Selective aerobic synthesis of vitamin K3 catalyzed by alloy-like Mn/Fe-decorated pentetic acid-modified chitosan/konjac glucomannan biocompatible scaffold embedded on Rice Hull-(Fe²⁺)Al₂O₄ spinel structure.

Authors

D S Rezaeidanesh, Z Hekmatian, P Fooladpanjeh, A Samadian, E Dashtabadi, R Moghimi, B Javani, A R Faraji

Published in

International journal of biological macromolecules. Pages 154019. Aug 12, 2026. Epub Aug 12, 2026.

Abstract

Due to its vital medicinal and nutritional roles, including bone mineralization and anti-cancer activity, developing eco-friendly, energy-efficient routes for Vitamin K3 synthesis is of significant scientific and industrial value. High-performance aerobic processes utilizing sustainable carbohydrate-based precursors provide a compelling strategy to achieve this goal. Herein, a series of (Fe²⁺)(Al₂O₄)-rice husk wrapped in MnFe alloy functionalized 3D porous chitosan-pentatic acid-konjac glucomannan (MF/CPKRH-xyz) are fabricated via simple co- precipitation/impregnation method for the first time. This green catalytic platform leverages the synergistic properties of the N/O-enriched CPK framework, which facilitates an optimal dispersion of single/alloy-like active centers and enhances the accessible surface area. Structural/morphological analyses proved the successful embedding of alloy-like/single sites within CPK-biopolymer scaffold. The optimized fabrication (e.g., CPK weight ratio, calcination temperature, and mono/bimetallic site) and operating conditions (e.g., reagent/promoter dosage, contact time, temperature, kind of oxidant, and solvent) were assessed in detail. Catalytic activity was assessed using O₂ as the sole, additive-free oxidant. Under optimized conditions, the bimetallic system exhibited exceptional efficiency, achieving 94.50% conversion and 89.10% selectivity within 3.0 h, significantly outperforming its monometallic counterparts. Mechanistic insights suggest that the high activity is attributed to the mesoporous architecture and the cooperative interaction between Mn_xO_y and Fe_mO_n centers, which lowers the energy barrier for proxo species generation and accelerates the redox cycles (Mn²⁺↔Mn³⁺↔Mn⁴⁺↔Mn²⁺ and Fe³⁺↔Fe⁴⁺↔Fe³⁺). Thermodynamic-kinetic assessments revealed that the VK3 synthesis is a feasible one-step aerobic process, with an activation enthalpy of +20.19 kJ mol^-1 and an activation energy of 25.13 kJ mol^-1.This research offers valuable insights into the carbohydrate-based macromolecular composites in the efficient synthesis of high-value chemicals.

PMID:
42586343
Bibliographic data and abstract were imported from PubMed on 13 Aug 2026.

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