Multivalent Assembly of Ultrasmall Nanoparticles: One-, Two-, and Three-Dimensional Architectures of 2 nm Gold Nanoparticles
)
Download citation
437
Views
7
Downloads
26
Crossref
N/A
WoS
24
Scopus
6
CSCD
The assembly of nanoparticles (NPs) into complex structures is a fundamental topic in nanochemistry. Although progress has been made in this respect, the classical treatment of NPs as hard building blocks that lack the ability to anisotropically "bond" to each other limits the construction of more complex assemblies. More importantly, extension of methods of assembly of robust NPs to the assembly of ultrasmall ones with size below 2 nm is still challenging. Here we report the controlled self-assembly of ~2 nm gold NPs into one-dimensional (1D) nanochain, two-dimensional (2D) nanobelt and three-dimensional (3D) nanocomet architectures by kinetically controlling the diffusion of ultrasmall gold NPs with anisotropic surfaces in solution. This process is presumed to allow selective ligand exchange with linkers at different binding sites on the NP surface, and results in "multivalent" interactions between NPs. Different from the assembly of "hard building blocks", our results demonstrate the significance of surface effects for ultrasmall NPs (or clusters) in determining the structure of complex self-assemblies, and suggest the possibility of assembling these "molecule-like" ultrasmall nanocrystals into novel complex materials on a nanoscale approaching that of real atoms or molecules.
menu
Multivalent Assembly of Ultrasmall Nanoparticles: One-, Two-, and Three-Dimensional Architectures of 2 nm Gold Nanoparticles
)
Abstract
The assembly of nanoparticles (NPs) into complex structures is a fundamental topic in nanochemistry. Although progress has been made in this respect, the classical treatment of NPs as hard building blocks that lack the ability to anisotropically "bond" to each other limits the construction of more complex assemblies. More importantly, extension of methods of assembly of robust NPs to the assembly of ultrasmall ones with size below 2 nm is still challenging. Here we report the controlled self-assembly of ~2 nm gold NPs into one-dimensional (1D) nanochain, two-dimensional (2D) nanobelt and three-dimensional (3D) nanocomet architectures by kinetically controlling the diffusion of ultrasmall gold NPs with anisotropic surfaces in solution. This process is presumed to allow selective ligand exchange with linkers at different binding sites on the NP surface, and results in "multivalent" interactions between NPs. Different from the assembly of "hard building blocks", our results demonstrate the significance of surface effects for ultrasmall NPs (or clusters) in determining the structure of complex self-assemblies, and suggest the possibility of assembling these "molecule-like" ultrasmall nanocrystals into novel complex materials on a nanoscale approaching that of real atoms or molecules.
References(28)
Rosi, N. L.; Mirkin, C. A. Nanostructures in biodiagnostics. Chem. Rev. 2005, 105, 1547–1562.
Murray, C. B.; Kagan, C. R.; Bawendi, M. G. Self-organization of CdSe nanocrystallites into three-dimensional quantum dot superlattices. Science 1995, 270, 1335–1338.
Wang, D. S.; Xie, T.; Li, Y. D. Nanocrystals: Solution-based synthesis and applications as nanocatalysts. Nano Res. 2009, 2, 30–46.
Tang, Z. Y.; Zhang, Z. L.; Wang, Y.; Glotzer, S. C.; Kotov, N. A. Self-assembly of CdTe nanocrystals into free-floating sheets. Science 2006, 314, 274–278.
Bai, F.; Wang, D. S.; Huo, Z. Y.; Chen, W.; Liu, L. P.; Liang, X.; Chen, C.; Wang, X.; Peng, Q.; Li, Y. D. A versatile bottom-up assembly approach to colloidal spheres from nanocrystals. Angew. Chem. Int. Ed. 2007, 46, 6650–6653.
Murray, C. B.; Kagan, C. R.; Bawendi, M. G. Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu. Rev. Mater. Sci. 2000, 30, 545–610.
Eldridge, M. D.; Madden, P. A.; Frenkel, D. Entropy-driven formation of a superlattice in a hard-sphere binary mixture. Nature 1993, 365, 35–37.
Xu, X. X.; Wang, X. Fine tuning of the sizes and phases of ZrO2 nanocrystals. Nano Res. 2009, 2, 891–902.
DeVries, G. A.; Brunnbauer, M.; Hu, Y.; Jackson, A. M.; Long, B.; Neltner, B. T.; Uzun, O.; Wunsch, B. H. Stellacci, F. Divalent metal nanoparticles. Science 2007, 315, 358–361.
Perepichka, D. F.; Rosei, F. Metal nanoparticles: From "artificial atoms" to "artificial molecules". Angew. Chem. Int. Ed. 2007, 46, 6006–6008.
Mucic, R. C.; Storhoff, J. J.; Mirkin, C. A.; Letsinger, R. L. DNA-directed synthesis of binary nanoparticle network materials. J. Am. Chem. Soc. 1998, 120, 12674–12675.
Häkkinen, H.; Barnett, R. N.; Landman, U. Electronic structure of passivated Au38(SCH3)24 nanocrystal. Phys. Rev. Lett. 1999, 82, 3264–3267.
Donkers, R. L.; Song, Y.; Murray, R. W. Substituent effects on the exchange dynamics of ligands on 1.6 nm diameter gold nanoparticles. Langmuir 2004, 20, 4703–4707.
Guo, R.; Song, Y.; Wang, G. L.; Murray, R. W. Does core size matter in the kinetics of ligand exchanges of monolayer-protected Au clusters? J. Am. Chem. Soc. 2005, 127, 2752–2757.
Song, Y.; Murray, R. W. Dynamics and extent of ligand exchange depend on electronic charge of metal nanoparticles. J. Am. Chem. Soc. 2002, 124, 7096–7102.
Rapino, S.; Zerbetto, F. Dynamics of thiolate chains on a gold nanoparticle. Small 2007, 3, 386–388.
Jin, R. C. Quantum sized, thiolate-protected gold nanoclusters. Nanoscale 2010, 2, 343–362.
Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R. Synthesis of thiol-derivatized gold nanoparticles in a two-phase liquid-liquid system. J. Chem. Soc. , Chem. Commun. 1994, 7, 801–802.
Kalsin, A. M.; Fialkowski, M.; Paszewski, M.; Smoukov, S. K.; Bishop, K. J. M.; Grzybowski, B. A. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 2006, 312, 420–424.
Kalsin, A. M.; Grzybowski, B. A. Controlling the growth of "ionic" nanoparticle supracrystals. Nano Lett. 2007, 7, 1018–1021.
Briñas, R. P.; Hu, M. H.; Qian, L. P.; Lymar, E. S.; Hainfeld, J. F. Gold nanoparticle size controlled by polymeric Au(Ⅰ) thiolate precursor size. J. Am. Chem. Soc. 2008, 130, 975–982.
Corbierre, M. K.; Lennox, R. B. Preparation of thiol-capped gold nanoparticles by chemical reduction of soluble Au(Ⅰ)-thiolates. Chem. Mater. 2005, 17, 5691–5696.
Corthey, G.; Giovanetti, L. J.; Ramallo-López, J. M.; Zelaya, E.; Rubert, A. A.; Benitez, G. A.; Requejo, F. G.; Fonticelli, M. H.; Salvarezza, R. C. Synthesis and characterization of gold@gold(I)–thiomalate core@shell nanoparticles. ACS Nano 2010, 4, 3413–3421.
Wu, Z. K.; MacDonald, M. A.; Chen, J.; Zhang, P.; Jin, R. C. Kinetic control and thermodynamic selection in the synthesis of atomically precise gold nanoclusters. J. Am. Chem. Soc. 2011, 133, 9670–9673.
Lin, J. Q.; Zhang, H. W.; Chen, Z.; Zheng, Y. G.; Zhang, Z. Q.; Ye, H. F. Simulation study of aggregations of monolayer-protected gold nanoparticles in solvents. J. Phys. Chem. C 2011, 115, 18991–18998.
Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; Kornberg, R. D. Structure of a thiol monolayer-protected gold nanoparticle at 1.1 Å resolution. Science 2007, 318, 430–433.
Jiang, D. E.; Tiago, M. L.; Luo, W. D.; Dai, S. The "staple" motif: A key to stability of thiolate-protected gold nano-clusters. J. Am. Chem. Soc. 2008, 130, 2777–2779.
Zhou, C.; Sun, C.; Yu, M. X.; Qin, Y. P.; Wang, J. G.; Kim, M.; Zheng, J. Luminescent gold nanoparticles with mixed valence states generated from dissociation of polymeric Au(Ⅰ) thiolates. J. Phys. Chem. C 2010, 114, 7727–7732.
Publication history
Copyright
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 91127040 and 20921001), and the State Key Project of Fundamental Research for Nanoscience and Nanotechnology (No. 2011CB932402).
FEEDBACK 
TOP