Consideration of reactivity to acute fish toxicity of α,ß-unsaturated carbonyl ketones and aldehydes.
SAR QSAR Environ Res
; 23(1-2): 169-84, 2012 Jan.
Article
em En
| MEDLINE
| ID: mdl-22150015
ABSTRACT
To understand the key factor for fish toxicity of 11 α,ß-unsaturated carbonyl aldehydes and ketones, we used quantum chemical calculations to investigate their Michael reactions with methanethiol or glutathione. We used two reaction schemes, with and without an explicit water molecule (Scheme-1wat and Scheme-0wat, respectively), to account for the effects of a catalytic water molecule on the reaction pathway. We determined the energies of the reactants, transition states (TS), and products, as well as the activation energies of the reactions. The acute fish toxicities of nine of the carbonyl compounds were evaluated to correlate with their hydrophobicities; no correlation was observed for acrolein and crotonaldehyde. The most toxic compound, acrolein, had the lowest activation energy. The activation energy of the reaction could be estimated with Scheme-1wat but not with Scheme-0wat. The complexity of the reaction pathways of the compounds was reflected in the difficulty of the TS structure searches when Scheme-1wat was used with the polarizable continuum model. The theoretical estimations of activation energies of α,ß-unsaturated carbonyl compounds with catalytic molecules or groups including hydrogen-bond networks may complement traditional tools for predicting the acute aquatic toxicities of compounds that cannot be easily obtained experimentally.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Aldeídos
/
Peixes
/
Cetonas
Tipo de estudo:
Prognostic_studies
Limite:
Animals
Idioma:
En
Revista:
SAR QSAR Environ Res
Assunto da revista:
SAUDE AMBIENTAL
Ano de publicação:
2012
Tipo de documento:
Article
País de afiliação:
Japão
País de publicação:
ENGLAND
/
ESCOCIA
/
GB
/
GREAT BRITAIN
/
INGLATERRA
/
REINO UNIDO
/
SCOTLAND
/
UK
/
UNITED KINGDOM