Abstract
Direct in situ reduction of silver ions by a biopolymer such as agar, without any other reducing nor capping agent is shown in this article to lead either to nanoparticles (typically 12(2) nm in an optimized case) or to more complex nanostructures depending on the reaction conditions used. This approach takes advantage of the porous polymer lattice acting as a template and leads to hybrid Ag–Agar materials with long-term synergic stability. Silver acts as an antibacterial agent for agar whereas the biopolymer prevents agglomeration of the inorganic nanoparticles leading to a stable nanocomposite formed by a thermoreversible biopolymer from which silver nanoparticles can eventually be recovered.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Akamatsu K, Takei S, Mizuhata M, Kajinami A, Deki S, Takeoka S, Fujii M, Hayashi S, Yamamoto K (2000) Preparation and characterization of polymer thin films containing silver and silver sulfide nanoparticles. Thin Solid Films 359:55–60. doi:10.1016/S0040-6090(99)00684-7
Akerman B (1999) Affinity gel electrophoresis of DNA. J Am Chem Soc 121:7292–7301. doi:10.1021/ja984154e
Chen CW, Chen MQ, Serizawa T, Akashi M (1998) In situ formation of silver nanoparticles on poly(N-isopropylacrylamide)-coated polystyrene microspheres. Adv Mater 10:1122–1126. doi:10.1002/(SICI)1521-4095(199810)10:14<1122::AID-ADMA1122>3.0.CO;2-N
Cole KD, Tellez CM (2002) Separation of large circular DNA by electrophoresis in agarose gels. Biotechnol Prog 18:82. doi:10.1021/bp010135o
Costanzo PJ, Beyer FL (2007) Thermally driven assembly of nanoparticles in polymer matrices. Macromolecules 40:3996–4001. doi:10.1021/ma070447t
Daniel MC, Astruc D (2004) Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev 104:293–346. doi:10.1021/cr030698+
Deshmukh RD, Composto RJ (2007) Surface segregation and formation of silver nanoparticles created in situ in poly(methyl methacrylate) films. Chem Mater 19:745–754. doi:10.1021/cm062030s
Dirix Y, Bastiaansen C, Caseri W, Smith P (1999) Oriented Pearl-necklace arrays of metallic nanoparticles in polymers: a new route toward polarization-dependent color filters. Adv Mater 11:223–227. doi:10.1002/(SICI)1521-4095(199903)11:3<223::AID-ADMA223>3.0.CO;2-J
Dong Y, Ma Y, Zhai T, Shen F, Zeng Y, Fu H, Yao J (2007) Silver nanoparticles stabilized by thermoresponsive microgel particles: synthesis and evidence of an electron donor-acceptor effect. Macromol Rapid Commun 28:2339–2345. doi:10.1002/marc.200700483
Elechiguerra JL, Bursa JL, Morones JR, Bragado AC, Gao X, Lara HH, Yacaman ML (2005) Interaction of silver nanoparticles with HIV-1. J Nanobiotechnol 3:6. doi:10.1186/1477-3155-3-6
Ganesan M, Freemantle RG, Obare SO (2007) Monodisperse thioether-stabilized palladium nanoparticles: synthesis, characterization, and reactivity. Chem Mater 19:3464–3471. doi:10.1021/cm062655q
Gómez-Romero P (2001) Hybrid organic-inorganic materials. In search of synergic activity. Adv Mater 13:163–174. doi:10.1002/1521-4095(200102)13:3<163::AID-ADMA163>3.0.CO;2-U
Gómez-Romero P, Lira-Cantú M (1997) Hybrid organic-inorganic electrodes: the molecular material formed between polypyrrole and the phosphomolybdate anion. Adv Mater 9:144–147. doi:10.1002/adma.19970090210
Gómez-Romero P, Torres-Gómez G (2000) Molecular batteries. Harnessing Fe(CN)6 3− electroactivity in hybrid polyaniline-hexacyanoferrate electrodes. Adv Mater 12:1454–1456. doi:10.1002/1521-4095(200010)12:19<1454::AID-ADMA1454>3.0.CO;2-H
Habas SE, Lee H, Radmilovic V, Somorjai GA, Yang P (2007) Shaping binary metal nanocrystals through epitaxial seeded growth. Nat Mater 6:692–697. doi:10.1038/nmat1957
He J, Kunitake T, Nakao A (2003) Facile in situ synthesis of noble metal nanoparticles in porous cellulose fibers. Chem mater 15:4401–4406. doi:10.1021/cm034720r
Hornebecq V, Antonietti M, Cardinal T, Treguer-Delapierre M (2003) Stable silver nanoparticles immobilized in mesoporous silica. Chem Mater 15:1993–1999. doi:10.1021/cm021353v
Huang H, Yang X (2004) Synthesis of polysaccharide-stabilized gold and silver nanoparticles: a green method. Carbohydr Res 339:2627–2631. doi:10.1016/j.carres.2004.08.005
Huber K, Witte T, Hollmann J, Keuker-Baumann S (2007) Controlled formation of Ag nanoparticles by means of long-chain sodium polyacrylates in dilute solution. J Am Chem Soc 129:1089–1094. doi:10.1021/ja063368q
Jin R, Cao YC, Hao E, Métraux GS, Schatz GC, Mirikin C (2003) Controlling anistropic nanoparticle growth through plasmon excitation. Nature 425:487–490. doi:10.1038/nature02020
Kattumuri V, Chandrasekhar M, Guha S (2006) Agarose-stabilized gold nanoparticles for surface-enhanced Raman spectroscopic detection of DNA nucleosides. App Phy Lett 88:153114-(1–3). doi:10.1063/1.2192573
Kim SW, Park J, Jang Y, Chung Y, Hwang S, Hyeon T (2003) Synthesis of monodisperse palladium nanoparticles. Nano Lett 3:1289–1291. doi:10.1021/nl0343405
Kusukawa N, Ostrovsky MV, Garner MM (1999) Effect of gelation conditions on the gel structure and resolving power of agarose-based DNA sequencing gels. Electrophoresis 20:1455–1461. doi:10.1002/(SICI)1522-2683(19990601)20:7<1455::AID-ELPS1455>3.0.CO;2-L
Lim B, Xiong Y, Xia Y (2007) A water-based synthesis of octahedral, decahedral, and icosahedral Pd nanocrystals. Angew Chem Int Ed 46:9279–9282. doi:10.1002/anie.200703755
Lira-Cantú M, Gómez-Romero P (1998) Electrochemical and chemical syntheses of the hybrid organic-inorganic electroactive material formed by phosphomolybdate and polyaniline. Application as cation-insertion electrodes. Chem Mater 10:698–704. doi:10.1021/cm970107u
Liu Z, Wang H, Li H, Wang X (1998) Red shift of plasmon resonance frequency due to the interacting Ag nanoparticles embedded in single crystal SiO2 by implantation. Appl Phys Lett 72:1823–1825. doi:10.1063/1.121196
Mbhele ZH, Salemane MG, Van Sittert CGCE, Nedeljković JM, Djoković V, Luyt AS (2003) Fabrication and characterization of silver-polyvinyl alcohol nanocomposites. Chem Mater 15:5019–5024. doi:10.1021/cm034505a
Mohan YM, Premkumar T, Lee K, Geckeler KE (2006) Fabrication of silver nanoparticles in hydrogel networks. Macromol Rapid Commun 27:1346–1354. doi:10.1002/marc.200600297
Mohan YM, Lee K, Premkumar T, Geckeler KE (2007) Hydrogel networks as nanoreactors: a novel approach to silver nanoparticles for antibacterial applications. Polymer 48:158–164. doi:10.1016/j.polymer.2006.10.045
Morones JR, Elechiguerra JL, Camacho A, Holt K, Kouri JB, Ramirez JT, Yacaman MJ (2005) The bactericidal effect of silver nanoparticles. Nanotechnology 16:2346–2353. doi:10.1088/0957-4484/16/10/059
Mott D, Galkowski J, Wang L, Luo J, Zhong CJ (2007) Synthesis of size-controlled and shaped copper nanoparticles. Langmuir 23:5740–5745. doi:10.1021/la0635092
Muñoz-Rojas D, Oró-Solé J, Ayyad O, Gómez-Romero P (2008a) Facile one-pot synthesis of self-assembled silver@polypyrrole core/shell nanosnakes. Small 4:1301–1306. doi:10.1002/smll.200701199
Muñoz-Rojas D, Oró-Solé J, Gómez-Romero P (2008b) From nanosnakes to nanosheets: a matrix-mediated shape evolution. J Phys Chem C 112:20312–20318. doi:10.1021/jp808187w
Murray CB, Kagan CR, Bawendi MG (2000) Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu Rev Mater Sci 30:545–610. doi:10.1146/annurev.matsci.30.1.545
Muthuswamy E, Ramadevi SS, Vasan HN, Garcia C, Noe L, Verelst M (2007) Highly stable Ag nanoparticles in agar-agar matrix as inorganic–organic hybrid. J Nanopart Res 9:561–567. doi:10.1007/s11051-006-9071-z
Narayanan R, El-Sayed MA (2004) Changing catalytic activity during colloidal platinum nanocatalysis due to shape changes: electron-transfer reaction. J Am Chem Soc 126:7194–7195. doi:10.1021/ja0486061
Oliveira MM, Ugarte D, Zanchet D, Zarbin AJG (2005) Influence of synthetic parameters on the size, structure, and stability of dodecanethiol-stabilized silver nanoparticles. J Colloid Interface Sci 292:429–435. doi:10.1016/j.jcis.2005.05.068
Oliveira MM, Castro EG, Canestraro CD, Zanchet D, Ugarte D, Roman LS, Zarbin AJG (2006) A simple two-phase route to silver nanoparticles/polyaniline structures. J Phys Chem B 110:1706–1769. doi:10.1021/jp060861f
Park P, Joo J, Kwon SG, Jang Y, Hyeon T (2007) Synthesis of monodisperse spherical nanocrystals. Angew Chem Int Ed 46:4630–4660. doi:10.1002/anie.200603148
Porel S, Singh S, Harsha SS, Rao DN, Radhakrishnan TP (2005a) Nanoparticle-embedded polymer: in situ synthesis, free-standing films with highly monodisperse silver nanoparticles and optical limiting. Chem Mater 17:9–12. doi:10.1021/cm0485963
Porel S, Singh S, Radhakrishnan TP (2005b) Polygonal gold nanoplates in a polymer matrix. Chem Commun 2387–2389. doi: 10.1039/b500536a
Qu L, Dai L, Osawa E (2006) Shape/size-controlled syntheses of metal nanoparticles for site-selective modification of carbon nanotubes. J Am Chem Soc 128:5523–5532. doi:10.1021/ja060296u
Radziuk D, Skirtach A, Sukhorukov G, Shchukin D, Möhwald H (2007) Stabilization of silver nanoparticles by polyelectrolytes and poly(ethylene glycol). Macromol Rapid Commun 28:848–855. doi:10.1002/marc.200600895
Rao CNR, Müller A, Cheetham AK (2004) The chemistry of nanomaterials: synthesis, properties and applications. Wiley-VCH, Weinheim
Salata OV (2004) Applications of nanoparticles in biology and medicine. J Nanobiotechnol 2:3. doi:10.1186/1477-3155-2-3
Singh N, Khanna PK (2007) In situ synthesis of silver nano-particles in polymethylmethacrylate. Mater Chem Phys 104:367–372. doi:10.1016/j.matchemphys.2007.03.026
Sun Y, Xia Y (2002) Shape-controlled synthesis of gold and silver nanoparticles. Science 298:2176–2179. doi:10.1126/science.1077229
Takagi D, Homma Y, Hibino H, Suzuki S, Kobayashi Y (2006) Single-walled carbon nanotube growth from highly activated metal nanoparticles. Nano Lett 6:2642–2645. doi:10.1021/nl061797g
Torres-Gómez G, Gómez-Romero P (1998) Conducting organic polymers with electroactive dopants. Synthesis and electrochemical properties of hexacyanoferrate-doped polypyrrole. Synth Met 98:95–102. doi:10.1016/S0379-6779(98)00150-7
Walker CH, St. John JV, Wisian-Neilson P (2001) Synthesis and size control of gold nanoparticles stabilized by poly(methylphenylphosphazene). J Am Chem Soc 123:3846–3847. doi:10.1021/ja005812+
Wang X, Egan CE, Zhou M, Prince K, Mitchell DRG, Caruso RA (2007) Effective gel for gold nanoparticle formation, support and metal oxide templating. Chem Commun 3060–3062. doi: 10.1039/b704825d
Wiley B, Sun Y, Mayers B, Xia Y (2005) Shape-controlled synthesis of metal nanostructures: the case of silver. Chem Eur J 11:454–463. doi:10.1002/chem.200400927
Wiley B, Sun Y, Xia Y (2007) Synthesis of silver nanostructures with controlled shapes and properties. Acc Chem Res 40:1067–1076. doi:10.1021/ar7000974
Xiong Y, Xia Y (2007) Shape-controlled synthesis of metal nanostructures: the case of palladium. Adv Mater 19:3385–3391. doi:10.1002/adma.200701301
Xue C, Li Z, Mirkin CA (2005) Large-scale assembly of single-crystal silver nanoprism monolayers. Small 1:513–516. doi:10.1002/smll.200400150
Yin YD, Xu XL, Xia CJ, Ge XW, Zhang ZC (1998) Synthesis and characterization of poly(butyl acrylate-co-styrene)-silver nanocomposites by γ-radiation in W/O microemulsions. Chem Commun 941–942. doi: 10.1039/a800676h
Zhang Z, Han M (2003) One-step preparation of size-selected and well-dispersed silver nanocrystals in polyacrylonitrile by simultaneous reduction and polymerization. J Mater Chem 13:641–643. doi:10.1039/b212428a
Zhang J, Liu H, Wang Z, Ming N (2007) Shape-selective synthesis of gold nanoparticles with controlled sizes, shapes, and plasmon resonances. Adv Funct Mater 17:3295–3303. doi:10.1002/adfm.200700497
Zhu YJ, Qian YT, Li X, Zhang M (1998) A nonaqueous solution route to synthesis of polyacrylamide-silver nanocomposites at room temperature. Nanostruct Mater 10:673–678. doi:10.1016/S0965-9773(98)00096-8
Acknowledgements
Funding for this research was possible by a grant from the Spanish Ministry of Science and Innovation (MICINN) (CTQ2008-06779-C02-01). We thank CSIC and the European Social Fund for financing through the I3P program (DMR); OA gratefully acknowledges earlier financial support from The Palestinian Ministry of Higher Education (Saudi Committee for the Relief of the Palestinian People) and a loan from Al-Quds University (Jerusalem, Palestine).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Ayyad, O., Muñoz-Rojas, D., Oró-Solé, J. et al. From silver nanoparticles to nanostructures through matrix chemistry. J Nanopart Res 12, 337–345 (2010). https://doi.org/10.1007/s11051-009-9620-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11051-009-9620-3