title: 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.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley , Berkeley, California 94720, United States.|Instituto de Investigaciones en Físicoquímica de Córdoba, INFIQC-CONICET, Facultad de Ciencias Químicas, Departamento de Química Orgánica, Universidad Nacional de Córdoba, Ciudad Universitaria , X5000HUA Córdoba, Argentina.
authors.forename: Alejandro M
authors.initials: AM
authors.lastname: Fracaroli
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley , Berkeley, California 94720, United States.
authors.forename: Peter
authors.initials: P
authors.lastname: Siman
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Nagib
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley , Berkeley, California 94720, United States.
authors.forename: Mitsuharu
authors.initials: M
authors.lastname: Suzuki
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley , Berkeley, California 94720, United States.
authors.forename: Hiroyasu
authors.initials: H
authors.lastname: Furukawa
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley , Berkeley, California 94720, United States.
authors.forename: Omar M
authors.initials: OM
authors.lastname: Yaghi
mesh_terms: D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D004798:Enzymes / Q000378:metabolism*; D000073396:Metal-Organic Frameworks / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D004798:Enzymes; D000073396:Metal-Organic Frameworks