniques is made. The latter reveals the crucial role played by LB techniques in basic surface science, current advanced material sciences and nanotechnologies.

25th anniversary article: what can be done with the Langmuir-Blodgett method? Recent developments and its critical role in materials science.

Surface-initiated controlled polymerization as a convenient method for designing functional polymer brushes: From self-assembled monolayers to patterned surfaces

Semi-crystalline poly(ε-caprolactone) brushes on gold substrate via “grafting from” method: New insights with AFM characterization

Exfoliated nanocomposites are prepared by dispersion of poly(-caprolactone) (PCL) grafted montmorillonite nanohybrids used as masterbatches in poly(styrene-co-acrylonitrile) (SAN). The PCL-grafted clay nanohybrids with high inorganic content are synthesized by in situ intercalative ring-opening polymerization of -caprolactone between silicate layers organomodified by alkylammonium cations bearing two hydroxyl functions. The polymerization is initiated by tin alcoholate species derived from the exchange reaction of tin(II) bis(2-ethylhexanoate) with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics) are dispersed as masterbatches in commercial poly(styrene-co-acrylonitrile) by melt blending. SAN-based nanocomposites containing 3 wt% of inorganics are accordingly prepared. The direct blend of SAN/organomodified clay is also prepared for sake of comparison. The clay dispersion is characterized by wide-angle X-ray diffraction (WAXD), atomic force microscopy (AFM), and solid state NMR spectroscopy measurements. The thermal properties are studied by thermogravimetric analysis. The flame retardancy and gas barrier resistance properties of nanocomposites are discussed both as a function of the clay dispersion and of the matrix/clay interaction.

Fire and gas barrier properties of (poly(styrene-co-acrylonitrile) nanocomposites using polycaprolactone / clay nanohybrid masterbatches

/pdf/fire-and-gas-barrier-properties-of-poly-styrene-co-5azdx1nsu0.pdf

Aurore Olivier

Papers

Surface-initiated controlled polymerization as a convenient method for designing functional polymer brushes: From self-assembled monolayers to patterned surfaces

Semi-crystalline poly(ε-caprolactone) brushes on gold substrate via “grafting from” method: New insights with AFM characterization

Fire and gas barrier properties of (poly(styrene-co-acrylonitrile) nanocomposites using polycaprolactone / clay nanohybrid masterbatches

Fire and Gas Barrier Properties of Poly(styrene-co-acrylonitrile) Nanocomposites Using Polycaprolactone/Clay Nanohybrid Based-Masterbatch

Reversible positioning at submicrometre scale of carbon nanotubes mediated by pH-sensitive poly(amino-methacrylate) patterns