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Abstract: Controlled β-cyclodextrin (β-CD) core-based cationic star polymers have attracted considerable attention as non-viral gene carriers. Atom transfer radical polymerization (ATRP) could be readily used to produce the star-shaped polymers. The precise control of the number of initiation sites on the multifunctional core was of crucial importance to the investigation of the structure–property relationship of the functional star gene carriers. Herein, the controlled multiarm star polymers consisting of a β-CD core and various arm lengths of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) were prepared via ATRP from the chloroacetylated β-CD with well-designed initiation sites. Generally, these star polycations can condense plasmid DNA into 100–150nm nanoparticles with positive zeta potentials of 30–40mV at N/P ratios (star polymer to DNA ratios) of 17 or higher. The effects of arm numbers and lengths on gene delivery were investigated in detail. With a fixed length of the PDMAEMA arm, the fewer the number of arms, the lower the toxicity. The star polycations with suitable arm numbers possess the best transfection ability. On the other hand, with the fixed molecular weights, the shorter the arms, the lower the toxicity. The polymers with 21 arms possess the lowest transfection efficiency. [Copyright &y& Elsevier]

Abstract: The design of efficient gene delivery vectors is a challenging task in gene therapy. Recent progress in living/controlled radical polymerizations (LRPs), in particular atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization providing a means for the design and synthesis of new polymeric gene vectors with well-defined compositions, architectures and functionalities is reviewed here. Polymeric gene vectors with different architectures, including homopolymers, block copolymers, graft copolymers, and star-shaped polymers, are conveniently prepared via ATRP and RAFT polymerization. The corresponding synthesis strategies are described in detail. The recent research activities indicate that ATRP and RAFT polymerization have become essential tools for the design and synthesis of advanced, noble and novel gene carriers. [Copyright &y& Elsevier]

Abstract: Thermoresponsive poly(N-isopropylacrylamide) (P(NIPAAm))-grafted polycaprolactone (PCL) films with a suitable amount of immobilized cell-adhesive collagen were prepared to improve cell adhesion and proliferation above the lower critical solution temperature (LCST, 32°C) of P(NIPAAm) without destroying cell detachment properties at lower temperatures. Covalently tethered P(NIPAAm) brushes on PCL film surfaces were first prepared via surface-initiated atom transfer radical polymerization (ATRP). The alkyl bromide end groups of the grafted P(NIPAAm) brushes were used in nucleophilic substitution reactions for the direct coupling of collagen to produce the collagen-immobilized thermoresponsive PCL surface. At 37°C, the cell attachments on the collagen-immobilized thermoresponsive PCL surface were enhanced substantially. The attached cells could be recovered simply by lowering culture temperature. The P(NIPAAm)-grafted PCL films with immobilized collagen are potentially useful as adhesion modifiers for advanced cell culture and tissue engineering applications. [Copyright &y& Elsevier]

Abstract: The ability to manipulate and control the surface properties, without altering the substrate properties, is of crucial importance in the designing of biomedical materials. In this work, surface-initiated atom transfer radical polymerization (ATRP) is employed to tailor the functionality of polycaprolactone (PCL) film surfaces in a well-controlled manner. Functional polymer brushes of glycidyl methacrylate (GMA) were prepared via surface-initiated ATRPs from the PCL film surfaces. Kinetics study revealed that the chain growth from the PCL films was consistent with a controlled process. The dense and reactive epoxide groups of the grafted P(GMA) brushes were used for the direct coupling of cell-adhesive collagen and Arg-Gly-Asp-Ser (RGDS) peptides to improve the cell-adhesion properties of the PCL film surface. These modified surfaces were evaluated by culturing of a cell line, 3T3 fibroblasts. The cell attachment and proliferation were improved remarkably on the collagen (or RGDS) functionalized PCL film surfaces. The adhesion results also indicated that the collagen-coupled PCL film surface is better for the cell-adhesion process. With the versatility of surface-initiated ATRP and the good biocompatibility nature of biomolecules, the PCL films with desirable surface functionalities can be precisely tailored to cater to various biomedical applications. [Copyright &y& Elsevier]

Abstract: Recent progress in controlled radical polymerizations, in particular atom transfer radical polymerization (ATRP), has provided a unique means for the design and synthesis of bioactive surfaces and functional biomaterials. This review summarizes such recent research activities. The synthesis strategies of bioactive surfaces and biomaterials via ATRP are described in detail. The highly robust and versatile ATRP technique is particularly suited for the preparation of functional bioactive surfaces, including antifouling, antibacterial, stimuli-responsive, biomolecule-coupled and micropatterned surfaces. In addition to bioactive surfaces, ATRP has also been widely used for the preparation of well-structured functional biomaterials, such as micellar delivery systems, hydrogels, cationic gene carriers and polymer–protein conjugates. The research activities in the last decade indicate that ATRP has become an essential tool for the design and synthesis of advanced, noble and novel biomaterials. [Copyright &y& Elsevier]

Abstract: We report a novel method for micropatterning of active proteins on anti-fouling surfaces via spatially well-defined and dense binary poly(ethylene glycol)s (PEGs) brushes with controllable protein-docking sites. Binary brushes of poly(poly(ethylene glycol) methacrylate-co-poly(ethylene glycol)methyl ether methacrylate), or P(PEGMA-co-PEGMEMA), and poly(poly(ethylene glycol)methyl ether methacrylate), or P(PEGMEMA), were prepared via consecutive surface-initiated atom transfer radical polymerizations (SI-ATRPs) from a resist-micropatterned Si(100) wafer surface. The terminal hydroxyl groups on the side chains of PEGMA units in the P(PEGMA-co-PEGMEMA) microdomains were activated directly by 1,1′-carbonyldiimidazole (CDI) for the covalent coupling of human immunoglobulin (IgG) (as a model active protein). The resulting IgG-coupled PEG microdomains interact only and specifically with target anti-IgG, while the other PEG microregions effectively prevent specific and non-specific protein fouling. When extended to other active biomolecules, microarrays for specific and non-specific analyte interactions with a high signal-to-noise ratio could be readily tailored. [Copyright &y& Elsevier]

Abstract: Well-defined comb-shaped copolymer-Si(100) hybrids were prepared, via successive surface-initiated atom transfer radical polymerizations (ATRPs) of glycidyl methacrylate (GMA) and N-isopropylacrylamide (NIPAAm), for accelerated cell detachment at a lower temperature. The Si–C bonded comb copolymer consisted of a well-defined (nearly monodispersed) poly(glycidyl methacrylate) (P(GMA)) main chain, a well-defined NIPAAm polymer (P(NIPAAm) block, and well-defined P(NIPAAm) side chains. The ring opening reaction of epoxy groups of the P(GMA) main chain with 2-chloropropionic acid resulted in the immobilization of the α-chloroester groups (the ATRP initiators for the NIPAAm side chains) and the concomitant formation of hydroxyl groups. P(NIPAAm) acted as the thermoresponsive side chains of the comb copolymer for control of cell adhesion and detachment, while the P(GMA) main chain with hydroxyl groups provided a local hydrophilic microenvironment. The unique microstructure of the comb copolymer brushes facilitated cell recovery at 20°C (below the lower critical solution temperature (LCST) of P(NIPAAm)) without restraining cell attachments and growth at 37°C. The accelerated detachment of cells indicated that the underlying hydrophilic environment of the comb copolymer brushes contributed to speedy hydration of the P(NIPAAm) segments below the LCST. The thermoresponsive comb copolymer-Si(100) hybrids are potentially useful as adhesion modifiers for cells in silicon-based biomedical devices. [Copyright &y& Elsevier]

Abstract: Removal of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from wastewater has caused great attention in recent years. In this study, quaternized cotton highly effective for the removal of PFOS and PFOA from aqueous solution was prepared by surface-initiated atom transfer radical polymerization (ATRP). The successful graft of long polymer brushes on the cotton surfaces was verified by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). XPS analysis indicated that the high density of quaternary ammonium cations on the long polymers grafted onto the cotton surface were responsible for the enhanced sorption of PFOS and PFOA. This novel quaternized cotton exhibited fast sorption and high sorption capacity for PFOS and PFOA. The sorption equilibrium of PFOA and PFOS on quaternized cotton was achieved at 4h and 12h, respectively, much faster than that on the porous adsorbents reported. The obtained maximum sorption capacities of PFOS and PFOA on quaternized cotton at pH 5.0 were 3.3 and 3.1mmol/g, respectively. Additionally, solution pH in the range of 3.0–10.0 had little effect on their high sorption. This quaternized cotton has promising application for the removal of perfluorinated compounds from wastewater. [Copyright &y& Elsevier]

Abstract: Thermo- and pH-responsive nylon membranes were prepared via consecutive surface-initiated atom transfer radical polymerizations (ATRPs) of N-isopropylacrylamide (NIPAAm) and N,N′-dimethyl aminoethyl methacrylate (DMAEMA). The amide groups of the membrane and pore surfaces were first activated for the immobilizing of alkyl halide ATRP initiator. The kinetics study revealed that the chain growth from the membranes was consistent with a “controlled” process. The dormant chain ends of the grafted NIPAAm polymer (PNIPAAm) or DMAEMA polymer (PDMAEMA) on the nylon membranes could be reactivated for the consecutive surface-initiated ATRP to produce the corresponding nylon membranes functionalized with PNIPAAm-b-PDMAEMA or PDMAEMA-b-PNIPAAm diblock copolymer brushes. The permeation of aqueous solution through the functional membranes showed an abrupt change with temperature between 30 and 35°C, and pH between 6 and 8. The temperature- and pH-responsive permeation through the functional nylon membranes was found to be reversible and irrespective of the sequence of the graft segments. [Copyright &y& Elsevier]

Abstract: A simple method by combined molecular self assembly and surface-initiated atom transfer radical polymerization (SI-ATRP) was proposed to prepare a biologically inert surface for micropatterning active proteins. The MPEG microdomains having a short terminal poly(ethylene glycol) (PEG) unit were prepared by self assembly of 2-(methyoxy(polyethylenoxy) propyl)trimethoxy silane (MPEG-silane). The remaining local regions or poly(poly(ethylene glycol)methyl ether methacrylate-co-glycidyl methacrylate) (P(PEGMEMA-co-GMA)) microdomains were produced via SI-ATRP of PEGMEMA and GMA comonomers. The epoxy groups of the P(PEGMEMA-co-GMA) microdomains were used directly for covalent coupling of an active protein (human immunoglobulin or IgG) via the ring-opening reaction to produce the IgG-coupled microdomains. The IgG-coupled microdomains interact only and specifically with target anti-IgG, while the other antifouling microregions from self-assembled monolayers with short terminal PEG units effectively prevent specific and non-specific protein fouling. When extended to other active biomolecules, microarrays for specific and non-specific analyte interactions with a high signal-to-noise ratio could be readily tailored. [Copyright &y& Elsevier]