TY - JOUR
T1 - Photoactivatable CO-Releasing Properties of {Ru(CO)2}-Core Pyridylbenzimidazole Complexes and Reactivity towards Lysozyme
AU - Mansour, Ahmed M.
AU - Shehab, Ola R.
N1 - Publisher Copyright:
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/10/10
Y1 - 2017/10/10
N2 - The photoinduced CO-releasing properties of [RuLPy(CO)2Cl2] (1), [Ru(LPy2Bz-ĸ2N1,N2)(CO)2Cl2] (2), and [Ru(LPy2Bz–Et-ĸ3N1,N2,N3)(CO)2(Cl)]·PF6 (3) [LPy = 2-(2-pyridyl)benzimidazole, LPy2Bz = 2,6-bis(benzimidazole-2′-yl)pyridine, and LPy2Bz–Et = 2,6-bis(1-ethyl-benzimidazol-2′-yl)pyridine] in both DMSO and reduced myoglobin solution are reported. Complexes 1 and 2 release CO upon illumination at 365 nm. The bidentate chelation mode of LPy2Bz in 2 is changed into a meridional tridentate mode upon the ethylation of the benzimidazolic NH groups, 3. The extension of the conjugation system and the shift of the MLCT band into the visible region in 3 give rise to the RuII dicarbonyl complex capable of releasing CO at 468 nm. During illumination of 2, the chelation mode of LPy2Bz is changed from ĸ2N1,N2 to ĸ3N1,N2,N3, as monitored by solution NMR spectroscopic studies. The spectral properties were studied by TD-DFT calculations. The interaction of 1–3 with hen-egg-white lysozyme, as a biocompatible carrier, has been studied by ESI-MS and UV/Vis spectroscopy in the dark and upon illumination. Stable protein adducts containing the RuII(CO)2 moiety, capable of photoinduced release of CO, are formed.
AB - The photoinduced CO-releasing properties of [RuLPy(CO)2Cl2] (1), [Ru(LPy2Bz-ĸ2N1,N2)(CO)2Cl2] (2), and [Ru(LPy2Bz–Et-ĸ3N1,N2,N3)(CO)2(Cl)]·PF6 (3) [LPy = 2-(2-pyridyl)benzimidazole, LPy2Bz = 2,6-bis(benzimidazole-2′-yl)pyridine, and LPy2Bz–Et = 2,6-bis(1-ethyl-benzimidazol-2′-yl)pyridine] in both DMSO and reduced myoglobin solution are reported. Complexes 1 and 2 release CO upon illumination at 365 nm. The bidentate chelation mode of LPy2Bz in 2 is changed into a meridional tridentate mode upon the ethylation of the benzimidazolic NH groups, 3. The extension of the conjugation system and the shift of the MLCT band into the visible region in 3 give rise to the RuII dicarbonyl complex capable of releasing CO at 468 nm. During illumination of 2, the chelation mode of LPy2Bz is changed from ĸ2N1,N2 to ĸ3N1,N2,N3, as monitored by solution NMR spectroscopic studies. The spectral properties were studied by TD-DFT calculations. The interaction of 1–3 with hen-egg-white lysozyme, as a biocompatible carrier, has been studied by ESI-MS and UV/Vis spectroscopy in the dark and upon illumination. Stable protein adducts containing the RuII(CO)2 moiety, capable of photoinduced release of CO, are formed.
KW - CO-releasing molecules
KW - Density functional calculations
KW - Lysozymes
KW - Photochemistry
KW - Ruthenium
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U2 - 10.1002/ejic.201700898
DO - 10.1002/ejic.201700898
M3 - Article
AN - SCOPUS:85031107914
SN - 1434-1948
VL - 2017
SP - 4299
EP - 4310
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 37
ER -