Mechanism of the highly effective peptide bond hydrolysis by MOF-808 catalyst under biologically relevant conditions

Conic, Dragan; Pierloot, Kristine; Parac‐Vogt, Tatjana N.; Harvey, Jeremy N.

doi:10.1039/d0cp04775a

Cited by 34 publications

(41 citation statements)

References 66 publications

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“…Previous DFT calculations have shown that GG binds the Zr 6 O 8 cluster preferably in a bidentate manner, bridging two metal ions in one cluster and activating the carbonyl group for nucleophilic attack of a water molecule. 62 The higher activity of Ce 6 compared to the Zr 6 cluster is consistent with the superior reactivity previously reported for Ce(IV) compared to Zr(IV) salts in peptide bond hydrolysis. 27 The reasons for the lower reactivity of CeZr 5 clusters are however still unclear and might be related to less preferred peptide coordination to two different metal centra, resulting in the decrease in the reaction rate.…”

Section: Articlesupporting

confidence: 87%

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

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Simms

Smolders

et al. 2021

ACS Appl. Nano Mater.

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The catalytic activity of metal−organic frameworks (MOFs) toward peptides and proteins provides an attractive route for the development of nanozymes for applications in biotechnology and proteomics, particularly in the field of protein identification using mass spectrometry. Here, we report that carefully tuning the Ce/Zr metal ratio is a promising strategy to overcome structural limitations that originate from the high connectivity of the Zr 6 node and also increase the peptidase activity of the MOF while preserving the material's nano-topology and stability. A series of bimetallic Ce/Zr-UiO-66 MOFs, in which the amount of Ce was systematically varied from 28 to 87 mol%, have been shown to efficiently catalyze peptide bond hydrolysis in a large variety of peptides with different functional groups, demonstrating their nanozyme potential. Detailed kinetic analysis of the hydrolysis of peptide bonds with a range of Ce/Zr MOFs suggests that among the different metallic clusters present in UiO-66, the Ce 6 clusters have superior reactivity compared to the CeZr 5 sites. In addition to increasing the catalytic potency of the MOF toward peptide bond hydrolysis, the introduction of Ce(IV) also broadens the reaction scope of MOF catalysts. Selective oxidation of the thiol sidechains and the formation of disulfide bridges have been observed at physiological pH both in cysteine and in glutathione tripeptide as substrates. The rate of oxidation is directly proportional to the amount of Ce present in the MOF, demonstrating that the introduction of Ce into these nanomaterials is a promising strategy to introduce oxidase activity toward biologically relevant substrates. In addition to this, adsorption of dipeptides onto MOF nanomaterials has been studied for the first time. These studies revealed a close link between the nature of peptide side chains and the extent of their adsorption, which has a direct influence on their ability to act as substrates in MOF-catalyzed reactions.

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Section: Articlesupporting

confidence: 87%

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

Loosen

Simms

Smolders

et al. 2021

ACS Appl. Nano Mater.

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“…This hypothesis is fully in line with our recent mechanistic studies. 38 The temperature also exerted a strong effect on the observed reaction rate, and calculation of activation parameters evidenced a large entropic contribution to the energy barrier, as observed before for the NU-1000 topology in these reactions. 20 The activity of Hf-NU-1000 was strongly affected by an increase in the reaction temperature with nearly 20-fold reduction to the half-life from 990 hours at 40 °C to 51 hours at 80 °C.…”

Section: Hydrolytic Activity Of Hf-nu-1000 Toward Peptide Bond Hydrolysissupporting

confidence: 68%

“…Notably, in this range the carboxylate group of GG is deprotonated, allowing for an efficient substrate-metal node interaction and a swift deprotonation of the entering water molecule. Such mechanism has been previously theoretically predicted for an analogous Zr-MOF, 38 and could explain the higher activity in mildly alkaline solutions. The observed lower adsorptions of GG at lower pH values indicates that the substrate-material interaction is less efficient, which is consistent with the lower rates observed in mildly acidic solutions (Figure S3).…”

Section: Hydrolytic Activity Of Hf-nu-1000 Toward Peptide Bond Hydrolysissupporting

confidence: 60%

Heterogeneous nanozymatic activity of Hf oxo-clusters embedded in a metal–organic framework towards peptide bond hydrolysis

et al. 2021

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“…Balancing the loss of Zn II -OSO 3 connectivity,t here is an increase in Ce-monomer-sulfate bonding (Table S10). S4), crystallizes in the triclinic P " 1space group (V = 16 197 3 ). An isomorphic Cu-analogue was also obtained, but only the Ni structure will be discussed here.Asthe main feature of all the U 70 and Ce 70 frameworks,t he rings are offset stacked along the a-axis (Figure 2c).…”

Section: Resultsmentioning

confidence: 99%

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Colliard

Nyman

2021

Angewandte Chemie

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MIV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce70, a wheel‐shaped oxo‐cluster, [CeIV70(OH)36(O)64(SO4)60(H2O)10]4−. Ce70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce‐monomer linkers. Eight crystal‐structures feature four framework types in which the Ce70‐rings are linked as propellers, in offset‐stacks, in a tartan pattern, and as isolated rings. Small‐angle X‐ray scattering of Ce70 dissolved in butylamine, with and without added cations (CeIV, alkaline earths, MnII), shows the metals‘ differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion‐exchange behavior, demonstrated with UIV and NdIII. Frameworks featuring CeIII/IV‐monomer linkers demonstrate both oxidation and reduction. This study opens the door to mixed‐metal, highly porous framework catalysts, and new clusters for metal‐organic framework design

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Mechanism of the highly effective peptide bond hydrolysis by MOF-808 catalyst under biologically relevant conditions

Abstract: Efficient and selective hydrolysis of inert peptide bonds is of paramount importance. MOF-808, a metal-organic framework based on Zr6 nodes, can hydrolyze peptide bonds efficiently under biologically relevant conditions. However,...

Cited by 34 publications

References 66 publications

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

Heterogeneous nanozymatic activity of Hf oxo-clusters embedded in a metal–organic framework towards peptide bond hydrolysis

Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

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Mechanism of the highly effective peptide bond hydrolysis by MOF-808 catalyst under biologically relevant conditions

Abstract: Efficient and selective hydrolysis of inert peptide bonds is of paramount importance. MOF-808, a metal-organic framework based on Zr6 nodes, can hydrolyze peptide bonds efficiently under biologically relevant conditions. However,...

Cited by 34 publications

References 66 publications

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

Bimetallic Ce/Zr UiO-66 Metal–Organic Framework Nanostructures as Peptidase and Oxidase Nanozymes

Heterogeneous nanozymatic activity of Hf oxo-clusters embedded in a metal–organic framework towards peptide bond hydrolysis

CeIV70Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

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Ce^IV₇₀Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**