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Sustainable Catalysis and Biomedical Applications: Advancing Iron-Based Oxygen Atom Transfer through Bioinspired Ligand DesignCROSSMARK Color horizontal
Ghassan Shannan1, Zeina S. Malek2, Nasser Thallaj3

1Prof. (Dr.) Ghassan Shannan, Department of Biochemistry, Arab International University, Damascus, Syria.

2Prof. (Dr.) Zeina S. Malek, Department of Physiology, Arab International University, Damascus, Syria.

3Prof. (Dr.) Nasser Thallaj, Department of Pharmaceutical Chemistry and Drug Quality Control, Arab International University, Damascus, Syria.

Manuscript received on 16 December 2025 | Revised Manuscript received on 07 January 2026 | Manuscript Accepted on 15 February 2026 | Manuscript published on 28 February 2026 | PP: 7-19 | Volume-6 Issue-2, February 2026 | Retrieval Number: 100.1/ijapsr.B410206020226 | DOI: 10.54105/ijapsr.B4102.06020226

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© The Authors. Published by Lattice Science Publication (LSP). This is an open-access article under the CC-BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)

Abstract: This review analyses innovative semi-hemic bioinspired iron (III) complexes and their utility as catalysts for oxygen atom transfer (OAT) in both chemical and photochemical contexts. The research is motivated by the biological function of human endosulfatases (e.g., HSulf1 and HSulf2), enzymes that regulate heparan sulfate (HS) sulfation—a modification with profound roles in cancer, inflammation, and related pathologies. We detail the synthesis and characterization of novel dipyrrinsupported iron complexes engineered to stabilize high-valent ironoxo intermediates, which are critical reactive species in OAT catalysis. Emphasis is placed on employing green oxidants such as dioxygen and water to promote sustainable and efficient catalytic processes consistent with environmentally benign principles. Mechanistic insights into OAT pathways, elucidated through spectroscopic techniques, reveal detailed interactions between the iron centre and substrate molecules. A primary obstacle in the field—the instability of high-valent iron intermediates—is being addressed through innovative activation strategies that enhance both catalytic reactivity and complex stability. Additionally, the review summarises progress in developing endosulfatase inhibitors, particularly sulfamate-based agents, which offer promising avenues for modulating HS sulfation patterns. By elucidating fundamental iron-catalyzed mechanisms and refining the design of selective inhibitors, this work establishes a foundation for novel therapeutic approaches targeting diseases driven by aberrant HS activity. Future directions will focus on improving inhibitor potency and selectivity, as well asinvestigating targeted delivery methods. Together, these developments not only advance the fundamental understanding of iron-mediated oxidation chemistry but also forge new connections between glycochemistry and biomedical applications.

Keywords: Bioinspired; Iron (III) Complexes; Oxygen Atom Transfer (OAT); Catalysis; High-Valent Iron-Oxo Species; Sustainable Chemistry; Dipyrrin.
Scope of the Article: Medicinal Chemistry/ Pharmaceutical Chemistry (drug design)