Nanostructured alkyl carboxylic acid-based restricted access solvents: Application to the combined microextraction and cleanup of polycyclic aromatic hydrocarbons in mosses.
Alkyl carboxylic acid-based nanostructured solvents, synthesized in mixtures of tetrahydrofuran (THF) and water through self-assembly and coacervation, were proved to behave as restricted access liquids. Both physical and chemical mechanisms were found responsible for exclusion of macromolecules such as proteins and polysaccharides. The potential of these solvents for extracting small molecules from complex solid samples, without interference from large biomolecules, was here evaluated. For this purpose, they were applied to the extraction of 14 priority polycyclic aromatic hydrocarbons (PAHs) from mosses prior to their separation by liquid chromatography and fluorescence detection (LC-FLD). Sample treatment involved the vortex shaking of 200 mg of moss with 200 μL of decanoic acid-based solvent for 5 min, subsequent centrifugation for 8 min and analysis of the extract by LC-FLD using external calibration. Proteins precipitated during extraction because of both the decrease of the dielectric constant of the solution caused by THF and the formation of macromolecular complexes with decanoic acid. Polysaccharides were not solubilized in the aqueous cavities of the solvent because of their size exclusion. In-house method validation was performed according to the recommendations of the European Commission Decision 202/657/EC. Method detection and quantification limits for the different PAHs were in the ranges 0.04-0.24 and 0.14-0.80 μg kg(-1), respectively. The method was applied to the determination of different moss species collected in both polluted and unpolluted sites in the South of Spain. Recoveries were within the range 71-110%. The results obtained show that solvents with restricted access properties have the potential to expand the scope of application of restricted access materials to areas other than biological fluids because of their suitability to combine analyte isolation and sample cleanup of solid samples in a single step.
Department of Analytical Chemistry, Institute of Fine Chemistry and Nanochemistry, University of Córdoba, Edificio Anexo Marie Curie, Campus de Rabanales, 14071 Córdoba, Spain.
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Caballero-Casero
Department of Chemistry, Faculty of Arts and Sciences, Bülent Ecevit Universiy, 67100 Zonguldak, Turkey.
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Çabuk
Department of Botany, Ecology and Plant Physiology, University of Córdoba, "José Celestino Mutis" Building (C-4), Campus de Rabanales, 14071 Córdoba, Spain.
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Martínez-Sagarra
Department of Botany, Ecology and Plant Physiology, University of Córdoba, "José Celestino Mutis" Building (C-4), Campus de Rabanales, 14071 Córdoba, Spain.
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Devesa
Department of Analytical Chemistry, Institute of Fine Chemistry and Nanochemistry, University of Córdoba, Edificio Anexo Marie Curie, Campus de Rabanales, 14071 Córdoba, Spain. Electronic address: qa1rubrs@uco.es.
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Rubio
D044002:Bryophyta / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D005663:Furans / Q000737:chemistry; D059627:Liquid Phase Microextraction; D049329:Nanostructures / Q000737:chemistry*; D011084:Polycyclic Aromatic Hydrocarbons / Q000032:analysis* / Q000302:isolation & purification; D012997:Solvents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
D002264:Carboxylic Acids; D005663:Furans; D011084:Polycyclic Aromatic Hydrocarbons; D012997:Solvents; D014867:Water; C018674:tetrahydrofuran
Liquid chromatography-Fluorescence detection; Mosses; Polycyclic aromatic hydrocarbons; Restricted access liquids; Restricted access materials; Supramolecular solvents