Citation: Zhu Kangning, Zhu Zhiyuan, Zhou Haiou, Zhang Jingyan, Liu Shiyong. Precisely installing gold nanoparticles at the core/shell interface of micellar assemblies of triblock copolymers[J]. Chinese Chemical Letters, ;2017, 28(6): 1276-1284. doi: 10.1016/j.cclet.2017.03.020 shu

Precisely installing gold nanoparticles at the core/shell interface of micellar assemblies of triblock copolymers

a.
CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, iChem(Collaborative Innovation Center of Chemistry for Energy Materials), Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
b.
School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei 230022, China

Corresponding author: Zhang Jingyan, zhangjy8@mail.ustc.edu.cn Liu Shiyong, sliu@ustc.edu.cn
Received Date: 8 February 2017
Revised Date: 28 February 2017
Accepted Date: 10 March 2017
Available Online: 16 June 2017

Figures(8)

Two reduction-cleavable ABA triblock copolymers possessing two disulfide linkages, PMMA-ss-PMEO₃MA-ss-PMMA and PDEA-ss-PEO-ss-PDEA were synthesized via facile substitution reactions from homopolymer precursors, where PMMA, PMEO₃MA, PDEA, and PEO represent poly(methyl methacrylate), poly(tri(ethylene glycol) monomethyl ether methacrylate, poly(2-(diethylamino)ethyl methacrylate), and poly(ethylene oxide), respectively. Spherical micelles were obtained through supramolecular self-assembly of these two triblock copolymers in aqueous solutions. The resultant micelles with abundant disulfide bonds could serve as soft templates and precisely accommodate gold nanoparticles in the core/shell interface as a result of the formation of Au-S bonds.
- Triblock copolymer,
- Disulfide bond,
- Self-assembly,
- Gold nanoparticle,
- Core/shell interface
1. [1]
  Daniel M.C., Astruc D.. Gold nanoparticles:assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology catalysis, and nanotechnology[J]. Chem. Rev., 2004,104:293-346. doi: 10.1021/cr030698+
2. [2]
  Shan J., Tenhu H.. Recent advances in polymer protected gold nanoparticles:synthesis, properties and applications[J]. Chem. Commun., 2007:4580-4598.
3. [3]
  Tam J.M., Tam J.O., Murthy A., Ingram D.R., Ma L.L., Travis K., Johnston K.P., Sokolov K.V.. Controlled assembly of biodegradable plasmonic nanoclusters for near-infrared imaging and therapeutic applications[J]. ACS Nano, 2010,4:2178-2184. doi: 10.1021/nn9015746
4. [4]
  Huang Y.F., Xia K., He N.Y., Lu Z.X., Zhang L.M., Deng Y., Nie L.B.. Size-tunable synthesis of gold nanorods using pyrogallol as a reducing agent[J]. Sci. China Chem., 2015,58:1759-1765. doi: 10.1007/s11426-015-5437-3
5. [5]
  Zu X.H., Jian Z.H., Yi G.B., Huang H.L., Zhong B.B., Luo H.S., Huang J.R., Wang C.. Surface-enhanced Raman scattering effect of ordered gold nanoparticle array for rhodamine B with different morphologies[J]. Chin. J. Polym. Sci., 2015,33:1470-1476. doi: 10.1007/s10118-015-1690-3
6. [6]
  Mashhadizadeh M.H., Talemi R.P.. Application of diazo-thiourea and gold nano-particles in the design of a highly sensitive and selective DNA biosensor[J]. Chin. Chem. Lett., 2015,26:160-166. doi: 10.1016/j.cclet.2014.09.004
7. [7]
  Filali M., Meier M.A.R., Schubert U.S., Gohy J.F.. Star-block copolymers as templates for the preparation of stable gold nanoparticles[J]. Langmuir, 2005,21:7995-8000. doi: 10.1021/la050377o
8. [8]
  Li J.B., Shi L.Q., An Y.L., Li Y., Chen X., Dong H.J.. Reverse micelles of star-block copolymer as nanoreactors for preparation of gold nanoparticles[J]. Polymer, 2006,47:8480-8487. doi: 10.1016/j.polymer.2006.09.071
9. [9]
  Zhao F., Li L., Tian Y.C., Liu J.J., Wang J.J., Zhou Z.M., Lv C.X., Guo X.H.. Preparation of Au/Ag multilayers via layer-by-layer self-assembly in spherical polyelectrolyte brushes and their catalytic activity[J]. Chin. J. Polym. Sci., 2015,33:1421-1430. doi: 10.1007/s10118-015-1700-5
10. [10]
  Sakai T., Alexandridis P.. Size-and shape-controlled synthesis of colloidal gold through autoreduction of the auric cation by poly(ethylene oxide)-poly (propylene oxide) block copolymers in aqueous solutions at ambient conditions[J]. Nanotechnology, 2005,14:S344-S353.
11. [11]
  Sakai T., Alexandridis P.. Ag and au monometallic and bimetallic colloids:morphogenesis in amphiphilic block copolymer solutions[J]. Chem. Mater., 2006,18:2577-2583. doi: 10.1021/cm051757y
12. [12]
  Chen X., Liu Y., An Y., Lu J., Li J., Xiong D., Shi L.. Novel structured composites formed from gold nanopartnocles and diblock copolymers[J]. Macromol. Rapid Commun., 2007,28:1350-1355. doi: 10.1002/(ISSN)1521-3927
13. [13]
  Xu H.X., Xu J., Jiang X.Z., Zhu Z.Y., Rao J.Y., Yin J., Wu T., Liu H.W., Liu S.Y.. Thermosensitive unimolecular micelles surface-decorated with gold nanoparticles of tunable spatial distribution[J]. Chem. Mater., 2007,19:2489-2494. doi: 10.1021/cm070088g
14. [14]
  Lee W.R., Kim M.G., Choi J.R., Park J.I., Ko S.J., Oh S.J., Cheon J.. Redox-transmetalation process as a generalized synthetic strategy for core-shell magnetic nanoparticles[J]. J. Am. Chem. Soc., 2005,127:16090-16097. doi: 10.1021/ja053659j
15. [15]
  Zhao W.R., Gu J.L., Zhang L.X., Chen H.R., Shi J.L.. Fabrication of uniform magnetic nanocomposite spheres with a magnetic core/mesoporous silica shell structure[J]. J. Am. Chem. Soc., 2005,127:8916-8917. doi: 10.1021/ja051113r
16. [16]
  Wang L.Y., Luo J., Fan Q., Suzuki M., Suzuki I.S., Engelhard M.H., Lin Y.H., Kim N., Wang J.Q., Zhong C.J.. Monodispersed core-shell Fe₃O₄@Au nanoparticles[J]. J. Phys. Chem. B, 2005,109:21593-21601. doi: 10.1021/jp0543429
17. [17]
  Kobayashi H., Yamauchi M., Kitagawa H., Kubota Y., Kato K., Takata M.. Hydrogen absorption in the core/shell interface of Pd/Pt nanoparticles[J]. J. Am. Chem. Soc., 2008,1301818. doi: 10.1021/ja078126k
18. [18]
  Klaikherd A., Ghosh S., Thayumanavan S.. A facile method for the synthesis of cleavable block copolymers from ATRP-based homopolymers[J]. Macromolecules, 2007,40:8518-8520. doi: 10.1021/ma071852n
19. [19]
  Satoh K., Lee D.H., Nagai K., Kamigaito M.. Precision synthesis of bio-based acrylic thermoplastic elastomer by RAFT polymerization of itaconic acid derivatives[J]. Macromol. Rapid Commun., 2014,35:161-167. doi: 10.1002/marc.201300638
20. [20]
  Zhang H., Tong X., Zhao Y.. Diverse thermoresponsive behaviors of uncharged UCST block copolymer micelles in physiological medium[J]. Langmuir, 2014,30:11433-11441. doi: 10.1021/la5026334
21. [21]
  Pham T., Jackson J.B., Halas N.J., Lee T.R.. Preparation and characterization of gold nanoshells coated with self-assembled monolayers[J]. Langmuir, 2002,18:4915-4920. doi: 10.1021/la015561y
22. [22]
  Ge Z., Liu S.. Functional block copolymer assemblies responsive to tumor and intracellular microenvironments for site-specific drug delivery and enhanced imaging performance[J]. Chem. Soc. Rev., 2013,42:7289-7325. doi: 10.1039/c3cs60048c
23. [23]
  Liu H.H., Tang D.D., Tang R.P., Zhao Y.L.. Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP, RAFT and ATRP processes[J]. Sci. China Chem., 2015,58:1724-1733. doi: 10.1007/s11426-015-5436-4
24. [24]
  Tang W., He J., Yang Y.. A facile synthesis of cleavable block copolymers via tandem polymerizations of NMRP and ATRP[J]. J. Macromol. Sci. A, 2006,43:1553-1567. doi: 10.1080/10601320600896850
25. [25]
  Goldbach J.T., Russell T.P., Penelle J.. Synthesis and thin film characterization of poly(styrene-block-methyl methacrylate) containing an anthracene dimer photocleavable junction point[J]. Macromolecules, 2002,35:4271-4276. doi: 10.1021/ma011940m
26. [26]
  Lee M.H., Yang Z., Lim C.W., Lee Y.H., Dongbang S., Kang C., Kim J.S.. Disulfidecleavage-triggered chemosensors and their biological applications[J]. Chem. Rev., 2013,113:5071-5109. doi: 10.1021/cr300358b
27. [27]
  Jiang Y., Liu G., Wang X., Hu J., Zhang G., Liu S.. Cytosol-specific fluorogenic reactions for visualizing intracellular disintegration of responsive polymeric nanocarriers and triggered drug release[J]. Macromolecules, 2015,48:764-774. doi: 10.1021/ma502389w
28. [28]
  Hu J., Wang X., Qian Y., Yu Y., Jiang Y., Zhang G., Liu S.. Cytoplasmic reactive cationic amphiphiles for efficient intracellular delivery and self-reporting smart release[J]. Macromolecules, 2015,48:5959-5968. doi: 10.1021/acs.macromol.5b01110
29. [29]
  Hu X., Liu G., Li Y., Wang X., Liu S.. Cell-penetrating hyperbranched polyprodrug amphiphiles for synergistic reductive milieu-triggered drug release and enhanced magnetic resonance signals[J]. J. Am. Chem. Soc., 2015,137:362-368. doi: 10.1021/ja5105848
30. [30]
  Song J., Cheng L., Liu A., Yin J., Kuang M., Duan H.. Plasmonic vesicles of amphiphilic gold nanocrystals:self-assembly and external-stimuli-triggered destruction[J]. J. Am. Chem. Soc., 2011,133:10760-10763. doi: 10.1021/ja204387w
31. [31]
  Hu J., Wu T., Zhang G., Liu S.. Efficient synthesis of single gold nanoparticle hybrid amphiphilic triblock copolymers and their controlled self-assembly[J]. J. Am. Chem. Soc., 2012,134:7624-7627. doi: 10.1021/ja302019q
32. [32]
  Mai Y., Xiao L., Eisenberg A.. Morphological control in aggregates of amphiphilic cylindrical metal-polymer brushes[J]. Macromolecules, 2013,46:3183-3189. doi: 10.1021/ma400236g
33. [33]
  Deng H., Zhong Y., Du M., Liu Q., Fan Z., Dai F., Zhang X.. Theranostic selfassembly structure of gold nanoparticles for NIR photothermal therapy and XRay computed tomography imaging[J]. Theranostics, 2014,4:904-918. doi: 10.7150/thno.9448
34. [34]
  Yi S.L., Li M.C., Hu X.Q., Mo W.M., Shen Z.L.. An efficient and convenient method for the preparation of disulfides from thiols using oxygen as oxidant catalyzed by tert-butyl nitrite[J]. Chin. Chem. Lett., 2016,27:1505-1508. doi: 10.1016/j.cclet.2016.03.016
35. [35]
  Mai Y., Eisenberg A.. Self-assembly of block copolymers[J]. Chem. Soc. Rev., 2012,41:5969-5985. doi: 10.1039/c2cs35115c
36. [36]
  Chu J., Lv Q.L., Guo C.L., Xu D.Z., Wang K., Liu M.Y., Huang H.Y., Zhang X.Y., Wei Y.. One-step preparation of branched PEG functionalized AIE-active luminescent polymeric nanoprobes[J]. Sci. China Chem., 2016,59:1003-1009. doi: 10.1007/s11426-016-5578-z
37. [37]
  Wang C.Y., Yuan Q., Yang S.G., Xu J.. Effect of water content on the size and membrane thickness of polystyrene-block-poly(ethylene oxide) vesicles[J]. Chin. J. Polym. Sci., 2015,33:661-668. doi: 10.1007/s10118-015-1618-y
38. [38]
  Chen J.C., Li J.Z., Liu J.H., Xu L.Q.. Amphiphilic poly(ethylene glycol)-b-poly (ethylene brassylate) copolymers:one-pot synthesis, self-assembly, and controlled drug release[J]. Chin. Chem. Lett., 2015,26:1319-1321. doi: 10.1016/j.cclet.2015.05.050
39. [39]
  Wei R.B., Wang X.G., He Y.N.. Synthesis, self-assembly and photo-responsive behavior of AB(2) shaped amphiphilic azo block copolymer[J]. Chin. Chem. Lett., 2015,26:857-861. doi: 10.1016/j.cclet.2015.04.019
40. [40]
  Ge Z., Xie D., Chen D., Jiang X., Zhang Y., Liu H., Liu S.. Stimuli-Responsive double hydrophilic block copolymer micelles with switchable catalytic activity[J]. Macromolecules, 2007,40:3538-3546. doi: 10.1021/ma070550i
41. [41]
  Xiao J.J., Li X.B., Wang X., Yi C.W., Su S.P.. Effect of temperature-responsive solution behavior of PNIPAM-b-PPEOMA-b-PNIPAM on its inclusion complexation with alpha-cyclodextrin[J]. Chin. J. Polym. Sci., 2015,33:456-464. doi: 10.1007/s10118-015-1598-y
42. [42]
  Huang H., Remsen E.E., Kowalewski T., Wooley K.L.. Nanocages derived from shell cross-linked micelle templates[J]. J. Am. Chem. Soc., 1999,121:3805-3806. doi: 10.1021/ja983610w
43. [43]
  Lutz J.-F.. Polymerization of oligo(ethylene glycol) (meth)acrylates:toward newgenerations of smart biocompatible materials[J]. J. Polym. Sci. Part A:Polym. Chem., 2008,46:3459-3470. doi: 10.1002/(ISSN)1099-0518
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