Novel amino-functionalized magnetic metal-organic framework/layered double hydroxide adsorbent for microfluidic solid phase extraction: Application for vitamin D₃

Vitamin D deficiency is highly prevalent worldwide, especially with limited sun exposure and sun avoidance. Thus, reliable monitoring of vitamin D levels in food and biological samples is vital for medicinal diagnosis. Herein, a potent method for the extraction and determination of vitamin D₃ is presented using a microchip-based solid-phase extraction (SPE) device followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) detection. A new magnetic adsorbent based on Fe₃O₄ magnetic nanoparticles (MNPs) modified ZnFe layered double hydroxide (LDH)/2-aminoterephthalic acid-Zn²⁺ metal-organic framework (IRMOF-3) composite (IRMOF-3@MLDH) was successfully synthesized and fixed inside a rectangular micro-column (4 × 2 × 12 mm). The porous structure and high surface area of IRMOF-3@MLDH provide abundant adsorbing sites and make it a potent SPE adsorbent, with an exceptional ability to retain vitamin D₃. The adsorption isotherm showed that the composite was highly efficient at extracting vitamin D₃ with an extraction capacity of 126 mg g⁻¹. The designed extraction microchip simplified the SPE process, paving the way for automated SPE systems. The developed method presented a broad linear range of 5–2000 ng mL⁻¹, with a detection limit of 1.4 ng mL⁻¹. In comparison to conventional silica-based adsorbents, a higher sensitivity was obtained in the determination of vitamin D₃ using the IRMOF-3@MLDH adsorbent. The selectivity of the method was also satisfactory, enabling the measurement of vitamin D₃ in food and blood samples with high recovery values in the range from 95.2 to 101%. Thus, the newly developed adsorbent and method offer an efficient alternative to the commonly used C18-based approach.