Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals
Abstract
The design of enzyme-like complexity within metal-organic frameworks (MOFs) requires multiple reactions to be performed on a MOF crystal without losing access to its interior. Here, we show that seven post-synthetic reactions can be successfully achieved within the pores of a multivariate MOF, MTV-IRMOF-74-III, to covalently incorporate tripeptides that resemble the active sites of enzymes in their spatial arrangement and compositional heterogeneity. These reactions build up H2N-Pro-Gly-Ala-CONHL and H2N-Cys-His-Asp-CONHL (where L = organic struts) amino acid sequences by covalently attaching them to the organic struts in the MOFs, without losing porosity or crystallinity. An enabling feature of this chemistry is that the primary amine functionality (-CH2NHBoc) of the original MOF is more reactive than the commonly examined aromatic amines (-NH2), and this allowed for the multi-step reactions to be carried out in tandem within the MOF. Preliminary findings indicate that the complexity thus achieved can affect reactions that were previously accomplished only in the presence of enzymes.
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Universidad Nacional de Córdoba, Córdoba (Argentina). Instituto de Investigaciones en Físicoquímica de Córdoba, INFIQC–CONICET
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1530245
- Grant/Contract Number:
- AC02-05CH11231; SC0001015
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 27; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Fracaroli, Alejandro M., Siman, Peter, Nagib, David A., Suzuki, Mitsuharu, Furukawa, Hiroyasu, Toste, F. Dean, and Yaghi, Omar M. Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b04204.
Fracaroli, Alejandro M., Siman, Peter, Nagib, David A., Suzuki, Mitsuharu, Furukawa, Hiroyasu, Toste, F. Dean, & Yaghi, Omar M. Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals. United States. https://doi.org/10.1021/jacs.6b04204
Fracaroli, Alejandro M., Siman, Peter, Nagib, David A., Suzuki, Mitsuharu, Furukawa, Hiroyasu, Toste, F. Dean, and Yaghi, Omar M. Tue .
"Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals". United States. https://doi.org/10.1021/jacs.6b04204. https://www.osti.gov/servlets/purl/1530245.
@article{osti_1530245,
title = {Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals},
author = {Fracaroli, Alejandro M. and Siman, Peter and Nagib, David A. and Suzuki, Mitsuharu and Furukawa, Hiroyasu and Toste, F. Dean and Yaghi, Omar M.},
abstractNote = {The design of enzyme-like complexity within metal-organic frameworks (MOFs) requires multiple reactions to be performed on a MOF crystal without losing access to its interior. Here, we show that seven post-synthetic reactions can be successfully achieved within the pores of a multivariate MOF, MTV-IRMOF-74-III, to covalently incorporate tripeptides that resemble the active sites of enzymes in their spatial arrangement and compositional heterogeneity. These reactions build up H2N-Pro-Gly-Ala-CONHL and H2N-Cys-His-Asp-CONHL (where L = organic struts) amino acid sequences by covalently attaching them to the organic struts in the MOFs, without losing porosity or crystallinity. An enabling feature of this chemistry is that the primary amine functionality (-CH2NHBoc) of the original MOF is more reactive than the commonly examined aromatic amines (-NH2), and this allowed for the multi-step reactions to be carried out in tandem within the MOF. Preliminary findings indicate that the complexity thus achieved can affect reactions that were previously accomplished only in the presence of enzymes.},
doi = {10.1021/jacs.6b04204},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 138,
place = {United States},
year = {Tue Jun 28 00:00:00 EDT 2016},
month = {Tue Jun 28 00:00:00 EDT 2016}
}
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