Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow-fiber micro-solid-phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design.

A sensitive technique to determinate naproxen in hair samples was developed using hollow-fiber micro-solid-phase combined with fluorescence spectrophotometry. The incorporation of multi-walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol-gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow-fiber micro-solid-phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4(6) ) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2-10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103-95%. The relative standard deviation for fiber-to-fiber repeatability was 3.9%.

Rational design of heteropolyacid-based nanosorbent for hollow fiber solid phase microextraction of organophosphorus residues in hair samples.

A novel heteropolyacid-based supported ionic liquid (IL) mediated sol-gel hybrid organic-inorganic material is presented for effective use in hollow fiber solid phase microextraction (HF-SPME). We examined a Keggin-based IL that was evaluated in conjunction with sol-gel. This study shows that Keggin-based IL sol-gel generated porous morphology pro effective extraction media. The method was developed for the extraction of the organophosphorus pesticides (OPs); diazinon, fenitrothion and malathion from human hair samples. The OPs were subsequently analyzed with high performance liquid chromatography and photodiode array detection (HPLC-PDA). In the basic condition (pH 10-11), the gel growth process in the presence of IL was initiated. Afterward, this sol was injected into a polypropylene hollow fiber segment for in situ-gelation process. Parameters affecting the efficiency of HF-SPME were thoroughly investigated. Linearity was observed over a range of 0.02-50,000 µg/g and 0.0001-25,000 ng/mL with detection limits between 0.0074-1.3000 µg/g and 0.00034-0.84 ng/mL for the OPs in hair and aqueous matrices, respectively. The relative recoveries in the real samples, for OPs in the storekeeper hair ranged from 86 to 95.2%.

Synthesis and characterization of two novel organic-inorganic compounds based on tetrahexyl and tetraheptyl ammonium ions and the Preyssler anion and their catalytic activities in the synthesis of 4-aminopyrazolo[3,4-d]- pyrimidines.

Two novel organic-inorganic compounds based on tetrahexylammonium (THA) and tetraheptylammonium (THPA) ions and the Preyssler anion, [NaP5W30O110]14-, were synthesized and formulated as (THA)7.7H6.3 [NaP5W30O110] (A) and (THPA)7.5 H6.5[NaP5W30O110] (B). The synthesized compounds were characterized by IR, UV, and TGA and used for the catalytic synthesis of 4-aminopyrazolo[3,4,-d]pyrimidine derivatives 2a-2d. Our findings showed efficient catalytic activities for A and B.