Formation of Thermoresponsive Gold Nanoparticle/PNIPAAm Hybrids by Surface‐Initiated, Atom Transfer Radical Polymerization in Aqueous Media

We investigated the formation of thermoresponsive gold nanoparticle/poly(N-isopropylacrylamde) (AuNP/ PNIPAAm) core/shell hybrid structures by surface-initiated, atom transfer radical polymerization (SI-ATRP) in aqueous media and the effect of cross-linking on the thermoresponsiveness of the AuNP/PNIPAAm hybrids. The disulfide containing an ATRP initiator was attached onto AuNPs and the monomer, NIPAAm, was polymerized from the surface of AuNPs in the absence or presence of a cross-linker, ethylene diacrylate, in aqueous media at room temperature. The resulting brush-type and cross-linked AuNP/PNIPAAm hybrids were characterized by Fourier-transform infrared spectroscopy, transmission electron microscopy, and variable temperature dynamic light scattering.

[1]  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.

[2]  T. Okano,et al.  Temperature-responsive liquid chromatography. 2. Effects of hydrophobic groups in N-isopropylacrylamide copolymer-modified silica. , 1997, Analytical chemistry.

[3]  W. Yun,et al.  Surface‐Initiated, Enzymatic Polymerization of Biodegradable Polyesters , 2003 .

[4]  Zhibing Hu,et al.  Hydrogel Nanoparticle Dispersions with Inverse Thermoreversible Gelation , 2004 .

[5]  A. P. de Silva,et al.  Fluorescent polymeric AND logic gate with temperature and pH as inputs. , 2004, Journal of the American Chemical Society.

[6]  P. Degée,et al.  Controlled Ring‐Opening (Co)Polymerization of Lactones Initiated from Cadmium Sulfide Nanoparticles , 2004 .

[7]  R. Murray,et al.  Nanometer Gold Clusters Protected by Surface-Bound Monolayers of Thiolated Poly(ethylene glycol) Polymer Electrolyte , 1998 .

[8]  I. Choi,et al.  Biosurface Organic Chemistry: Interfacial Chemical Reactions for Applications to Nanobiotechnology and Biomedical Sciences , 2005 .

[9]  George C Schatz,et al.  What controls the melting properties of DNA-linked gold nanoparticle assemblies? , 2000, Journal of the American Chemical Society.

[10]  Noriaki Hara,et al.  SPR sensor chip for detection of small molecules using molecularly imprinted polymer with embedded gold nanoparticles. , 2005, Analytical chemistry.

[11]  Sung Min Kang,et al.  Formation of thermoresponsive surfaces by surface-initiated, aqueous atom-transfer radical polymerization of N-isopropylacrylamide: Application to cell culture , 2004 .

[12]  A. Ulman,et al.  Nanocomposites by Surface-Initiated Living Cationic Polymerization of 2-Oxazolines on Functionalized Gold Nanoparticles , 2001 .

[13]  Wuli Yang,et al.  Monodisperse Temperature‐Sensitive Microcontainers , 2002 .

[14]  T. Emrick,et al.  Preparation of cadmium selenide-polyolefin composites from functional phosphine oxides and ruthenium-based metathesis. , 2002, Journal of the American Chemical Society.

[15]  M. Shibayama,et al.  Thermal properties of copolymer gels containing N-isopropylacrylamide , 1996 .

[16]  Sung Wan Kim,et al.  Biodegradable block copolymers as injectable drug-delivery systems , 1997, Nature.

[17]  I. Choi,et al.  Silica/Poly(1,5‐dioxepan‐2‐one) Hybrid Nanoparticles by “Direct” Surface‐Initiated Polymerization , 2004 .

[18]  P. Griffiths,et al.  Calorimetric Investigation of the Influence of Cross-Linker Concentration on the Volume Phase Transition of Poly(N-isopropylacrylamide) Colloidal Microgels , 2003 .

[19]  H. Jiang,et al.  Synthesis of Gold Nanoparticles Grafted with a Thermoresponsive Polymer by Surface-Induced Reversible-Addition-Fragmentation Chain-Transfer Polymerization , 2003 .

[20]  K. Edwards,et al.  A New Double-Responsive Block Copolymer Synthesized via RAFT Polymerization: Poly(N-isopropylacrylamide)-block-poly(acrylic acid) , 2004 .

[21]  P. Alivisatos.  The use of nanocrystals in biological detection , 2004, Nature Biotechnology.

[22]  I. Choi,et al.  Formation of Silica/Poly(p-dioxanone) Microspheres by Surface-Initiated Polymerization , 2003 .

[23]  I. Choi,et al.  Formation of Thermoresponsive Poly(N‐isopropylacrylamide)/Dextran Particles by Atom Transfer Radical Polymerization , 2003 .

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

[25]  A Paul Alivisatos,et al.  A single-electron transistor made from a cadmium selenide nanocrystal , 1997, Nature.

[26]  Todd Emrick,et al.  Nitroxide-Mediated Radical Polymerization from CdSe Nanoparticles , 2004 .

[27]  Y. Tong,et al.  Preparation and characterization of temperature-sensitive poly(N-isopropylacrylamide)-b-poly(D,L-lactide) microspheres for protein delivery. , 2003, Biomacromolecules.

[28]  K. Fischer,et al.  New perspectives for the design of molecular actuators: thermally induced collapse of single macromolecules from cylindrical brushes to spheres. , 2004, Angewandte Chemie.

[29]  T. Teranishi,et al.  Size Control of Palladium Nanoparticles and Their Crystal Structures , 1998 .

[30]  Shozaburo Saito,et al.  Phase Transition of N-Substituted Acrylamide Gels , 1990 .

[31]  J. Sommers,et al.  Alkanethiolate-Protected Copper Nanoparticles: Spectroscopy, Electrochemistry, and Solid-State Morphological Evolution† , 2001 .

[32]  Teruo Okano,et al.  Temperature dependence of swelling of crosslinked poly(N,N′-alkyl substituted acrylamides) in water , 1990 .

[33]  T. Teranishi,et al.  Synthesis of Monodisperse Gold Nanoparticles Using Linear Polymers as Protective Agents , 1998 .

[34]  Luca Quaroni,et al.  Preparation of Polymer-Coated Functionalized Silver Nanoparticles , 1999 .

[35]  Vish Viswanathan,et al.  Temperature-sensitive membranes prepared by UV photopolymerization of N-isopropylacrylamide on a surface of porous hydrophilic polypropylene membranes , 1999 .

[36]  J. Hilborn,et al.  Surface-initiated ring-opening polymerization: A versatile method for nanoparticle ordering. , 2002 .

[37]  Ian D. Rees,et al.  Using Atom Transfer Radical Polymerization To Amplify Monolayers of Initiators Patterned by Microcontact Printing into Polymer Brushes for Pattern Transfer , 2000 .

[38]  L. Lyon,et al.  Interfacial nonradiative energy transfer in responsive core-shell hydrogel nanoparticles. , 2001, Journal of the American Chemical Society.

[39]  B. Sumerlin,et al.  Facile preparation of transition metal nanoparticles stabilized by well-defined (co)polymers synthesized via aqueous reversible addition-fragmentation chain transfer polymerization. , 2002, Journal of the American Chemical Society.

[40]  M. L. Hallensleben,et al.  Gold Nanoparticles with Covalently Attached Polymer Chains. , 2001, Angewandte Chemie.

[41]  Jaeyoung Lee,et al.  Role of Bound Water and Hydrophobic Interaction in Phase Transition of Poly(N-isopropylacrylamide) Aqueous Solution , 2003 .

[42]  D. Resasco,et al.  Polymer brushes on single-walled carbon nanotubes by atom transfer radical polymerization of n-butyl methacrylate. , 2004, Journal of the American Chemical Society.

[43]  K. Otake,et al.  Thermal analysis of the volume phase transition with N-isopropylacrylamide gels , 1990 .

[44]  K. Koh,et al.  Synthesis of Gold Nanoparticles Coated with Well-Defined, High-Density Polymer Brushes by Surface-Initiated Living Radical Polymerization , 2002 .

[45]  Itamar Willner,et al.  Electroanalytical and Bioelectroanalytical Systems Based on Metal and Semiconductor Nanoparticles , 2004 .

[46]  L. Lyon,et al.  Shell-Restricted Swelling and Core Compression in Poly(N-isopropylacrylamide) Core−Shell Microgels , 2003 .

[47]  Karl Kratz,et al.  PNIPAM-co-polystyrene core-shell microgels: structure, swelling behavior, and crystallization. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[48]  Gabriel P. Lopez,et al.  Synthesis and Characterization of Silica−Poly(N-isopropylacrylamide) Hybrid Membranes: Switchable Molecular Filters , 2002 .

[49]  Joachim P. Spatz,et al.  Solution behavior of poly(styrene)-block-poly(2-vinylpyridine micelles containing gold nanoparticles , 2000 .

[50]  J. Hubbell,et al.  Atom Transfer Radical Polymerization as a Tool for Surface Functionalization , 2002 .

[51]  K. Healy,et al.  Synthesis and characterization of injectable poly(N-isopropylacrylamide-co-acrylic acid) hydrogels with proteolytically degradable cross-links. , 2003, Biomacromolecules.

[52]  Adam D. McFarland,et al.  Single Silver Nanoparticles as Real-Time Optical Sensors with Zeptomole Sensitivity , 2003 .

[53]  I. Choi,et al.  Surface-initiated, ring-opening polymerization of p-dioxanone from gold and silicon oxide surfaces , 2003 .

[54]  G. K. Jennings,et al.  Physicochemical Properties of Surface‐Initiated Polymer Films in the Modification and Processing of Materials , 2004 .

[55]  D. Walt,et al.  Preparation of Polymer Coated Gold Nanoparticles by Surface-Confined Living Radical Polymerization at Ambient Temperature , 2002 .

[56]  D. Bergbreiter,et al.  Poly(N-isopropylacrylamide) Soluble Polymer Supports in Catalysis and Synthesis , 1998 .

[57]  T. Emrick,et al.  Reversible addition fragmentation chain transfer (RAFT) polymerization from unprotected cadmium selenide nanoparticles. , 2004, Angewandte Chemie.

[58]  Itamar Willner,et al.  Gold Nanoparticle/Hydrogel Composites with Solvent‐Switchable Electronic Properties , 2001 .

[59]  R. V. Van Duyne,et al.  A nanoscale optical biosensor: sensitivity and selectivity of an approach based on the localized surface plasmon resonance spectroscopy of triangular silver nanoparticles. , 2002, Journal of the American Chemical Society.