Nickel oxide nanoparticles modified with dimethylglyoxime grafted on a cellulose surface as an efficient adsorbent for thin film microextraction of tramadol in biological fluids followed by its determination using HPLC†

In the current study, nickel oxide nanoparticles (NiO NPs) modified with dimethylglyoxime (DMG) were deposited onto the cellulose surface (Ni(DMG)₂-NiO-Cell) and used as an efficient adsorbent for thin film microextraction (TFME) of tramadol (TRA). The extracted TRA was determined using a high-performance liquid chromatography-ultraviolet detector (HPLC-UV). NiO NPs were synthesized by co-precipitation method on the surface of the cellulose substrate; afterward, its surface was modified by DMG to increase the extraction capability of the thin film toward TRA. The synthesized NiO-Cell and Ni(DMG)₂-NiO-Cell thin films were characterized using various techniques. The effect of modification of the NiO thin film with DMG reagent on the extraction efficiency was investigated. The crucial parameters influencing the extraction efficiency, including extraction time, desorption time, desorption solvent, pH and salt content, were investigated via a one-at-a-time approach. The figures of merit for the developed method were evaluated in urine, plasma, and deionized water under the optimized extraction and desorption condition. The limits of detection and limits of quantification were in the range of 0.1 to 1 ng mL⁻¹ and 0.3 to 3 ng mL⁻¹, respectively, for the studied samples. The linear dynamic ranges of the developed TFME-HPLC-UV method were 0.3–1000, 1–2500, and 3–5000 ng mL⁻¹ for the deionized water, urine, and plasma samples, respectively. The reproducibility and repeatability of the developed method was assayed in terms of intra-day, inter-day, and inter-thin film precisions by conducting six-replicate experiments at the concentration level of 0.1 and 1 μg mL⁻¹, which were in the range of 5.9% to 8.3%. The sufficiency and applicability of the developed TFME-HPLC-UV method was investigated by determining TRA in urine and plasma samples, and the resulting relative recoveries (RR%) were 85.9% and 91.7%, respectively.