Resonance Raman spectra of transient free radicals using stopped flow multichannel and rapid scan methods

Merlin, J.; Lorriaux, J. L.; Hester, R. E.

doi:10.1002/jrs.1250110517

Cited by 6 publications

(3 citation statements)

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“…8 The radical cation (DABCO +. ) has also been studied in liquid solution using optical absorption and RR spectroscopy, 9,10 but because the spectra reported did not agree with those obtained for the isolated molecule and the results of our calculations, we remeasured them in the present work.…”

Section: Introductionmentioning

confidence: 94%

“…Such a situation could in principle be explained by the different excitation wavelengths used. Previous experiments used 476.2 and 488 nm excitation, respectively, , while our excitation wavelength was 460 nm. While changes in relative intensities usually do occur with varying excitation wavelength, the reported differences for 476.2 and 488 nm excitation were small.…”

Section: Experimental Absorption and Resonance Raman Spectra Of Dabco+mentioning

confidence: 99%

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The Radical Cation and Lowest Rydberg States of 1,4-Diaza[2.2.2]bicyclooctane (DABCO)

et al. 2000

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The radical cation and the two lowest excited singlet Rydberg states of DABCO (1,4-diazabicyclo[2.2.2]octane) are studied. Experimentally, the radical cation of DABCO is generated by either laser flash photolysis in solution at room temperature or by γ-irradiation in a Freon glass at 77 K, and its electronic absorption and resonance Raman spectra in these two media are reported. The present resonance Raman spectra differ substantially from previous reports given in the literature, and it is concluded that a number of bands attributed previously to the DABCO radical cation are due to other species. Theoretically, the absorption and resonance Raman spectra are interpreted on the basis of density functional theory (DFT; B3LYP/6-31G(d)) calculations and wave packet propagation methods. The same DFT calculations are used to interpret excitation and multiphoton ionization spectra of the two lowest singlet Rydberg states, making use of the close similarity between a Rydberg state and its ionic core. From the combined results it is concluded that DFT calculations with a relatively modest basis set provide a valuable framework to predict potential energy surfaces of radical cations and Rydberg states in terms of minima and Hessians.

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Section: Introductionmentioning

confidence: 94%

Section: Experimental Absorption and Resonance Raman Spectra Of Dabco+mentioning

confidence: 99%

The Radical Cation and Lowest Rydberg States of 1,4-Diaza[2.2.2]bicyclooctane (DABCO)

et al. 2000

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“…By using a spectroelectrochemical circulating cell, the formal reduction potential of cytochrome c has been titrated and determined potentiometrically . Stopped‐flow RR spectroscopy has been applied to study organic oxidation reactions, which proceed through radical cations . For protein conformational changes, a stopped‐flow RR instrument with a time interval of 200 ms after mixing has been reported using a combination of a triple monochromator and an intensified photodiode array detector as a Raman spectrophotometer, whereas a stopped‐flow apparatus for infrared spectroscopy has been reported .…”

Section: Introductionmentioning

confidence: 99%

Improved stopped‐flow time‐resolved resonance Raman spectroscopy device for studying enzymatic reactions

Yanagisawa

Deshpande

Hirota

et al. 2017

J Raman Spectroscopy

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An improved stopped-flow resonance Raman spectroscopy device was constructed using a stopped-flow mixer with a dead time of 3 ms and a mixing volume of 0.1 mL. The device was tested using myoglobin, where the formation reaction of a high-valent heme species, ferryl-oxo heme, was monitored by time-resolved resonance Raman spectroscopy after mixing a ferric myoglobin solution with a hydrogen peroxide solution. The ferryl-oxo heme formation rate constant obtained by Raman spectroscopy is in good agreement with the rate constant obtained by conventional stopped-flow absorption spectroscopy for the same reaction under the same conditions. It is proved by these results that the present device is generally applicable to enzyme-substrate reactions with a significantly higher time resolution than previously reported.

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1995

Infrared and Raman Spectroscopy

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Resonance Raman spectra of transient free radicals using stopped flow multichannel and rapid scan methods

Cited by 6 publications

References 5 publications

The Radical Cation and Lowest Rydberg States of 1,4-Diaza[2.2.2]bicyclooctane (DABCO)

The Radical Cation and Lowest Rydberg States of 1,4-Diaza[2.2.2]bicyclooctane (DABCO)

Improved stopped‐flow time‐resolved resonance Raman spectroscopy device for studying enzymatic reactions

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