Pipette-tip SPE based on Graphene/ZnCr LDH for Pb(II) analysis in hair samples followed by GFAAS.

In this work, a nanocomposite of ZnCr layered double hydroxide (ZnCr LDH) and graphene oxide (GO) was successfully assembled. An efficient pipette-tip solid-phase extraction (PT-SPE) based on GO/ZnCr LDH followed by GFAAS analysis was used for to preconcentrate Pb(II) in hair samples. Hair samples were treated using acid digestion to make the solid samples suitable for performing the PT-SPE procedure and decrease the interactions between Pb(II) ions and the sample matrix. The sorbent was characterized by FT-IR, SEM, TEM, EDX, elemental mapping, and XRD. Effective extraction parameters were thoroughly investigated. Under the best conditions, the calibration plot was linear within the range of 0.5-15 ng mL-1 (R2 = 0.991). Preconcentration factor (PF) of 10 and absolute recovery (%) of 100% were obtained. LOD and LOQ were found to be 0.1 µg g-1 and 0.5 µg g-1, respectively. The intra-day and inter-day precisions (n = 3) at the concentrations of 2.0 and 10 ng mL-1 were less than 6.8% and 12.5%, respectively. Finally, the method efficiency was investigated for the analysis of Pb(II) in hair samples, and good relative recoveries (RR%) were obtained within the range of 92%-104%.

In-tube stir bar sorptive extraction based on 3-aminopropyl triethoxysilane surface-modified Ce-doped ZnAl layered double hydroxide thin film for determination of nonsteroidal anti-inflammatory drugs in saliva samples.

A thin-film based on 3-aminopropyl triethoxysilane surface-modified Ce-doped zinc-aluminum layered double hydroxide was synthesized on the inner surface of an aluminum tube. It has been applied to in-tube stir bar sorptive extraction of nonsteroidal anti-inflammatory drugs in saliva samples followed by high-performance liquid chromatography. The sorbent was characterized by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and elemental mapping. The extraction parameters including sample pH (4.2), extraction time (10 min), stirring speed (800 rpm), type of eluent (acidified tetrahydrofuran), eluent volume (100 µL), and desorption time (6 min) were thoroughly optimized. Under the optimum conditions, limits of detection were found to be less than 5.0 ng mL-1. Calibration plots were linear within the range 10-1000 ng mL-1 (R2 > 0.9982). Absolute recoveries were calculated in the range 63.5 to 72.4%. The repeatability (intra- and inter-day precision) and reproducibility (tube-to-tube precision) at concentrations of 50, 250, and 500 ng mL-1 were less than 7.6% and 9.4%, respectively. The method accuracy based on the relative error was calculated at these concentrations and ranged from - 4.9 to - 9.3% for intra-day relative error (%) and - 6.8 to - 11% for inter-day relative error (%). Finally, the method applicability was examined for the determination of nonsteroidal anti-inflammatory drugs in saliva samples, and good relative recoveries were obtained within the range 86.5 to 95.2%. As a result, the introduced method can be applied as a suitable alternative to measuring nonsteroidal anti-inflammatory drugs in biological fluids. Graphical abstract A surface-modified Ce-doped ZnAl LDH thin film was synthesized on the inner surface of an Al tube and applied for in-tube stir bar sorptive extraction of NSAIDs in saliva.