Citation: Qingchao Li, Fengmin Ma, Pu Wang, Yu Fu, Jinhui Cao, Chunxiao Xu, Jialin Chen, Lingli Wang, Zhaohui Wang. Photoreduction of Fe(Ⅲ) mediated by structurally different plant-related organic compounds: An EPR study[J]. Chinese Chemical Letters, ;2026, 37(2): 111281. doi: 10.1016/j.cclet.2025.111281 shu

Photoreduction of Fe(Ⅲ) mediated by structurally different plant-related organic compounds: An EPR study

Qingchao Li ^a ,
Fengmin Ma ^a ,
Pu Wang ^a ,
Yu Fu ^a ,
Jinhui Cao ^a ,
Chunxiao Xu ^a ,
Jialin Chen ^a ,
Lingli Wang ^{a, *,} ,
Zhaohui Wang ^{a, b, c, d, *,}

a.
Shanghai Key Lab for Urban Ecological Processes and Eco-Restoration, School of Ecological and Environmental Sciences, East China Normal University, Shanghai 200241, China
b.
Technology Innovation Center for Land Spatial Eco-restoration in Metropolitan Area, Ministry of Natural Resources, Shanghai 200062, China
c.
Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste, Shanghai 200241, China
d.
State Key Laboratory of Precision Spectroscopy (East China Normal University), Shanghai 200241, China

w120905034@163.com

zhwang@des.ecnu.edu.cn

Received Date: 19 December 2024
Revised Date: 5 March 2025
Accepted Date: 30 April 2025
Available Online: 30 April 2025

Figures(4)

Plant-related organic compound (PROC) may interact with redox-active metals like iron while they are present in soil or aquatic environment, but their effects on the photoreduction of Fe(Ⅲ) remain largely unexplored. This study investigates the photochemical behavior of Fe(Ⅲ)-PROC complexes using alkaline lignin (AL), betaine hydrochloride (BH), and phytic acid (PA) as representative proxies for PROC. The reductive agent AL demonstrated the ability to directly reduce Fe(Ⅲ) to Fe(Ⅱ). In contrast, BH, being unable to form strong complexes with Fe(Ⅲ), was able to quench ^•OH, thereby resulting in a shift of the redox equilibrium towards Fe(Ⅱ). PA exhibited a strong binding affinity for Fe(Ⅲ), effectively inhibiting its photoreduction. Electron paramagnetic resonance (EPR) analysis, utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap, revealed that the DMPO-OH signal detected in photolyzed Fe(Ⅲ)-PROC solutions originated from various pathways. Specifically, uncomplexed Fe(Ⅲ) in AL or BH solutions was shown to oxidize DMPO directly, leading to the formation of a false DMPO-OH adduct. The addition of ethanol to the photolyzed Fe(Ⅲ)-AL and Fe(Ⅲ)-BH systems resulted in the generation of the DMPO-CH(CH₃)OH adduct, thereby confirming the presence of authentic ^•OH in these systems. The photolysis of the Fe(Ⅲ)-PA complex may proceed via a photodissociation mechanism, where the resulting loosely bound Fe(Ⅲ) can oxidize DMPO, followed by a nucleophilic attack from water. This research highlights the multifaceted roles of PROC in facilitating the redox cycling of iron within soil and aquatic ecosystems.
- Alkaline lignin,
- Hydrochloric betaine,
- Phytic acid,
- Free radical,
- Photochemistry
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