C O M M U N I C A T I O N S
in an increased tunneling probability. The fullerene arrangements
were separated in most cases by 6-7 nm, a distance that
corresponds to the distance between fullerenes in the previously
described model B (Scheme 1), again confirming the peptide
nanotube structure and its capability to organize the fullerene
deposition.
Supporting Information Available: Additional AFM, STM, and
TEM pictures. This material is available free of charge via the Internet
References
(1) (a) Barth, J. V.; Constantini, G.; Kern, K. Nature 2005, 437, 671. (b) Crespo-
Biel, O.; Jan Ravoo, B.; Reinhoudt, D. N.; Huskens, J. J. Mater. Chem.
2003, 16, 3997. (c) Heath, J. R.; Ratner, M. A. Phys. Today 2003, 56, 43.
(d) Rosi, N. L.; Mirkin, C. A. Chem. ReV. 2005, 105, 1547.
(2) (a) For recent reviews on supramolecular chemistry and self-assembly, see
this special issue: Soft Matter 2009, 5, 1109. (b) Rein, V.; Ulijn, R. V.;
Smith, A. M. Chem. Soc. ReV 2008, 37, 664. (c) Palmer, L. C.; Stupp, S. I.
Acc. Chem. Res. 2008, 41, 1674.
(3) (a) Brea, R. J.; Granja, J. R. In Dekker Encyclopedia of Nanoscience and
Nanotechnology; Schwarz, J. A., Contescu, C. I., Putyera, K, Eds.; Marcel
Dekker: New York, 2004; p 3439. (b) Bong, D. T.; Clark, T. D.; Granja,
J. R.; Ghadiri, M. R. Angew. Chem., Int. Ed. 2001, 40, 988.
(4) (a) Ghadiri, M. R.; Granja, J. R.; Buehler, L. K. Nature 1994, 369, 301.
(b) Granja, J. R.; Ghadiri, M. R. J. Am. Chem. Soc. 1994, 116, 10785. (c)
Dartois, V.; Sanchez-Quesada, J.; Cabezas, E.; Chi, E.; Dubbelde, C.; Dunn,
C.; Gritzen, C.; Weinberger, D.; Granja, J. R.; Ghadiri, M. R.; Parr, T. R.,
Jr. Antimicrob. Agents Chemother. 2005, 49, 3302. (d) Vollmer, M. S.;
Clark, T. D.; Steinem, C.; Ghadiri, M. R. Angew. Chem., Int. Ed. 1999,
38, 1598. (e) Motesharei, K.; Ghadiri, M. R. J. Am. Chem. Soc. 1997, 119,
11306. (f) Couet, J.; Samuel, J. D. J. S.; Kopyshev, A.; Santer, S.; Biesalski,
M. Angew. Chem., Int. Ed. 2005, 44, 3297. (g) Ashkenasy, N.; Horne, W. S.;
Ghadiri, M. R. Small 2006, 2, 99.
(5) (a) Amor´ın, M.; Castedo, L.; Granja, J. R. J. Am. Chem. Soc. 2003, 125,
2844. (b) Amor´ın, M.; Castedo, L.; Granja, J. R. Chem.sEur. J. 2005, 11,
6539. (c) Brea, R. J.; Castedo, L.; Granja, J. R. Chem. Commun. 2007,
3267. (d) Amor´ın, M.; Castedo, L.; Granja, J. R. Chem.sEur. J. 2008, 14,
2100.
Figure 3. (A) Constant-current STM image of self-assembled r,γ-CP-2
on highly ordered pyrolytic graphite, in which two parallel strands ∼1 nm
in height are observed. (B) 3D topographic STM image representative of
the r,γ-CP-1 arrangement to form the observed parallel C60 organization.
(C) Height profile measured along the blue line shown in (A), confirming
the proposed nanotube organization.
(6) (a) Brea, R. J.; Amor´ın, M.; Castedo, L.; Granja, J. R. Angew. Chem., Int.
Ed. 2005, 44, 5710. (b) Brea, R. J.; Castedo, L.; Granja, J. R.; Herranz, M.
In conclusion, we have demonstrated the formation and full
characterization by AFM, STM, and TEM of a new class of peptide
nanotubes from R,γ-CPs. These CPs are able to align the C60
moieties to form 1D fullerene arrangements in which the fullerenes
point outward from the nanotube on both sides (180° orientation)
of the SPN. It is worth noting that the observed structure relies on
the aforementioned design principles in which the formation of the
four nonidentical antiparallel ꢀ-sheet forms per CP-CP hydrogen-
bonding interaction present in the nanotube (Dr, Dγ; Scheme SI-1
in the Supporting Information)12 is restricted and controlled by the
interstrand salt-bridge interactions. This control of the self-assembly
process is able to organize the fullerene deposition to give 1D
structures. As a consequence of this special arrangement, the
fullerenes form two parallel wires separated by an insulating
material, i.e., the peptide nanotube. The precise nanotube register
control demonstrated here opens up opportunities not only for 1D
alignment of other materials but also for other supramolecular
organizations, such as helical. These structure types may have
applications as nanowire components and/or in optical and electronic
devices.
´
A.; Sanchez, L.; Mart´ın, N.; Seitz, W.; Guldi, D. M. Proc. Natl. Acad. Sci.
U.S.A. 2007, 104, 5291. (c) Brea, R. J.; Va´zquez, M. E.; Mosquera, M.;
Castedo, L.; Granja, J. R. J. Am. Chem. Soc. 2007, 129, 1653.
(7) Feng, M.; Lee, J.; Zhao, J.; Yates, J. T., Jr.; Petek, H. J. Am. Chem. Soc.
2007, 129, 12394.
(8) (a) Sa´nchez, L.; Otero, J.; Gallego, J. M.; Miranda, R.; Mart´ın, N. Chem.
ReV. 2009, 109, 2081. (b) Giacalone, F.; Mart´ın, N. Chem. ReV. 2006, 106,
5136. (c) Special issue on supramolecular chemistry of fullerenes, edited
by N. Martin and J.-F.; Nierengarten: Tetrahedron 2006, 62, 1905. (d) The
Chemistry of Fullerenes; Hirsch, A., Ed.; Wiley-VCH: Weinheim, Germany,
2005.
(9) (a) Li, M.; Deng, K.; Lei, S.-B.; Yang, Y.-L.; Wang, T.-S.; Shen, Y.-T.;
Wang, C.-R.; Zeng, Q.-D.; Wang, C. Angew. Chem., Int. Ed. 2008, 47,
6717. (b) Wang, Y.; Yamachika, R.; Wachowiak, A.; Grobis, M.; Crommie,
M.-F. Nat. Mater. 2008, 7, 194. (c) Georgakilas, V.; Pellarini, F.; Prato,
M.; Guldi, D. M.; Melle-Franco, M.; Zerbetto, F. Proc. Natl. Acad. Sci.
U.S.A. 2002, 99, 5075.
(10) (a) Theobal, J. A.; Oxtoby, N. S.; Philips, M. A.; Champness, N. R.; Beton,
P. H. Nature 2003, 424, 1029. (b) Guldi, D. M.; Zerbetto, F.; Georgakilas,
V.; Prato, M. Acc. Chem. Res. 2005, 38, 38.
(11) (a) Okamoto, H.; Nakanishi, T.; Nagai, Y.; Takeda, K.; Obataya, I.; Mihara,
H.; Azehara, H.; Mizutani, W. Jpn. J. Appl. Phys. 2003, 43, 67. (b)
Okamoto, H.; Yamada, T.; Miyazaki, H.; Nakanishi, T.; Takeda, K.; Usui,
K.; Obataya, L.; Mihara, H.; Azehara, H.; Mizutani, W.; Hashimoto, K.;
Yamaguchi, H.; Hirayama, Y. Jpn. J. Appl. Phys. 2005, 44, 8240.
(12) (a) Kobayashi, K.; Granja, J. R.; Ghadiri, M. R. Angew. Chem., Int. Ed.
Engl. 1995, 34, 95. (b) Hartgerink, J. D.; Granja, J. R.; Milligan, R. A.;
Ghadiri, M. R. J. Am. Chem. Soc. 1996, 118, 43. (c) Horne, W. S.;
Ashkenasy, N.; Ghadiri, M. R. Chem.sEur. J. 2005, 11, 1137. (d) Murota,
K.; Sakamoto, S.; Kudo, K. Chem. Lett. 2007, 36, 1070.
Acknowledgment. This work was supported by the Spanish Ministry
of Education and Science and the ERDF [SAF2007-61015 and Consolider
Ingenio 2010 (CSD2007-00006)] and the Xunta de Galicia (GRC2006/
132, PGIDIT06PXIB209018PR, PGIDIT08CSA047209PR, and R2006/
124). The work by J.M.V. and J.L.C. was supported by Grants BFU2007-
62382/BMC from the Spanish MEC (J.M.V.) and S-0505/MAT/0283
from the Madrid Regional Government (J.M.V. and J.L.C.). C.R. and
R.J.B. thank the Spanish MEC for their FPU Fellowships. We also thank
Dr. Carmen Serra (Nanotechnology and Surface Analysis Service at
C.A.C.T.I., University of Vigo) for her help with STM. We also thank
Dowpharma for their kind gift of ENZA enzymes used in the preparation
of D-Boc-γ-Acp-OH.
(13) Hummelen, J.; Knight, B.; LePeq, F.; Wudl, F.; Yao, J. J. Org. Chem.
1995, 60, 532.
(14) (a) Ulijn, R. V.; Smith, A. M. Chem. Soc. ReV. 2008, 37, 664. (b)
Whitehouse, C.; Fang, J.; Aggeli, A.; Bell, M.; Brydson, R.; Fishwick,
C. W. G.; Henderson, J. R.; Knobler, C. M.; Owens, R. W.; Thomson,
N. H.; Smith, D. A.; Boden, N. Angew. Chem., Int. Ed. 2005, 44, 1965.
(15) (a) Ghadiri, M. R.; Granja, J. R.; Milligan, R. A.; McRee, D. E.;
Khazanovich, N. Nature 1993, 366, 324. (b) Khazanovich, N.; Granja, J. R.;
McRee, D. E.; Milligan, R. A.; Ghadiri, M. R. J. Am. Chem. Soc. 1994,
116, 6011.
(16) Horcas, I.; Fernandez, R.; Gomez-Rodriguez, J. M.; Colchero, J.; Gomez-
Herrero, J.; Baro, A. M. ReV. Sci. Instrum. 2007, 78, 013705.
(17) Scheres, S. H. W.; Valle, M.; Nu´n˜ez, R.; Sorzano, C. O. S.; Marabini, R.;
Herman, G. T.; Carazo, J. M. J. Mol. Biol. 2005, 348, 139.
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