10.1002/anie.201800673
Angewandte Chemie International Edition
COMMUNICATION
[10] G. A. DeVries, M. Brunnbauer, Y. Hu, A. M. Jackson, B. Long, B. T.
Neltner, O. Uzun, B. H. Wunsch, F. Stellacci, Science 2007, 315, 358–
361.
co-adsorption onto gold nanoparticles (Supporting Information,
Section 7). The results of these studies showed that whereas
the dependence of χ on θ was particularly weak for the 1/2
combination (most likely because of two positive charges and
consequently strong electrostatic interactions involving 1), the
phenomenon was general and applicable to different charged
groups (e.g., pyridinium and tetraalkylammonium) and ligand
lengths.
[11] H. Kim, R. P. Carney, J. Reguera, Q. K. Ong, X. Liu, F. Stellacci, Adv.
Mater. 2012, 24, 3857–3863.
[12] S. Borsley, E. R. Kay, Chem. Commun. 2016, 52, 9117–9120.
[13] T. Moldt, D. Brete, D. Przyrembel, S. Das, J. R. Goldman, P. K. Kundu,
C. Gahl, R. Klajn, M. Weinelet, Langmuir 2015, 31, 1048–1057.
[14] P. K. Kundu, S. Das, J. Ahrens, R. Klajn, Nanoscale 2016, 8, 19280–
19286.
In sum, we found that co-adsorption of a positively charged
viologen-based ligand and a zwitterionic sulfobetaine ligand onto
metallic nanoparticles can favor a narrow range of molar ratios
of these two ligands on the functionalized particles. Molecular
dynamics simulations revealed that this result could be attributed
to attractive electrostatic interactions between the two ligands
upon adsorption onto the NPs. Additional studies involving other
charged thiols showed that the phenomenon is general and not
limited to viologen- / sulfobetaine-based ligands. Interestingly,
our results are complementary to those of Bishop of co-workers,
who found that co-adsorption of ligands exhibiting repulsive
interactions (polar and nonpolar) favors the formation of “Janus”
NPs decorated with single-component patches of each ligand.[40]
[15] J. F. Hicks, F. P. Zamborini, A. Osisek, R. W. Murray, J. Am. Chem.
Soc. 2001, 123, 7048–7053.
[16] C. A. Simpson, A. C. Agrawal, A. Balinski, K. M. Harkness, D. E. Cliffel,
ACS Nano 2011, 5, 3577–3584.
[17] S. M. Bradford, E. A. Fisher, M.-V. Meli, Langmuir 2016, 32, 9790–9796.
[18] A. M. Kalsin, B. Kowalczyk, P. Wesson, M. Paszewski, B. A.
Grzybowski, J. Am. Chem. Soc. 2007, 129, 6664–6665.
[19] M. Sologan, C. Cantarutti, S. Bidoggia, S. Polizzi, P. Pengo, L.
Pasquato, Faraday Discuss. 2016, 191, 527–543.
[20] H. Choo, E. Cutler, Y. S. Shon, Langmuir 2003, 19, 8555–8559.
[21] R. S. Ingram, M. J. Hostetler, R. W. Murray, J. Am. Chem. Soc. 1997,
119, 9175–9178.
[22] A. M. Smith, L. E. Marbella, K. A. Johnston, M. J. Hartmann, S. E.
Crawford, L. M. Kozycz, D. S. Seferos, J. E. Millstone, Anal. Chem.
2015, 87, 2771–2778.
Our results are important in the context of attaining
a
fundamental understanding of self-assembly on nanostructured
and planar surfaces as well as self-assembly in solution[41] and
they pave the way towards developing novel redox-responsive
nanomaterials.
[23] A. Manna, P. L. Chen, H. Akiyama, T. X. Wei, K. Tamada, W. Knoll,
Chem. Mater. 2003, 15, 20–28.
[24] R. Klajn, K. J. M. Bishop, B. A. Grzybowski, Proc. Natl. Acad. Sci. USA
2007, 104, 10305–10309.
[25] C. Raimondo, F. Reinders, U. Soydaner, M. Mayor, P. Samori, Chem.
Commun. 2010, 46, 1147–1149.
[26] D. B. Liu, W. W. Chen, K. Sun, K. Deng, W. Zhang, Z. Wang, X. Y.
Jiang, Angew. Chem. Int. Ed. 2011, 50, 4103–4107.
Acknowledgements
[27] D. Manna, T. Udayabhaskararao, H. Zhao, R. Klajn, Angew. Chem. Int.
Ed. 2015, 54, 12394–12397.
This work was supported by the European Research Council
(grant #336080 to R.K.), the Israel Ministry of Science (China–
Israel cooperation, grant 3-13555 to R.K.), and the NSF
(Division of Materials Research, grant #1506886 to P.K.). Z.C.
acknowledges support from the Planning and Budgeting
Committee of the Council for Higher Education, the Koshland
Foundation, and a McDonald-Leapman grant. We gratefully
acknowledge Dr. Liat Avram and Dr. Tong Bian for their
assistance with NMR experiments and gel electrophoresis,
respectively.
[28] H. B. He, M. Feng, Q. D. Chen, X. Q. Zhang, H. B. Zhan, Angew. Chem.
Int. Ed. 2016, 55, 936–940.
[29] R. Klajn, L. Fang, A. Coskun, M. A. Olson, P. J. Wesson, J. F. Stoddart,
B. A. Grzybowski, J. Am. Chem. Soc. 2009, 131, 4233–4235.
[30] M. A. Olson, A. Coskun, R. Klajn, L. Fang, S. K. Dey, K. P. Browne, B.
A. Grzybowski, J. F. Stoddart, Nano Lett. 2009, 9, 3185–3190.
[31] J. G. Weers, J. F. Rathman, F. U. Axe, C. A. Crichlow, L. D. Foland, D.
R. Scheuing, R. J. Wiersema, A. G. Zielske, Langmuir 1991, 7, 854–
867.
[32] Z. L. Chu, Y. J. Feng, Langmuir 2012, 28, 1175-1181.
[33] L. E. Marbella, J. E. Millstone, Chem. Mater. 2015, 27, 2721–2739.
[34] A. Badia, W. Gao, S. Singh, L. Demers, L. Cuccia, L. Reven, Langmuir
1996, 12, 1262–1269.
Keywords: Nanoparticles • Surface chemistry • Ligand
exchange • Supramolecular chemistry • Self-assembly
[35] A. C. Templeton, S. W. Chen, S. M. Gross, R. W. Murray, Langmuir
1999, 15, 66–76.
[36] B. S. Zelakiewicz, A. C. de Dios, Y. Y. Tong, J. Am. Chem. Soc. 2003,
125, 18–19.
[1]
[2]
E. S. Cho, J. Kim, B. Tejerina, T. M. Hermans, H. Jiang, H. Nakanishi,
M. Yu, A. Z. Patashinski, S. C. Glotzer, F. Stellacci, B. A. Grzybowski,
Nat. Mater. 2012, 11, 978–985.
[37] M. P. Rowe, K. E. Plass, K. Kim, C. Kurdak, E. T. Zellers, A. J. Matzger,
Chem. Mater. 2004, 16, 3513–3517.
S. Yapar, M. Oikonomou, A. H. Velders, S. Kubik, Chem. Commun.
2015, 51, 14247–14250.
[38] H. Y. Zhou, X. Li, A. Lemoff, B. Zhang, B. Yan, Analyst 2010, 135,
1210–1213.
[3]
[4]
G. F. Wang, H. Y. Park, R. J. Lipert, Anal. Chem. 2009, 81, 9643–9650.
M. Gellner, K. Kompe, S. Schlucker, Anal. Bioanal. Chem. 2009, 394,
1839–1844.
[39] E. A. Fisher, S. J. Duffy, M. V. Meli, RSC Adv. 2015, 5, 33289–33293.
[40] D. M. Andala, S. H. R. Shin, H.-Y. Lee, K. J. M. Bishop, ACS Nano
2012, 6, 1044–1050.
[5]
M. Moreno, F. J. Ibanez, J. B. Jasinski, F. P. Zamborini, J. Am. Chem.
Soc. 2011, 133, 4389–4397.
[41] E. W. Kaler, K. L. Herrington, A. Kamalakara Murthy, J. A. N.
Zasadzinski, J. Phys. Chem. 1992, 96, 6698–6707.
[6]
[7]
[8]
[9]
G. Pieters, L. J. Prins, New J. Chem. 2012, 36, 1931–1939.
A. Verma, F. Stellacci, Small 2010, 6, 12–21.
M. Zheng, X. Y. Huang, J. Am. Chem. Soc. 2004, 126, 12047–12054.
X. S. Liu, H. Li, Q. Jin, J. Ji, Small 2014, 10, 4230–4242.
This article is protected by copyright. All rights reserved.