title: Optimization of a NH4PF6-enhanced, non-organic solvent, dual microextraction method for determination of phthalate metabolites in urine by high performance liquid chromatography.
abstract: In conventional ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME) procedures, most of the IL disperser remains in the aqueous phase resulting in low recovery for moderately and weakly polar analytes due to the "carry-over effect". Herein, we successfully developed a "NH4PF6-enhanced, non-organic solvent, dual microextraction" method (ANSDM) for pretreatment of phthalate (PAE) metabolites with weak to moderate polarity. This method utilized in situ reaction of NH4PF6 as an ion-exchange reagent and disperser to realize two microextractions after using [C8MIM]PF6 as an extraction solvent and [C4MIM]BF4 as a disperser for conventional DLLME. Single-factor experiments, a two-level full factorial experimental design and central composite design were applied for optimizing operational parameters using 3D response surfaces and contour lines. Under optimized conditions, the newly developed method provided high extraction recoveries (93.8-99.1%) and low LODs (ca. 0.3μgL(-1)) for three phthalate metabolites in human urine. The primary advantages of the ANSDM method include: (1) integration of in situ reaction and conventional DLLME techniques to effectively extract both weak and moderately polar pollutants simultaneously; (2) non-organic solvent use in the microextraction procedure making the process safer and more environmental friendly; and (3) a time-saving, simple operation that is fully compatibility with HPLC analysis. To the best of our knowledge, our group is the first to develop the "non-organic solvent, dual microextraction" method and it has great potential as a sample pre-treatment technique for organic pollutants with weak to moderate polarity in biological and environmental matrices.
authors: Key Laboratory for Laboratory Medicine, Ministry of Education, Zhejiang Provincial Key Laboratory of Medical Genetics, School of Laboratory Medicine and Life Science, Wenzhou Medical University, Wenzhou 325035 China.
authors: Jia
authors: J
authors: Wu
authors: Key Laboratory for Laboratory Medicine, Ministry of Education, Zhejiang Provincial Key Laboratory of Medical Genetics, School of Laboratory Medicine and Life Science, Wenzhou Medical University, Wenzhou 325035 China.
authors: Zhihan
authors: Z
authors: Ye
authors: Key Laboratory for Laboratory Medicine, Ministry of Education, Zhejiang Provincial Key Laboratory of Medical Genetics, School of Laboratory Medicine and Life Science, Wenzhou Medical University, Wenzhou 325035 China.
authors: Xiaolong
authors: X
authors: Li
authors: Key Laboratory of Watershed Science and Health of Zhejiang Province, Wenzhou 325035, China. Electronic address: zjuwxd@163.com.
authors: Xuedong
authors: X
authors: Wang
authors: Department of Clinical Laboratory, Zhuji Affiliated Hospital of Wenzhou Medical University, Zhuji 311800, China.
authors: Fangjun
authors: F
authors: Luo
authors: Department of Clinical Laboratory, Taizhou Affiliated Hospital of Wenzhou Medical University, Linhai 317000, China.
authors: Bo
authors: B
authors: Sheng
authors: Department of Clinical Laboratory, Zhoushan Affiliated Hospital of Wenzhou Medical University, Dinghai 316000, China.
authors: Yiwei
authors: Y
authors: Li
authors: Key Laboratory for Laboratory Medicine, Ministry of Education, Zhejiang Provincial Key Laboratory of Medical Genetics, School of Laboratory Medicine and Life Science, Wenzhou Medical University, Wenzhou 325035 China. Electronic address: jxlu313@163.com.
authors: Jianxin
authors: J
authors: Lyu
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D004785:Environmental Pollutants / Q000378:metabolism* / Q000652:urine*; D006801:Humans; D052578:Ionic Liquids / Q000737:chemistry; D057230:Limit of Detection; D059627:Liquid Phase Microextraction / Q000379:methods*; D010756:Phosphoric Acids / Q000737:chemistry*; D010795:Phthalic Acids / Q000378:metabolism* / Q000652:urine*; D012997:Solvents / Q000737:chemistry
chemical_list: D004785:Environmental Pollutants; D052578:Ionic Liquids; D010756:Phosphoric Acids; D010795:Phthalic Acids; D012997:Solvents; C032279:phthalic acid; C513217:ammonium hexafluorophosphate
keywords: Central composite design; Dual microextraction; Human urine; NH(4)PF(6)-enhanced; Non-organic solvent; Phthalate metabolites; Weak and moderately polar chemicals