Preparation of amine-modified lignin and its applicability toward online micro-solid phase extraction of valsartan and losartan in urine samples.

In the present work, with the focus on an environmentally-friendly approach, some gels were prepared by synthesizing amine-modified lignin, extracted from sugarcane bagasse, and further esterification and subsequent freeze-drying. These lignin-based gels were implemented as extractive phases in an online micro-solid phase extraction (μSPE) setup in conjunction with high performance liquid chromatography (HPLC) with UV detector. The developed method was used for analytical determination of valsartan and losartan in urine samples. To study the effect of the functionalization process, the efficiency of the unmodified lignin and the functionalized lignin were compared both in the absence and the presence of graphene oxide (GO), presumably as a suitable doping agent. Surprisingly, higher extraction efficiency for the functionalized lignin, compared to both unmodified lignin and GO was observed. The amination process for the prepared gel was analyzed and proved by CHNS elemental analysis and Fourier transform infrared (FT-IR) spectroscopy. The morphology of sorbet was investigated via scanning electron microscope (SEM) imaging and a nanoscale cauliflower feature was observed. The method was optimized and subsequently applied to the analysis of the urine samples. Limits of detection (LOD) of 8 and 6 µg L  , limits of quantification (LOQ) of 27 and 20 µg L   and linear dynamic range (LDR) of 27-2000 and 20-2000 µg L   with intraday relative standard deviations (RSD%) of 4 and 3% were obtained for valsartan and losartan, respectively. The whole online μSPE-HPLC setup was conveniently used for the analysis of a patient urine sample and a quantity of 352 μg L   of losartan was found. Acceptable relative recoveries (109-108 and 95-94% for valsartan and losartan) revealed the analytical potential of the method for the determination of drugs in complex urine samples.