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@ARTICLE{Deka:631969,
author = {Deka, Dhruba Jyoti and Boro, Bishal and Chen, Yuping and
Chahal, Kapil and Nandy, Subhajit and Wang, Caiqi and Lin,
Hongfei and Tang, Qing and Mondal, John},
title = {{T}yrosinase {E}nzyme-{I}nspired {C}u({I})-{P}orous
{O}rganic {P}olymer for {S}elective {O}xidation of
{B}iomass-{D}erived 5-{HMF}},
journal = {ACS applied materials $\&$ interfaces},
volume = {17},
number = {25},
issn = {1944-8244},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PUBDB-2025-02084},
pages = {36840 - 36854},
year = {2025},
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.},
cin = {FS-PETRA-S / DOOR ; HAS-User},
ddc = {600},
cid = {I:(DE-H253)FS-PETRA-S-20210408 /
I:(DE-H253)HAS-User-20120731},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3},
experiment = {EXP:(DE-H253)P-P64-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:40512020},
doi = {10.1021/acsami.5c09657},
url = {https://bib-pubdb1.desy.de/record/631969},
}