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@ARTICLE{Herr:1032079,
author = {Herr, Kevin and Höfler, Mark V. and Heise, Henrike and
Aussenac, Fabien and Kornemann, Felix and Rosenberger, David
and Brodrecht, Martin and de Oliveira, Marcos and
Buntkowsky, Gerd and Gutmann, Torsten},
title = {{B}iradicals based on {PROXYL} containing building blocks
for efficient dynamic nuclear polarization in biotolerant
media},
journal = {Journal of magnetic resonance open},
volume = {20},
issn = {2666-4410},
address = {Amsterdam},
publisher = {Elsevier},
reportid = {FZJ-2024-05982},
pages = {100152 -},
year = {2024},
abstract = {A versatile strategy for synthesizing tailored peptide
based biradicals is presented. By labeling the protected
amino acid hydroxyproline with PROXYL via the OH
functionality and using this building block in solid phase
peptide synthesis (SPPS), the obtained peptides become
polarization agents for DNP enhanced solid-state NMR in
biotolerant media. To analyze the effect of the radical
position on the enhancement factor, three different
biradicals are synthesized. The PROXYL spin-label is
inserted in a collagen inspired artificial peptide sequence
by binding through the OH group of the hydroxyproline
moieties at specific position in the chain. This labeling
strategy is universally applicable for any hydroxyproline
position in a peptide sequence since solid-phase peptide
synthesis is used to insert the building block. High
performance liquid chromatography (HPLC) and mass
spectrometry (MS) analyses show the successful introduction
of the spin label in the peptide chain and electron
paramagnetic resonance (EPR) spectroscopy confirms its
activity. Dynamic nuclear polarization (DNP) enhanced
solid-state nuclear magnetic resonance (NMR) experiments
performed on frozen aqueous glycerol-d8 solutions containing
these peptide radicals show significantly higher enhancement
factors of up to 45 in 1H→13C cross polarization magic
angle spinning (CP MAS) experiments compared to an analogous
mono-radical peptide including this building block (ε ≈
14). Compared to commercial biradicals such as AMUPol for
which enhancement factors > 100 have been obtained in the
past and which have been optimized in their structure, the
obtained enhancement up to 45 for our biradicals presents a
significant progress in radical design.},
cin = {IBI-7},
ddc = {530},
cid = {I:(DE-Juel1)IBI-7-20200312},
pnm = {5241 - Molecular Information Processing in Cellular Systems
(POF4-524)},
pid = {G:(DE-HGF)POF4-5241},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001255177000001},
doi = {10.1016/j.jmro.2024.100152},
url = {https://juser.fz-juelich.de/record/1032079},
}