Damage of amino acids by aliphatic peroxyl radicals: a kinetic and computational study

Nathanael, Joses G.; Yuan, Bing; Smith, Trevor A.; Wille, Uta

doi:10.1039/d2ob02302d

Cited by 2 publications

(2 citation statements)

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“…The experimental setup used for time-resolved emission measurements is described elsewhere. 41 The excitation power was 15.5 mW at 10 Hz at 477 nm (spot size ∼ 0.4 cm fwhm, 1.5 mJ/pulse).…”

Section: ■ Methodsmentioning

confidence: 99%

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

Xu,

Marlton,

Flint

et al. 2024

J. Phys. Chem. A

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The metal−ligand charge transfer ( 3 MLCT) and phosphorescence-quenching metal-centered ( 3 MC) states of the helicate and mesocate diastereoisomers of a double-stranded dinuclear polypyridylruthenium(II) complex have been investigated using ultrafast transient absorption spectroscopy. At 294 K, transient signals of the helicate decayed significantly slower than those of the mesocate, whereas at 77 K, no clear contrast in kinetics was observed. Contributions to excited-state decay from high-lying 3 MLCT states were identified at both temperatures. Spectroscopic data (294 K) suggest that the 3 MC state of the helicate lies above the 3 MLCT and that the reverse is true for the mesocate; this was further validated by density functional theory calculations. The stabilization of the 3 MC state relative to the 3 MLCT state in the mesocate was explained by a reduction in ligand field strength due to distortion near the ligand bridge, which causes further deviation from octahedral geometry compared to the helicate. This work illustrates how minor structural differences can significantly influence excited state dynamics.

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Section: ■ Methodsmentioning

confidence: 99%

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

Xu,

Marlton,

Flint

et al. 2024

J. Phys. Chem. A

Self Cite

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show abstract

“…The experimental setup used for time-resolved emission measurements is described elsewhere. 56 The excitation power was 15.5 mW at 10 Hz at 477 nm (spot size ⇠ 0.4 cm FWHM,…”

Section: Emission Decay Measurementsmentioning

confidence: 99%

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

Xu,

Marlton,

Flint

et al. 2023

Preprint

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The metal-ligand charge transfer (3MLCT) and the phosphorescence-quenching metal-centered (3MC) states of the helicate and mesocate conformers of a double- stranded dinuclear polypyridylruthenium(II) complex have been investigated using ultrafast transient absorption spectroscopy. At 294 K, transient signals of the helicate decayed significantly slower than the mesocate, whereas at 77 K, no clear contrast in kinetics was observed. Contributions to excited-state decay from high-lying 3MLCT states were identified at both temperatures. Spectroscopic data (294 K) suggest that the 3MC state of the helicate lies above the 3MLCT and the reverse is true for the mesocate; this was further validated by DFT calculations. The stabilization of the 3MC state relative to the 3MLCT state in the mesocate was explained by a reduction in ligand field strength due to distortion near the ligand bridge which causes further deviation from octahedral geometry compared to the helicate. This work illustrates how minor structural differences can significantly influence excited state dynamics.

show abstract

Damage of amino acids by aliphatic peroxyl radicals: a kinetic and computational study

Abstract: Absolute second-order rate coefficients for the reaction of the N- and C-protected amino acids tyrosine (Tyr), tryptophan (Trp), methionine (Met) and proline (Pro) with triethylamine-derived aliphatic peroxyl radical TEAOO•, which...

Cited by 2 publications

References 42 publications

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

Photophysical Studies of Helicate and Mesocate Double-Stranded Dinuclear Ru(II) Complexes

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