title: pH-controlled dispersive liquid-liquid microextraction for the analysis of ionisable compounds in complex matrices: Case study of ochratoxin A in cereals.
abstract: A new sample preparation procedure, termed pH-controlled dispersive liquid-liquid microextraction (pH-DLLME), has been developed for the analysis of ionisable compounds in highly complex matrices. This DLLME mode, intended to improve the selectivity and to expand the application range of DLLME, is based on two successive DLLMEs conducted at opposite pH values. pH-DLLME was applied to determination of ochratoxin A (OTA) in cereals. The hydrophobic matrix interferences in the raw methanol extract (disperser, 1mL) were removed by a first DLLME (I DLLME) performed at pH 8 to reduce the solubility of OTA in the extractant (CCl(4), 400μL). The pH of the aqueous phase was then adjusted to 2, and the analyte was extracted and concentrated by a second DLLME (extractant, 150μL C(2)H(4)Br(2)). The main factors influencing the efficiency of pH-DLLME including type and volume of I DLLME extractant, as well as the parameters affecting the OTA extraction by II DLLME, were studied in detail. Under optimum conditions, the method has detection and quantification limits of 0.019 and 0.062μg kg(-1), respectively, with OTA recoveries in the range of 81.2-90.1% (n=3). The accuracy of the analytical procedure, evaluated with a reference material (cereal naturally contaminated with OTA), is acceptable (accuracy of 85.6%±1.7, n=5). The applicability of pH-DLLME to the selective extraction of other ionisable compounds, such as acidic and basic pharmaceutical products was also demonstrated. The additional advantages of pH-DLLME are a higher selectivity and the extension of this microextraction technique to highly complex matrices.
authors.affiliation: Dipartimento di Scienze Farmaceutiche e Biomediche, Università degli Studi di Salerno, via Ponte Don Melillo, 84084 Fisciano (SA), Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: Campone
authors.forename: Anna Lisa
authors.initials: AL
authors.lastname: Piccinelli
authors.forename: Rita
authors.initials: R
authors.lastname: Celano
authors.forename: Luca
authors.initials: L
authors.lastname: Rastrelli
mesh_terms: D002851:Chromatography, High Pressure Liquid; D002523:Edible Grain / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D059627:Liquid Phase Microextraction; D009793:Ochratoxins / Q000032:analysis*; D012995:Solubility
chemical_list: D009793:Ochratoxins; C025589:ochratoxin A