Chiral and isotope analyses for assessing the degradation of organic contaminants in the environment: Rayleigh dependence.
The Rayleigh equation is frequently used to describe isotope fractionation as a function of conversion. In this article we propose to draw a parallel between isotope and enantiomeric enrichments and derive a set of conditions that allow the use of the Rayleigh approach to describe the enantiomeric enrichment-conversion dependencies. We demonstrate an implementation of the Rayleigh equation for the enantioselective enzymatic hydrolysis of Mecoprop-methyl, Dichlorprop-methyl, and dimethyl-methylsuccinate by lipases from Pseudomonas fluorescens, Pseudomonas cepacia, and Candida rugosa. The data obtained for all the studied reactions gave good fits to the Rayleigh equation, with a linear regression R(2) > 0.96. In addition to that, our analysis of four microcosm studies on the hydrolysis of the individual enantiomers of Dichloroprop methyl, Lactofen, Fenoxaprop-ethyl, and Metalaxyl reported in the literature by other research groups revealed a suitability of the Rayleigh dependence. Two dimensional plots describing the isotope fractionation versus enantiomeric enrichment are demonstrated for all studied cases. Processes not accompanied by enantiomeric enrichment (acid and base hydrolysis) and by isotope enrichment (transesterification) are demonstrated, their 2-D plots are either horizontal or vertical which can illuminate concealed degradation pathways.
The Casali Center of Applied Chemistry, The Institute of Chemistry, The Hebrew University of Jerusalem , Jerusalem 91904, Israel.
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S
Jammer
A
A
Voloshenko
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F
Gelman
O
O
Lev
D008456:2-Methyl-4-chlorophenoxyacetic Acid / Q000031:analogs & derivatives* / Q000032:analysis / Q000737:chemistry / Q000378:metabolism; D000465:Algorithms; D001673:Biodegradation, Environmental; D019149:Bioreactors; D004784:Environmental Monitoring / Q000379:methods*; D007554:Isotopes / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D008049:Lipase / Q000378:metabolism; D010080:Oxazoles / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D011422:Propionates / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D012989:Soil Pollutants / Q000032:analysis* / Q000737:chemistry; D013237:Stereoisomerism
D007554:Isotopes; D010080:Oxazoles; D011422:Propionates; D012989:Soil Pollutants; C008340:mecoprop; C416661:fenoxaprop ethyl; D008456:2-Methyl-4-chlorophenoxyacetic Acid; D008049:Lipase