Lassalle Yannick, Jellouli Héla, Ballerini Laurie, Souissi Yasmine, Nicol Édith, Bourcier Sophie, Bouchonnet Stéphane
Laboratoire de Chimie Moléculaire UMR-9168, École Polytechnique, 91128 Palaiseau Cedex, France.
Département de Génie Biologique, Université Libre de Tunis, Institut Polytechnique IP2 - 30, Av. Kheireddine Pacha, 1002 Tunis, Tunisia.
J Chromatogr A. 2014 Dec 5;1371:146-53. doi: 10.1016/j.chroma.2014.10.051. Epub 2014 Oct 24.
The UV-vis photodegradation of iprodione in water was investigated with a high pressure mercury lamp photoreactor. Five photoproducts of iprodione were characterized by LC-HR-MS/MS and isotopic labeling; none of them has been reported in previous studies. Three of them result from the elimination of one or two chlorine atoms followed by hydroxy or hydrogen addition while the two others are cyclic isomers of iprodione. An ICR mass spectrometer was used for by-products identification; concentrations of photoproducts were estimated with a triple quadrupole instrument, using iprodione-D5 as an internal standard. Phototransformation mechanisms were postulated to rationalize photoproducts formation. In silico QSAR toxicity predictions were conducted with the Toxicity Estimation Software Tool (T.E.S.T.) considering oral rat LD50, mutagenicity and developmental toxicity. Low oral rat LD50 values of 350 mg/kg and 759 mg/kg were predicted for cyclic isomers of iprodione, compared to that of the parent molecule (2776 mg/kg). Toxicity estimations exhibited that all the iprodione photoproducts could be mutagenic while the parent compound is not. In vitro assays on Vibrio fischeri were achieved on both irradiated and non-irradiated aqueous solutions of iprodione and on HPLC fractions containing isolated photoproducts. Phenolic photoproducts were shown to be mainly responsible for toxicity enhancement with EC50 values of 0.3 and 0.5 ppm, for the bi- and mono-phenolic compounds issued from chlorine elimination.
使用高压汞灯光反应器研究了异菌脲在水中的紫外 - 可见光降解。通过液相色谱 - 高分辨质谱联用仪(LC - HR - MS/MS)和同位素标记对异菌脲的五种光产物进行了表征;之前的研究中均未报道过这些光产物。其中三种是通过消除一个或两个氯原子,随后添加羟基或氢原子形成的,另外两种是异菌脲的环状异构体。使用离子回旋共振质谱仪(ICR)进行副产物鉴定;以异菌脲 - D5作为内标,使用三重四极杆仪器估算光产物的浓度。推测了光转化机制以合理解释光产物的形成。使用毒性估计软件工具(T.E.S.T.)进行了计算机辅助定量构效关系(QSAR)毒性预测,考虑了大鼠经口半数致死量(LD50)、致突变性和发育毒性。预测异菌脲环状异构体的大鼠经口LD50值较低,分别为350 mg/kg和759 mg/kg,而母体分子的LD50值为2776 mg/kg。毒性估计表明,所有异菌脲光产物都可能具有致突变性,而母体化合物则不具有。对异菌脲的辐照和未辐照水溶液以及含有分离出的光产物的高效液相色谱馏分进行了费氏弧菌的体外试验。结果表明,酚类光产物是毒性增强的主要原因,对于由氯消除产生的双酚和单酚化合物,其半数有效浓度(EC50)值分别为0.3 ppm和0.5 ppm。