Solution Phase Photolysis of 1,2-Dithiane Alone and with Single-Walled Carbon Nanotubes

Engel, Paul S.; Gudimetla, Vittal B.; Gancheff, Jorge S.; Denis, Pablo A.

doi:10.1021/jp306384u

Cited by 6 publications

(2 citation statements)

References 77 publications

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“…It is well known that tunneling is of great importance for the light particles transfer [28,[39][40][41][42][43][44][45][46][47][48]. As may be seen from Fig.…”

Section: Tunneling Factormentioning

confidence: 86%

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

et al. 2013

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This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions at alkane by the ÁC 2 H 5 radical on-the-fly. The linear energy relationship (LER), developed for acyclic alkanes, was also proven to hold for cyclic alkanes. We have derived all RC-TST parameters from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 50 % systematic errors on the average exist in the predicted rate constants using either the RC-TST/LER or RC-TST/BHG method, while in comparison with explicit rate calculations, the differences are within a factor of 2 on the average. The results also show that the RC-TST method is not sensitive to the choice of density functional theory used.

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“…It is well known that tunneling is of great importance for the light particles transfer [28,[39][40][41][42][43][44][45][46][47][48]. As may be seen from Fig.…”

Section: Tunneling Factormentioning

confidence: 86%

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

et al. 2013

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“…The fission of the S-S bond is the primary reaction reported upon irradiation with wavelengths greater than ~ 250 nm. 8,[25][26][27][28][29][30][31][32][33] Nevertheless, several studies account for the photoproducts of C-S bond scission. [34][35][36][37][38][39][40][41] Notably, these are reported predominantly on tertiary disulfides such as tertbutyl disulfide and penicillamine disulfide.…”

Section: Introductionmentioning

confidence: 99%

UV photochemistry of the L-cystine disulfide bridge in aqueous solution investigated by femtosecond X-ray absorption spectroscopy

Ochmann,

Harich,

et al. 2024

Preprint

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Despite the biological relevance of the disulfide bond as the motive, which stabilizes the tertiary structure of many proteins, its photostability, UV-induced bond cleavage mechanisms and secondary photochemistry are still contested after decades of research. In this study, we employed femtosecond X-ray absorption spectroscopy to unravel the photochemistry of the aliphatic disulfide bridge of the semi-essential proteinogenic amino acid L-cysteine (L-cystine) in aqueous solution. We observe homolytic bond cleavage upon UV irradiation and the emergence of thiyl radicals as the single primary photoproduct and its ultrafast decay due to geminate recombination at remarkably high quantum yield in excess of 80% within 20 ps. These dynamics coincide with the emergence of a secondary product, attributed to the perthiyl radical. More than 70% of broken disulfide bridges form within the first nanosecond after bond cleavage. From these observations, we establish a dynamic photostability of the disulfide bridge and a mechanism of perthiyl radical formation from a 'hot' ground-state parent molecule that asymmetrically fragments along a carbon-sulfur bond, resolving long-standing questions in the photochemistry of disulfide bridges in condensed phase.

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Recent Progress on the Chemical Reactions of Single-Walled Carbon Nanotubes

Maeda

Akasaka

2015

Chemical Science of Π-Electron Systems

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Solution Phase Photolysis of 1,2-Dithiane Alone and with Single-Walled Carbon Nanotubes

Cited by 6 publications

References 77 publications

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

UV photochemistry of the L-cystine disulfide bridge in aqueous solution investigated by femtosecond X-ray absorption spectroscopy

Recent Progress on the Chemical Reactions of Single-Walled Carbon Nanotubes

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