Protein adsorption and cell adhesion/detachment behavior on dual-responsive silicon surfaces modified with poly(N-isopropylacrylamide)-block-polystyrene copolymer.

Diblock copolymer grafts covalently attached to surfaces have attracted considerable attention because of their special structure and novel properties. In this work, poly(N-isopropylacrylamide)-block-polystyrene (PNIPAAm-b-PS) brushes were prepared via surface-initiated consecutive atom-transfer radical polymerization on initiator-immobilized silicon. Because of the inherent thermosensitivity of PNIPAAm and the hydrophobicity difference between the two blocks, the modified surfaces were responsive to both temperature and solvent. Moreover, the diblock copolymer brushes exhibited both resistance to nonspecific protein adsorption and unique cell interaction properties. They showed strong protein resistance in both phosphate-buffered saline and blood plasma. In particular, fibrinogen adsorption from plasma at either room temperature or body temperature was less than 8 ng/cm(2), suggesting that the surfaces might possess good blood compatibility. In addition, the adhesion and detachment of L929 cells could be "tuned", and the ability to control the detachment of cells thermally was restored by block polymerization of hydrophobic, cell-adhesive PS onto a thicker PNIPAAm layer. In addition to providing a simple and effective design for advanced cell-culture surfaces, these results suggest new biomedical applications for PNIPAAm.

[1]  Jongseung Yoon,et al.  Enabling nanotechnology with self assembled block copolymer patterns , 2003 .

[2]  Teruo Okano,et al.  Nanostructured designs of biomedical materials: applications of cell sheet engineering to functional regenerative tissues and organs. , 2005, Journal of controlled release : official journal of the Controlled Release Society.

[3]  Shaoyi Jiang,et al.  Protein adsorption on oligo(ethylene glycol)-terminated alkanethiolate self-assembled monolayers: The molecular basis for nonfouling behavior. , 2005, The journal of physical chemistry. B.

[4]  Rui L Reis,et al.  Smart thermoresponsive coatings and surfaces for tissue engineering: switching cell-material boundaries. , 2007, Trends in biotechnology.

[5]  Darren M. Jones,et al.  Controlled growth of triblock polyelectrolyte brushes. , 2002, Chemical communications.

[6]  N. Ayres,et al.  Stimuli-responsive polyelectrolyte polymer brushes prepared via atom-transfer radical polymerization. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[7]  Thomas A Horbett,et al.  Fibrinogen and von Willebrand's factor adsorption are both required for platelet adhesion from sheared suspensions to polyethylene preadsorbed with blood plasma. , 2005, Journal of biomedical materials research. Part A.

[8]  J. Genzer,et al.  Tailoring Cell Adhesion Using Surface‐Grafted Polymer Gradient Assemblies , 2005 .

[9]  Kai Yu,et al.  Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement , 2009 .

[10]  Hong Chen,et al.  Protein adsorption on poly(N-vinylpyrrolidone)-modified silicon surfaces prepared by surface-initiated atom transfer radical polymerization. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[11]  D. Castner,et al.  Temperature dependent activity and structure of adsorbed proteins on plasma polymerized N-isopropyl acrylamide , 2006, Biointerphases.

[12]  B. Donose,et al.  Self-assembling polystyrene-block-poly(ethylene oxide) copolymer surface coatings: resistance to protein and cell adhesion. , 2009, Biomaterials.

[13]  Jan Feijen,et al.  Effect of comonomer hydrophilicity and ionization on the lower critical solution temperature of N-isopropylacrylamide copolymers , 1993 .

[14]  G. Whitesides,et al.  Effect of Surface Wettability on the Adsorption of Proteins and Detergents , 1998 .

[15]  N. Ayres,et al.  Stimuli-responsive surfaces using polyampholyte polymer brushes prepared via atom transfer radical polymerization. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[16]  Ronald P. Manginell,et al.  Programmed Adsorption and Release of Proteins in a Microfluidic Device , 2003, Science.

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

[18]  W. Brittain,et al.  Synthesis and Characterization of Stimuli-Responsive Semifluorinated Polymer Brushes Prepared by Atom Transfer Radical Polymerization , 2004 .

[19]  Shiping Zhu,et al.  A facile method of forming nanoscale patterns on poly(ethylene glycol)-based surfaces by self-assembly of randomly grafted block copolymer brushes. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[20]  Michael J. Fasolka,et al.  Effect of Block Length on Solvent Response of Block Copolymer Brushes: Combinatorial Study with Block Copolymer Brush Gradients , 2006 .

[21]  I. Choi,et al.  The control of cell adhesion and detachment on thin films of thermoresponsive poly[(N-isopropylacrylamide)-r-((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide)]. , 2009, Biomaterials.

[22]  Nitin Kumar,et al.  Nanoscale protein patterning using self-assembled diblock copolymers. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[23]  Shaoyi Jiang,et al.  Strong resistance of phosphorylcholine self-assembled monolayers to protein adsorption: insights into nonfouling properties of zwitterionic materials. , 2005, Journal of the American Chemical Society.

[24]  Masayuki Yamato,et al.  Preparation of thermoresponsive polymer brush surfaces and their interaction with cells. , 2008, Biomaterials.

[25]  William J. Brittain,et al.  Polymer brushes––surface immobilized polymers , 2004 .

[26]  P. C. Rieke,et al.  Temperature-Sensitive Surfaces Prepared by UV Photografting Reaction of Photosensitizer and N-Isopropylacrylamide , 2000 .

[27]  W. Brittain,et al.  Thermoresponsive Behavior of Semifluorinated Polymer Brushes , 2005 .

[28]  H. G. Schild Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .

[29]  K. Neoh,et al.  Surface-active and stimuli-responsive polymer--Si(100) hybrids from surface-initiated atom transfer radical polymerization for control of cell adhesion. , 2004, Biomacromolecules.

[30]  B. Dalton,et al.  Polystyrene chemistry affects vitronectin activity: an explanation for cell attachment to tissue culture polystyrene but not to unmodified polystyrene. , 1993, Journal of biomedical materials research.

[31]  K. Neoh,et al.  Thermoresponsive comb-shaped copolymer-Si(100) hybrids for accelerated temperature-dependent cell detachment. , 2006, Biomaterials.

[32]  Dong Ha Kim,et al.  Self‐assembly of Protein Nanoarrays on Block Copolymer Templates , 2008 .

[33]  Anders Hult,et al.  Intelligent dual-responsive cellulose surfaces via surface-initiated ATRP. , 2008, Biomacromolecules.

[34]  W. Brittain,et al.  Polymer brushes: surface-immobilized macromolecules , 2000 .

[35]  Y. D. Kim,et al.  Temperature-dependent intermolecular force measurement of poly(N-isopropylacrylamide) grafted surface with protein. , 2005, Journal of Colloid and Interface Science.

[36]  Robert Langer,et al.  From Advanced Biomedical Coatings to Multi‐Functionalized Biomaterials , 2006 .

[37]  Lei Jiang,et al.  Reversible switching between superhydrophilicity and superhydrophobicity. , 2004, Angewandte Chemie.

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

[39]  Min Chen,et al.  Synthesis and Surface Properties of Poly(methyl methacrylate)/Poly(ethylene glycol) Binary Brushes , 2007 .

[40]  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.

[41]  Masayuki Yamato,et al.  Ultrathin poly(N-isopropylacrylamide) grafted layer on polystyrene surfaces for cell adhesion/detachment control. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[42]  N. Yoshino,et al.  Preparation of thin polymer films with drug release and protein adsorption resistance. , 2007, Colloids and surfaces. B, Biointerfaces.

[43]  G. Whitesides,et al.  A Survey of Structure−Property Relationships of Surfaces that Resist the Adsorption of Protein , 2001 .

[44]  M. D. Rowe,et al.  Synthesis of Surface-Initiated Stimuli-Responsive Diblock Copolymer Brushes Utilizing a Combination of ATRP and RAFT Polymerization Techniques , 2008 .

[45]  Changyou Gao,et al.  Fabrication of thermoresponsive polymer gradients for study of cell adhesion and detachment. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[46]  W. Brittain,et al.  Synthesis, Characterization, and Properties of Polyelectrolyte Block Copolymer Brushes Prepared by Atom Transfer Radical Polymerization and Their Use in the Synthesis of Metal Nanoparticles , 2003 .

[47]  W. Brittain,et al.  Synthesis, characterization, and properties of tethered polystyrene-b-polyacrylate brushes on flat silicate substrates , 2000 .

[48]  S. Krishnamoorthy,et al.  Nanoscale patterning with block copolymers , 2006 .

[49]  W. Brittain,et al.  Stimuli‐Responsive Semi‐Fluorinated Polymer Brushes on Porous Silica Substrates , 2004 .

[50]  Xiaohong Wang,et al.  Reversibly Switchable Double-Responsive Block Copolymer Brushes , 2007 .

[51]  W. Brittain,et al.  Surface rearrangement of diblock copolymer brushes : Stimuli responsive films , 2006 .

[52]  I. Hamley Nanostructure fabrication using block copolymers , 2003 .

[53]  Ian Soutar,et al.  Studies of the smart thermoresponsive behavior of copolymers of N-isopropylacrylamide and N, N-dimethylacrylamide in dilute aqueous solution , 2003 .

[54]  A. Mayes,et al.  Block copolymer thin films : Physics and applications , 2001 .

[55]  W. Brittain,et al.  Synthesis of Tethered Polystyrene-block-Poly(methyl methacrylate) Monolayer on a Silicate Substrate by Sequential Carbocationic Polymerization and Atom Transfer Radical Polymerization , 1999 .

[56]  D. Castner,et al.  Multivariate surface analysis of plasma-deposited tetraglyme for reduction of protein adsorption and monocyte adhesion , 2003 .

[57]  A. Metters,et al.  Swelling Behavior of Multiresponsive Poly(methacrylic acid)‐block‐‐poly(N‐isopropylacrylamide) Brushes Synthesized Using Surface‐Initiated Photoiniferter‐Mediated Photopolymerization , 2008 .

[58]  H Koyanagi,et al.  In vivo protein adsorption on polymers: visualization of adsorbed proteins on vascular implants in dogs. , 1992, Journal of biomaterials science. Polymer edition.

[59]  Massimo Lazzari,et al.  Block Copolymers as a Tool for Nanomaterial Fabrication , 2003 .

[60]  Tao Wang,et al.  Protein nanopatterning on self-organized poly(styrene-b-isoprene) thin film templates. , 2009, Langmuir : the ACS journal of surfaces and colloids.