Diacetylene-containing ligand as a new capping agent for the preparation of water-soluble colloidal nanoparticles of remarkable stability.

A new type of strategically designed functional ligands was used to cap gold nanocrystals and form robust colloidal nanoparticles, resistant to pH changes, temperature, and ionic strength variations as well as ligand-exchange reactions. The nanoparticles are coated with ligands that polymerize upon UV-irradiation, consequently embedding the particles in a stable organic shell. The ligand consists of an anchoring thiol group, which binds directly to the nanocrystal surface and two units, one hydrophobic and one hydrophilic. The hydrophobic alkyl unit contains a diacetylene group, which undergoes a 1,4-topochemical polymerization leading to a poly(enyne) structure during UV-irradiation. The hydrophilic unit contains an oligo-ethylene glycol chain, which ensures water solubility, and a terminal carboxylic group. Derived particles were characterized by transmission electron microscopy, surface enhanced Raman spectroscopy, and visible spectroscopy. Their stability was investigated and compared to particles capped with nonpolymerized ligands.

[1]  Marco Zanella,et al.  Biological applications of gold nanoparticles. , 2008, Chemical Society reviews.

[2]  Ilan Gur,et al.  Hybrid Organic-Nanocrystal Solar Cells , 2005 .

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

[4]  Tierui Zhang,et al.  TiO2 nanoparticles as a soft X-ray molecular probe. , 2008, Chemical communications.

[5]  R. Stevens,et al.  Morphological manipulation of bolaamphiphilic polydiacetylene assemblies by controlled lipid doping. , 2002, Chemistry and physics of lipids.

[6]  S. Nie,et al.  Quantum dot bioconjugates for ultrasensitive nonisotopic detection. , 1998, Science.

[7]  Emilia Giorgetti,et al.  Polydiacetylene-Functionalized Noble Metal Nanocages , 2009 .

[8]  Chen Chang,et al.  Multifunctional composite nanoparticles: Magnetic, luminescent, and mesoporous , 2006 .

[9]  Mathias Brust,et al.  Uptake and intracellular fate of surface-modified gold nanoparticles. , 2008, ACS nano.

[10]  G. Ellman,et al.  Tissue sulfhydryl groups. , 1959, Archives of biochemistry and biophysics.

[11]  Mathias Brust,et al.  Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system , 1994 .

[12]  M. Alloisio,et al.  Spectroscopical investigation on colloidal suspensions of diacetylene-capped gold nanoparticles , 2008 .

[13]  J. Hillier,et al.  A study of the nucleation and growth processes in the synthesis of colloidal gold , 1951 .

[14]  I. Willner,et al.  Biosensing and probing of intracellular metabolic pathways by NADH-sensitive quantum dots. , 2009, Angewandte Chemie.

[15]  H. Park,et al.  Universal Colorimetric Detection of Nucleic Acids Based on Polydiacetylene (PDA) Liposomes , 2008 .

[16]  K. Schaumburg,et al.  Thioalkylated tetraethylene glycol: a new ligand for water soluble monolayer protected gold clusters. , 2002, Chemical communications.

[17]  Tierui Zhang,et al.  A general approach for transferring hydrophobic nanocrystals into water. , 2007, Nano letters.

[18]  C. Mirkin,et al.  A fluorescence-based method for determining the surface coverage and hybridization efficiency of thiol-capped oligonucleotides bound to gold thin films and nanoparticles. , 2000, Analytical chemistry.

[19]  A. Baiker,et al.  A new hydrosol of gold clusters. 2. A comparison of some different measurement techniques , 1993 .

[20]  A. Mohs,et al.  Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain. , 2009, Nature nanotechnology.

[21]  Warren C W Chan,et al.  Nanoparticle-mediated cellular response is size-dependent. , 2008, Nature nanotechnology.

[22]  Mathias Brust,et al.  A multidentate peptide for stabilization and facile bioconjugation of gold nanoparticles. , 2009, Bioconjugate chemistry.

[23]  Wolfgang J Parak,et al.  Multifunctionalized polymer microcapsules: novel tools for biological and pharmacological applications. , 2007, Small.

[24]  G. Brunklaus,et al.  Tuning Plasmonic Properties by Alloying Copper into Gold Nanorods , 2009 .

[25]  Jeremy J. Baumberg,et al.  Electrochemical SERS at a structured gold surface , 2005 .

[26]  Vincent Noireaux,et al.  In Vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles , 2002, Science.

[27]  L. Lechuga,et al.  LSPR-based nanobiosensors , 2009 .

[28]  Jong-Man Kim,et al.  Fluorogenic polydiacetylene supramolecules: immobilization, micropatterning, and application to label-free chemosensors. , 2008, Accounts of chemical research.

[29]  Yanli Liu,et al.  Synthesis, stability, and cellular internalization of gold nanoparticles containing mixed peptide-poly(ethylene glycol) monolayers. , 2007, Analytical chemistry.

[30]  Raphaël Lévy.  Peptide‐Capped Gold Nanoparticles: Towards Artificial Proteins , 2006, Chembiochem : a European journal of chemical biology.

[31]  Vincent M. Rotello,et al.  The biomacromolecule-nanoparticle interface , 2007 .

[32]  A. Singh,et al.  One-step, chemisorbed immobilization of highly stable, polydiacetylenic phospholipid vesicles onto gold films. , 2001, Journal of the American Chemical Society.

[33]  Andrea Ragusa,et al.  Water solubilization of hydrophobic nanocrystals by means of poly(maleic anhydride-alt-1-octadecene) , 2008 .

[34]  P. Jain,et al.  Au nanoparticles target cancer , 2007 .

[35]  G. Hermanson.  3 – Zero-Length Cross-linkers , 1996 .

[36]  G. Mie.  Beiträge zur Optik trüber Medien, speziell kolloidaler Metallösungen , 1908 .

[37]  Emilia Giorgetti,et al.  Photopolymerization of diacetylene-capped gold nanoparticles. , 2008, Physical chemistry chemical physics : PCCP.

[38]  Yoshio Kobayashi,et al.  Direct coating of gold nanoparticles with silica by a seeded polymerization technique. , 2003, Journal of colloid and interface science.

[39]  A Paul Alivisatos,et al.  Hybrid solar cells with prescribed nanoscale morphologies based on hyperbranched semiconductor nanocrystals. , 2007, Nano letters.

[40]  Francesco Stellacci,et al.  Surface-structure-regulated cell-membrane penetration by monolayer-protected nanoparticles. , 2008, Nature materials.

[41]  M. Alloisio,et al.  Self-assembled monolayers of disulfide-functionalized diacetylenes on gold films and nanoparticles , 2007 .

[42]  A Paul Alivisatos,et al.  DNA-Based Assembly of Gold Nanocrystals. , 1999, Angewandte Chemie.