PMID- 14613148
OWN - NLM
STAT- MEDLINE
DCOM- 20041013
LR  - 20131121
IS  - 0947-6539 (Print)
IS  - 0947-6539 (Linking)
VI  - 9
IP  - 21
DP  - 2003 Nov 7
TI  - Mechanism of hydroxyl radical-induced breakdown of the herbicide 
      2,4-dichlorophenoxyacetic acid (2,4-d).
PG  - 5379-87
AB  - Oxidative transformations by the hydroxyl radical are significant in advanced 
      oxidation processes for the breakdown of organic pollutants, yet mechanistic 
      details of the reactions are lacking. A combination of experimental and 
      computational methods has been employed in this study to elucidate the reactivity 
      of the hydroxyl radical with the widely used herbicide 2,4-D 
      (2,4-dichlorophenoxyacetic acid). The experimental data on the reactivity of the 
      hydroxyl radical in the degradation of the herbicide 2,4-D were obtained from 
      gamma-radiolysis experiments with both (18)O-labeled and unlabeled water. These 
      were complemented by computational studies of the (.)OH attack on 2,4-D and 
      2,4-DCP (2,4-dichlorophenol) in the gas phase and in solution. These studies 
      firmly established the kinetically controlled attack ipso to the ether 
      functionality as the main reaction pathway of (.)OH and 2,4-D, followed by 
      homolytic elimination of the ether side chain. In addition, the majority of the 
      early intermediates in the reaction between the hydroxyl radical and 2,4-DCP, the 
      major intermediate, were identified experimentally. While the hydroxyl radical 
      attacks 2,4-D by (.)OH-addition/elimination on the aromatic ring, the oxidative 
      breakdown of 2,4-DCP occurs through (.)OH addition followed by either elimination 
      of chlorine or formation of the ensuing dichlorophenoxyl radical.
FAU - Peller, Julie
AU  - Peller J
AD  - Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, 
      IN 46556-5670, USA.
FAU - Wiest, Olaf
AU  - Wiest O
FAU - Kamat, Prashant V
AU  - Kamat PV
LA  - eng
PT  - Journal Article
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - Germany
TA  - Chemistry
JT  - Chemistry (Weinheim an der Bergstrasse, Germany)
JID - 9513783
RN  - 0 (Herbicides)
RN  - 0 (Oxidants)
RN  - 2577AQ9262 (2,4-Dichlorophenoxyacetic Acid)
RN  - 3352-57-6 (Hydroxyl Radical)
SB  - IM
MH  - 2,4-Dichlorophenoxyacetic Acid/*chemistry
MH  - Gas Chromatography-Mass Spectrometry
MH  - Herbicides/*chemistry
MH  - Hydroxyl Radical/*chemistry
MH  - Models, Molecular
MH  - Oxidants/*chemistry
MH  - Oxidation-Reduction
MH  - Time Factors
EDAT- 2003/11/13 05:00
MHDA- 2004/10/14 09:00
CRDT- 2003/11/13 05:00
PHST- 2003/11/13 05:00 [pubmed]
PHST- 2004/10/14 09:00 [medline]
PHST- 2003/11/13 05:00 [entrez]
AID - 10.1002/chem.200204469 [doi]
PST - ppublish
SO  - Chemistry. 2003 Nov 7;9(21):5379-87. doi: 10.1002/chem.200204469.