A liquid-phase microextraction coupled with LC method has been developed for the determination of organophosphorus pesticides (methidation, quinalphos and profenofos) in drinking water samples. In this method, a small amount (3 microL) of isooctane as the acceptor phase was introduced continually to fill-up the channel of a 1.5 cm polypropylene hollow fiber using a microsyringe while the hollow fiber was immersed in an aqueous donor solution. A portion of the acceptor phase (ca. 0.4 microL) was first introduced into the hollow fiber and additional amounts (ca. 0.2 microL) of the acceptor phase were introduced to replenish at intervals of 3 min until set end of extraction (40 min). After extraction, the acceptor phase was withdrawn and transferred into a 2 mL vial for a drying step prior to injection into a LC system. Parameters that affect the extraction efficiency were studied including the organic solvent, length of fiber, volume of acceptor and donor phase, stirring rate, extraction time, and effect of salting out. The proposed method provided good enrichment factors of up to 189.50, with RSD ranging from 0.10 to 0.29%, analyte recoveries of over 79.80% and good linearity ranging from 10.0 to 1.25 mg/L. The LOD ranged from 2.86 to 82.66 microg/L. This method was applied successfully to the determination of organophosphorus pesticides in selected drinking water samples.
In this work, the novel imprinted zeolite (IZ) was synthesized, and its properties and performance in terms of adsorption of p-Cresol, which represent the protein-bounded uremic toxins in aqueous phase under phosphate buffer saline, were studied and compared with the synthesized zeolite-Y (ZeoY-S) and commercial CBV 100 zeolite-Y (ZeoY-C). The ZeoY-S was synthesized from sodium aluminate, NaOH, H2O and SiO2 under aging for 24 h at room temperature and hydrothermal condition for 24 h at 100 °C, with an initial composition of 10SiO2:Al2O3:4Na2O:180H2O. The ZeoY-S has been modified by using the imprinting technology to produce the IZ via the use of p-Cresol as a template. The p-Cresol successfully imprinted on the zeolite-Y was proved through the multipoint Brunauer-Emmett-Teller (BET) and the performance of IZ that was compared to ZeoY-S and ZeoY-C. Based on the BET results, it proves that the pore size of IZ is in accordance with the target compound, which is p-Cresol at 0.79 nm. This modification was able to adsorb p-Cresol 2.5 and 3.5 times higher than ZeoY-S and ZeoY-C can, respectively. Langmuir and Freundlich adsorption isotherm models, together with the pseudo-first and -second order and intra-particle diffusion kinetics models, were used to investigate the adsorption behavior of p-Cresol on the zeolites. The IZ has 4.30 times greater competitive molecules than ZeoY-S and the properties of IZ were not influenced by the content of other phenolic group uremic toxins as competitive molecules. It can be concluded that the micropores of zeolite as adsorbent can be modified using the imprinting technology in order to increase its sensitivity and selectivity towards p-Cresol.
The adequacy in uremic toxin removal upon hemodialysis treatment is essential in patients with kidney failure diseases as poor removal leads to heart failure, hypertension, and stroke. The combination of adsorption and diffusion processes has become very advantageous for hemodialysis membranes. By this mechanism, water-soluble uremic toxins (WSUTs) and protein-bounded uremic toxins (PBUTs) could be removed at one time. Therefore, this study aimed to develop a novel imprinted zeolite by p-cresol (IZC) and then incorporated it into polyethersulfone (PES) and poly(vinyl pyrrolidone) (PVP) to produce hollow fiber mixed matrix membrane (HF-MMM). The IZC proved to be sensitive in attracting the adsorbate, classifying it as having a strong adsorption behavior. Accordingly, IZC is very promising to be applied as an adsorbent in the hemodialysis treatment. In this study, IZC as p-cresol's adsorbent was incorporated into a PES-based polymeric membrane with a small addition of PVP to produce HF-MMM using a dry/wet spinning process. The effect of air gap distance between the spinneret and coagulant bath and percentage loading for PES, PVP, and IZC were studied and optimized to obtain the best performance of HF-MMM. The 40 cm of air gap distance, 16 wt% of PES, 2 wt% of PVP, and 1 wt% of IZC loading were able to produce a superior hemodialysis membrane. These optimized parameters showed sufficient uremic toxin removal, i.e., 60.74% of urea, 52.35% of p-cresol in the phosphate buffer saline solution, and 66.29% of p-cresol in bovine serum albumin solution for 4 h permeation using the dialysis system. These HF-MMMs also achieved pure water flux of 67.57 L m-2 h-1 bar-1 and bovine serum albumin rejection of 95.05%. Therefore, this membrane has proven to be able to clean up WSUT and PBUT through a one-step process. Moreover, as compared to the neat PES membrane, MMM was able to remove p-cresol at 186.22 times higher capability.
Hollow fiber membranes of polyvinylidene fluoride (PVDF) were prepared by incorporating varying concentrations of hydrophilic surface-modifying macromolecules (LSMM) and a constant amount of polyethylene glycol (PEG) additives. The membranes were fabricated by the dry-wet spinning technique. The prepared hollow fiber membranes were dip-coated by hydrophobic surface-modifying macromolecules (BSMM) as the final step fabrication. The additives combination is aimed to produce hollow fiber membranes with high flux permeation and high salt rejection in the matter of seawater desalination application. This study prepares hollow fiber membranes from the formulation of 18 wt. % of PVDF mixed with 5 wt. % of PEG and 3, 4, and 5 wt. % of LSMM. The membranes are then dip-coated with 1 wt. % of BSMM. The effect of LSMM loading on hydrophobicity, morphology, average pore size, surface porosity, and membrane performance is investigated. Coating modification on LSMM membranes showed an increase in contact angle up to 57% of pure, unmodified PVDF/PEG membranes, which made the fabricated membranes at least passable when hydrophobicity was considered as one main characteristic. Furthermore, The PVDF/PEG/4LSMM-BSMM membrane exhibits 161 °C of melting point as characterized by the DSC. This value indicates an improvement of thermal behavior shows so as the fabricated membranes are desirable for membrane distillation operation conditions range. Based on the results, it can be concluded that PVDF/PEG membranes with the use of LSMM and BSMM combination could enhance the permeate flux up to 81.32 kg·m-2·h-1 at the maximum, with stable salt rejection around 99.9%, and these are found to be potential for seawater desalination application.