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}
}
Web of Science
Works referenced in this record:
Metal–Organic Frameworks with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water
journal, June 2014
- Fracaroli, Alejandro M.; Furukawa, Hiroyasu; Suzuki, Mitsuharu
- Journal of the American Chemical Society, Vol. 136, Issue 25, p. 8863-8866
Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks
journal, August 2009
- Garibay, Sergio J.; Wang, Zhenqiang; Tanabe, Kristine K.
- Inorganic Chemistry, Vol. 48, Issue 15
Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012
- Deng, H.; Grunder, S.; Cordova, K. E.
- Science, Vol. 336, Issue 6084, p. 1018-1023
A viral cleavage site cassette: identification of amino acid sequences required for tobacco etch virus polyprotein processing.
journal, May 1988
- Carrington, J. C.; Dougherty, W. G.
- Proceedings of the National Academy of Sciences, Vol. 85, Issue 10
MOF-Supported Selective Ethylene Dimerization Single-Site Catalysts through One-Pot Postsynthetic Modification
journal, March 2013
- Canivet, Jerome; Aguado, Sonia; Schuurman, Yves
- Journal of the American Chemical Society, Vol. 135, Issue 11
Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks
journal, February 2010
- Deng, H.; Doonan, C. J.; Furukawa, H.
- Science, Vol. 327, Issue 5967, p. 846-850
Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177
journal, February 2015
- Zhang, Yue-Biao; Furukawa, Hiroyasu; Ko, Nakeun
- Journal of the American Chemical Society, Vol. 137, Issue 7
Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks
journal, September 2011
- Cohen, Seth M.
- Chemical Reviews, Vol. 112, Issue 2, p. 970-1000
Postsynthetic modification of metal–organic frameworks—a progress report
journal, January 2011
- Tanabe, Kristine K.; Cohen, Seth M.
- Chem. Soc. Rev., Vol. 40, Issue 2
Isoreticular synthesis and modification of frameworks with the UiO-66 topology
journal, January 2010
- Garibay, Sergio J.; Cohen, Seth M.
- Chemical Communications, Vol. 46, Issue 41, p. 7700-7702
A General Thermolabile Protecting Group Strategy for Organocatalytic Metal−Organic Frameworks
journal, April 2011
- Lun, David J.; Waterhouse, Geoffrey I. N.; Telfer, Shane G.
- Journal of the American Chemical Society, Vol. 133, Issue 15
Engineering a Metal-Organic Framework Catalyst by Using Postsynthetic Modification
journal, September 2009
- Tanabe, Kristine K.; Cohen, Seth M.
- Angewandte Chemie International Edition, Vol. 48, Issue 40
Enantiopure Peptide-Functionalized Metal–Organic Frameworks
journal, July 2015
- Bonnefoy, Jonathan; Legrand, Alexandre; Quadrelli, Elsje Alessandra
- Journal of the American Chemical Society, Vol. 137, Issue 29
The fluorenylmethoxycarbonyl group in solid phase synthesis
journal, January 2003
- Sheppard, Robert
- Journal of Peptide Science, Vol. 9, Issue 9
Advances in Fmoc solid‐phase peptide synthesis
journal, January 2016
- Behrendt, Raymond; White, Peter; Offer, John
- Journal of Peptide Science, Vol. 22, Issue 1
Structural Basis for the Substrate Specificity of Tobacco Etch Virus Protease
journal, October 2002
- Phan, Jason; Zdanov, Alexander; Evdokimov, Artem G.
- Journal of Biological Chemistry, Vol. 277, Issue 52
Dynamic Kinetic Resolution of Biaryl Atropisomers via Peptide-Catalyzed Asymmetric Bromination
journal, June 2010
- Gustafson, J. L.; Lim, D.; Miller, S. J.
- Science, Vol. 328, Issue 5983
The advent and development of organocatalysis
journal, September 2008
- MacMillan, David W. C.
- Nature, Vol. 455, Issue 7211
Asymmetric Enamine Catalysis
journal, December 2007
- Mukherjee, Santanu; Yang, Jung Woon; Hoffmann, Sebastian
- Chemical Reviews, Vol. 107, Issue 12
Organocatalysis—after the gold rush
journal, January 2009
- Bertelsen, Søren; Jørgensen, Karl Anker
- Chemical Society Reviews, Vol. 38, Issue 8
Direct and Enantioselective Organocatalytic α-Chlorination of Aldehydes
journal, April 2004
- Brochu, Michael P.; Brown, Sean P.; MacMillan, David W. C.
- Journal of the American Chemical Society, Vol. 126, Issue 13
Nucleophilic Substitution Catalyzed by a Supramolecular Cavity Proceeds with Retention of Absolute Stereochemistry
journal, October 2014
- Zhao, Chen; Toste, F. Dean; Raymond, Kenneth N.
- Journal of the American Chemical Society, Vol. 136, Issue 41
Works referencing / citing this record:
The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials
journal, February 2020
- Ploetz, Evelyn; Engelke, Hanna; Lächelt, Ulrich
- Advanced Functional Materials, Vol. 30, Issue 41
Homochiral MOF–Polymer Mixed Matrix Membranes for Efficient Separation of Chiral Molecules
journal, October 2019
- Lu, Yizhihao; Zhang, Huacheng; Chan, Jun Yong
- Angewandte Chemie, Vol. 131, Issue 47
Significant Enhancement of C 2 H 2 /C 2 H 4 Separation by a Photochromic Diarylethene Unit: A Temperature- and Light-Responsive Separation Switch
journal, April 2017
- Fan, Cong Bin; Le Gong, Le; Huang, Ling
- Angewandte Chemie International Edition, Vol. 56, Issue 27
Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment
journal, March 2018
- Grigoropoulos, Alexios; McKay, Alasdair I.; Katsoulidis, Alexandros P.
- Angewandte Chemie International Edition, Vol. 57, Issue 17
Homochiral MOF–Polymer Mixed Matrix Membranes for Efficient Separation of Chiral Molecules
journal, October 2019
- Lu, Yizhihao; Zhang, Huacheng; Chan, Jun Yong
- Angewandte Chemie International Edition, Vol. 58, Issue 47
Amidation, Esterification, and Thioesterification of a Carboxyl‐Functionalized Covalent Organic Framework
journal, January 2020
- Guo, Lei; Jia, Shang; Diercks, Christian S.
- Angewandte Chemie International Edition, Vol. 59, Issue 5
The proton conductivities of two silver-thiophene-2-carboxylate coordination polymer and the relationship between the dimensionality and properity: proton conductivities of silver-thiophene-2-carboxylate polymer
journal, August 2018
- Du, Jun; Sun, Xingyu; He, Yuanchun
- Applied Organometallic Chemistry, Vol. 32, Issue 11
Solvent-Controlled Phase Transition of a Co II -Organic Framework: From Achiral to Chiral and Two to Three Dimensions
journal, April 2017
- Wang, Xing-Po; Chen, Wen-Miao; Qi, Hao
- Chemistry - A European Journal, Vol. 23, Issue 33
Solid-state NMR studies of the acidity of functionalized metal-organic framework UiO-66 materials
journal, July 2019
- Tang, Jing; Li, Shenhui; Chu, Yueying
- Magnetic Resonance in Chemistry
Construction and anion exchange of silver(I) complexes bearing 1,2,3-tris(isonicotinoyloxy)benzene
journal, July 2019
- Jeong, Hyun Chul; Min, Siyeon; Park, Hansol
- Transition Metal Chemistry, Vol. 44, Issue 8
Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework
journal, June 2020
- Mon, Marta; Bruno, Rosaria; Sanz-Navarro, Sergio
- Nature Communications, Vol. 11, Issue 1
A metal–organic framework as a flask: photophysics of confined chromophores with a benzylidene imidazolinone core
journal, January 2017
- Dolgopolova, Ekaterina A.; Moore, Thomas M.; Ejegbavwo, Otega A.
- Chemical Communications, Vol. 53, Issue 53
Linker functionalisation triggers an alternative 3D-topology for Zn-isophthalate-4,4′-bipyridine frameworks
journal, January 2017
- Schneemann, Andreas; Rudolf, Robin; Henke, Sebastian
- Dalton Transactions, Vol. 46, Issue 25
The chemistry of titanium-based metal–organic frameworks
journal, January 2017
- Nguyen, Ha L.
- New Journal of Chemistry, Vol. 41, Issue 23
Mimicking horseradish peroxidase and oxidase using ruthenium nanomaterials
journal, January 2017
- Cao, Gao-Juan; Jiang, Xiumei; Zhang, Hui
- RSC Advances, Vol. 7, Issue 82
Overcoming double-step CO 2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg 2 (dobpdc)
journal, January 2018
- Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.
- Chemical Science, Vol. 9, Issue 1
Photoswitching storage of guest molecules in metal–organic framework for photoswitchable catalysis: exceptional product, ultrahigh photocontrol, and photomodulated size selectivity
journal, January 2017
- Gong, Le Le; Yao, Wan Ting; Liu, Zhi Qiang
- Journal of Materials Chemistry A, Vol. 5, Issue 17
Fine-tuning metal–organic framework performances by spatially-differentiated postsynthetic modification
journal, January 2018
- Zhang, Hai-Feng; Li, Mian; Wang, Xue-Zhi
- Journal of Materials Chemistry A, Vol. 6, Issue 10
Post-synthetic diamine-functionalization of MOF-74 type frameworks for effective carbon dioxide separation
journal, January 2019
- Kang, Minjung; Kang, Dong Won; Hong, Chang Seop
- Dalton Transactions, Vol. 48, Issue 7
Metal–organic framework nanoparticles for magnetic resonance imaging
journal, January 2018
- Peller, Michael; Böll, Konstantin; Zimpel, Andreas
- Inorganic Chemistry Frontiers, Vol. 5, Issue 8
Post-synthetic modulation of the charge distribution in a metal–organic framework for optimal binding of carbon dioxide and sulfur dioxide
journal, January 2019
- Li, Lei; da Silva, Ivan; Kolokolov, Daniil I.
- Chemical Science, Vol. 10, Issue 5
Realising the environmental benefits of metal–organic frameworks: recent advances in microwave synthesis
journal, January 2018
- Thomas-Hillman, Ieuan; Laybourn, Andrea; Dodds, Chris
- Journal of Materials Chemistry A, Vol. 6, Issue 25
Uniform and simultaneous orthogonal functionalization of a metal–organic framework material
journal, January 2020
- Samarakoon, Kanchana P.; Yazdanparast, Mohammad S.; Day, Victor W.
- Molecular Systems Design & Engineering, Vol. 5, Issue 4
The synthesis and applications of chiral pyrrolidine functionalized metal–organic frameworks and covalent-organic frameworks
journal, January 2020
- Zhou, Mi; El-Sayed, El-Sayed M.; Ju, Zhanfeng
- Inorganic Chemistry Frontiers, Vol. 7, Issue 6
Multivariate metal-organic frameworks
journal, February 2017
- Helal, Aasif; Yamani, Zain H.; Cordova, Kyle E.
- National Science Review, Vol. 4, Issue 3
Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment
journal, March 2018
- Grigoropoulos, Alexios; McKay, Alasdair I.; Katsoulidis, Alexandros P.
- Angewandte Chemie, Vol. 130, Issue 17
Amidation, Esterification, and Thioesterification of a Carboxyl‐Functionalized Covalent Organic Framework
journal, December 2019
- Guo, Lei; Jia, Shang; Diercks, Christian S.
- Angewandte Chemie, Vol. 132, Issue 5
Significant Enhancement of C 2 H 2 /C 2 H 4 Separation by a Photochromic Diarylethene Unit: A Temperature- and Light-Responsive Separation Switch
journal, April 2017
- Fan, Cong Bin; Le Gong, Le; Huang, Ling
- Angewandte Chemie, Vol. 129, Issue 27
Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO) 4 – -Incorporated Cr-MIL-101
journal, March 2017
- Park, Hoyoung D.; Dincă, Mircea; Román-Leshkov, Yuriy
- ACS Central Science, Vol. 3, Issue 5
Conceptual Advances from Werner Complexes to Metal–Organic Frameworks
journal, October 2018
- Diercks, Christian S.; Kalmutzki, Markus J.; Diercks, Nicolas J.
- ACS Central Science, Vol. 4, Issue 11
Energy-Transfer Metal–Organic Nanoprobe for Ratiometric Sensing with Dual Response to Peroxynitrite and Hypochlorite
journal, August 2018
- Ding, Zhaoyang; Wang, Chunfei; Feng, Gang
- ACS Omega, Vol. 3, Issue 8
Nanoscale metal–organic frameworks coated with poly(vinyl alcohol) for ratiometric peroxynitrite sensing through FRET
journal, January 2017
- Ding, Zhaoyang; Tan, Jinyun; Feng, Gang
- Chemical Science, Vol. 8, Issue 7