A paper-based polymeric ionic liquid (p-Poly-(MMA-IL)) was successfully developed by grafting the polymeric ionic liquid on the surface of commercial filter paper (FP) by using the dipping method, presenting a new cost-effective film. The newly developed p-Poly-(MMA-IL) FP was then applied as a paper-based thin-film microextraction (p-TFME) analytical device to extract 14 compounds as representative of five groups of antibiotic drugs, which were sulfonamides, tetracyclines, fluoroquinolones, penicillin and macrolides in environmental water samples. Besides, p-Poly-(MMA-IL) FP, p-Poly-(MMA) FP, and unmodified filter paper were successfully characterised by FTIR, NMR, FESEM, TGA, and XRD techniques. They underwent significant parameters optimisation, which affected the extraction efficiency. Under optimal conditions, the proposed (p-Poly-(MMA-IL) FP-TFME) device method was evaluated and applied to analyse multi-class antibiotic drugs in environmental water samples by using a liquid chromatography-mass spectrometry (LC-MS). The validation method showed that a good linearity (0.1 μg L-1 - 500 μg L-1) was noted (R2 > 0.993, n = 3). Detection and quantification limits were within 0.05 μg L-1 - 4.52 μg L-1 and 0.15 μg L-1 - 13.6 μg L-1, respectively. The relative standard deviation (RSD) values ranged at 1.4%-12.2% (intra-day, n = 15) and 4.4%-11.0% (inter-day, n = 10). The extraction recoveries of environmental water samples ranged from 79.1% to 126.8%, with an RSD of less than 15.4% (n = 3). The newly developed paper-based polymeric ionic liquid (p-Poly-(MMA-IL) FP) for analysis of multi-class antibiotic drugs under the p-TFME analytical device procedure was successfully achieved with limited sample volume and organic solvent, fast extraction, and feasible in daily analysis. The detection concentration and relative RSD of multi-class antibiotics determined in various environmental water samples by the proposed method (n = 5) were within 0.44 μg L-1 - 54.41 μg L-1 and 0.69%-15.56%, respectively. These results signified the potential of the p-Poly-(MMA-IL) FP-TFME device as an efficient, sensitive and environmentally friendly approach for analysing antibiotics.
In this work, we reported the synthesis, characterization and adsorption study of two β-cyclodextrin (βCD) cross-linked polymers using aromatic linker 2,4-toluene diisocyanate (2,4-TDI) and aliphatic linker 1,6-hexamethylene diisocyanate (1,6-HDI) to form insoluble βCD-TDI and βCD-HDI. The adsorption of 2,4-dinitrophenol (DNP) on both polymers as an adsorbent was studied in batch adsorption experiments. Both polymers were well characterized using various tools that include Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis and scanning electron microscopy, and the results obtained were compared with the native βCD. The adsorption isotherm of 2,4-DNP onto polymers was studied. It showed that the Freundlich isotherm is a better fit for βCD-TDI, while the Langmuir isotherm is a better fit for βCD-HMDI. The pseudo-second-order kinetic model represented the adsorption process for both of the polymers. The thermodynamic study showed that βCD-TDI polymer was more favourable towards 2,4-DNP when compared with βCD-HDI polymer. Under optimized conditions, both βCD polymers were successfully applied on various environmental water samples for the removal of 2,4-DNP. βCD-TDI polymer showed enhanced sorption capacity and higher removal efficiency (greater than 80%) than βCD-HDI (greater than 70%) towards 2,4-DNP. The mechanism involved was discussed, and the effects of cross-linkers on βCD open up new perspectives for the removal of toxic contaminants from a body of water.
In this present study, magnetic nanoparticles (MNPs) nanocomposites modified with polyaniline (PANI) coated newly synthesised dicationic ionic liquid (DICAT) forming MNP-PANI-DICAT were successfully synthesised as new generation material for magnetic solid phase extraction (MSPE). MNP-PANI-DICAT was characterised by FT-IR NMR, CHN, BET, SEM, TEM, and VSM techniques and the results were compared with MNP-PANI and native MNP. This new material was applied as a magnetic adsorbent for the pre-concentration and separation of polycyclic aromatic hydrocarbons (PAHs) due to the π-π interaction between polyaniline shell and dicationic ionic liquid (DICAT) with PAHs compounds. Under the optimal conditions, the proposed method was evaluated and applied for the analysis of PAHs in environmental samples using gas chromatography-mass spectrometry (GC-MS). The validation method showed good linearity (0.005-500µgL-1) with the coefficient of determination (R2) > 0.999. The limits of detection (LOD) and quantification (LOQ) of the developed method (MNP-PANI-DICAT-MSPE) were in the range of 0.0008-0.2086µgL-1and 0.0024-0.6320µgL-1, respectively. The enrichment factor (EF) of PAHs on MNP-PANI-DICAT-MSPE were in the range of 7.546-29.632. The extraction recoveries of natural water, sludge, and soil samples were ranged from 80.2% to 111.9% with relative standard deviation (RSD) less than 5.6%. The newly synthesised MNP-PANI-DICAT possess good sensitivity, reusability, and fast extraction of PAHs under the MSPE procedure in various environmental samples.
A chiral separation method coupled with capillary electrophoresis (CE) analysis for ketoconazole and miconazole enantiomers using chiral selectors such as β-cyclodextrin (β-CD) and hydroxypropyl-β-CD (HP-β-CD) was developed in this study, which included the optimisation, validation and application of the method on the antifungal cream samples. The formation of inclusion complex between the hosts (β-CD and HP-β-CD) and guests (ketoconazole and miconazole) were compared and analysed using ultraviolet-visible spectrophotometry, nuclear magnetic resonance (NMR) spectroscopy and molecular docking methods. Results from the study showed that in a concentration that ranged between 0.25 and 50 mg L-1 , the linear calibration curves of each enantiomer had a high coefficient of regression (R2 > 0.999), low limit of detection (0.075 mg L-1 ) and low limit of quantification (0.25 mg L-1 ). The relative standard deviation (RSD) of the intraday and interday analyses ranged from 0.79% to 8.01% and 3.30% to 11.43%, respectively, while the recoveries ranged from 82.0% to 105.7% (RSD < 7%, n = 3). The most probable structure of the inclusion complexes was proposed based on the findings from the molecular docking studies conducted using the PatchDock server.