Triazene UV-triggered photogeneration of silver/gold nanoparticles in block copolymer templates

  • Violeta Melinte
  • Andreea Chibac
  • Tinca Buruiana
  • Gabriela Hitruc
  • Emil C. Buruiana
Research Paper


This article describes an attractive way to in situ create noble metal nanoparticles in block copolymer matrixes through the UV-triggered photodecomposition of the photolabile triazene units without the use of any conventional reducing agent. The poly(isodecyl methacrylate-co-triazene urethane methacrylate) random copolymer containing pendent photocleavable triazene junctions (COP-1) was synthesized under RAFT conditions and subsequently employed as macroinitiator to obtain a block copolymer, namely poly(isodecyl methacrylate-co-triazene urethane methacrylate)-block-poly(acrylic acid) (COP-2). The photogeneration of silver/gold metal nanoparticles (NPs) from noble metal precursors (1 wt% AgNO3 or AuBr3 metal salts) induced through the UV decomposition of triazene units with the formation of some radical active species was monitored in solution and thin films. The in situ growth of Ag/Au nanostructures into polymer matrixes for which the light is a key element has been confirmed by UV spectroscopy and TEM analysis. The TEM images allowed the visualization of the silver NPs (sizes of 4–16 nm in COP-1 and of 2–6 nm in COP-2) as well as of the gold NPs (sizes between 10 and 20 nm in COP-1 and from 15 to 25 nm in COP-2), which are mainly spherical in shape, even though there is some triangular or hexagonal gold nanoparticles.


Triazene block copolymer UV irradiation Photodecomposition Silver/gold nanoparticles Nanocomposite materials 



This work was financially supported by CNCSIS-UEFISCDI, project number PN-II-ID-PCE-2011-3-0164 (40/5.10.2011).


  1. Boufi S, Vilar MR, Ferraria AM, do Rego AMB (2013) In situ photochemical generation of silver and gold nanoparticles on chitosan. Colloids Surf A 439:151–158. doi: 10.1016/j.colsurfa.2012.12.036 CrossRefGoogle Scholar
  2. Buruiana EC, Buruiana T, Hahui L, Lippert T, Urech L, Wokaun A (2006) Synthesis and properties of new photosensitive triazene polyacrylates. J Polym Sci Part A 44:5271–5282. doi: 10.1002/pola.21653 CrossRefGoogle Scholar
  3. Buruiana EC, Melinte V, Buruiana T, Simionescu BC, Lippert T, Urech L (2007) Synthesis and photochemical investigations of novel bistriazene polyurethanes. J Photochem Photobiol A 186:270–277. doi: 10.1016/j.jphotochem.2006.08.017 CrossRefGoogle Scholar
  4. Buruiana EC, Melinte V, Buruiana T, Simionescu BC (2008) Synthesis and properties of new poly(urethane-acrylates) with pendant triazene moieties. Des Monom Polym 11:423–433. doi: 10.1163/156855508X328130 CrossRefGoogle Scholar
  5. Buruiana EC, Chibac AL, Buruiana T, Melinte V, Balan L (2012) A benzophenone-bearing acid oligodimethacrylate and its application to the preparation of silver/gold nanoparticles/polymer nanocomposites. J Nanopart Res 14:1335. doi: 10.1007/s11051-012-1335-1 Google Scholar
  6. Buruiana EC, Chibac AL, Melinte V, Buruiana T (2013) Preparation of amphiphilic block copolymer containing triazene moieties and fluorescence study. J Chem Sci 125:193–202. doi: 10.1007/s12039-012-0350-1 CrossRefGoogle Scholar
  7. Cabane E, Malinova V, Meier W (2010) Synthesis of photocleavable amphiphilic block copolymers: toward the design of photosensitive nanocarriers. Macromol Chem Phys 211:1847–1856. doi: 10.1002/macp.201000151 CrossRefGoogle Scholar
  8. Carias V, Wang J, Toomey R (2014) Poly(N-isopropylacrylamide) cross-linked coatings with phototunable swelling. Langmuir 30:4105–4110. doi: 10.1021/la500462q CrossRefGoogle Scholar
  9. Chander N, Khan AF, Thouti E, Sardana SK, Chandrasekhar PS, Dutta V, Komarala VK (2014) Size and concentration effects of gold nanoparticles on optical and electrical properties of plasmonic dye sensitized solar cells. Sol Energy 109:11–23. doi: 10.1016/j.solener.2014.08.011 CrossRefGoogle Scholar
  10. Chen Y, Zheng XC, Wang X, Wang CZ, Ding Y, Jiang XQ (2014) Near-infrared emitting gold cluster-poly(acrylic acid) hybrid nanogels. ACS Macro Lett 3:74–76. doi: 10.1021/mz4005748 CrossRefGoogle Scholar
  11. Chibac AL, Melinte V, Buruiana T, Buruiana EC (2014) Obtaining of hybrid nanocomposites by simultaneous photopolymerization of some urethane monomers and photoinduced formation of gold nanoparticles. J Polym Sci Part A 52:728–738. doi: 10.1002/pola.27056 CrossRefGoogle Scholar
  12. Chibac AL, Melinte V, Buruiana T, Mangalagiu I, Buruiana EC (2015) Preparation of photocrosslinked sol-gel composites based on urethane-acrylic matrix, silsesquioxane sequences, TiO2, and Ag/Au NPs for use in photocatalytic applications. J Polym Sci Part A 53:1189–1204. doi: 10.1002/pola.27548 CrossRefGoogle Scholar
  13. Darmanin T, Nativo P, Gilliland D, Ceccone G, Pascual C, De Berardis B, Guittard F, Rossi F (2012) Microwave-assisted synthesis of silver nanoprisms/nanoplates using a “modified polyol process”. Colloids Surf A 395:145–151. doi: 10.1016/j.colsurfa.2011.12.020 CrossRefGoogle Scholar
  14. Ellison J, Wykoff G, Paul A, Mohseni R, Vasiliev A (2014) Efficient dispersion of coated silver nanoparticles in the polymer matrix. Colloids Surf A 447:67–70. doi: 10.1016/j.colsurfa.2014.01.071 CrossRefGoogle Scholar
  15. Fritzsche W, Porwol H, Wiegand A, Bornmann S, Kohler JM (1998) In-situ formation of Ag-containing nanoparticles in thin polymer films. Nanostruct Mater 10:89–97. doi: 10.1016/S0965-9773(98)00023-3 CrossRefGoogle Scholar
  16. Gaud V, Rougé F, Gnanou Y, Desvergne JP (2012) Synthesis and properties of new photosensitive triazene and o-nitrobenzene methacrylates. React Funct Polym 72:521–532. doi: 10.1016/j.reactfunctpolym.2012.04.014 CrossRefGoogle Scholar
  17. Khanam Z, Sadon NA, Adam F (2014) Synthesis and characterization of a novel paramagnetic polyaniline composite with uniformly distributed metallic nanoparticles sandwiched between polymer matrices. Synth Met 192:1–9. doi: 10.1016/j.synthmet.2014.03.001 CrossRefGoogle Scholar
  18. Klan P, Solomek T, Bochet CG, Blanc A, Givens R, Rubina M, Popik V, Kostikov A, Wirz J (2013) Photoremovable protecting groups in chemistry and biology: reaction mechanisms and efficacy. Chem Rev 113:119–191. doi: 10.1021/cr300177k CrossRefGoogle Scholar
  19. Leiva A, Fuentes I, Bossel E, Urzua M, Mendez M, Pino M, Radic D, Marquez V, Gonzalez-Nilo FD (2014) Block copolymers in the synthesis of gold nanoparticles. Two new approaches: copolymer aggregates as reductants and stabilizers and simultaneous formation of copolymer aggregates and gold nanoparticles. J Polym Sci Part A 52:3069–3079. doi: 10.1002/pola.27354 CrossRefGoogle Scholar
  20. Lu Y, Mei Y, Schrinner M, Ballauff M, Moller MW, Breu J (2007) In situ formation of Ag nanoparticles in spherical polyacrylic acid brushes by UV irradiation. J Phys Chem C 111:7676–7681. doi: 10.1021/jp070973m CrossRefGoogle Scholar
  21. Luty-Blocho M, Fitzner K, Hessel V, Löb P, Maskos M, Metzke D, Pacławski K, Wojnicki M (2011) Synthesis of gold nanoparticles in an interdigital micromixer using ascorbic acid and sodium borohydride as reducers. Chem Eng J 171:279–290. doi: 10.1016/j.cej.2011.03.104 CrossRefGoogle Scholar
  22. Mahouche-Chergui S, Guerrouache M, Carbonnier B, Chehimi MM (2013) Polymer-immobilized nanoparticles. Colloids Surf A 439:43–68. doi: 10.1016/j.colsurfa.2013.04.013 CrossRefGoogle Scholar
  23. Marques-Hueso J, Abargues R, Canet-Ferrer J, Valdes JL, Martinez-Pastor J (2010) Resist-based silver nanocomposites synthesized by lithographic methods. Microelectron Eng 87:1147–1149. doi: 10.1016/j.mee.2009.10.043 CrossRefGoogle Scholar
  24. Melinte V, Buruiana T, Balan L, Buruiana EC (2012) Photocrosslinkable acid urethane dimethacrylates from renewable natural oil and their use in the design of silver/gold polymeric nanocomposites. React Funct Polym 72:252–259. doi: 10.1016/j.reactfunctpolym.2012.01.004 CrossRefGoogle Scholar
  25. Nagel M, Hany R, Lippert T, Molberg M, Nuesch FA, Rentsch D (2007) Aryltriazene photopolymers for UV-laser applications: improved synthesis and photodecomposition study. Macromol Chem Phys 208:277–286. doi: 10.1002/macp.200600492 CrossRefGoogle Scholar
  26. Nuyken O, Dahn U (1997) New polyesters with photosensitive backbones based on the triazene unit. J Polym Sci Part A 35:3017–3025. doi: 10.1002/(SICI)1099-0518(199710)35:14<3017:AID-POLA23>3.0.CO;2-K CrossRefGoogle Scholar
  27. Nuyken O, Dahn U, Ehrfeld W, Hessel V, Hesch K, Landsiedel J, Diebel J (1997) Synthesis of polysulfides containing the triazeno group and their application as photoresists in excimer laser polymer ablation. Chem Mater 9:485–494. doi: 10.1021/cm9603415 CrossRefGoogle Scholar
  28. Sacarescu L, Simionescu M, Sacarescu G, Hitruc EG (2011) Photocatalytic synthesis of silver nanoparticles using polysilane initiator. J Nanopart Res 13:997–1005. doi: 10.1007/s11051-010-0120-2 CrossRefGoogle Scholar
  29. Sangermano M, Yagci Y, Rizza G (2007) In situ synthesis of silver-epoxy nanocomposites by photoinduced electron transfer and cationic polymerization processes. Macromolecules 40:8827–8829. doi: 10.1021/ma702051g CrossRefGoogle Scholar
  30. Schmidl G, Dellith J, Schneidewind H, Zopf D, Stranik O, Gawlik A, Anders S, Tympel V, Katzer C, Schmidl F, Fritzsche W (2015) Formation and characterization of silver nanoparticles embedded in optical transparent materials for plasmonic sensor surfaces. Mater Sci Eng B 193:207–216. doi: 10.1016/j.mseb.2014.12.001 CrossRefGoogle Scholar
  31. Sharma D (2013) Single step, pH induced gold nanoparticle chain formation in lecithin/water system. Colloids Surf B 107:262–266. doi: 10.1016/j.colsurfb.2013.01.024 CrossRefGoogle Scholar
  32. Wang Y, Black KC, Luehmann H, Li W, Zhang Y, Cai X, Wan D, Liu SY, Li M, Kim P, Li ZY, Wang LV, Liu Y, Xia Y (2013) Comparison study of gold nanohexapods, nanorods, and nanocages for photothermal cancer treatment. ACS Nano 7:2068–2077. doi: 10.1021/nn304332s CrossRefGoogle Scholar
  33. Wei XJ, Yang ZD, Wang YX, Tay SL, Gao W (2014) Polymer antimicrobial coatings with embedded fine Cu and Cu salt particles. Appl Microbiol Biotechnol 98:6265–6274. doi: 10.1007/s00253-014-5670-2 CrossRefGoogle Scholar
  34. Wei L, Lu J, Xu H, Patel A, Chen ZS, Chen G (2015) Silver nanoparticles: synthesis, properties, and therapeutic applications. Drug Discov Today. doi: 10.1016/j.drudis.2014.11.014 Google Scholar
  35. Yagci Y, Sangermano M, Rizza G (2008) In situ synthesis of gold-cross-linked poly(ethylene glycol) nanocomposites by photoinduced electron transfer and free radical polymerization processes. Chem Commun 24:2771–2773. doi: 10.1039/B803279C CrossRefGoogle Scholar
  36. Yang ZQ, Nguyen KT, Chen HY, Qian HJ, Fernando LP, Christensen KA, Anker JN (2011) Plasmonic silver nanobelts via citrate reduction in the presence of HCl and their orientation-dependent scattering properties. J Phys Chem Lett 2:1742–1746. doi: 10.1021/jz200754d CrossRefGoogle Scholar
  37. Yu H, He Y (2015) Seed-assisted synthesis of dendritic Au–Ag bimetallic nanoparticles with chemiluminescence activity and their application in glucose detection. Sens Actuators B 209:877–882. doi: 10.1016/j.snb.2014.12.058 CrossRefGoogle Scholar
  38. Zhang F, Song WJ, Zhao ZS, Cheng Y (2014) Photo-catalytic properties of doped or substituted polyaniline-coated Fe3O4 nanoparticles. J Nanopart Res 16:2666. doi: 10.1007/s11051-014-2666-x CrossRefGoogle Scholar
  39. Zhao H, Gu W, Sterner E, Russell TP, Coughlin EB, Theato P (2011) Highly ordered nanoporous thin films from photocleavable block copolymers. Macromolecules 44:6433–6440. doi: 10.1021/ma201416b CrossRefGoogle Scholar
  40. Zhao H, Sterner ES, Coughlin EB, Theato P (2012) o-Nitrobenzyl alcohol derivatives: opportunities in polymer and materials science. Macromolecules 45:1723–1736. doi: 10.1021/ma201924h CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Violeta Melinte
    • 1
  • Andreea Chibac
    • 1
  • Tinca Buruiana
    • 1
  • Gabriela Hitruc
    • 1
  • Emil C. Buruiana
    • 1
  1. 1.Polyaddition and Photochemistry DepartmentPetru Poni Institute of Macromolecular ChemistryIasiRomania

Personalised recommendations