Photopolymerization of diacetylene-capped gold nanoparticles.

Gold nanoparticles (AuNPs) coated with the diacetylene henicosa-10,12-diyn-1-yl (DS9) disulfide were successfully prepared by direct synthesis in toluene solutions. The average size of the nanohybrid metal core was finely adjusted by manipulation of the preparative conditions in the diameter range from 1.6 to 7.5 nm, as determined by TEM characterization. The topochemical polymerization of DS9 chemisorbed onto the gold nanoclusters of different size was carried out in colloidal suspensions by exposure to UV radiation and the process was monitored by UV-Vis and Raman spectroscopies. The results showed that in these assemblies the monomer undergoes an intra-particle polymerization and that the dominant polydiacetylene phase present is ruled by the core size. The deposition of the photoirradiated colloids onto different substrates was found to leave the polydiacetylene conjugation unaltered.

[1]  A. Ulman,et al.  Formation and Structure of Self-Assembled Monolayers. , 1996, Chemical reviews.

[2]  R. Crooks,et al.  Polymeric Self-Assembled Monolayers. 4. Chemical, Electrochemical, and Thermal Stability of ω-Functionalized, Self-Assembled Diacetylenic and Polydiacetylenic Monolayers , 1997 .

[3]  Chad A Mirkin,et al.  Maximizing DNA loading on a range of gold nanoparticle sizes. , 2006, Analytical chemistry.

[4]  Ray H. Baughman,et al.  Optical Nonlinearities in One-Dimensional-Conjugated Polymer Crystals. , 1976 .

[5]  T. Rosso,et al.  Photodegradation of PAMAM G5-stabilized aqueous suspensions of gold nanoparticles , 2007 .

[6]  C. E. Evans,et al.  The synthesis of conjugated diacetylene monomers for the fabrication of polymerized monolayer assemblies , 1997 .

[7]  R. Nuzzo,et al.  Synthesis, Structure, and Properties of Model Organic Surfaces , 1992 .

[8]  D. J. Ahn,et al.  Patterned Color and Fluorescent Images with Polydiacetylene Supramolecules Embedded in Poly(vinyl alcohol) Films , 2006 .

[9]  H. Sasabe,et al.  Enhanced photopolymerization of diacetylene in colloidal gold solution , 1995 .

[10]  David G. Fernig,et al.  Extremely Stable Water-Soluble Ag Nanoparticles , 2005 .

[11]  Marc D. Porter,et al.  Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm: Core and Monolayer Properties as a Function of Core Size , 1998 .

[12]  Bruno M. Humbel,et al.  Preparation of Functional Silane-Stabilized Gold Colloids in the (Sub)nanometer Size Range , 1997 .

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

[14]  William M. Gelbart,et al.  Thermodynamic Control of Gold Nanocrystal Size: Experiment and Theory , 1995 .

[15]  H. Menzel,et al.  Surface‐Confined Nanoparticles as Substrates for Photopolymerizable Self‐Assembled Monolayers , 1999 .

[16]  M. Sukwattanasinitt,et al.  Layer-by-layer assembly of intact polydiacetylene vesicles with retained chromic properties. , 2006, Journal of colloid and interface science.

[17]  Z. Kam,et al.  Absorption and Scattering of Light by Small Particles , 1998 .

[18]  H. Menzel,et al.  Diacetylene polymerization in self-assembled monolayers: influence of the odd/even nature of the methylene spacer , 2000 .

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

[20]  G. Whitesides,et al.  Modeling Organic Surfaces with Self‐Assembled Monolayers , 1989 .

[21]  R. Murray,et al.  Monolayer-protected cluster molecules. , 2000, Accounts of chemical research.

[22]  Hajime Tanaka,et al.  Study of the correlation between the backbone conformation and the electronic structure of polydiacetylenes by solid state 13C n.m.r. , 1991 .

[23]  J. Kimling,et al.  Turkevich method for gold nanoparticle synthesis revisited. , 2006, The journal of physical chemistry. B.