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@ARTICLE{Raveendran:639369,
author = {Raveendran, Dhanya and Dalloul, Feras and Mietner, J.
Benedikt and Barba, Enguerrand and Chen, Shouzheng and
Zaytseva-Zotova, Daria and Sochor, Benedikt and Koyiloth
Vayalil, Sarathlal and Müller-Buschbaum, Peter and Tiainen,
Hanna and Roth, Stephan V. and Navarro, Julien R. G.},
title = {3{D} {P}rintable {H}ydrogel {B}ased on {TEMPO}-{O}xidized
{C}ellulose {N}anofibrils and {F}moc-{FF} for {E}nhanced
{B}iological {P}erformance and {C}ell {A}dhesion},
journal = {ACS applied nano materials},
volume = {8},
number = {38},
issn = {2574-0970},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {PUBDB-2025-04464},
pages = {18571 - 18583},
year = {2025},
abstract = {Herein, we report a 3D printable ink made of a
peptide-polysaccharide hybrid hydrogel composed of
fluorenylmethyloxycarbonyl-diphenylalanine (Fmoc-FF) peptide
and TEMPO-oxidized cellulose nanofibrils (ToCNF),
synthesized using a pH-dependent sol–gel transition
method. The ToCNF suspension is synthesized through the
mechanical breakdown of a cellulose pulp using a
microfluidizer, followed by its oxidation mediated with
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). The properties
of the hybrid inks are compared in the presence
(ToCNF/Fmoc-FF-Ca2+) and absence (ToCNF/Fmoc-FF) of the
divalent cation Ca2+, which acts as the cross-linker, at two
optimized weight ratios (r) of ToCNF and Fmoc-FF (r = 4.5
and 6.5). The rheological measurements show that the yield
strength of the ToCNF/Fmoc-FF-Ca2+ gel is almost double that
of the hydrogel composite without Ca2+ ions, especially at
the concentration (C) of 10 mM CaCl2. This finding is
further verified by 3D gel printing, which produced good
quality prints with the cation cross-linked hydrogel. The
structural analysis by Field Emission Scanning Electron
Microscopy shows that the calcium ions can cross-link the
ToCNF and also enhance the self-assembly of Fmoc-FF, which
leads to the formation of rigid compact nanofibers even at
physiological pH. The electrostatic interaction of the
positively charged Ca2+ ions onto the negatively charged
surface carboxylate groups of ToCNF and Fmoc-FF is analyzed
by zeta potential (ζ) measurements. Small-angle X-ray
scattering measurements give deeper structural insights into
the interaction of Fmoc-FF with ToCNF. Cell responses to the
hydrogels are studied in human dermal fibroblasts (NHDFs) in
a direct contact test using a live/dead assay and in extract
test using Alamar Blue and lactate dehydrogenase assays. The
results show that high loading of Fmoc-FF decreases cell
viability, while additional cross-linking with calcium
reduces this cytotoxic effect.},
cin = {FS DOOR-User / FS-SMA / FS-PETRA-D},
ddc = {540},
cid = {$I:(DE-H253)FS_DOOR-User-20241023$ /
I:(DE-H253)FS-SMA-20220811 / I:(DE-H253)FS-PETRA-D-20210408},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) /
FS-Proposal: I-20230937 (I-20230937)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 /
G:(DE-H253)I-20230937},
experiment = {EXP:(DE-H253)P-P03-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/acsanm.5c03356},
url = {https://bib-pubdb1.desy.de/record/639369},
}