Nanostructured binuclear Fe(III) and Mn(III) porphyrin materials: Tuning the mimics of catalase and peroxidase activity

Martins, Mariana B.M.S.; Corrêa, Gabriela A.; Moniz, Tânia; Medforth, Craig J.; Castro, Baltazar de; Rebelo, Susana L.H.

doi:10.1016/j.jcat.2023.02.001

Cited by 21 publications

(5 citation statements)

References 39 publications

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“…18 In this study, we employed a biomimetic catalase, FeP, which includes a hemin group crucial for its catalytic functions in both ROS scavenging and O 2 generation. 69 Importantly, we used FeP as a cross-linking agent to create a wound dressing composed of biocompatible 4-arm-PEG-NH 2. 20 By carefully adjusting the synthesis conditions, we achieved a dressing with properties beneficial for wound repair.…”

Section: Discussionmentioning

confidence: 99%

Fe-Porphyrin Cross-Linked Hydrogel for Reactive Oxygen Species Scavenging and Oxygen Generation in Diabetic Wounds

Kim,

Ji,

Min

et al. 2024

ACS Appl. Mater. Interfaces

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Healing chronic diabetic wounds is challenging because of excessive reactive oxygen species (ROS) and hypoxia in the wound microenvironment. To address this issue, we propose a hydrogel wound dressing composed of polyethylene glycol (PEG) cross-linked with a biomimetic catalase, Fe-containing porphyrin (FeP) (i.e., FeP hydrogel). The immobilized FeP can serve as a catalyst for both ROS scavenging and O 2 generation. The properties of the hydrogels were optimized by varying the composition ratios of the two constituent materials based on their mechanical properties and catalytic activity. Our in vitro cell experiments revealed that the FeP-80 hydrogel enhanced the proliferation and migration of keratinocytes and dermal fibroblasts and promoted the expression of angiogenic growth factors in keratinocytes. When tested with an in vivo diabetic chronic wound model, the FeP-80 hydrogel promoted wound healing by facilitating re-epithelialization, promoting angiogenesis, and suppressing inflammation, compared with other control groups.

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Section: Discussionmentioning

confidence: 99%

Fe-Porphyrin Cross-Linked Hydrogel for Reactive Oxygen Species Scavenging and Oxygen Generation in Diabetic Wounds

Kim,

Ji,

Min

et al. 2024

ACS Appl. Mater. Interfaces

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“…The 4-hydroxy-tautomers were observed as the major products. It should be noted that the ferric center of [Fe(TPFPP)Cl] has a markedly acidic character [40] and may confers acidity to the reaction media, favoring the presence of hydroxyl-tautomers 2b* and 2c*. The 1 H NMR spectrum of the total reaction, after evaporation at RT (Path II, Table 2, entry 2), was obtained in DMSO-d6 (SM, Figure S11 and S12).…”

Section: Quinoline (2)mentioning

confidence: 99%

Section: Quinoline (2)mentioning

confidence: 99%

“…Catalytic performance of the [Fe(TPFPP)Cl] (FePF) might be associated with the typical acidic character of iron porphyrins [40], which is intensified by the strong electronwithdrawing porphyrin ligand due to extensive fluorination. The iron-hydroperoxy-species [PFe(III)-OOH] formed by coordination of hydrogen peroxide to the metal center and subsequent deprotonation, has been considered the active oxidant in the catalytic cycle.…”

Section: Considerations On the Mechanismmentioning

confidence: 99%

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Green Aromatic Epoxidation with an Iron Porphyrin Catalyst for One-Pot Functionalization of Renewable Xylene, Quinoline, and Acridine

2023

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Sustainable functionalization of renewable aromatics is a key step to supply our present needs for specialty chemicals and pursuing the transition to a circular, fossil-free economy. In the present work, three typically stable aromatic compounds, representative of products abundantly obtainable from biomass or recycling processes, were functionalized in one-pot oxidation reactions at room temperature, using H2O2 as a green oxidant and ethanol as a green solvent in the presence of a highly electron withdrawing iron porphyrin catalyst. The results show unusual initial epoxidation of the aromatic ring by the green catalytic system. The epoxides were isolated or evolved through rearrangement, ring opening by nucleophiles, and oxidation. Acridine was oxidized to mono- and di-oxides in the peripheral ring: 1:2-epoxy-1,2-dihydroacridine and anti-1:2,3:4-diepoxy-1,2,3,4-tetrahydroacridine, with TON of 285. o-Xylene was oxidized to 4-hydroxy-3,4-dimethylcyclohexa-2,5-dienone, an attractive building block for synthesis, and 3,4-dimethylphenol as an intermediate, with TON of 237. Quinoline was directly functionalized to 4-quinolone or 3-substituted-4-quinolones (3-ethoxy-4-quinolone or 3-hydroxy-4-quinolone) and corresponding hydroxy-tautomers, with TON of 61.

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“…[135] A combination of Fe(III) and Mn(III) porphyrin complexes showed interesting activity tuning through, most probably, a range of charge inductions; the heterometallic pair achieved, however, still less than 5 % of the typical catalase activity. [136] In most catalase-inspired inorganic catalysts, activity is seldom even close to the enzymatic counterpart. This indicates the complexity of designing artificial structures that bind and cleave substrates with high specificity and stability at the first coordination sphere, while also requiring a three-dimensional associated structure at the second coordination sphere to induce electrostatic effects, provide pathways for electron and proton transfers and means to directional mass-transport through hydrophobic/hydrophilic interactions.…”

Section: State-of-art In Biomimetic and Bioinspired Electrocatalystsmentioning

confidence: 99%

Insights from Enzymatic Catalysis: A Path towards Bioinspired High‐Performance Electrocatalysts

2023

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Enzymes, especially some metalloenzymes, are exceptional catalysts for redox reactions with technological applications in several fields, including energy conversion systems and producing fuels and value‐added chemicals. Because of that, they have inspired the development of synthetic catalysts to obtain high‐performance materials. However, several fundamental aspects should be better understood to achieve this goal, such as enzyme catalysis and the role of the three‐dimensional catalytic site. Therefore, this review addresses key structural and activity aspects of some remarkable metalloenzymes and discusses three‐dimensional catalysis as an approach to enzyme catalysis. Also, the case of the multicopper oxidase enzymes is shown as an example of how the three‐dimensional coordination environment of the copper ions in the active site can impact catalysis.

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Nanostructured binuclear Fe(III) and Mn(III) porphyrin materials: Tuning the mimics of catalase and peroxidase activity

Cited by 21 publications

References 39 publications

Fe-Porphyrin Cross-Linked Hydrogel for Reactive Oxygen Species Scavenging and Oxygen Generation in Diabetic Wounds

Fe-Porphyrin Cross-Linked Hydrogel for Reactive Oxygen Species Scavenging and Oxygen Generation in Diabetic Wounds

Green Aromatic Epoxidation with an Iron Porphyrin Catalyst for One-Pot Functionalization of Renewable Xylene, Quinoline, and Acridine

Insights from Enzymatic Catalysis: A Path towards Bioinspired High‐Performance Electrocatalysts

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