Synthesis of random terpolymers bearing multidentate imidazole units and their use in functionalization of cadmium sulfide nanowires

This work reports on a new random ternary polymerization method for the synthesis of multidentate imidazole polymers. The polymers can behave as ligands for the functionalization of cadmium sulfide nanowires. Due to the intrinsic differences in the electronegativity of the groups next to the vinyl bond, the vinyl groups displayed unique NMR signals, and allowed for the measurement of the individual monomer conversions in the random terpolymer system. The activated ester bearing terpolymer was postmodified with N-alkyl imidazole units, followed by the boc deprotection of the amine terminal groups. The resulting poly(imid-PEGMA-MAMamine) provided water solubility, dye loading capability as well as the ability to coordinate with metal chalcogenide surfaces using the imidazole units. Upon the attachment of a rhodamine dye, studies were performed to analyze the potential of such polymers to modify CdS nanowires using fluorescence microscopy. The fluorescence microscopy results provided confirmation of the polymeric ligand attachment, and sets the foundation for further optical studies using this system.

[1]  Yi Shen,et al.  Copolymerization and Synthesis of Multiply Binding Histamine Ligands for the Robust Functionalization of Quantum Dots , 2014 .

[2]  S. Mochrie,et al.  Dynamics of Cadmium Sulfide Nanoparticles within Polystyrene Melts , 2014 .

[3]  G. Pau,et al.  Observation of multiple, identical binding sites in the exchange of carboxylic acid ligands with CdS nanocrystals. , 2014, Nano letters.

[4]  P. Geissler,et al.  Orientational ordering of passivating ligands on CdS nanorods in solution generates strong rod-rod interactions. , 2014, Nano letters.

[5]  Mikhail Artemyev,et al.  CdSe-CdS nanoheteroplatelets with efficient photoexcitation of central CdSe region through epitaxially grown CdS wings. , 2013, Journal of the American Chemical Society.

[6]  U. Krull,et al.  Adapting fluorescence resonance energy transfer with quantum dot donors for solid-phase hybridization assays in microtiter plate format. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[7]  U. Krull,et al.  Quantum dot and gold nanoparticle immobilization for biosensing applications using multidentate imidazole surface ligands. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[8]  Ping Gong,et al.  Click-functionalized compact quantum dots protected by multidentate-imidazole ligands: conjugation-ready nanotags for living-virus labeling and imaging. , 2012, Journal of the American Chemical Society.

[9]  Moungi G Bawendi,et al.  Alternating layer addition approach to CdSe/CdS core/shell quantum dots with near-unity quantum yield and high on-time fractions. , 2012, Chemical science.

[10]  T. Long,et al.  Controlled Radical Polymerization of 4-Vinylimidazole , 2012 .

[11]  Chunhui Luo,et al.  Pathway-dependent re-assembly of dual-responsive ABC terpolymer in water , 2012 .

[12]  Hans Ågren,et al.  Role of surface ligands in optical properties of colloidal CdSe/CdS quantum dots. , 2011, Physical chemistry chemical physics : PCCP.

[13]  R. Agarwal,et al.  Variable temperature spectroscopy of as-grown and passivated CdS nanowire optical waveguide cavities. , 2011, The journal of physical chemistry. A.

[14]  T. Gao,et al.  Two-Dimensional Single Crystal CdS Nanosheets: Synthesis and Properties , 2010 .

[15]  Megan L. Hoarfrost,et al.  Ionic Conductivity of Nanostructured Block Copolymer/Ionic Liquid Membranes , 2010 .

[16]  Peidong Yang,et al.  Semiconductor nanowires for energy conversion , 2010, 2010 3rd International Nanoelectronics Conference (INEC).

[17]  R. Jain,et al.  Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand. , 2009, Journal of the American Chemical Society.

[18]  C. Niemeyer,et al.  Photocatalytic activity of colloidal CdS nanoparticles with different capping ligands , 2009 .

[19]  Shana O Kelley,et al.  One-step DNA-programmed growth of luminescent and biofunctionalized nanocrystals. , 2009, Nature nanotechnology.

[20]  Patrick Theato,et al.  Synthesis of well‐defined polymeric activated esters , 2008 .

[21]  R. Coşkun,et al.  Novel copolymers of N-(4-bromophenyl)-2-methacrylamide with glycidyl methacrylate: Synthesis, characterization, monomer reactivity ratios and thermal properties , 2008 .

[22]  Patrick D. Carpenter,et al.  Role of molecular surface passivation in electrical transport properties of InAs nanowires. , 2008, Nano letters (Print).

[23]  Igor L. Medintz,et al.  Kinetics of metal-affinity driven self-assembly between proteins or peptides and CdSe-ZnS quantum dots , 2007 .

[24]  Su Chen,et al.  Synthesis of nanocrystal-polymer transparent hybrids via polyurethane matrix grafted onto functionalized CdS nanocrystals. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[25]  Michael F. Drenski,et al.  Quantitative Contrasts in the Copolymerization of Acrylate- and Methacrylate-Based Comonomers , 2006 .

[26]  R. Kane,et al.  Synthesis of copolymers containing an active ester of methacrylic acid by RAFT: controlled molecular weight scaffolds for biofunctionalization. , 2006, Biomacromolecules.

[27]  R. Shunmugam,et al.  Efficient route to well‐characterized homo, block, and statistical polymers containing terpyridine in the side chain , 2005 .

[28]  Joshua E. Goldberger,et al.  SEMICONDUCTOR NANOWIRES AND NANOTUBES , 2004 .

[29]  A. Wamsley,et al.  Synthesis of random terpolymers and determination of reactivity ratios of N‐carboxyanhydrides of leucine, β‐benzyl aspartate, and valine , 2004 .

[30]  S. Naidu,et al.  Synthesis and characterization of poly(N‐phenyl methacrylamide‐co‐methyl methacrylate) and reactivity ratios determination , 2003 .

[31]  Renata Lubczak,et al.  Copolymerization of hydroxyalkyl methacrylates with acrylamide and methacrylamide. I. Determination of reactivity ratios , 1997 .