title: Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts.
abstract: Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril 'gate-keeper' onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Gulen Yesilbag
authors.initials: GY
authors.lastname: Tonga
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Youngdo
authors.initials: Y
authors.lastname: Jeong
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Bradley
authors.initials: B
authors.lastname: Duncan
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Tsukasa
authors.initials: T
authors.lastname: Mizuhara
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Rubul
authors.initials: R
authors.lastname: Mout
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Riddha
authors.initials: R
authors.lastname: Das
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Sung Tae
authors.initials: ST
authors.lastname: Kim
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Yi-Cheun
authors.initials: YC
authors.lastname: Yeh
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Bo
authors.identifier: 0000000342684757
authors.initials: B
authors.lastname: Yan
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Singyuk
authors.initials: S
authors.lastname: Hou
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, 710 North Pleasant Street, Amherst, Massachusetts 01003, USA.
authors.forename: Vincent M
authors.initials: VM
authors.lastname: Rotello
mesh_terms: D002384:Catalysis; D006367:HeLa Cells; D006801:Humans; D053768:Metal Nanoparticles / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D028561:Transition Elements