Chain-end functionalized nanopatterned polymer brushes grown via in situ nitroxide free radical exchange.

The patterning of biologically active materials has been accomplished by the use of imprint lithography of functional photopolymer resins to create controlled nanoscale patterns of a cross-linked photopolymer containing embedded initiator groups. Functionalized polymer brushes consisting of polystyrene and poly(N,N-dimethylacrylamide) were grown from these patterned layers by nitroxide-mediated polymerization. Chain-end functionalization of the brush layer was accomplished by nitroxide radical exchange during the polymerization. Accordingly, brush layers terminated by pyrene and biotin functional groups were obtained by exchange with the appropriate alkoxyamines. The presence of pyrene functionality at the chain ends of the brushes was confirmed by fluorescent emission measurements. Fluorescently labeled streptavidin protein was selectively attached with high selectivity to the patterned biotinylated brush layer through biotin-streptavidin interactions. The functionalized polymer grafted surfaces and nanopatterns have been successfully characterized using a fluorescence spectrophotometer, AFM, SEM, confocal microscopy, and water contact angle measurements.

[1]  J. C. Scott,et al.  Mold and metallization: nanocontact molding for the fabrication of metal structures. , 2007, Small.

[2]  D. Reinhoudt,et al.  Creating nanopatterns of His-tagged proteins on surfaces by nanoimprint lithography using specific NiNTA-histidine interactions. , 2007, Small.

[3]  D. Irvine,et al.  Patterned surfaces as tools to study ligand recognition and synapse formation by T cells. , 2007, Current opinion in immunology.

[4]  K. Christman,et al.  Nanopatterning proteins and peptides. , 2006, Soft matter.

[5]  J. Frommer,et al.  Patterned polyfluorene surfaces by functionalization of nanoimprinted polymeric features. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[6]  G. Whitesides,et al.  New approaches to nanofabrication: molding, printing, and other techniques. , 2005, Chemical reviews.

[7]  Marcus Textor,et al.  A Novel Approach to Produce Protein Nanopatterns by Combining Nanoimprint Lithography and Molecular Self-Assembly , 2004 .

[8]  Li-Jing Cheng,et al.  Nanoscale protein patterning by imprint lithography , 2004 .

[9]  M. Radosz,et al.  Atom Transfer Radical Polymerization of N,N-Dimethylacrylamide , 2004 .

[10]  P. Fabre,et al.  Acrylamide-Based Amphiphilic Block Copolymers via Nitroxide-Mediated Radical Polymerization , 2003 .

[11]  K. Matyjaszewski,et al.  Stereoblock copolymers and tacticity control in controlled/living radical polymerization. , 2003, Journal of the American Chemical Society.

[12]  M. Hong,et al.  Protein−Ligand Interactions at Poly(amidoamine) Dendrimer Monolayers on Gold , 2003 .

[13]  Seong Ihl Woo,et al.  Surface modification of poly(glycolic acid) (PGA) for biomedical applications. , 2003, Journal of pharmaceutical sciences.

[14]  Robert Langer,et al.  Reactive polymer coatings: a first step toward surface engineering of microfluidic devices. , 2003, Analytical chemistry.

[15]  K. Matyjaszewski,et al.  Copolymerization of N,N-Dimethylacrylamide with n-Butyl Acrylate via Atom Transfer Radical Polymerization , 2003 .

[16]  David S. Germack,et al.  A versatile method for tuning the chemistry and size of nanoscopic features by living free radical polymerization. , 2003, Journal of the American Chemical Society.

[17]  Aliasger K. Salem,et al.  Porous Polymer and Cell Composites That Self‐Assemble In Situ , 2003 .

[18]  K. M. Faucher,et al.  Fabrication and Characterization of Glycocalyx-Mimetic Surfaces † , 2003 .

[19]  Mahesh Uttamchandani,et al.  Array-based technologies and their applications in proteomics. , 2003, Current topics in medicinal chemistry.

[20]  C. Hawker,et al.  A modular approach toward functionalized three-dimensional macromolecules: from synthetic concepts to practical applications. , 2003, Journal of the American Chemical Society.

[21]  D. Brooks,et al.  Synthesis of poly(N, N-dimethylacrylamide) brushes from charged polymeric surfaces by aqueous ATRP: Effect of surface initiator concentration , 2003 .

[22]  Masayuki Yamato,et al.  Novel approach for achieving double-layered cell sheets co-culture: overlaying endothelial cell sheets onto monolayer hepatocytes utilizing temperature-responsive culture dishes. , 2002, Journal of biomedical materials research.

[23]  W. Knoll,et al.  Synthesis of lipo-glycopolymer amphiphiles by nitroxide- mediated living free-radical polymerization , 2002 .

[24]  Margaret Evans Best,et al.  Nanoscale patterning of magnetic islands by imprint lithography using a flexible mold , 2002 .

[25]  K. M. Faucher,et al.  Design and synthesis of biotin chain-terminated glycopolymers for surface glycoengineering. , 2002, Journal of the American Chemical Society.

[26]  Stephen Z. D. Cheng,et al.  Synthesis, Characterization, and Properties of ABA Type Triblock Copolymer Brushes of Styrene and Methyl Acrylate Prepared by Atom Transfer Radical Polymerization , 2002 .

[27]  B. Sumerlin,et al.  RAFT Polymerization of N,N-Dimethylacrylamide in Water† , 2002 .

[28]  B. Sumerlin,et al.  Raft Polymerization of N,N-Dimethylacrylamide Utilizing Novel Chain Transfer Agents Tailored for High Reinitiation Efficiency and Structural Control† , 2002 .

[29]  Soong Ho Um,et al.  Self-Assembly of Avidin and d-Biotin-Tethering Zeolite Microcrystals into Fibrous Aggregates , 2002 .

[30]  Robert Langer,et al.  Reactive Polymer Coatings: A Platform for Patterning Proteins and Mammalian Cells onto a Broad Range of Materials , 2002 .

[31]  S. Nishimura,et al.  Preparation of Self-Organized Micro-Patterned Polymer Films Having Cell Adhesive Ligands , 2002 .

[32]  M. Shim,et al.  Functionalization of Carbon Nanotubes for Biocompatibility and Biomolecular Recognition , 2002 .

[33]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[34]  A. Chilkoti,et al.  Microstamping on an Activated Polymer Surface: Patterning Biotin and Streptavidin onto Common Polymeric Biomaterials , 2001 .

[35]  A. Chilkoti,et al.  Micropatterning biological molecules on a polymer surface using elastomeric microwells. , 2001, Journal of the American Chemical Society.

[36]  D. Fang,et al.  Fast DNA sequencing up to 1000 bases by capillary electrophoresis using poly(N,N‐dimethylacrylamide) as a separation medium , 2001, Electrophoresis.

[37]  N. Turro,et al.  A Living Free Radical Exchange Reaction for the Preparation of Photoactive End-Labeled Monodisperse Polymers , 2000 .

[38]  C. Willson,et al.  Step and flash imprint lithography: Template surface treatment and defect analysis , 2000 .

[39]  Ian D. Rees,et al.  End‐group fidelity in nitroxide‐mediated living free‐radical polymerizations , 2000 .

[40]  Didier Benoit,et al.  Development of a Universal Alkoxyamine for “Living” Free Radical Polymerizations , 1999 .

[41]  Didier Benoit,et al.  Controlled Synthesis of Polymer Brushes by “Living” Free Radical Polymerization Techniques , 1999 .

[42]  T. Matsuda,et al.  Protein adsorption on self-assembled monolayers with water-soluble non-ionic oligomers using quartz-crystal microbalance , 1998 .

[43]  C. S. Chen,et al.  Geometric control of cell life and death. , 1997, Science.

[44]  C. Hawker,et al.  RADICAL CROSSOVER IN NITROXIDE MEDIATED LIVING FREE RADICAL POLYMERIZATIONS , 1996 .

[45]  S. Chou,et al.  Imprint Lithography with 25-Nanometer Resolution , 1996, Science.

[46]  T. Horbett,et al.  Proteins at Interfaces: An Overview , 1995 .

[47]  John L. Brash,et al.  Proteins at Interfaces: Current Issues and Future Prospects , 1987 .

[48]  C. T. Rettnera,et al.  Contact mechanics of a flexible imprinter for photocured nanoimprint lithography , 2006 .

[49]  M. Wilchek,et al.  Introduction to avidin-biotin technology. , 1990, Methods in enzymology.

[50]  Green Nm,et al.  Avidin and streptavidin. , 1990 .

[51]  N M Green,et al.  Avidin and streptavidin. , 1990, Methods in enzymology.

[52]  F. Macritchie.  Proteins at interfaces. , 1978, Advances in protein chemistry.