Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028, China.
Zhejiang Textile Testing Research Institute, Hangzhou 310013, China.
J Chromatogr A. 2018 May 18;1550:45-56. doi: 10.1016/j.chroma.2018.03.040. Epub 2018 Mar 21.
Allergenic disperse dyes are a group of environmental contaminants, which are toxic and mutagenic to human beings. In this work, a method of dispersive solid-phase extraction (d-SPE) using graphene-coated polystyrene-divinylbenzene (G@PS-DVB) microspheres coupled with supercritical fluid chromatography (SFC) was proposed for the rapid determination of 10 allergenic disperse dyes in industrial wastewater samples. G@PS-DVB microspheres were synthesized by coating graphene (G) sheets onto polystyrene-divinylbenzene (PS-DVB) polymers. Such novel sorbents were employed in d-SPE for the purification and concentration of allergenic disperse dyes in wastewater samples prior to the determination by SFC with UV detection. To achieve the maximum extraction efficiency for the target dyes, several parameters influencing d-SPE process such as sorbent dosage, extraction time, desorption conditions were investigated. SFC conditions including stationary phase, modifier composition and percentage, column temperature, backpressure and flow rate were optimized to well separate the allergenic disperse dyes. Under the optimum conditions, satisfactory linear relationship (R ≥ 0.9989) was observed with the concentration of dyes ranging from 0.02 to 10.0 μg/mL. The limits of detection (LOD, S/N = 3) for the ten dyes were in the range of 1.1-15.6 ng/mL. Recoveries for the spiked samples were between 89.1% and 99.7% with relative standard deviations (RSD) lower than 10.5% in all cases. The proposed method is time-saving, green, precise and repeatable for the analysis of the target dyes. Furthermore, the application of G@PS-DVB based d-SPE process can be potentially expanded to isolate and concentrate other aromatic compounds in various matrices and supercritical fluid chromatography methodology featuring rapidity, accuracy and green will be an ideal candidate for the analysis of these compounds.
致敏分散染料是一组对人类有毒和致突变的环境污染物。在这项工作中，提出了一种使用石墨烯包覆的聚苯乙烯-二乙烯基苯（G@PS-DVB）微球与超临界流体色谱（SFC）结合的分散固相萃取（d-SPE）方法，用于快速测定工业废水中的 10 种致敏分散染料水样。G@PS-DVB 微球是通过将石墨烯（G）片涂覆到聚苯乙烯-二乙烯基苯（PS-DVB）聚合物上合成的。这种新型吸附剂用于 d-SPE，在通过 SFC 与紫外检测之前，用于净化和浓缩废水中的致敏分散染料。为了获得目标染料的最大萃取效率，研究了影响 d-SPE 过程的几个参数，如吸附剂用量、萃取时间、解吸条件等。优化了 SFC 条件，包括固定相、改性剂组成和百分比、柱温、背压和流速，以很好地分离致敏分散染料。在最佳条件下，观察到染料浓度在 0.02 至 10.0μg/mL 范围内具有令人满意的线性关系（R≥0.9989）。十种染料的检出限（LOD，S/N=3）在 1.1-15.6ng/mL 范围内。在所有情况下，加标样品的回收率在 89.1%至 99.7%之间，相对标准偏差（RSD）均低于 10.5%。该方法省时、绿色、精确且可重复，适用于目标染料的分析。此外，基于 G@PS-DVB 的 d-SPE 过程的应用可以潜在地扩展到各种基质中分离和浓缩其他芳香族化合物，并且超临界流体色谱方法以快速、准确和绿色为特点，将成为分析这些化合物的理想选择。
