An approach based on liquid chromatography/electrospray ionization-mass spectrometry to detect diol metabolites as biomarkers of exposure to styrene and 1,3-butadiene.

An approach based on liquid chromatography/electrospray ionization-mass spectrometry to detect diol metabolites as biomarkers of exposure to styrene and 1,3-butadiene.
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DOI:
10.1016/j.ab.2008.12.007
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发表时间:
2009-03-15
影响因子:
2.9
通讯作者:
Zheng J
Zheng J
中科院分区:
生物学4区
文献类型:
--
作者:
Shen S;Zhang F;Zeng S;Zheng J

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苯乙烯和1,3-丁二烯是塑料工业中广泛使用的重要中间体。它们主要通过细胞色素P450介导的氧化代谢为相应的环氧化物,随后通过环氧化物水解酶或通过自发水合作用转化为二醇。由此产生的苯乙烯乙二醇和3-丁烯-1,2-二醇已被建议分别作为接触苯乙烯和1,3-丁二烯的生物标志物。不幸的是,在电喷雾质谱仪中二醇的差的电离成为通过液相色谱/电喷雾电离-质谱(LC/ESI-MS)检测两种二醇的障碍。建立了一种2-溴吡啶-5-硼酸(BPBA)衍生化的LC/ESI-MS方法,用于苯乙烯乙二醇和3-丁烯-1,2-二醇的分析,不仅大大提高了二醇检测的灵敏度,而且有利于二醇的鉴定。所开发的分析方法简单,快速,令人信服,不需要复杂的化学衍生。为了评估BPBA作为二醇衍生试剂的可行性,我们使用建立的LC/ESI-MS方法研究了二醇构型对选择的二醇对BPBA的亲和力的影响。我们发现顺式和反式二醇都可以被BPBA衍生化。因此,BPBA可作为LC/MS检测邻二醇的通用衍生试剂。
Styrene and 1,3-butadiene are important intermediates used extensively in the plastics industry. They are metabolized mainly through cytochrome P450-mediated oxidation to the corresponding epoxides, which are subsequently converted to diols by epoxide hydrolase or through spontaneous hydration. The resulting styrene glycol and 3-butene-1,2-diol have been suggested as biomarkers of exposure to styrene and 1,3-butadiene, respectively. Unfortunately, poor ionization of the diols within electrospray mass spectrometers becomes an obstacle to the detection of the two diols by liquid chromatography/electrospray ionization–mass spectrometry (LC/ESI–MS). We developed an LC/ESI–MS approach to analyze styrene glycol and 3-butene-1,2-diol by means of derivatization with 2-bromopyridine-5-boronic acid (BPBA), which not only dramatically increases the sensitivity of diol detection but also facilitates the identification of the diols. The analytical approach developed was simple, quick, and convincing without the need for complicated chemical derivatization. To evaluate the feasibility of BPBA as a derivatizing reagent of diols, we investigated the impact of diol configuration on the affinity of a selection of diols to BPBA using the established LC/ESI–MS approach. We found that both cis and trans diols can be derivatized by BPBA. In conclusion, BPBA may be used as a general derivatizing reagent for the detection of vicinal diols by LC/MS.
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