Journal Article

PUBDB-2025-02084

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Tyrosinase Enzyme-Inspired Cu(I)-Porous Organic Polymer for Selective Oxidation of Biomass-Derived 5-HMF

Deka, D. J.Extern* ; Boro, B. ; Chen, Y. ; Chahal, K. ; Nandy, S.DESY* ; Wang, C. ; Lin, H. ; Tang, Q. ; Mondal, J. (Corresponding author)Extern*

2025
Soc. Washington, DC

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Please use a persistent id in citations: doi:10.1021/acsami.5c09657  doi:10.3204/PUBDB-2025-02084

Abstract: In biobased PET, terephthalic acid (TPA) can be replaced with biobase alternatives like bioderived 5-diformylfuran (DFF). In this work, we have selectively synthesized DFF from the oxidation of 5-hydroxymethylfurfural (HMF) using our tyrosinase enzyme-inspired catalysts vicinal V-Cu-POP and nonvicinal NV-Cu-POP, respectively. Motivated by the oxygenated form of tyrosinase, we introduced binuclear copper(I) moieties into a porous organic polymer to create enzyme-inspired heterogeneous catalysts for the selective oxidation of HMF. V-Cu-POP can effectively activate O$_2$ for mild and selective oxidation because the two Cu centers are in close proximity, which is impossible in the case of NV-Cu-POP. For the determination of the coordination environment of the catalytically active site, the X-ray absorption near-edge structure (XANES) studies and the copper(I) state for both the enzyme-inspired catalysts V-Cu-POP and NV-Cu-POP are identified through characteristic features in the absorption spectra. The fitting parameters and EXAFS spectra rule out the formation of the Cu–Cu bond. Further, the key intermediate μ-hydroxy species (Cu (II)–O–O–Cu (II)), which forms during the reaction in the case of the enzyme-inspired catalyst, V-Cu-POP is also confirmed by time-resolved in situ ATR-IR spectroscopy and DFT computational study. This intermediate is not formed in the case of nonvicinal NV-Cu-POP, which is the main reason for lower catalytic activity toward HMF oxidation. NV-Cu-POP still retains the peaks of reactants at the same reaction conditions, which is confirmed by time-resolved in situ ATR-IR spectroscopy. Overall, in this study, we have shown how a tyrosinase enzyme-inspired catalyst exhibits greater catalytic activity toward the oxidation reaction due to the formation of its vicinal conformer compared to the nonvicinal conformer.

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Contributing Institute(s):

1. PETRA-S (FS-PETRA-S)
2. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)

Experiment(s):

1. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2025

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Engineering, Computing and Technology ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 5 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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