Research output: Contribution to journal › Article › peer-review
Hydrophilic Reduction-Resistant Spin Labels of Pyrrolidine and Pyrroline Series from 3,4-Bis-hydroxymethyl-2,2,5,5-tetraethylpyrrolidine-1-oxyl. / Usatov, Mikhail S.; Dobrynin, Sergey A.; Polienko, Yuliya F. et al.
In: International Journal of Molecular Sciences, Vol. 25, No. 3, 1550, 02.2024.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Hydrophilic Reduction-Resistant Spin Labels of Pyrrolidine and Pyrroline Series from 3,4-Bis-hydroxymethyl-2,2,5,5-tetraethylpyrrolidine-1-oxyl
AU - Usatov, Mikhail S.
AU - Dobrynin, Sergey A.
AU - Polienko, Yuliya F.
AU - Morozov, Denis A.
AU - Glazachev, Yurii I.
AU - An’kov, Sergey V.
AU - Tolstikova, Tatiana G.
AU - Gatilov, Yuri V.
AU - Bagryanskaya, Irina Yu
AU - Raizvikh, Arthur E.
AU - Bagryanskaya, Elena G.
AU - Kirilyuk, Igor A.
N1 - This work has been supported by the grants the Russian Science Foundation, RSF 23-13-00178.
PY - 2024/2
Y1 - 2024/2
N2 - Highly resistant to reduction nitroxides open new opportunities for structural studies of biological macromolecules in their native environment inside living cells and for functional imaging of pH and thiols, enzymatic activity and redox status in living animals. 3,4-Disubstituted nitroxides of 2,2,5,5-tetraethylpyrrolidine and pyrroline series with a functional group for binding to biomolecules and a polar moiety for higher solubility in water and for more rigid attachment via additional coordination to polar sites were designed and synthesized. The EPR spectra, lipophilicities, kinetics of the reduction in ascorbate-containing systems and the decay rates in liver homogenates were measured. The EPR spectra of all 3,4-disubstituted pyrrolidine nitroxides showed additional large splitting on methylene hydrogens of the ethyl groups, while the spectra of similar pyrroline nitroxides were represented with a simple triplet with narrow lines and hyperfine structure of the nitrogen manifolds resolved in oxygen-free conditions. Both pyrrolidine and pyrroline nitroxides demonstrated low rates of reduction with ascorbate, pyrrolidines being a bit more stable than similar pyrrolines. The decay of positively charged nitroxides in the rat liver homogenate was faster than that of neutral and negatively charged radicals, with lipophilicity, rate of reduction with ascorbate and the ring type playing minor role. The EPR spectra of N,N-dimethyl-3,4-bis-(aminomethyl)-2,2,5,5-tetraethylpyrrolidine-1-oxyl showed dependence on pH with pKa = 3, ΔaN = 0.055 mT and ΔaH = 0.075 mT.
AB - Highly resistant to reduction nitroxides open new opportunities for structural studies of biological macromolecules in their native environment inside living cells and for functional imaging of pH and thiols, enzymatic activity and redox status in living animals. 3,4-Disubstituted nitroxides of 2,2,5,5-tetraethylpyrrolidine and pyrroline series with a functional group for binding to biomolecules and a polar moiety for higher solubility in water and for more rigid attachment via additional coordination to polar sites were designed and synthesized. The EPR spectra, lipophilicities, kinetics of the reduction in ascorbate-containing systems and the decay rates in liver homogenates were measured. The EPR spectra of all 3,4-disubstituted pyrrolidine nitroxides showed additional large splitting on methylene hydrogens of the ethyl groups, while the spectra of similar pyrroline nitroxides were represented with a simple triplet with narrow lines and hyperfine structure of the nitrogen manifolds resolved in oxygen-free conditions. Both pyrrolidine and pyrroline nitroxides demonstrated low rates of reduction with ascorbate, pyrrolidines being a bit more stable than similar pyrrolines. The decay of positively charged nitroxides in the rat liver homogenate was faster than that of neutral and negatively charged radicals, with lipophilicity, rate of reduction with ascorbate and the ring type playing minor role. The EPR spectra of N,N-dimethyl-3,4-bis-(aminomethyl)-2,2,5,5-tetraethylpyrrolidine-1-oxyl showed dependence on pH with pKa = 3, ΔaN = 0.055 mT and ΔaH = 0.075 mT.
KW - EPR
KW - hyperfine coupling
KW - reduction-resistant nitroxide
KW - spin label
KW - spin probe
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85184677319&origin=inward&txGid=4dbc89ea373d9f9bfc61dc9804f286de
UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001160339200001
UR - https://www.mendeley.com/catalogue/7c696cc5-4968-3cd6-9929-149ee6aac6cd/
U2 - 10.3390/ijms25031550
DO - 10.3390/ijms25031550
M3 - Article
C2 - 38338825
VL - 25
JO - International Journal of Molecular Sciences
JF - International Journal of Molecular Sciences
SN - 1661-6596
IS - 3
M1 - 1550
ER -
ID: 61201448