1346

DOI: 10.1002/marc.200600297

Communication

Summary: This paper describes a simple and facile approach to fabricate well dispersed silver nanoparticles (AgNPs) in poly[N-isopropylacrylamide-co-(sodium acrylate)] hydrogels. The silver nanoparticles formed are spherical in shape with a narrow size distribution in the hydrogel networks in which the nanoparticles are stabilized by the polymer network. Uniformly dispersed silver nanoparticles were obtained with poly[N-isopropylacrylamide-co-[sodium acrylate)]

hydrogels, whereas a poly(N-isopropylacrylamide)/poly(sodium acrylate) IPN gel showed aggregated nanoparticles. It is demonstrated that the hydrogel network structure determines the size and shape of the nanoparticles. These particles are more stable in the gel networks compared to other reduction methods. The hydrogel/silver nanohybrids were well characterized by XRD, UV-vis spectrometry, scanning electron microscopy and transmission electron microscopy.

Schematic representation of the preparation of Ag nanoparticles in hydrogel networks.

Fabrication of Silver Nanoparticles in Hydrogel Networksa

Y. Murali Mohan, Thathan Premkumar, Kyungjae Lee, Kurt E. Geckeler*
Laboratory of Applied Macromolecular Chemistry, Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), 1 Oryong-dong, Buk-gu, Gwangju 500-712, South Korea E-mail: keg@gist.ac.kr

Received: April 28, 2006; Revised: June 20, 2006; Accepted: June 21, 2006; DOI: 10.1002/marc.200600297 Keywords: crosslinking; hydrogels; poly(N-isopropylacrylamide); poly(sodium acrylate); silver nanoparticles

Introduction
Metal nanoparticles and nanostructured materials are novel classes of materials,[1] which have attracted great attention in catalysis,[25] optics,[6,7] electronics,[8,9] and biomedicine[1,2] as well as quantum-size domain applications[10,11] due to their unusual physicochemical properties that are quite different from those of the bulk solids. The synthesis
a

: Supporting information for this article is available at the bottom of the articles abstract page, which can be accessed from the journals homepage at http://www.mrc-journal.de, or from the author.

of metal nanoparticles is a major research area in nanoscience and technology. Chemical reduction via microemulsion,[12] co-precipitation,[13,14] carbon nanotubes[15] and polymer protection[1618] has been extensively used as the best way to obtain metal nanoparticles with a narrow size distribution. Many approaches indicate that, despite simple organic polymer templates including biological macromolecules,[19,20] block copolymers,[21,22] dendrimers,[2325] liquid crystals,[26] latex particles,[27] mesoporous inorganic materials,[28] microgels[29] and hydrogels[30,31] can produce well dened morphologies of the metal nanoparticles. Recent research efforts have been

Macromol. Rapid Commun. 2006, 27, 13461354

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fabrication of Silver Nanoparticles in Hydrogel Networks

1347

directed towards exploiting the in situ synthesis of metal nanoparticles within polymeric network architectures[32,33] and the products of these approaches are new hybrid or composite systems in chemistry and engineering science. It has been reported that colloidal particles present in gels could be utilized as sensors,[34] photonic crystals,[35] for catalysis,[5,36] switchable electronics,[37,38] bio-separation, drug delivery[34] and biological labeling[39] materials. In fact, three-dimensional network hydrogels are more suitable as templates for the production of nanoparticles than the conventional non-aqueous or polymeric systems for biomedical applications, considering their exceptional compatibility with biological molecules, cells and tissues. In addition, the main advantages of hydrogels provide free space between the networks in the swollen stage, which can serve for nucleation and growth of the nanoparticles. Furthermore, the size and morphology of the nanoparticles can be controlled by the functionalization of hydrogels, varying the crosslinking density of networks and modication of the hydrogels. Poly(N-isopropylacrylamide) (PNIPAM) hydrogel is an excellent thermosensitive material that exhibits a sudden change in the solvent-swollen mass in response to small changes in external stimuli such as pH, temperature, ionic strength, light sensitivity and electric eld. Silver nanoparticles have been known for a long time as a non-toxic and environmentally friendly antibacterial material. The corresponding would be more attractive for a wide variety of biomedical applications and recent advances aimed at exploring possible ways to obtain Ag nanoparticles in polymer networks. A controlled Ag nanocluster deposition into poly[(N-isopropylacrylamide)-co-(acrylic acid)-co-(2hydroxylethyl acrylate)] microgel[29] has been reported.[33] Xu et al.[35] developed an Ag-microgel hybrid for photonic crystals and studied its thermosensitive characteristics. Pich et al.[40] described the synthesis and characterization of hybrid microgels consisting of poly[vinylcaprolactamco-(acetoacetoxy methacrylate)] and Ag nanoparticles. An approach for the stabilization of Au nanoparticles in hydrogel networks through thiol ester bonds was developed by employing the N,N0 -cystaminebisacrylamide crosslinker.[41] Most of the above mentioned studies required special techniques to prepare the precursor of the microgels or hydrogels to be employed as templates for the nanoparticles. In this communication, we report a novel and facile strategy to fabricate narrow sized silver nanoparticles in chemically crosslinked poly[N-isopropylacrylamide-co(sodium acrylate)] hydrogels. This novel approach demonstrates the preparative conditions needed to obtain silver nanoparticles of 3 nm in the hydrogel networks. In addition, the current approach provides the possibility to tailor the size and features of silver particles in the hydrogel network architecture.
Macromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de

Experimental Part
Materials N-isopropylacrylamide (NIPAM), sodium acrylate (SA), ammonium persulfate (APS), N,N0 -methylenebisacrylamide (MBA), N,N,N0 ,N0 -tetramethylethylenediamine (TEMED) and sodium borohydride (NaBH4) were received from Aldrich (USA). Poly(sodium acrylate) (PSA) (M 5 100 kg mol1) and silver nitrate (AgNO3) were obtained from Fluka (Germany) and Junsei Chemical Co. (Japan), respectively. All the chemicals and reagents were used as received without any further purication. Distilled water was utilized for all polymerizations and solutions. Preparation of Silver Nanoparticles The silver nanoparticles were prepared by reduction of AgNO3 using NaBH4. These were prepared by adding a 10 103 M aqueous solution (5 mL) of NaBH4 to 5 mL of a 5 103 M aqueous solution of AgNO3. Synthesis of Ag Nanoparticles in Poly(NIPAM-co-SA) Hydrogel Networks Poly[N-isopropylacrylamide-co-(sodium acrylate)], poly(NIPAM-co-SA), hydrogels were synthesized by means of simultaneous free-radical crosslinking polymerization. In detail, N-isopropylacrylamide (NIPAM) (800 mg), sodium acrylate (SA) (200 mg) and different amounts (4.88, 6.48, 8.73, and 12.97 103 M) of N,N-methylenebisacrylamide (MBA) were dissolved in test tubes containing 8 mL of distilled water. The resulting solution was stirred for 5 min to obtain a homogeneous phase and purged with nitrogen to expel the air. The polymerizations were initiated by adding APS (1 wt.-%, 1 mL) and TEMED (1 wt.-%, 1 mL), started vigorously, and resulted in the formation of a hydrogel within a few minutes at 25 8C. To achieve complete network formation for the hydrogels, the polymerizations were continued for 1 d; the gels obtained were removed from the polymerization tubes and the as-prepared gels were cut into discs (3 mm high, 12 mm diameter). The hydrogel discs were thoroughly washed with distilled water for 3 d to leach out the unreacted compounds. These swollen gel discs were utilized for the Ag salt loading and the subsequent reduction with NaBH4. Similarly, the poly(NIPAM)/poly(SA) semi-IPN hydrogels were prepared by polymerizing 800 mg of NIPAM in the presence of 200 mg of PSA using 6.48 103 M of MBA. These hydrogels with different crosslinking densities and the IPN hydrogels were utilized in producing the Ag nanoparticles.[41] Freshly swollen gel discs were equilibrated in 30 mL of AgNO3 aqueous solution (5 103 M) and the gel discs were then transferred into 60 mL of NaBH4 aqueous solution (10 /103 M) for 30 min to reduce the Ag salt to the Ag colloidal particles. Characterization Dispersed AgNP-hydrogel solutions (10 mg/10 mL water) were utilized for measuring the optical properties. Spectra
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1348

Y. M. Mohan, T. Premkumar, K. Lee, K. E. Geckeler

were recorded on a Carry 1E UV-vis spectrophotometer (Varian 95011211) over the range 300 to 700 nm with a 1 nm resolution. XRD analyses for the samples were performed using a Rikagu diffractometer (Cu radiation, l 0.1546 nm) running at 40 kV and 40 mA. Scanning electron microscopic (SEM) measurements were carried out on a Hitachi S-4700 (Japan) instrument operating at an acceleration voltage of 15 kV. The SEM specimens were prepared on a silicone wafer. A silicone wafer was placed on a piece of lter paper and 23 drops of water containing ground gel particles were applied using a pipette. If any excess solution was present on the silicone wafer, the lter paper absorbed it and the sample was dried in air. Finally samples were coated with a thin palladium layer in order to get good contrast and good quality images. TEM measurements of Ag nanoparticles stabilized by hydrogels were carried out with a JEOL JEM-2000 transmission electron microscope. The samples were dispersed in distilled water and a copper mesh covered with a carbon lm was applied as the carrier. Swelling ratio (Q) Accurately weighed pure hydrogel discs were equilibrated in distilled water at 30 8C for 3 d. These pure gels were treated with Ag salt and subsequently with NaBH4 solutions as explained in the preparation procedure. The equilibrium swelling ratio (Q) of the gels was calculated using Q We/Wd, where We is the weight of water/solution in the swollen hydrogel under certain conditions and Wd is the dry weight of the pure hydrogel.

Results and Discussion

In this communication, we report well dispersed silver nanoparticles in hydrogel networks. The templates or precursor hydrogels prepared in this investigation had random sequence distributions of NIPAM and SA repeat units along the copolymer chains with a number of crosslinking networks, which can act as reactors or carriers for producing AgNPs in the networks. In the present approach, silver nitrate-loaded hydrogel networks were reduced in situ with NaBH4 to form spontaneously highly dispersed Ag

nanoparticles within the hydrogel networks, as shown in Scheme 1. In general, the stabilization of nanoparticles is achieved by either attaching them to larger protecting polymer chains or protecting macromolecules will encapsulate or cover the nanoparticles. A number of different natural and synthetic polymers have been considered as stabilizers for metal nanoparticles. Recently, direct reduction, chemical and gamma radiation methods proposed that poly(sodium acrylate) effectively works as a stabilizing agent for AgNPs.[4244] The main advantage of the current technique is that it provides controlled and uniformly distributed nanoparticles within the networks without addition of any further stabilizer. This is conrmed in Figure 1(b) and 1(c), which show nanoparticles evenly distributed between the polymeric chain networks. At the same time, the pure hydrogel did not show any particles in the SEM image (Figure 1(a)). Moreover, the porosity or free space between the networks has the potential to suppress the aggregation of the nanoparticles. This porosity affords an opportunity for the rapid diffusion of other small molecules into and out of the polymers and this property is widely important in sensor and catalytic applications. Ag nanoparticles produced without any stabilizer showed a highly aggregative pattern with a size of 225 nm [Figure 1(d) and 1(e)]. In the case of silver nanoparticles prepared with polyNIPAM/SA semiIPN hydrogel, the nanoparticles showed irregular growth as depicted in Figure 1(f). This might be due to the higher entanglement of poly(sodium acrylate) chains over PNIPAM hydrogel networks. Therefore, it is very clear that a uniform dispersion of nanoparticles could be achieved only in the case of copolymer hydrogels. Such uniformly dispersed nanoparticles in the networks can be seen in the transmission electron micrographs in the coming section. Here, we propose a reason for the protection of nanoparticles in the hydrogel networks: the intra- and intermolecular associations of the NIPAM/sodium acrylate units facilitate extensive physical networks of hydrogen bonds,

Scheme 1. Schematic representation of the preparation of Ag nanoparticles in hydrogel networks.

Macromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fabrication of Silver Nanoparticles in Hydrogel Networks

1349

Figure 1. SEM images of (a) hydrogel; (b) and (c) Ag nanoparticles in hydrogel networks; (d) and (e) Ag nanoparticles without any stabilizer; (f) Ag nanoparticles in the IPN hydrogel.

which provides nanoscopic domains for the growth of the nanoparticles. Furthermore, the poly(sodium acrylate) chains or sodium acrylate units in the copolymer gels could also effectively participate in the reduction process. However, this is very effective only at higher temperature.[43] We expected homogeneously distributed silver nanoparticles throughout the hydrogel networks, although there is a rapid reduction of the Ag into Ag nanoparticles with NaBH4. The reason is that the Ag nanoparticles initially formed in the networks cause expansion of the free space in the hydrogel, since the hydrogel-Ag salt features physical crosslinks of the Ag with the sodium acrylate moieties. Thus, it is possible for NaBH4 to enter into the entire gel network to reduce the Ag salt present in the network. Similarly, the NIPAM hydrogel crosslinked with two different crosslinkers, N,N-methylenebisacrylamide (MBA) and N,N-cystaminebisacrylamide (CBA), showed enhanced hydrogel networks for easy penetration of NaBH4 into the networks, and consequently a completely uniform distribuMacromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de

Figure 2. gels.

Swelling ratio of the hydrogels and modied hydro-

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1350

Y. M. Mohan, T. Premkumar, K. Lee, K. E. Geckeler

tion of Au nanoparticles in the bulk gel.[41] Therefore, we assume that there is no blocking of the hydrogel porosity or free spaces available in the networks during the reduction process. The swelling results obtained for these hydrogels also support higher exibility while nanoparticle formation proceeds in the network (Figure 2). The gel variation with the salt loading and the subsequent formation of Ag nanoparticles is shown in the Supporting Information. The as-prepared AgNPs in the hydrogel networks certainly have an inuence on the bulk properties of the hydrogels, since they change the chemical environment of the networks. Precursor hydrogels with different amounts of MBA crosslinker were prepared and it was noted that, as the crosslinker concentration increased in the hydrogels, their swelling ratio decreased to a greater extent, as shown in Figure 2. This phenomenon is quite common and is widely acceptable due to

the smaller mesh size of the networks. A large variation in the swelling ratio of morphologically modied hydrogels was identied for the Ag salt and Ag nanoparticle-containing hydrogels compared with the precursor hydrogels.[29] The order of swelling ratios was found to be: pure hydrogel > AgNP hydrogel > Ag salt-hydrogel. It was observed that the presence of salt solutions lead to a decrease of the swelling capacity of the hydrogels. In fact, it was attributed to a decrease in the expansion of the gel networks, which is caused by the repulsive forces of counter ions on the polymeric chain shielded by the bound ionic charge. During the reduction of the Ag salt to the Ag nanoparticles in the hydrogels, different amounts of Ag nanoparticle surface charges (different size of the AgNPs) cause a moderate expansion of the hydrogel networks. This is ultimately responsible for the improved swelling capacity of the hydrogels, and therefore

Figure 3. (a) UV-vis spectra of Ag nanoparticles in the hydrogels and pristine hydrogel (inset); (b) luminescence spectra of Ag nanoparticles in the hydrogels; (c) XRD patterns of Ag nanoparticles in the hydrogel and the pristine hydrogel (inset).
Macromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fabrication of Silver Nanoparticles in Hydrogel Networks

1351

the AgNP-containing hydrogels showed higher swelling capacities than the Ag-salt containing hydrogels. The immobilization of the silver nanoparticles throughout the hydrogel networks could be due to a strong localization of the Ag ions within the networks. The formation of the silver nanoparticles in the hydrogel networks was indicated by a brown color (Supporting Information). This should be due to the complexation of the Ag ions with either nitrogen atoms and/or oxygen atoms present in the hydrogel chains. To prove the formation of silver nanoparticles in the networks using the current approach, we carried out UV-visible absorption studies and the results are presented in Figure 3(a). A distinct absorption peak around 404 nm was observed for AgNPs in the hydrogels due to the characteristic surface plasmon resonance effect originating

from the quantum size of the silver nanoparticles.[17,43,45] Wang et al.[46] reported a similar well-dened surface plasmon resonance at 411 nm for 2.5 nm sized AgNPs, whereas the pristine hydrogel showed no absorbance in the UV-vis region [Figure 3(a) inset]. A comparison of the four samples in the UV-vis spectra indicates that increasing the crosslinker content during the preparation of hydrogel decreased the reduction rate of silver ions, since networks with a higher density restrict the penetration capacity of the solute (NaBH4). Recent UV studies clearly revealed that with an increase of the size of nanoparticles (pure) and the nanoparticles in a NIPAM-MBA gel, the peak under the area or the height of the peak increased.[38] On the other hand, the plasmon absorption increment in the UV-vis spectra represents the

Figure 4. Effect of the hydrogel network on the nanoparticle formation: (a) SEM image of the hydrogel with 4.86 mM MBA (20.07 0.53 nm); (b)(d) TEM images of hydrogels with 6.48 (4.57 0.16 nm), 9.73 (3.73 0.20 nm) and 12.97 (3.00 0.09 nm) mM MBA, respectively.
Macromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1352

Y. M. Mohan, T. Premkumar, K. Lee, K. E. Geckeler

formation of a higher number of nanoparticles. A signicantly improved absorbance peak was found around 400 nm in the UV spectrum of silver-loaded poly[vinylcaprolactamco-(acetoacetoxy methacrylate)] microgels (0 to 52.8%).[40] As the stabilization of nanoparticles is very important, we evaluated the stability of the AgNP in the hydrogel networks by studying the photoluminescence properties. The luminescence of silver could be induced by irradiating the silver metal with electron, photon or laser beams with reported emission peak position.[4749] The luminescence of the silver metal is attributed to the electronic transitions between the upper d-band and conduction sp-band.[50] The luminescence spectra of the AgNPs stabilized by hydrogel networks clearly demonstrate an emission peak at 466 nm upon excitation at 404 nm (Figure 3(b)). Interestingly, the silver nanoparticles are stabilized more by the MBA crosslinked hydrogel (12.97 103 M). The reason could be due to the sodium acrylate units in the hydrogel chains being closer to the nanoparticles in highly crosslinked hydrogels, which are responsible for the higher stabilization in the present case.[43] Figure 3(c) shows the XRD patterns of the hydrogel and AgNPs in the hydrogel. The diffraction peaks for Aghydrogel nanohybrid found at 2y 38.1, 44.26, 64.50 and 77.42 were attributed to the (111), (200), (220) and (311) planes of fcc silver, respectively.[51,52] In contrast, the

hydrogel alone did not show any peaks in the XRD, thus indicating no crystalline behavior. The control or alignment of nanoparticles could be possible by modifying the hydrogel network architecture.[29,35,38,41] This could be achieved by varying the crosslinker concentration in the preparation of the hydrogel itself. The production of different metal nanoparticles in the NIPAM-based nanogel reactor represents a narrative strategy for controlling the size and distribution by changing the preparative composition of the gel.[29] It has also been proven that formation of nanoparticles occurring in the free spaces of the bulk gel can be managed by varying the concentration of the crosslinker, and the aggregative pattern of the nanoparticles completely disappeared as the CBA concentration increased.[41] After optimizing various parameters for making gels, we found that the variation of the MBA concentration in the polymerizations remarkably changed the crosslinking density of the gel networks, but also gave an interesting result in terms of a good dispersion throughout the networks. The SEM, TEM images and histograms of the as-prepared silver nanoparticles in the hydrogel networks crosslinked with different amounts of MBA are shown in Figure 4. It is apparent that the silver nanoparticles formed in different crosslinked networks showed a uniformly spherical shape and were well dispersed, but were different in size. Furthermore, we observed

Scheme 2. Illustration of the controlled silver nanoparticle formation between the hydrogel networks: (a) less crosslinked networks; (b) highly crosslinked networks.
Macromol. Rapid Commun. 2006, 27, 13461354 www.mrc-journal.de 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fabrication of Silver Nanoparticles in Hydrogel Networks

1353

that the MBA concentration inuenced the particle size of the nanoparticles. This indicates that highly dense hydrogel networks (using a high MBA concentration) favor 3.0 0.09 nm silver nanoparticles, since they allow the establishment of inter- and intramolecular attractions between the hydrogel networks due to less free space in the hydrogel networks. This would help to stabilize as well as control the size of the nanoparticles. A possible illustration of the controlled silver nanoparticle formation between the hydrogel networks is presented in Scheme 2. Accordingly, the scheme shows that less crosslinked networks (with a low MBA concentration) provide a lot of free space between the networks and act as big nanoreactors, whereupon the nanoparticles are allowed to grow into particles with larger diameters. It can be seen from Figure 4(a) that by using 4.86 103 M MBA (20.07 0.53 nm) very large nanometer-sized particles were obtained. The diffraction pattern recorded by aligning the electron beam perpendicular to the square faces of the Ag nanoparticles in the hydrogel networks (12.97 103 M MBA, 3.0 0.09 nm) also clearly demonstrates the spherical shape of the particles in the gel networks (Supporting Information). Finally, from the viewpoint of their stability, the resulting nanoparticles stored for more than three months did not show any sign of decay under aerobic conditions.

Conclusion
In conclusion, we have reported a facile method for the production of silver nanoparticles with better monodispersity in hydrogel networks. The silver nanoparticles were stabilized by hydrogel networks. Highly crosslinked networks provided very small size and more stable nanoparticles.

Acknowledgements: Financial support from the Korean Research Foundation (KRF) is gratefully acknowledged.

[1] Functional Nanomaterials, K. E. Geckeler, E. Rosenberg, Eds., American Scientic Publishers, Valencia, USA 2006. [2] M.-C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293. [3] L. N. Lewis, Chem. Rev. 1993, 93, 2693. [4] H. Ohde, C. M. Wai, H. Kim, J. Kim, M. Ohde, J. Am. Chem. Soc. 2002, 124, 4540. [5] A. Bifs, N. Orlandi, B. Corain, Adv. Mater. 2003, 15, 1551. [6] R. C. Hayward, D. A. Saville, I. A. Aksay, Nature 2000, 404, 56. [7] R. G. Ispasoiu, L. Balogh, O. P. Varnavski, D. A. Tomalia, T. Goodson, J. Am. Chem. Soc. 2000, 122, 11005.

[8] A. Kiesow, J. E. Morris, C. Radehaus, A. Heilmann, J. Appl. Phys. 2003, 94, 6988. [9] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.-M. Tarascon, Nature 2000, 407, 496. [10] R. Wang, J. Yang, Z. Zheng, M. D. Carducci, J. Jiao, S. Seraphin, Angew. Chem. Int. Ed. 2001, 40, 549. [11] M. L. Anderson, C. A. Morris, R. M. Stroud, C. I. Merzbacher, D. R. Rolison, Langmuir 1999, 15, 674. [12] I. Lisiecki, M. P. Pileni, J. Am. Chem. Soc. 1993, 115, 3887. [13] D. H. Chen, Y. Y. Chen, Mater. Res. Bull. 2002, 37, 801. [14] M. Haruta, N. Yamada, T. Kobayashi, S. Iijima, J. Catal. 1989, 115, 301. [15] D. Kim, T. Lee, K. E. Geckeler, Angew. Chem. Int. Ed. 2005, 45, 104. [16] N. Yanagihara, Y. Tanaka, H. Okamoto, Chem. Lett. 2001, 796. [17] J. Gao, J. Fu, C. Lin, J. Lin, Y. Han, X. Yu, C. Pan, Langmuir 2004, 20, 9775. [18] P.-L. Kuo, W.-F. Chen, J. Phys. Chem. B. 2003, 107, 11267. [19] S. Behrens, W. Habicht, K. Wagner, E. Unger, Adv. Mater. 2006, 18, 284. [20] R. R. Naik, S. E. Jones, C. J. Murray, J. C. McAulifee, R. A. Vaia, M. O. Stone, Adv. Funct. Mater. 2004, 14, 25. [21] S. K. Jewrajka, U. Chatterjee, J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 1841. [22] R. B. Grubbs, J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 4323. [23] X. Sun, X. Jiang, S. Dong, E. Wang, Macromol. Rapid Commun. 2003, 24, 1024. [24] A. Okugaichi, K. Torigoe, T. Yoshimura, K. Esumi, Colloids Surf. A: Phys. Eng. Asp. 2006, 273, 154. [25] M. Zhao, R. M. Crooks, Chem. Mater. 1999, 11, 3379. [26] L. Qi, Y. Gao, J. Ma, Colloids Surf. A: Phys. Eng. Asp. 1999, 157, 285. [27] R. M. Crooks, M. Zhao, L. Sun, V. Chechik, L. K. Yeung, Acc. Chem. Res. 2001, 34, 181. [28] A. Ghosh, C. R. Patra, P. Mukherjee, M. Sastry, R. Kumar, Microporous and Mesoporous Mater. 2003, 58, 201. [29] J. Zhang, S. Xu, E. Kumacheva, J. Am. Chem. Soc. 2004, 126, 7908. [30] R.-H. Jin, J.-J. Yuan, J. Mater. Chem. 2005, 15, 4513. [31] Advanced Macromolecular and Supramolecular Materials and Processes, K. E. Geckeler, Ed., Kluwer Academic/ Plenum Publishers, New York 2002. [32] C. Aymonier, U. Schlotterbeck, L. Antonietti, P. Zacharias, R. Thomann, J. C. Tiller, S. Mecking, Chem. Commun. 2002, 3018. [33] C. H. Ho, J. Tobis, C. Sprich, R. Tomann, J. C. Tiller, Adv. Mater. 2004, 16, 957. [34] Y. Y. Li, F. Cunin, J. R. Link, T. Gao, R. E. Betts, S. H. Reiver, V. Chin, S. N. Bhatia, M. J. Sailor, Science 2003, 299, 2045. [35] S. Xu, J. Zhang, C. Paquet, Y. Lin, E. Kumacheva, Adv. Funct. Mater. 2003, 13, 468. [36] C. Aymonier, D. Bortzmeyer, R. Thomann, R. Mulhaupt, Chem. Mater. 2003, 15, 4874. [37] B. T. Holland, C. F. Blanford, A. Stein, Science 1998, 281, 538. [38] E. A. Kazimierska, M. Ciszkowska, Electroanalysis 2005, 17, 1384. [39] M. Han, X. Gao, J. Z. Su, S. Nie, Nat. Biotechnol. 2001, 19, 631. [40] A. Pich, A. Karak, Y. Lu, A. K. Ghosh, H.-J. P. Adler, Macromol. Rapid Commun. 2006, 27, 344. [41] C. Wang, N. T. Flynn, R. Langer, Adv. Mater. 2004, 16, 1074.

Macromol. Rapid Commun. 2006, 27, 13461354

www.mrc-journal.de

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1354

Y. M. Mohan, T. Premkumar, K. Lee, K. E. Geckeler

[42] B. G. Ershov, A. Henglein, J. Phys. Chem. B 1998, 102, 10663. [43] I. Hussain, M. Brust, A. J. Papworth, A. I. Cooper, Langmuir 2003, 19, 4831. [44] Y. Shiraishi, N. Toshima, Colloids Surf. A: Physicochem. Eng. Aspects. 2000, 169, 59. [45] K. Sudhir, Langmuir 1998, 14, 1021. [46] W. Wang, S. A. Asher, J. Am. Chem. Soc. 2001, 123, 12528.

[47] M. Zivitz, E. W. Thomas, Phys. Rev. B 1976, 13, 2747. [48] G. L. Eesley, Phys. Rev. B 1981, 24, 5477. [49] K. U. Von Raben, R. K. Chang, B. L. Laube, Chem Phys. Lett. 1981, 79, 465. [50] A. Mooradian, Phys. Rev. Lett. 1969, 22, 185. [51] D. V. Leff, L. Brandt, J. R. Heath, Langmuir 1996, 12, 4723. [52] A. Swami, A. Kumar, P. R. Selvakannan, S. Mandal, R. Pasricha, M. Sastry, Chem. Mater. 2003, 15, 17.

Macromol. Rapid Commun. 2006, 27, 13461354

www.mrc-journal.de

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim