Journal of the American Chemical Society
Communication
To exploit the versatility of 1 and to explore the scope of this
PSM methodology, we prepared 3, a succinimide-modified
version of 1 that is ideal for coupling to primary amines, such as
those at the N-terminus of peptides. Reaction of 3 with N3-bio-
MOF-100 yields the succinimide-decorated product MOF.
Soaking this MOF in a solution of di-L-phenylalanine, a bulky
dipeptide, yields Phe2-bio-MOF-100 with di-L-phenylalanine
peptides anchored to its channel walls (Figure 3; section 8 of
REFERENCES
■
(1) The diverse chemistry of MOFs is detailed in various reviews
within the following special issues: (a) Long, J. R.; Yaghi, O. M. Chem.
Soc. Rev. 2009, 38, 1213. (b) Zhou, H. C.; Long, J. R.; Yaghi, O. M.
Chem. Rev. 2012, 112, 673.
(2) Cohen, S. M. Chem. Rev. 2012, 112, 970.
(3) (a) Fang, Q.-R.; Makal, T. A.; Young, M. D.; Zhou, H.-C.
Comments Inorg. Chem. 2010, 31, 165. (b) Xuan, W.; Zhu, C.; Liu, Y.;
Cui, Y. Chem. Soc. Rev. 2012, 41, 1677.
(4) (a) Suzuki, K.; Kawano, M.; Sato, S.; Fujita, M. J. Am. Chem. Soc.
2007, 129, 10652. (b) Deng, H.; Grunder, S.; Cordova, K. E.; Valente,
C.; Furukawa, H.; Hmadeh, M.; Gandara, F.; Whalley, A. C.; Liu, Z.;
Asahina, S.; Kazumori, H.; O’Keeffe, M.; Terasaki, O.; Stoddart, J. F.;
Yaghi, O. M. Science 2012, 336, 1018.
(5) (a) Huisgen, R. Angew. Chem., Int. Ed. Engl. 1963, 2, 565.
(b) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.
Angew. Chem., Int. Ed. 2002, 41, 2596. (c) Tornøe, C. W.; Christensen,
C.; Meldal, M. J. Org. Chem. 2002, 67, 3057. (d) Goto, Y.; Sato, H.;
Shinkai, S.; Sada, K. J. Am. Chem. Soc. 2008, 130, 14354. (e) Gadzikwa,
T.; Lu, G.; Stern, C. L.; Wilson, S. R.; Hupp, J. T.; Nguyen, S. T. Chem.
Commun. 2008, 5493. (f) Savonnet, M.; Bazer-Bachi, D.; Bats, N.;
Perez-Pellitero, J.; Jeanneau, E.; Lecocq, V.; Pinel, C.; Farrusseng, D. J.
Am. Chem. Soc. 2010, 132, 4518.
(6) (a) Wang, Z. C.; Cohen, S. M. J. Am. Chem. Soc. 2007, 129,
12368. (b) Ingleson, M. J.; Barrio, J. P.; Guilbaud, J. B.; Khimyak, Y.
Z.; Rosseinsky, M. J. Chem. Commun. 2008, 2680. (c) Morris, W.;
Doonan, C. J.; Furukawa, H.; Banerjee, R.; Yaghi, O. M. J. Am. Chem.
Soc. 2008, 130, 12626. (d) Savonnet, M.; Aguado, S.; Ravon, U.;
Bazer-Bachi, D.; Lecocq, V.; Bats, N.; Pinel, C.; Farrusseng, D. Green
Chem. 2009, 11, 1729.
(7) (a) Deshpande, R. K.; Minnaar, J. L.; Telfer, S. G. A Angew.
Chem., Int. Ed. 2010, 49, 4598. (b) Deshpande, R. K.; Waterhouse, G.
I.; Jameson, G. B.; Telfer, S. G. Chem. Commun. 2012, 48, 1574.
(c) Tanabe, K. K.; Allen, C. A.; Cohen, S. M. Angew. Chem., Int. Ed.
2010, 49, 9730.
(8) (a) Chen, C.; Allen, C. A.; Cohen, S. M. Inorg. Chem. 2011, 50,
10534. (b) Roy, P.; Schaate, A.; Behrens, P.; Godt, A. Chem. Eur. J.
2012, 18, 6979.
Figure 3. Scheme for the strain-promoted “click” introduction of
succinimidyl ester groups into bio-MOF-100 and the subsequent
bioconjugation of the Phe2 peptide.
(9) (a) Sletten, E. M.; Bertozzi, C. R. Angew. Chem., Int. Ed. 2009, 48,
6974. (b) Jewett, J. C.; Bertozzi, C. R. Chem. Soc. Rev. 2010, 39, 1272.
(c) Sletten, E. M.; Bertozzi, C. R. Acc. Chem. Res. 2011, 44, 666.
(10) (a) Baskin, J. M.; Prescher, J. A.; Laughlin, S. T.; Agard, N. J.;
Chang, P. V.; Miller, I. A.; Lo, A.; Codelli, J. A.; Bertozzi, C. R. Proc.
Natl. Acad. Sci. U.S.A. 2007, 104, 16793. (b) Debets, M. F.; van Berkel,
S. S.; Schoffelen, S.; Rutjes, F. P.; van Hest, J. C.; van Delft, F. L. Chem.
Commun. 2010, 46, 97.
Supporting Information). In principle, this straightforward
bioconjugation strategy could be used to tether other peptides,
proteins (including enzymes), or aminated nucleic acids and
biomolecules, polymers, dyes, and nanoparticles to the internal
surface of a mesoporous MOF.
(11) An, J.; Farha, O. K.; Hupp, J. T.; Pohl, E.; Yeh, J. I.; Rosi, N. L.
Nat. Commun. 2012, 3, 604.
(12) Friedrichs, O. D.; O’Keeffe, M. O.; Yaghi, O. M. Acta
Crystallogr., Sect. A 2003, 59, 515.
ASSOCIATED CONTENT
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S
* Supporting Information
Synthetic details and characterization data. This material is
(13) (a) Olkhovik, V. K.; Vasilevskii, D. A.; Pap, A. A.; Kalechyts, G.
V.; Matveienko, Y. V.; Baran, A. G.; Halinouski, N. A.; Petushok, V. G.
ARKIVOC 2008, 69. (b) Ol’khovik, V. K.; Pap, A. A.; Vasilevskii, V. A.;
Galinovskii, N. A.; Tereshko, S. N. Russ. J. Org. Chem. 2008, 44, 1172.
(c) Sato, H.; Matsuda, R.; Sugimoto, K.; Takata, M.; Kitagawa, S. Nat.
Mater. 2010, 9, 661.
(14) (a) Campbell-Verduyn, L. S.; Mirfeizi, L.; Schoonen, A. K.;
Dierckx, R. A.; Elsinga, P. H.; Feringa, B. L. Angew. Chem., Int. Ed.
2011, 50, 11117. (b) Cho, H.; Iwama, Y.; Sugimoto, K.; Mori, S.;
Tokuyama, H. J. Org. Chem. 2010, 75, 627.
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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Funding for this work was provided by the University of
Pittsburgh. The authors thank the Petersen NanoFabrication
and Characterization Facilty for provision of access to PXRD
and FTIR instrumentation. C.L. acknowledges the University of
Pittsburgh Dietrich School of Arts and Sciences for funding
through an Arts and Sciences Fellowship.
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dx.doi.org/10.1021/ja307713q | J. Am. Chem. Soc. 2012, 134, 18886−18888