Novel Structured Composites Formed from Gold Nanoparticles and Diblock Copolymers

Communication

1350

Novel Structured Composites Formed fromGold Nanoparticles and Diblock Copolymers

Xi Chen, Yang Liu, Yingli An, Juan Lu, Junbo Li, Dean Xiong, Linqi Shi*

We report a simple procedure to prepare a novel Au-micelle composite with a core-shell-corona structure. This composite is prepared by reduction of tetrachloroauric acid(HAuCl4 �3H2O) in dilute aqueous solution containing polystyrene-block-poly(4-vinylpyridine)micelles and poly(ethylene oxide)-block-poly(4-vinylpyridine) copolymers. The micelles witha polystyrene core and a poly(4-vinylpyridine)shell are transformed into Au-micelle compo-sites with a polystyrene core, a swollen hybridAu/poly(4-vinylpyridine) inner shell, and apoly(ethylene oxide) corona by direct physisorp-tion of gold particles with poly(4-vinylpyridine)chains.

Introduction

Gold nanoparticles have received great attention in the

past few years because of their unusual optical, electronic,

and catalytic properties.[1] Many strategies have been

developed to control the synthesis of gold nanoparticles, to

consider the effects of their sizes and shapes, their aggre-

gate state, and the medium on their properties.[2] A typical

example is the use of low-molecular-weight surfactant to

synthesize gold nanoparticles, because it allows the

simultaneous tuning of the size and shape of the resulting

gold nanoparticles as well as their stabilization.[3]

From a viewpoint of handling, gold nanoparticles

should be held on substrates. However, it is difficult to

obtain the expected effects by use of low-molecular-

weight surfactants because of their structure limitations.[4]

In contrast, block copolymers not only afford powerful

capabilities to synthesize gold nanocomposites but also

simultaneously provide a facile operation.[5] Furthermore,

X. Chen, Y. Liu, Y. An, J. Lu, J. Li, D. Xiong, L. ShiKey Laboratory of Functional Polymer Materials, Ministry ofEducation, Institute of Polymer Chemistry, Nankai University,Tianjin 300071, P. R. ChinaFax: þ86 22 23503510; E-mail: [email protected]

Macromol. Rapid Commun. 2007, 28, 1350–1355

� 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

block copolymers can provide an effective means to

control particle location and pattern based on their rich

diversity of structures.[6] In most cases, gold nanoparticles

are formed in the micelle cores of amphiphilic block

copolymers in selective solvents when the polymeric

system is already nanostructured.[7] In these systems, one

block is soluble in the solvent, while the other block forms

the core, which is able to consume gold compounds by

coordination. Thus, the cores are regarded as nanoreactors

for the reductive nucleation and growth of gold nano-

particles, and the formed composites possess a core-shell

structure with Au located in the core. However, many

important performances based on gold nanoparticles have

been inhibited because they have been embedded in the

dense core. One of the effective strategies to overcome this

is to fix Au on the surface of the micelle.

Furthermore, recent significant new advances in the

fabrication of gold nanoparticles are needed to form novel-

structured gold hybrid nanoparticles for further develop-

ment of nanometer-scale tools and devices. To this end,

tremendous attention has been paid to fabricate novel

structured gold composites such as core-shell nanoparti-

cles with gold nanoparticles fixed between the core and

the shell by use of core-shell particles as templates,[8] core-

shell composites with iron oxide nanoparticles located in

DOI: 10.1002/marc.200700166

Novel Structured Composites Formed from Gold . . .

Scheme 1. Au-micelle composite forming process.

the core and gold nanoparticles located in the shell,[6b] and

a gold-polymer chain formed by linking gold nanoparticles

onto a polymer chain through covalent bonding,[9] etc.

Herein, we develop a simple strategy to prepare novel

structured hybrid Au-micelle composites comprising a

polystyrene core, a hybrid Au/poly(4-vinylpyridine) inner

shell, and a poly(ethylene oxide) corona. This composite

has a swollen inner shell, which is thought to benefit

the gold nanoparticles property. In addition, the present

composites may be modified to prepare multifunctional

products as a result of the different chemistry in their core,

shell, and corona. The gold-micelle composites are pro-

duced by reduction of amixed solution of preexisting block

copolymer, poly(ethylene oxide)-block-poly(4-vinylpyridine)

(PEO-b-P4VP) and a micelle formed by polystyrene-block-

poly(4-vinylpyridine) (PS-b-P4VP), and tetrachloroauric acid,

and the process is shown in Scheme 1.

Experimental Part

Materials and Instrumentation

Block copolymer PEO-b-P4VP was synthesized by atom transfer

radical polymerization (ATRP) of 4-vinylpyridine with PEO-Br as

the macroinitiator and CuCl/Me6TREN (tri[2-(dimethylamino)

ethyl]amine) as the catalyst.[10] PS-b-P4VP was synthesized by

sequential ATRP of styrene and 4-vinylpyridine(4-VP) with 1-

chlorophenylethane (PECl) as the initiator and CuCl/Me6TREN as

the catalyst.[11] These block copolymers can be denoted as

PEO114-b-P4VP52 and PS109-b-P4VP61 where the subscript indicates

the number of repeating units. The polydispersity indexes (PDIs) of

PEO114-b-P4VP52 and PS109-b-P4VP61 are 1.30 and 1.10, respec-

tively. Dynamic laser scattering (DLS) was performed at 532 nm

on a laser light scattering spectrometer (BI-200SM) equipped with

a digital correlator (BI-9000AT). All samples were prepared by

filtering about 1mL of solutionwith a 0.45 mmMillipore filter into

a clean scintillation vial and then characterized at room tempe-

rature. The detailed method of DLSmeasurements can be found in

the literature.[12] Transmission electron microscopy (TEM) was

performed using a Tecnai G2 20 S-TWIN electron microscope

equipped with a Model 794 CCD camera at 200 kV accelerating

voltage, where a small drop of micellar solution was deposited

onto a carbon-coated copper TEM grid and dried at 25 8C at

atmospheric pressure. UV-vis spectra were recorded on a Cary



50 Bio UV-Visible Spectrophotometer (Varian, USA), equipped

with two silicon diode detectors and a xenon flash lamp.

Preparation of the Micelles of PS109-b-P4VP61

PS109-b-P4VP61 was first dissolved in N,N-dimethylformamide

(DMF) and stirred overnight to form the original polymer/DMF

solution with a concentration of 0.1 wt.-%. Subsequently, acidic

water (pH¼ 2) was added to the polymer/DMF solution (�10 mL)

at a rate of 1 drop every 5–10 s with vigorous stirring until

turbidity appeared in the solution, which indicated the occurrence

of aggregates of PS blocks of the block copolymers. The colloid

solutions were vigorously stirred overnight to avoid the appear-

ance of transient morphologies and to eliminate the effect of the

rate of stirring. After that, a five-fold excess of acidicwater (pH¼2)

was rapidly added to the colloid solutions. The resultant colloid

solutions were placed in dialysis bags and dialyzed against acidic

water (pH¼2) for 7 d to remove the DMF and then fixed at a

concentration of 5�10�5 g �mL�1.

Preparation of the Composites

HAuCl4 �3H2O with a mole ratio of 1/1 (Au/4-VP) was added to 5 g

of the above micelle solution, and the mixture was then con-

tinually stirred for at least 24 h. Five grams of PEO114-b-P4VP52solution (pH¼2) with a concentration of 5�10�5 g �mL�1 was

then added. After stirring for another 24 h, a five-fold excess of

NaBH4 was slowly added to the solution and the color gradually

changed from yellow to red. The composite solution was charac-

terized after 7 d.

Results and Discussion

Core-Shell Micelles of PS109-b-P4VP61

As described in the experimental part, the PS109-b-PV4P61micelles are prepared by adding acidic water (pH¼ 2) into

a DMF solution of PS109-b-P4VP61. Water is a selective

solvent for the P4VP block but a precipitant for the PS block

under this condition, thus core-shell micelles with PS chains

as a core and P4VP chains as a shell formwhen acidicwater

is added into the polymer solution. With the continuous

addition of acidic water into the micellar solution and the

subsequent dialysis of the solution against water (pH¼ 2),

the structure of the core-shell micelles is kinetically frozen

in solution. DLS is used to characterize the micelle solution

and the result is shown in Figure 1a. From Figure 1a, one

can determine that the average hydrodynamic diameter of

the micelle is about 70 nm with a distribution range from

40 to 100 nm. A TEM image of the micelles is shown in

Figure 1b, where the micelles show a uniform spherical

morphology and the average diameter is about 33 nmwith

a range from 26 to 40 nm. Obviously, the size of the

micelles shown in the TEM is much smaller than that

measured by DLS. It is likely that the TEM result is obtained

from the dry state of the micelle in which the polymer

www.mrc-journal.de 1351

X. Chen et al.

Figure 1. Hydrodynamic diameter distribution f(Dh) of micelle ofPS-b-P4VP in water (pH¼ 2) (a), and the corresponding TEMimage (b). The Dh measurement was carried out at a scatteringangle of 908 and a temperature of 25 8C. The TEM sample wasprepared by depositing micelle solution onto a carbon-coatedcopper grid and drying at room temperature.

1352

chain has collapsed, while the DLS result shows the

hydrated state of the micelle in which the shell polymer

chain remains swollen or stretched. In addition, the smaller

TEM sizes are also caused by the fact that the P4VP shell

may not have enough contrast to the background to be

detected.

Figure 2. UV-vis absorption spectra recorded (a) before and(b) after using NaBH4 to reduce the mixed solution of PS109-b-P4VP61/PEO125-b-P4VP52/HAuCl4.

Core-Shell-Corona Au-Micelle Composites

It has been reported that core-shell-corona micelles can

be facilely prepared through the interaction between one



diblock copolymer micelle and another different diblock

copolymer. Munk et al. suggested a co-precipitationmethod

to prepare three-layered micelles from two different diblock

copolymers AB and BC.[13] Based on the hydrogen bonding

or electrostatic affinity between two polymers in solution,

we previously reported a facile method to prepare a three-

layered core-shell-corona micellar complex.[13b,13c] In the

present case, the formation of the core-shell-corona struc-

ture is through the attachment of gold nanoparticles to the

P4VP blocks of the PS-b-P4VP micelle and PEO-b-P4VP

copolymers. The core-shell-corona Au-micelle composites

were prepared by using NaBH4 to reduce a mixture solu-

tion comprised of PEO-b-P4VP copolymer, PS-b-P4VP mi-

celle, and tetrachloroauric acid. As NaBH4 was added, the

solution changed from yellow to red, which indicated that

NaBH4 reduced tetrachloroauric acid to Au.[14] UV-vis

spectroscopy was used to detect the formed gold nano-

particle, by a correlation that exists between the position

of the plasmon band and the gold particle.[15] Figure 2

shows the UV spectra of the mixed solution of PS109-b-

P4VP61/PEO125-b-P4VP52/HAuCl4 before and after adding

NaBH4 reductant. The peak that appears at about 520 nm

indicates the formation of a gold particle. The DLS results of

the sample are presented in Figure 3a. Compared with the

results shown in Figure 1a, the Dh value shows two

distributions. One distribution, with a peak value located

at about 140 nm and a range from 100 to 180 nm, may be

ascribed to the composites of PEO-b-P4VP/Au/PS-b-P4VP.

The other distribution with a peak value located at about

30 nmand a range from 20 to 40 nmmay be ascribed to the

composites of Au/PEO-b-P4VP. The TEM image of this

sample presented in Figure 3b shows ring structures.

It should be noted that these ring-like structures are

two-dimension pictures but the Au particles are actually

formed in a spherical shell in three dimensions. These

shapes are very similar to that formed by the covalent

DOI: 10.1002/marc.200700166


Figure 3. Hydrodynamic diameter distribution f(Dh) of Au-micellecomposites formed from micelles of PS-b-P4VP, block copolymerPEO-b-P4VP, and Au (a), and the corresponding TEM image(b), where the insert in (b) is a typical magnification image.The measurement condition was the same as for Figure 1.

attachment of gold nanoparticles to a polylysine backbone

followed by ring closure of polylysine chains,[9] but they

have been formed by a completely differentmechanism. In

the present case, the ring-like composites are considered to

comprise a PS core, a hybrid gold and P4VP middle layer

(inner shell), and a PEO corona. According to the pre-

paration process of the composites, the gold precursor

HAuCl4 was added to a pre-existing PS-b-P4VP core-shell

micelle solution to first complex with the P4VP shell. The

later added PEO-b-P4VP then reacted with the residual

HAuCl4 in the solution. When the reductant NaBH4 was

added, it initially led to the formation of primary gold



atoms that further aggregated to form larger clusters by a

nucleation and growth process.[16] In this process, the gold

cluster or gold nanoparticle formed was simultaneously

adsorbed by P4VP chains of the PS-b-P4VP core-shell

micelles and the PEO-b-P4VP block copolymers, thus, the

hybrid Au-micelle composite with a PS core, a gold/P4VP

inner shell, and a PEO corona was formed. The inner shell

remained in a swollen state since the P4VP chains were

partially ionized under acid conditions (pH¼ 2). The sizes

of the ring or half-ring structures formed are in the range

from 50 to 130 nm and are smaller than those obtained

from the DLS measurement, the possible reason is the

same as discussed above. The PS core was not observed

under TEM, the reason is likely because of the large dif-

ference in contrast between the core and the inner shell.

This is similar to the study reported by Armes et al. In their

experiment the core was also not observed under TEM

when silica was deposited onto the shell of micelles with

hydrophobic poly(2-(diisopropylamino)ethyl methacry-

late) (PDPA) cores and cationic poly(2-(dimethylamino)-

ethyl methacrylate) (PDMA) shells.[17] The small amount of

random aggregates are possibly the hybrids of the gold and

PEO-b-P4VP. The TEM observation results are in reasonable

agreement with the DLS results if polydispersity effects

and the difference of the two measurement methods are

taken into account. A close look at the TEM image shows

that these ring or half-ring structures actually comprise

many gold nanoparticles that range from 3 to 10 nm with

an average diameter of 5 nm (insert in Figure 3b). This is in

good agreement with the UV-vis absorption spectrum of

this sample (Figure 2b), in which an absorbance peak at

520 nm indicates the gold diameter of about 10 nm

or smaller.[18]

In order to confirm the above-mentioned ring structures,

it is necessary to exclude the possibility that the ring is

formed only from Au and core-shell micelles of PS-b-P4VP

or Au and copolymers of PEO-b-P4VP, based on the

components of the system in the preparation process.

For this purpose, two ‘blank’ experiments were performed.

In one experiment, reduction was carried out in the

solution of HAuCl4/PS-b-P4VP based on the same experi-

mental conditions for reducing the HAuCl4 in its mixture

solution with PS-b-P4VP micelles and PEO-b-P4VP chains.

The morphologies of the resultant composites are shown

in Figure 4a. Clearly, many randomly distributed gold

nanoparticles (dark) are on the micelle of PS-b-P4VP (gray)

despite some also arranged on the periphery of the micelle

with a ring-like shape. In addition, the density of the

gold nanoparticle is exiguous in comparison with that in

Figure 3a, which indicates less gold is coated on themicelle

surface. The TEM results in this ‘blank’ experiment are

obviously different from that shown in Figure 3a. The

composite solution is also studied by DLS and the results

are shown in Figure 5. The hydrodynamic diameters of the


X. Chen et al.

Figure 4. TEM images of Au-micelle composites composed of Au/PS-b-P4VP (a), and Au/PEO-b-P4VP (b).

Figure 5. Hydrodynamic diameter distribution f(Dh) of PEO-b-P4VP(~), gold/PEO-b-P4VP (&), and Au-micelle composites formedfrom gold/micelles of PS-b-P4VP (�) in water (pH¼ 2). Themeasurement condition was the same as for Figure 1.

1354

gold-loaded micelles (Figure 5) show two separate

distributions. The first one shows micelles 10 nm smaller

than the pure micelle (Figure 1a), possibly because of the

collapse of the P4VP chain after it complexed with gold.

The second one shows a larger hydrodynamic diameter

than the pure micelles (Figure 1a), which indicates a

micelle cluster is formed in the solution. The DLS results

are matched with the TEM observation shown in Figure 4a

where single micelle and micelle aggregates are seen. The

number distribution from the DLS measurement shows

that the number percent of the single micelle is about 96

and the micelle cluster is about 4. The cluster is most likely

a result of the pyridine units of different micelle shells

complexing with the same gold particles. The phenomena

in the blank experiment reliably indicate that the ring

structure shown in Figure 3 is not produced only from Au

and micelles of PS-b-P4VP.



In the other blank experiment, the composites of PEO-b-

P4VP/Au were examined to further confirm that the ring

structure shown in Figure 3 is the core-shell-coronal

composite formed by gold particles linked to P4VP blocks

of the PEO-b-P4VP chain and of the PS-b-P4VPmicelles. The

PEO-b-P4VP is dissolved in water (pH¼ 2) to form an

aqueous solution with a concentration of 5� 10�5 g �mL�1

and a hydrodynamic diameter of about 8.8 nm (Figure 5),

which shows that PEO-b-P4VP is maintained in a unimer

state. After HAuCl4 (themole ratio of HAuCl4 to 4-VP is 1/1)

is added to fully react with PEO-b-P4VP, NaBH4 is intro-

duced to the mixture solution to reduce HAuCl4 to Au. The

hydrodynamic diameter increases to 58.5 nmwith a broad

size distribution range from 15 to 100 nm (Figure 5), which

indicates that composites of gold and PEO-b-P4VP are

formed. These composites are composed of a core of Au/

P4VP and a corona of PEO as a result of the adsorption of

the P4VP block to Au. The TEM images of the gold/

PEO-b-P4VP composites (Figure 4b) show that the aggre-

gates are random and very different from those shown in

Figure 3b.This result indicates that the ring-like structure

(Figure 3b) is not formed from gold and PEO-b-P4VP.

In addition, experimental results indicate that the Au-

micelle composites with and without PEO-b-P4VP polymer

show very different stabilities. The composite solution

that contains PEO-b-P4VP shows no color change and no

precipitates for about a period of six months. However, the

solution without PEO-b-P4VP changed color from red to

black, and dark aggregates were found in the bottom of

the bottle after a month. The solution was taken out and

observed by TEM. It was found that many holes (bright

part in micelle) had appeared in the micelles and the size

was similar to the gold particles. These holes appeared

presumably because of the escape of the gold particles

DOI: 10.1002/marc.200700166


from themicelles. The aggregates in the bottomof the bottle

could be the products from the collision of the escaped gold

particles. From the above experimental results, we conclude

that composites that have a PS core, a P4VP/Au inner shell,

and a PEO corona can be formed by reducing HAuCl4 in a

mixed solution with PS-b-P4VP micelles and PEO-b-P4VP

copolymers. The reduced Au nanoparticle can be adsorbed

by the P4VP blocks in both the PS-b-P4VP micelle and the

PEO-b-P4VP polymer. This structure greatly enhances the

stability of the hybrid micelles because of the protection

from the PEO-b-P4VP chains.

Conclusion

A novel method has been developed to prepare Au-micelle

composites by in-situ gold nanoparticle formation in an

acidic aqueous solution of core-shell micelle (PS-b-P4VP)

and block copolymers (PEO-b-P4VP) (pH¼ 2). These com-

posites comprise a PS core, a swollen hybrid Au-P4VP inner

shell (formed by the binding of gold to P4VP), and a PEO

corona. TEM observations indicate that the gold nanopar-

ticles show a ring-like arrangement on the composites in a

dry state. These structured composites also show much

higher stability than the core-shell composites with Au

coated on the shell layer of the PS-b-P4VPmicelle because of

the protection provided by PEO-b-P4VP. The composites

could be modified to prepare multifunctional products as a

result of the different chemistry in their core, shell, and

corona. For example, since the outer layer of the gold hybrid

nanoparticle is believed to be biocompatible, it could po-

tentially be used for delivering various water-soluble and

insoluble bioactive agents by an intravenous route.

Acknowledgements: We thank the National Natural ScienceFoundation of China (No. 20474032), Program for New CenturyExcellent Talents in Universities, and the Outstanding Youth Fund(No. 50625310) for financial support.

Received: March 2, 2007; Revised: April 9, 2007; Accepted: April11, 2007; DOI: 10.1002/marc.200700166

Keywords: composites; core-shell-corona; gold; micelles; nano-particles

[1] [1a] K. Akamatsu, M. Kimura, Y. Shibata, S-i. Nakano, D.Miyoshi, H. Nawafune, N. Sugimoto, Nano Lett. 2006, 6,491; [1b] I. Tokareva, S. Minko, J. H. Fendler, E. Hutter, J. Am.Chem. Soc. 2006, 126, 15950; [1c] G. S. Huang, Y.-S. Chen,H.-W. Yeh, Nano Lett. 2006, 6, 2467; [1d] C. Jiang, V. V.



Tsukruk, Adv. Mater. 2006, 18, 829; [1e] M.-C. Daniel, D.Astruc, Chem. Rev. 2004, 104, 293.

[2] [2a] R. F. Service, Science 1996, 271, 920; [2b] S. Sun, P.Mendes, K. Critchley, S. Diegoli, M. Hanwell, S. D. Evans, G. J.Leggett, J. A. Preece, T. H. Richardson, Nano Lett. 2006, 6,345; [2c] C. N. R. Rao, G. U. Kulkarni, P. J. Thomas, P. P.Edwards, Chem. Eur. J. 2002, 8, 29.

[3] [3a] D. V. Leff, L. Brandt, J. R. Heath, Langmuir 1996, 12,4723; [3b] K. Esumi, A. Suzuki, A. Yamahira, K. Torigoe,Langmuir 2000, 16, 2604; [3c] S. Weisbecker, M. V. Merritt,G. M. Whitesides, Langmuir 1996, 12, 3763.

[4] [4a] G. Riess, Prog. Polym. Sci. 2003, 28, 1107; [4b] J.-F. Gohy,Adv. Polym. Sci. 2005, 190, 65; [4c] M. Filali, M. A. R. Meier,U. S. Schubert, J.-F. Gohy, Langmuir 2005, 21, 7995.

[5] [5a] K. H. Bae, S. H. Choi, S. Y. Park, Y. Lee, T. G. Park,Langmuir 2006, 22, 6380; [5b] C.-A. Fustin, C. Colard,M. Filali,P. Guillet, A.-S. Duwez, M. A. R. Meier, U. S. Schubert, J.-F.Gohy, Langmuir 2006, 22, 6690; [5c] K. L. Genson, J. Holz-mueller, C. Jiang, J. Xu, J. D. Gibson, E. R. Zubarev, V. V.Tsukruk, Langmuir 2006, 22, 7011; [5d] T. F. Jaramillo, S.-H.Baeck, B. R. Cuenya, E. W. McFarland, J. Am. Chem. Soc. 2003,125, 7148.

[6] [6a] J. J. Chiu, B. J. Kim, E. J. Kramer, D. J. Pine, J. Am. Chem.Soc. 2005, 127, 5036; [6b] B.-H. Sohn, J.-M. Choi, S. I. Yoo, S.-H.Yun, W.-C. Zin, J. C. Jung, M. Kanehara, T. Hirata, T.Teranishi, J. Am. Chem. Soc. 2003, 125, 6368.

[7] [7a] M. Antonietti, E. Wenz, L. M. Bronstein, M. S. Seregina,Adv. Mater. 1995, 7, 1000; [7b] Y. Kang, T. A. Taton, Angew.Chem. Int. Ed. 2005, 44, 409; [7c] J. P. Spatz, A. Roescher, M.Moller, Adv. Mater. 1996, 8, 337; [7d] A. Roescher, M. Moller,Adv. Mater. 1995, 7, 151; [7e] S. T. Selvan, J. P. Spatz, H.-A.Klok, M. Moller, Adv. Mater. 1998, 10, 132; [7f] R. Djalali, N.Hugenberg, K. Fischer, M. Schmidt, Macromol. Rapid Com-mun. 1999, 20, 44; [7g] L. Bronstein, D. Chernyshov, P.Valetsky, N. Tkachenko, H. Lemmetyinen, J. Hartmann,S. Forster, Langmuir 1999, 15, 83.

[8] D. Suzuki, H. Kawaguchi, Langmuir 2005, 21, 12016.[9] Q. Dai, J. G. Worden, J. Trullinger, Q. Huo, J. Am. Chem. Soc.

2005, 127, 8008.[10] L. Gao, L. Shi, W. Zhang, Y. An, Z. Liu, G. Li, Q. Meng,

Macromolecules 2005, 38, 4548.[11] K. Wu, L. Shi, W. Zhang, Y. An, X. Zhang, Z. Li, X. X. Zhu,

Langmuir 2006, 22, 1474.[12] W. Q. Zhang, L. Q. Shi, Y. L. An, K. Wu, L. C. Gao, Z. Liu, R. J.

Ma, Q. B. Meng, C. J. Zhao, B. L. He,Macromolecules 2004, 37,2924.

[13] [13a] R. M. Talingting, P. Munk, S. E. Webber, Macromol-ecules 1999, 32, 1593; [13b] W. Q. Zhang, L. Q. Shi, L. C. Gao,Y. L. An, K. Wu, Macromol. Rapid Commun. 2005, 26, 1341;[13c] W. Q. Zhang, L. Q. Shi, Z.-J. Miao, K. Wu, Y. L. An,Macromol. Chem. Phys. 2005, 206, 2354.

[14] I. Hussain, M. Brust, A. J. Papworth, A. I. Cooper, Langmuir2003, 19, 4831.

[15] J. P. Wilcoxon, R. L. Williamson, R. Baughman, J. Chem. Phys.1993, 98, 9933.

[16] S. Forster, M. Antonietti, Adv. Mater. 1998, 10, 195.[17] J.-J. Yuan, O. O. Mykhaylyk, A. J. Ryan, S. P. Armes, J. Am.

Chem. Soc. 2007, 129, 1717.[18] J. P. Wilcoxon, J. E. Martin, P. Provencio, J. Chem. Phys. 2001,

115, 998.


Novel Structured Composites Formed from Gold Nanoparticles and Diblock Copolymers

Documents

Transcript of Novel Structured Composites Formed from Gold Nanoparticles and Diblock Copolymers