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@article{1407990,
author = {Corrochano Díaz, Pablo and Nachtigallová, Dana and Klán, Petr},
article_location = {WASHINGTON},
article_number = {23},
doi = {http://dx.doi.org/10.1021/acs.est.7b04510},
keywords = {AIR-ICE INTERFACE; EXPERIMENTAL-COMPUTATIONAL APPROACH; DISSOLVED ORGANIC-MATTER; HABER-WEISS CYCLE; HYDROGEN-PEROXIDE; SPECTROSCOPIC PROPERTIES; ISOTOPE FRACTIONATION; PHOTOEXCITED ANILINE; HYDRATED ELECTRONS; SELF-ASSOCIATION},
language = {eng},
issn = {0013-936X},
journal = {ENVIRONMENTAL SCIENCE AND TECHNOLOGY},
title = {Photooxidation of Aniline Derivatives Can Be Activated by Freezing Their Aqueous Solutions},
url = {https://pubs.acs.org/doi/10.1021/acs.est.7b04510},
volume = {51},
year = {2017}
}
TY - JOUR
ID - 1407990
AU - Corrochano Díaz, Pablo - Nachtigallová, Dana - Klán, Petr
PY - 2017
TI - Photooxidation of Aniline Derivatives Can Be Activated by Freezing Their Aqueous Solutions
JF - ENVIRONMENTAL SCIENCE AND TECHNOLOGY
VL - 51
IS - 23
SP - 13763-13770
EP - 13763-13770
PB - AMER CHEMICAL SOC
SN - 0013936X
KW - AIR-ICE INTERFACE
KW - EXPERIMENTAL-COMPUTATIONAL APPROACH
KW - DISSOLVED ORGANIC-MATTER
KW - HABER-WEISS CYCLE
KW - HYDROGEN-PEROXIDE
KW - SPECTROSCOPIC PROPERTIES
KW - ISOTOPE FRACTIONATION
KW - PHOTOEXCITED ANILINE
KW - HYDRATED ELECTRONS
KW - SELF-ASSOCIATION
UR - https://pubs.acs.org/doi/10.1021/acs.est.7b04510
L2 - https://pubs.acs.org/doi/10.1021/acs.est.7b04510
N2 - A combined experimental and computational approach was, used to investigate the spectroscopic properties of three different aniline derivatives (aniline, N,N-dimethylaniline, and N,N-diethylaniline) in aqueous solutions and at the air-ice interface in the temperature range of 243-298 K The absorption and diffuse reflectance spectra of ice samples prepared by different techniques, such as slow or shock freezing of the aqueous solutions or vapor deposition on ice grains, exhibited unequivocal bathochromic shifts of 10-15 nm of the absorption maxima of anilines in frozen samples compared to those in liquid aqueous solutions. DFT and SCS-ADC(2) calculations showed that contaminant contaminant and contaminant-ice interactions are responsible for these shifts. Finally, we demonstrate that irradiation of anilines in the presence of a hydrogen peroxide/O-2 system by wavelengths that overlap only with the red-shifted absorption tails of anilines in frozen samples (while having a marginal overlap with their spectra in liquid solutions) can almost exclusively trigger a photochemical oxidation process. Mechanistic and environmental considerations are discussed.
ER -
CORROCHANO DÍAZ, Pablo, Dana NACHTIGALLOVÁ a Petr KLÁN. Photooxidation of Aniline Derivatives Can Be Activated by Freezing Their Aqueous Solutions. \textit{ENVIRONMENTAL SCIENCE AND TECHNOLOGY}. WASHINGTON: AMER CHEMICAL SOC, 2017, roč.~51, č.~23, s.~13763-13770. ISSN~0013-936X. Dostupné z: https://dx.doi.org/10.1021/acs.est.7b04510.
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