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@article{c268f9feea81465d92ac574e73964e83,
title = "Novel NIR-Phosphorescent Ir(III) Complexes: Synthesis, Characterization and Their Exploration as Lifetime-Based O2 Sensors in Living Cells",
abstract = "A series of [Ir(NˆC)2 (NˆN)]+ NIR-emitting orthometalated complexes (1–7) has been prepared and structurally characterized using elemental analysis, mass-spectrometry, and NMR spectroscopy. The complexes display intense phosphorescence with vibrationally structured emission bands exhibiting the maxima in the range 713–722 nm. The DFT and TD DFT calculations showed that the photophysical characteristics of these complexes are largely determined by the properties of the metalating NˆC ligands, with their major contribution into formation of the lowest S1 and T1 excited states responsible for low energy absorption and emission, respectively. Emission lifetimes of 1–7 in degassed methanol solution vary from 1.76 to 5.39 µs and show strong quenching with molecular oxygen to provide an order of magnitude lifetime reduction in aerated solution. The photophysics of two complexes (1 and 7) were studied in model physiological media containing fetal bovine serum (FBS) and Dulbecco{\textquoteright}s Modified Eagle Medium (DMEM) to give linear Stern-Volmer calibrations with substantially lower oxygen-quenching constants compared to those obtained in methanol solution. These observations were interpreted in terms of the sensors{\textquoteright} interaction with albumin, which is an abundant component of FBS and cell media. The studied complexes displayed acceptable cytotoxicity and preferential localization, either in mitochondria (1) or in lysosomes (7) of the CHO-K1 cell line. The results of the phosphorescence lifetime imaging (PLIM) experiments demonstrated considerable variations of the sensors{\textquoteright} lifetimes under normoxia and hypoxia conditions and indicated their applicability for semi-quantitative measurements of oxygen concentration in living cells. The complexes{\textquoteright} emission in the NIR domain and the excitation spectrum, extending down to ca. 600 nm, also showed that they are promising for use in in vivo studies.",
keywords = "bioimaging, iridium complexes, oxygen sensors, phosphorescence, Oxygen, Magnetic Resonance Spectroscopy, Radiation, Ligands, Methanol",
author = "Kritchenkov, {Ilya S.} and Mikhnevich, {Vitaliya G.} and Stashchak, {Victoria S.} and Solomatina, {Anastasia I.} and Kozina, {Daria O.} and Sokolov, {Victor V.} and Tunik, {Sergey P.}",
note = "Publisher Copyright: {\textcopyright} 2022 by the authors. Licensee MDPI, Basel, Switzerland.",
year = "2022",
month = may,
day = "14",
doi = "10.3390/molecules27103156",
language = "English",
volume = "27",
journal = "Molecules",
issn = "1420-3049",
publisher = "MDPI AG",
number = "10",

}

RIS

TY - JOUR

T1 - Novel NIR-Phosphorescent Ir(III) Complexes

T2 - Synthesis, Characterization and Their Exploration as Lifetime-Based O2 Sensors in Living Cells

AU - Kritchenkov, Ilya S.

AU - Mikhnevich, Vitaliya G.

AU - Stashchak, Victoria S.

AU - Solomatina, Anastasia I.

AU - Kozina, Daria O.

AU - Sokolov, Victor V.

AU - Tunik, Sergey P.

N1 - Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2022/5/14

Y1 - 2022/5/14

N2 - A series of [Ir(NˆC)2 (NˆN)]+ NIR-emitting orthometalated complexes (1–7) has been prepared and structurally characterized using elemental analysis, mass-spectrometry, and NMR spectroscopy. The complexes display intense phosphorescence with vibrationally structured emission bands exhibiting the maxima in the range 713–722 nm. The DFT and TD DFT calculations showed that the photophysical characteristics of these complexes are largely determined by the properties of the metalating NˆC ligands, with their major contribution into formation of the lowest S1 and T1 excited states responsible for low energy absorption and emission, respectively. Emission lifetimes of 1–7 in degassed methanol solution vary from 1.76 to 5.39 µs and show strong quenching with molecular oxygen to provide an order of magnitude lifetime reduction in aerated solution. The photophysics of two complexes (1 and 7) were studied in model physiological media containing fetal bovine serum (FBS) and Dulbecco’s Modified Eagle Medium (DMEM) to give linear Stern-Volmer calibrations with substantially lower oxygen-quenching constants compared to those obtained in methanol solution. These observations were interpreted in terms of the sensors’ interaction with albumin, which is an abundant component of FBS and cell media. The studied complexes displayed acceptable cytotoxicity and preferential localization, either in mitochondria (1) or in lysosomes (7) of the CHO-K1 cell line. The results of the phosphorescence lifetime imaging (PLIM) experiments demonstrated considerable variations of the sensors’ lifetimes under normoxia and hypoxia conditions and indicated their applicability for semi-quantitative measurements of oxygen concentration in living cells. The complexes’ emission in the NIR domain and the excitation spectrum, extending down to ca. 600 nm, also showed that they are promising for use in in vivo studies.

AB - A series of [Ir(NˆC)2 (NˆN)]+ NIR-emitting orthometalated complexes (1–7) has been prepared and structurally characterized using elemental analysis, mass-spectrometry, and NMR spectroscopy. The complexes display intense phosphorescence with vibrationally structured emission bands exhibiting the maxima in the range 713–722 nm. The DFT and TD DFT calculations showed that the photophysical characteristics of these complexes are largely determined by the properties of the metalating NˆC ligands, with their major contribution into formation of the lowest S1 and T1 excited states responsible for low energy absorption and emission, respectively. Emission lifetimes of 1–7 in degassed methanol solution vary from 1.76 to 5.39 µs and show strong quenching with molecular oxygen to provide an order of magnitude lifetime reduction in aerated solution. The photophysics of two complexes (1 and 7) were studied in model physiological media containing fetal bovine serum (FBS) and Dulbecco’s Modified Eagle Medium (DMEM) to give linear Stern-Volmer calibrations with substantially lower oxygen-quenching constants compared to those obtained in methanol solution. These observations were interpreted in terms of the sensors’ interaction with albumin, which is an abundant component of FBS and cell media. The studied complexes displayed acceptable cytotoxicity and preferential localization, either in mitochondria (1) or in lysosomes (7) of the CHO-K1 cell line. The results of the phosphorescence lifetime imaging (PLIM) experiments demonstrated considerable variations of the sensors’ lifetimes under normoxia and hypoxia conditions and indicated their applicability for semi-quantitative measurements of oxygen concentration in living cells. The complexes’ emission in the NIR domain and the excitation spectrum, extending down to ca. 600 nm, also showed that they are promising for use in in vivo studies.

KW - bioimaging

KW - iridium complexes

KW - oxygen sensors

KW - phosphorescence

KW - Oxygen

KW - Magnetic Resonance Spectroscopy

KW - Radiation

KW - Ligands

KW - Methanol

UR - http://www.scopus.com/inward/record.url?scp=85130690065&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3bab6dd9-f9c1-3174-b6a5-0d5d839eef93/

U2 - 10.3390/molecules27103156

DO - 10.3390/molecules27103156

M3 - Article

C2 - 35630633

AN - SCOPUS:85130690065

VL - 27

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 10

M1 - 3156

ER -

ID: 95471533