Electronic structures and spectroscopic signatures of diiron intermediates generated by O<sub>2</sub> activation of nonheme iron(<scp>ii</scp>)–thiolate complexes

Ekanayake, Danushka M; Pham, Dao; Probst, A.; Miller, J.; Popescu, Codrina V.; Fiedler, Adam T.

doi:10.1039/d1dt02286e

Cited by 2 publications

(1 citation statement)

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“…Different roto-vibrational levels are also easily populated at achievable temperatures, vibronic coupling can be resolved at cryogenic measurements, and different coordination numbers, different adsorption modes, other equilibrium distributions, and other geometric isomers may be obtained depending on the atmosphere composition, pressure, and temperature. Recent examples are the cryogenic observation of vibronic coupling on Ru II complexes of tridentate bisphosphino-oligothiopentene (Figure ) and cycloreversion of dithienylethene compounds. ,− These types of variable temperature measurements are currently mostly limited to homogeneous complexes and enzymes. Cryogenic measurements in diffuse reflectance mode ( vide infra ) are scarce, but they have been successfully applied to study thermochromism in Salicylideneanilines .…”

Section: Role Of In Situ Uv–vis–nir Absorption Spectroscopiesmentioning

confidence: 99%

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

Bols,

Ma,

Rammal

et al. 2024

Chem. Rev.

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This review highlights in situ UV–vis–NIR range absorption spectroscopy in catalysis. A variety of experimental techniques identifying reaction mechanisms, kinetics, and structural properties are discussed. Stopped flow techniques, use of laser pulses, and use of experimental perturbations are demonstrated for in situ studies of enzymatic, homogeneous, heterogeneous, and photocatalysis. They access different time scales and are applicable to different reaction systems and catalyst types. In photocatalysis, femto- and nanosecond resolved measurements through transient absorption are discussed for tracking excited states. UV–vis–NIR absorption spectroscopies for structural characterization are demonstrated especially for Cu and Fe exchanged zeolites and metalloenzymes. This requires combining different spectroscopies. Combining magnetic circular dichroism and resonance Raman spectroscopy is especially powerful. A multitude of phenomena can be tracked on transition metal catalysts on various supports, including changes in oxidation state, adsorptions, reactions, support interactions, surface plasmon resonances, and band gaps. Measurements of oxidation states, oxygen vacancies, and band gaps are shown on heterogeneous catalysts, especially for electrocatalysis. UV–vis–NIR absorption is burdened by broad absorption bands. Advanced analysis techniques enable the tracking of coking reactions on acid zeolites despite convoluted spectra. The value of UV–vis–NIR absorption spectroscopy to catalyst characterization and mechanistic investigation is clear but could be expanded.

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Section: Role Of In Situ Uv–vis–nir Absorption Spectroscopiesmentioning

confidence: 99%

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

Bols,

Ma,

Rammal

et al. 2024

Chem. Rev.

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The Role of Ferric Nitrilotriacetate in Renal Carcinogenesis and Cell Death: From Animal Models to Clinical Implications

Okazaki

2022

Cancers

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Iron is essential for cellular growth, and various ferroproteins and heme-containing proteins are involved in a myriad of cellular functions, such as DNA synthesis, oxygen transport, and catalytic reactions. As a consequence, iron deficiency causes pleiotropic effects, such as hypochromic microcytic anemia and growth disturbance, while iron overload is also deleterious by oxidative injury. To prevent the generation of iron-mediated reactive oxygen species (ROS), ferritin is synthesized to store excess iron in cells that are consistent with the clinical utility of the serum ferritin concentration to monitor the therapeutic effect of iron-chelation. Among the animal models exploring iron-induced oxidative stress, ferric nitrilotriacetate (Fe-NTA) was shown to initiate hepatic and renal lipid peroxidation and the development of renal cell carcinoma (RCC) after repeated intraperitoneal injections of Fe-NTA. Here, current understanding of Fe-NTA-induced oxidative stress mediated by glutathione-cycle-dependent iron reduction and the molecular mechanisms of renal carcinogenesis are summarized in combination with a summary of knowledge of the relationship between the pathogenesis of human RCC and iron metabolism. In addition to iron-mediated carcinogenesis, the ferroptosis that is triggered by the iron-dependent accumulation of lipid peroxidation and is implicated in the carcinogenesis is discussed.

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Electronic structures and spectroscopic signatures of diiron intermediates generated by O₂ activation of nonheme iron(ii)–thiolate complexes

Abstract: Spectroscopic and computational methods are employed to elucidate the geometric and electronic structures of diiron intermediates arising from the reaction of biomimetic nonheme iron–thiolate complexes with O2.

Cited by 2 publications

References 77 publications

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

The Role of Ferric Nitrilotriacetate in Renal Carcinogenesis and Cell Death: From Animal Models to Clinical Implications

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Electronic structures and spectroscopic signatures of diiron intermediates generated by O2 activation of nonheme iron(ii)–thiolate complexes

Abstract: Spectroscopic and computational methods are employed to elucidate the geometric and electronic structures of diiron intermediates arising from the reaction of biomimetic nonheme iron–thiolate complexes with O2.

Cited by 2 publications

References 77 publications

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

The Role of Ferric Nitrilotriacetate in Renal Carcinogenesis and Cell Death: From Animal Models to Clinical Implications

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Electronic structures and spectroscopic signatures of diiron intermediates generated by O₂ activation of nonheme iron(ii)–thiolate complexes