Controlled Growth of PMMA Brushes on Silicon Surfaces at Room Temperature
TL;DR: In this article, the atom-transfer radical polymerization of methyl methacrylate at room temperature starting from monolayers of initiators, which are covalently anchored to silicon substrates, is described.
Abstract: The atom-transfer radical polymerization of methyl methacrylate at room temperature starting from monolayers of initiators, which are covalently anchored to silicon substrates, is described. The control of layer thickness and molecular weight, a constant graft density, and a narrow molecular weight distribution of the polymers produced provide evidence for a controlled surface-initiated polymerization, and dense surface-attached polymer brushes on the SiO 2 surfaces are obtained under mild reaction conditions.
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TL;DR: This data indicates that self-Assembled Monolayers and Walled Carbon Nanotubes with high adhesion to Nitroxide-Mediated Polymerization have potential in the well-Defined Polymer Age.
Abstract: Keywords: Fragmentation Chain-Transfer ; Self-Assembled Monolayers ; Walled Carbon Nanotubes ; Well-Defined Polymer ; Nitroxide-Mediated Polymerization ; Block-Copolymer Brushes ; Poly(Methyl Methacrylate) Brushes ; Transfer Raft Polymerization ; Quartz-Crystal Microbalance ; Poly(Acrylic Acid) Brushes Reference EPFL-REVIEW-148464doi:10.1021/cr900045aView record in Web of Science Record created on 2010-04-23, modified on 2017-05-10
1,542 citations
TL;DR: 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 as mentioned in this paper.
Abstract: 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...
681 citations
TL;DR: The results indicate that surface charge density, is a critical element in designing a surface for maximum kill efficiency and the relevance of this finding to the mechanism of action is discussed.
Abstract: Rational controlled synthesis of poly(quaternary ammonium) compounds has been used to prepare antimicrobial polymer brushes on inorganic surfaces. The systematic variation of several structural parameters of the polymeric brushes allowed us to elicit the minimum surface requirements and a probable mechanism of action for Escherichia coli cell kill. Polymeric brushes were prepared by surface-initiated atom transfer radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA), a method that allows the molecular weight of the polymer chains to be precisely controlled as they grow from the target surface. The tertiary amino groups of the polyDMAEMA were then quaternized with alkyl bromides to provide a surface with antimicrobial activity. Dry layer thickness of the polymer brushes was controlled by polymerization time and/or initiator density on the surface. This tunability of surface structure allows the antimicrobial polymer brushes to be tailored rationally. A combinatorial screening tool was developed to elucidate the role of chain length and chain density on cell kill in a single experiment. The results indicate that surface charge density, is a critical element in designing a surface for maximum kill efficiency. The most biocidal surfaces had charge densities of greater than 1-5 x 10(15) accessible quaternary amine units/cm(2). The relevance of this finding to the mechanism of action is discussed.
657 citations
Journal Article•
TL;DR: A review of surface-initiated living radical polymerization (LRP) can be found in this article, where a high-density polymer brush has characteristics, in both swollen and dry states, quite different and unpredictable from those of the semi-dilute or moderately dense polymer brushes previously studied.
Abstract: Surface modifications by polymers are becoming increasingly important for various applications ranging from biotechnology to advanced microelectronics. Recent successful applications of living radical polymerization (LRP) made it possible to graft various low-polydispersity polymers including simple homopolymers, end-functionalized polymers, block/random/gradient copolymers, and functional polymers. At the same time, this technique has brought about a striking increase of graft density. Graft chains in such a high-density polymer brush were found to be highly extended in good solvent, even to the order of their full lengths. It was also found that a high-density polymer brush has characteristic properties, in both swollen and dry states, quite different and unpredictable from those of the semi-dilute or moderately dense polymer brushes previously studied. This review highlights the recent development of surface-initiated LRP and the structures, properties, and potential applications of thereby obtainable high-density polymer brushes. It is believed that surface-initiated LRP is opening up a new route to "precision" surface modification.
493 citations
TL;DR: To better understand protein/material and cell/material interactions at the submolecular level, well-defined polymer brushes consisting of poly(2-methacryloyloy loxyethyl phosphorylcholine) (PMPC) on silicon wafers were prepared by atom transfer radical polymerization (ATRP).
Abstract: To better understand protein/material and cell/material interactions at the submolecular level, well-defined polymer brushes consisting of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) on silicon wafers were prepared by atom transfer radical polymerization (ATRP). Silicon wafers were treated with 3-(2-bromoisobutyryl)propyl dimethylchlorosilane (BDCS) to form a monolayer that acts as initiators for ATRP. Silicon-supported BDCS monolayers were soaked in a methanol/water mixture solution containing Cu(I)Br, bipyridine, and a sacrificial initiator. After MPC was added to the solution, ATRP was carried out for 18 h. The molecular weight and thickness of the PMPC brush layer on the silicon surface increased with an increase in the polymerization time. The dense polymer brushes were obtained by the “grafting from” system. By selective decomposition of the BDCS monolayer by UV light-irradiation, the PMPC brush region and the sizes were well controlled, resulting in fabricating micropatterns of the PMPC b...
274 citations