Synthesis of a New Molecularly Imprinted Polymer and Optimisation of Phenylglyoxylic Acid Extraction from Human Urine Samples Using a Central Composite Design within the Response Surface Methodology.

ABSTRACT

Styrene, a chemical widely used in various industries, undergoes metabolic breakdown in the human body, resulting in the production of phenylglyoxylic acid (PGA). A novel molecularly imprinted polymer (MIP) was synthesised for selective extraction and enrichment of PGA in urine samples prior to high-performance liquid chromatography. The MIP employed in this research was a 4-vinylpyridine molecularly imprinted polymer (4-VPMIP) prepared via mass polymerisation using a noncovalent method. The structural and morphological characteristics of the molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs) were evaluated using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The efficiency of the molecularly imprinted solid-phase extraction (MISPE) process was optimised by investigating critical variables such as sample pH, sorbent mass, sample flow rate, and volume of the elution solvent. A central composite design (CCD) within the response surface methodology was utilised to develop separate models for the adsorption and desorption steps. Analysis of variance (ANOVA) confirmed the excellent fit of the experimental data to the proposed response models. Under the optimised conditions, the molecularly imprinted polymers exhibited a higher degree of selectivity and affinity for PGA, with a relative selectivity coefficient (α) of 2.79 against hippuric acid. The limits of detection (LOD) and quantification (LOQ) for PGA were determined to be 0.5 mg/L and 1.6 mg/L, respectively. The recoveries of PGA ranged from 97.32% to 99.06%, with a relative standard deviation (RSD) lower than 4.6%. Furthermore, MIP(4VP)SPE demonstrated the potential for recycling up to three times without significant loss in analyte recovery.