The role of the iodine-atom adduct in the synthesis and kinetics of methyl vinyl ketone oxide-a resonance-stabilized Criegee intermediate

Physical Chemistry Chemical Physics : PCCP
Yen-Hsiu LinJim Jr-Min Lin

Abstract

Isoprene is the most abundant alkene in the atmosphere. Ozonolysis of isoprene produces three very reactive carbonyl oxides (Criegee intermediates), including formaldehyde oxide, methyl vinyl ketone oxide (MVKO, CH3(C2H3)COO), and methacrolein oxide. The latter two Criegee intermediates are resonance-stabilized due to the vinyl group. Recently, the electronic spectrum of thermalized MVKO has been reported [Caravan, et al., Proc. Natl. Acad. Sci. U. S. A., 2020, 117, 9733]. In this work, we utilized this strong UV/visible absorption to investigate the reaction kinetics of MVKO with SO2 under a wide pressure range of 4 to 700 Torr. We followed a new method [Barber, et al., J. Am. Chem. Soc., 2018, 140, 10866], in which MVKO is produced through the reaction of a resonance-stabilized iodoalkene radical with O2. The experimental data are consistent with a kinetic model that the reaction goes through an adduct of CH3(C2H3)CIOO, similar to the cases of H/alkyl substituted Criegee intermediates. However, different from the H/alkyl adducts, which are stable over the time scales of typical kinetic experiments, this vinyl adduct CH3(C2H3)CIOO is less stable and decomposes to MVKO + I at a time scale of 10-3 s (faster at higher temperature...Continue Reading

References

Jan 5, 2007·Physical Chemistry Chemical Physics : PCCP·Terry J DillonJohn N Crowley
Mar 7, 2008·Journal of Oral Rehabilitation·K-H ChungD C N Chan
Oct 12, 2013·Physical Chemistry Chemical Physics : PCCP·Daniel StonePaul Seakins
Apr 26, 2014·Physical Chemistry Chemical Physics : PCCP·Wei-Lun TingJim Jr-Min Lin
Aug 26, 2014·The Journal of Chemical Physics·Mica C SmithJim Jr-Min Lin
Nov 6, 2014·Physical Chemistry Chemical Physics : PCCP·Leonid ShepsKendrew Au
Jul 17, 2015·The Journal of Chemical Physics·Yuan-Pern Lee
Aug 19, 2015·Proceedings of the National Academy of Sciences of the United States of America·Hao-Li HuangJim Jr-Min Lin
Dec 19, 2013·The Journal of Physical Chemistry Letters·Leonid Sheps
Mar 30, 2016·Physical Chemistry Chemical Physics : PCCP·Tran B NguyenPaul O Wennberg
Aug 26, 2017·Chemical Society Reviews·Jim Jr-Min Lin, Wen Chao
Nov 29, 2017·Physical Chemistry Chemical Physics : PCCP·L VereeckenD Taraborrelli
Apr 4, 2018·Accounts of Chemical Research·Marsha I Lester, Stephen J Klippenstein
Jun 5, 2018·Physical Chemistry Chemical Physics : PCCP·Cangtao Yin, Kaito Takahashi
Apr 24, 2020·Proceedings of the National Academy of Sciences of the United States of America·Rebecca L CaravanMarsha I Lester

❮ Previous
Next ❯

Citations

Jul 28, 2021·The Journal of Physical Chemistry. a·Mei-Tsan KuoKaito Takahashi

❮ Previous
Next ❯

Software Mentioned

Andor Basic
MVKO

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.