Thermoresponsive anionic copolymer brushes containing strong acid moieties for effective separation of basic biomolecules and proteins.

A thermoresponsive copolymer brush possessing the sulfonic acid group, poly(N-isopropylacrylamide (IPAAm)-co-2-acrylamido-2-methylpropanesulfonic acid (AMPS)-co-tert-butylacrylamide (tBAAm)), was grafted onto the surface of silica beads through surface-initiated atom transfer radical polymerization. Prepared copolymer and copolymer brushes on silica beads were characterized by observing the phase transition profile, CHNS elemental analysis, X-ray photoelectron spectroscopy, and gel permeation chromatography. The phase transition profile indicated that an appropriate AMPS composition for enabling thermally modulated property changes is 5 mol %, while excessive amounts of sulfonic acid groups prevented copolymer phase transition. Chromatographic elutions of catecholamine derivatives and basic proteins were observed, using the prepared copolymer brush-modified beads as chromatographic matrices, and the results suggest that the beads interact with these analytes through relatively strong electrostatic interactions. Thus, poly(IPAAm-co-AMPS-co-tBAAm) brush-modified beads will be useful for effective thermoresponsive chromatography matrices that separate basic biomolecules through strong electrostatic interactions.

[1]  T. Okano,et al.  Monolithic silica rods grafted with thermoresponsive anionic polymer brushes for high-speed separation of basic biomolecules and peptides. , 2014, Biomacromolecules.

[2]  D. Grijpma,et al.  Thermoresponsive copolymer brushes possessing quaternary amine groups for strong anion-exchange chromatographic matrices. , 2014, Biomacromolecules.

[3]  T. Okano,et al.  Thermally modulated cationic copolymer brush on monolithic silica rods for high-speed separation of acidic biomolecules. , 2013, ACS applied materials & interfaces.

[4]  Hideo Namiki,et al.  Prevention of esophageal stricture after endoscopic submucosal dissection using tissue-engineered cell sheets ( , 2013 .

[5]  T. Okano,et al.  Dynamically cell separating thermo-functional biointerfaces with densely packed polymer brushes , 2012 .

[6]  Teruo Okano,et al.  Tissue engineered myoblast sheets improved cardiac function sufficiently to discontinue LVAS in a patient with DCM: report of a case , 2012, Surgery Today.

[7]  T. Okano,et al.  Effect of reaction solvent on the preparation of thermo-responsive stationary phase through a surface initiated atom transfer radical polymerization. , 2011, Journal of chromatography. A.

[8]  T. Okano,et al.  Thermoresponsive polymer brush on monolithic-silica-rod for the high-speed separation of bioactive compounds. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[9]  T. Aoyagi,et al.  Tunable stimuli-responsive self-assembly system that forms and stabilizes nanoparticles by simple mixing and heating/cooling of selected block copolymers , 2011 .

[10]  T. Okano,et al.  Thermo-responsive polymer brushes as intelligent biointerfaces: preparation via ATRP and characterization. , 2011, Macromolecular bioscience.

[11]  Simuck F. Yuk,et al.  Thermo-responsive protein adsorbing materials for purifying pharmaceutical protein on exposed charging surface , 2011 .

[12]  T. Okano,et al.  Thermally-modulated on/off-adsorption materials for pharmaceutical protein purification. , 2011, Biomaterials.

[13]  K. Ishihara,et al.  Reduction of protein adsorption on well-characterized polymer brush layers with varying chemical structures. , 2010, Colloids and surfaces. B, Biointerfaces.

[14]  T. Okano,et al.  Preparation of thermo-responsive polymer brushes on hydrophilic polymeric beads by surface-initiated atom transfer radical polymerization for a highly resolutive separation of peptides. , 2010, Journal of chromatography. A.

[15]  Hong Chen,et al.  Protein adsorption and cell adhesion/detachment behavior on dual-responsive silicon surfaces modified with poly(N-isopropylacrylamide)-block-polystyrene copolymer. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[16]  T. Okano,et al.  Thermo-responsive polymer brush-grafted porous polystyrene beads for all-aqueous chromatography. , 2010, Journal of chromatography. A.

[17]  T. Okano,et al.  Preparation of thermoresponsive anionic copolymer brush surfaces for separating basic biomolecules. , 2010, Biomacromolecules.

[18]  M. Diociaiuti,et al.  ATRP synthesis and association properties of thermoresponsive anionic block copolymers , 2008 .

[19]  J. Mano.  Stimuli‐Responsive Polymeric Systems for Biomedical Applications , 2008 .

[20]  T. Okano,et al.  Preparation of thermoresponsive cationic copolymer brush surfaces and application of the surface to separation of biomolecules. , 2008, Biomacromolecules.

[21]  T. Okano,et al.  Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[22]  Patrick S. Stayton,et al.  Conjugates of stimuli-responsive polymers and proteins , 2007 .

[23]  John M. Hoffman,et al.  Switchable surface traps for injectable bead-based chromatography in PDMS microfluidic channels. , 2006, Lab on a chip.

[24]  M. Ulbricht.  Advanced functional polymer membranes , 2006 .

[25]  A. Kishida,et al.  Protein Repellency of Well-Defined, Concentrated Poly(2-hydroxyethyl methacrylate) Brushes by the Size-Exclusion Effect , 2006 .

[26]  Shiping Zhu,et al.  Non-biofouling materials prepared by atom transfer radical polymerization grafting of 2-methacryloloxyethyl phosphorylcholine: separate effects of graft density and chain length on protein repulsion. , 2006, Biomaterials.

[27]  G. Masci,et al.  Atom transfer radical polymerization of sodium2‐acrylamido‐2‐methylpropanesulfonate , 2005 .

[28]  Shiping Zhu,et al.  Adsorption of fibrinogen and lysozyme on silicon grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom transfer radical polymerization. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[29]  W. Huck,et al.  Polymer brushes via surface-initiated polymerizations. , 2004, Chemical Society reviews.

[30]  E. Gil,et al.  Stimuli-reponsive polymers and their bioconjugates , 2004 .

[31]  T. Okano,et al.  Corneal reconstruction with tissue-engineered cell sheets composed of autologous oral mucosal epithelium. , 2004, The New England journal of medicine.

[32]  A. Takahara,et al.  Control of nanobiointerfaces generated from well-defined biomimetic polymer brushes for protein and cell manipulations. , 2004, Biomacromolecules.

[33]  P. Braun,et al.  Patterned poly(N-isopropylacrylamide) brushes on silica surfaces by microcontact printing followed by surface-initiated polymerization. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[34]  G. Masci,et al.  Atom Transfer Radical Polymerization of N-Isopropylacrylamide , 2004 .

[35]  M. Maeda,et al.  Temperature-responsive formation of colloidal nanoparticles from poly(N-isopropylacrylamide) grafted with single-stranded DNA. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[36]  T. Okano,et al.  Cross-linked thermoresponsive anionic polymer-grafted surfaces to separate bioactive basic peptides. , 2003, Analytical chemistry.

[37]  Sergio Mendez,et al.  Thermal Response of Poly(N-isopropylacrylamide) Brushes Probed by Surface Plasmon Resonance. , 2003, Langmuir : the ACS journal of surfaces and colloids.

[38]  J. Genzer,et al.  Combinatorial study of the mushroom-to-brush crossover in surface anchored polyacrylamide. , 2002, Journal of the American Chemical Society.

[39]  T. Okano,et al.  Intelligent thermoresponsive polymeric stationary phases for aqueous chromatography of biological compounds , 2002 .

[40]  M. Wirth,et al.  Kinetics of Surface-Initiated Atom Transfer Radical Polymerization of Acrylamide on Silica , 2002 .

[41]  T. Okano,et al.  Gene expression control by temperature with thermo-responsive polymeric gene carriers. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

[42]  Teruo Okano,et al.  Thermo-responsive polymer nanoparticles with a core-shell micelle structure as site-specific drug carriers , 1997 .

[43]  T. Okano,et al.  Temperature-Responsive Chromatography Using Poly(N-isopropylacrylamide)-Modified Silica. , 1996, Analytical chemistry.

[44]  T. Okano,et al.  Mechanism of cell detachment from temperature-modulated, hydrophilic-hydrophobic polymer surfaces. , 1995, Biomaterials.

[45]  A S Hoffman,et al.  Site-specific conjugation of a temperature-sensitive polymer to a genetically-engineered protein. , 1994, Bioconjugate chemistry.

[46]  T. Okano,et al.  Thermo‐responsive polymeric surfaces; control of attachment and detachment of cultured cells , 1990 .

[47]  J. Kopeček,et al.  Hydrogels for site‐specific oral delivery. Poly[(acrylic acid)‐co‐(butyl acrylate)] crosslinked with 4,4′‐bis(methacryloylamino)azobenzene , 1990 .

[48]  Ronald A. Siegel,et al.  pH-Dependent Equilibrium Swelling Properties of Hydrophobic Polyelectrolyte Copolymer Gels , 1988 .

[49]  D. Urry,et al.  pK shift of functional group in mechanochemical coupling due to hydrophobic effect: evidence for an apolar-polar repulsion free energy in water. , 1988, Biochemical and Biophysical Research Communications - BBRC.

[50]  B. Karger,et al.  Multiple peak formation in reversed-phase liquid chromatography of papain , 1984 .

[51]  M. Heskins,et al.  Solution Properties of Poly(N-isopropylacrylamide) , 1968 .

[52]  M. Ciampolini,et al.  Five-Coordinated High-Spin Complexes of Bivalent Cobalt, Nickel, andCopper with Tris(2-dimethylaminoethyl)amine , 1966 .