The presence of pharmaceuticals and endocrine-disrupting compounds in aquatic systems is a matter of great concern. The occurrence, fate, and potential toxicity of these compounds have triggered the interest of the scientific community. As a result of their high solubility and low volatility, they are common in aquatic systems, and wastewater treatment plants (WWTP) are the main reservoir for these contaminants. Conventional WWTPs have demonstrated an inability to remove these contaminants completely; hence, different advanced treatment processes have been explored to compensate for the lapses of the conventional system. The outcome of this study revealed the significant improvements made using advanced treatment processes to diminish the number of contaminants; however, some contaminants have proven to be refractory. Thus, there is a need to modify various advanced treatment processes or employ additional treatment processes. Polymer inclusion membranes (PIMs) are a liquid membrane technology that is highly efficient at removing contaminants from water. They have been widely studied for the removal of heavy metals and nutrients from aquatic systems; however, only a few studies have investigated the use of PIMs to remove pharmaceutically active compounds from aquatic systems. This research aims to raise awareness on the application of PIMs as a promising water treatment technology which has a great potential for the remediation of pharmaceuticals and endocrine disruptors in the aquatic system, due to its versatility, ease/low cost of preparation and high contaminant selectivity.
The use of a polymer inclusion membrane (PIM) as a sensing material is a new approach to overcome the selectivity and stability drawbacks of the optical chemical sensor (optode). In this study, non-plasticized PIM containing poly(vinyl chloride) as a support base, sodium morin-5-sulfonate (NaMSA) as a reagent and Aliquat 336 as a fixed carrier (ionophore) was prepared and its performance was tested for application in an optode to determine Al3+ ions. The results showed that PIM properties are greatly influenced by the membrane composition. The studies revealed that the optode response was dependent on film thickness, the presence of plasticizer, stirring effect, concentration of NaMSA, concentration of Aliquat 336 and pH of the aqueous solution used. The dynamic range of Al3+ ions concentration determined using this optode was linear from 5.19 × 10-7 to 6.00 × 10-5 mol L-1 and the calculated limit of detection (L.O.D.) was found to be 4.07 × 10-7 mol L-1. The maximum emission wavelength (λem) for the PIM based optode was 512 nm. Scanning electron microscopy analysis of the PIM revealed that a dense texture was formed. Fourier transform infra-red and thermal gravimetry analysis characterizations proved that all of the constituents of the PIM remain within the membrane. The PIM developed in this work was found to be stable, has good mechanical strength, and is sensitive and reusable. Lastly, the PIM was successfully applied as an optical sensor for determination of Al3+ ions in an aqueous solution.
The aggressive search for unique materials in recent years has put forward chitosan and modified-chitosan as materials with unique structural and morphological characteristics for various important applications. Just as imidazolium-based ionic liquids are the commonly applied ionic liquids (ILs) type for chitosan modifications for various applications, their further modifications into beads for enhancing their properties is now gaining most attention. However, most of the currently prepared imidazolium ILs modified-chitosan beads are not in nano size due to preparation difficulties. In response to this and referencing the research works in the literature, the possible breakthrough directions including synthesis routes, and physical and mechanical transformation processes are proposed. These procedures are expected to provide certain theoretical and empirical basis, as well as technical guide for developing nano-micro size chitosan beads using imidazolium based ILs.
Chitosan-deep eutectic solvent (DES) beads were prepared from chitosan and DESs. The DESs used were choline chloride-urea (DES A) and choline chloride-glycerol (DES B). Both chitosan-DES beads were used to remove malachite green (MG) dye from an aqueous solution. The optimum pH for chitosan-DES A was recorded at pH 8.0 while optimum pH for chitosan-DES B was pH 9.0. The maximum adsorption capacity obtained for chitosan-DES A and chitosan-DES B were 6.54 mg/g and 8.64 mg/g, respectively. The optimum conditions for both chitosan-DES beads to remove MG were 0.08 g of adsorbent and 20 min of agitation time. Five kinetic models were applied to analyse the data and the results showed that the pseudo-second-order and intraparticle diffusion model fitted best with R2 > 0.999. For the adsorption capacity, results show that the Freundlich and Langmuir adsorption isotherms fitted well with chitosan-DES A and chitosan-DES B, respectively. The maximum adsorption capacities (qmax) obtained from chitosan-DES A and chitosan-DES B were 1.43 mg/g and 17.86 mg/g, respectively. Desorption indicated good performance in practical applications.
In recent times, research interest into the development of biodegradable, cost-effective and environmental friendly adsorbents with favourable properties for adsorption of pollutants is a challenge. Modification of chitosan via different physical and chemical methods have gained attention as a promising approach for removing organic (such as dyes and pharmaceuticals) and inorganic (such as metal/metal ions) pollutants from aqueous medium. In this regard, researchers have reported grafting and cross-linking approach among others as a potentially useful method for chitosan's modification for improved adsorption efficiency with respect to pollutant uptake. This article reviews the trend in chitosan modification, with regards to the summary of some recently published works on modification of chitosan and their adsorption application in pollutants (metal ion, dyes and pharmaceuticals) removal from aqueous medium. The review uniquely highlights some common cross-linkers and grafting procedures for chitosan modification, their influence on structure and adsorption capacity of modified-chitosan with respect to pollutants removal. Findings revealed that the performance of modified chitosan for adsorption of pollutants depends largely on the modification method adopted, materials used for the modification and adsorption experimental conditions. Cross-linking is commonly utilized for improving the chemical and mechanical stabilities of chitosan but usually decreases adsorption capacity of chitosan/modified-chitosan for adsorption of pollutants. However, literature survey revealed that adsorption capacity of cross-linked chitosan based materials have been enhanced in recently published works either by grafting, incorporation of solid adsorbents (e.g metals, clays and activated carbon) or combination of both prior to cross-linking.
In this study, chitosan/porous carbon composite (C-PC) modified in 1-Allyl-3-methyl imidazolium bromide [AMIM][Br] under airtight condition was prepared for the removal of Acid Blue-25 dye (AB-25) from aqueous medium. For comparison of adsorption efficiency of C-PC, chitosan-activated carbon composite (C-AC) was also prepared in 1% acetic acid. The adsorbents were characterised using SEM, EDX, XRD, BET, TGA and FTIR. The micrograph of C-PC revealed cavities and slightly rough surfaces dominated with similar sized and irregular shaped stone-like materials which differ from the precursors' micrograph. BET analysis revealed the domination of mesopores on the C-PC and C-AC surfaces, as the hydroxyl and amino group on C-PC are the main active sites for AB-25 dye uptake. The dye was better adsorbed onto C-PC at pH 2 and C-AC at pH 4. The adsorption capacity obtained for C-PC, C-AC, activated carbon (AC) and chitosan (CH) using Langmuir isotherm model are 3333.33 mg/g, 909.90 mg/g, 909.09 mg/g and 833.33 mg/g, respectively. The experimental data are well described by Langmuir and Fruendlich isotherms for adsorption of the dye onto C-PC, AC and CH. C-AC fitted into Langmuir isotherm only. The kinetics of the adsorption fitted into pseudo-second order indicating the possibility of chemical interactions in the adsorption process.
The presence of dyes in the aquatic environment as a result of anthropogenic activities, especially textile industries, is a critical environmental challenge that hinders the availability of potable water. Different wastewater treatment approaches have been used to remediate dyes in aquatic environments; however, most of these approaches are limited by factors ranging from high cost to the incomplete removal of the dyes and contaminants. Thus, the use of adsorption as a water treatment technology to remove dyes and other contaminants has been widely investigated using different adsorbents. This study evaluated the significance of chitosan as a viable adsorbent for removing dyes from water treatment. We summarised the literature and research results obtained between 2009 and 2020 regarding the adsorption of dyes onto chitosan and modified chitosan-based adsorbents prepared through physical and chemical processing, including crosslinking impregnation, grafting, and membrane preparation. Furthermore, we demonstrated the effects of various chitosan-based materials and modifications; they all improve the properties of chitosan by promoting the adsorption of dyes. Hence, the application of chitosan-based materials with various modifications should be considered a cutting-edge approach for the remediation of dyes and other contaminants in aquatic environments toward the global aim of making potable water globally available.
Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R2>0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (qmax) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg-1 and 0.24mgg-1 respectively.
Adsorption efficiency of a duo-material blend featuring the fabrication of modified chitosan adsorbents (powder (C-emimAc), bead (CB-emimAc) and sponge (CS-emimAc)) for the removal of Cd(II) from aqueous solution was investigated. The chitosan@activated carbon (Ch/AC) blend was developed in a green ionic solvent, 1-ethyl-3-methyl imidazolium acetate (EmimAc) and its characteristics was examined using FTIR, SEM, EDX, BET and TGA. The possible mechanism of interaction between the composites and Cd(II) was also predicted using the density functional theory (DFT) analysis. The interactions of various blend forms (C-emimAc, CB-emimAc and CS-emimAc) with Cd(II) gave better adsorption at pH 6. The composites also present excellent chemical stability in both acidic and basic conditions. The monolayer adsorption capacities obtained (under the condition 20 mg/L [Cd], adsorbent dosage 5 mg, contact time 1 h) for the CB-emimAc (84.75 mg/g) > C-emimAc (72.99 mg/g) > CS-emimAc (55.25 mg/g), as this was supported by their order of increasing BET surface area (CB-emimAc (120.1 m2/g) > C-emimAc (67.4 m2/g) > CS-emimAc (35.3 m2/g)). The feasible adsorption interactions between Cd(II) and Ch/AC occurs through the O-H and N-H groups of the composites, as supported by DFT analysis in which an electrostatic interactions was predicted as the dominant force. The interaction energy (-1309.35 eV) calculated via DFT shows that the Ch/AC with amino (-NH) and hydroxyl (-OH) groups are more effective with four significant electrostatic interactions with the Cd(II) ion. The various form of Ch/AC composites developed in EmimAc possess good adsorption capacity and stability for the adsorption Cd(II).
Several water and wastewater technologies have been implored for the removal of dyes during wastewater treatments; however; different types have been reportedly found in surface and groundwater systems. Hence, there is a need to investigate other water treatment technologies for the complete remediation of dyes in aquatic environments. In this study, novel chitosan-based polymer inclusion membranes (PIMs) were synthesized for the removal of malachite green dye (MG) which is a recalcitrant of great concern in water. Two types of PIMs were synthesized in this study, the first PIM (PIMs-A) was composed of chitosan, bis-(2-ethylhexyl) phosphate (B2EHP), and dioctyl phthalate (DOP). While, the second PIMs (PIMs-B) were composed of chitosan, Aliquat 336, and DOP. The physico-thermal stability of the PIMs was investigated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA), both PIMs demonstrated good stability with a weak intermolecular force of attraction amongst the various components of the membranes. The effects of the initial concentration of MG, pH of the MG solution, stripping solution, and time were investigated. At optimum conditions, both membranes (PIM-A and B) recorded the highest efficiencies of 96 % and 98 % at pH 4 and initial contaminants concentration of 50 mg/L, respectively. Finally, both PIMs were used for the removal of MG in different environmental samples (river water, seawater, and tap water) with an average removal efficiency of 90 %. Thus, the investigated PIMs can be considered a potential suitable technique for the removal of dyes and other contaminants from aquatic matrices.
In this study, a unique magnetic molecularly imprinted polymer (MMIP) adsorbent towards bisphenol A (BPA) as a template molecule was developed by bulk polymerization using β-cyclodextrin (β-CD) as a co-monomer with methacrylic acid (MAA) to form MMIP MAA-βCD as a new adsorbent. β-CD was hybridized with MAA to obtain water-compactible imprinting sites for the effective removal of BPA from aqueous samples. Benzoyl peroxide and trimethylolpropane trimethacrylate were used as the initiator and cross-linker, respectively. The adsorbents were characterized by Fourier transform infrared spectroscopy, scanning electronic microscopy, transmission electron microscopy, vibrating sample magnetometer, Brunauer-Emmett-Teller and X-ray diffraction. 1H nuclear magnetic resonance spectroscopy was used to characterize the MAA-βCD and BPA-MAA-βCD complex. Several parameters influencing the adsorption efficiency of BPA such as adsorbent dosage, pH of sample solution, contact time, initial concentrations and temperature as well as selectivity and reusability study have been evaluated. MMIP MAA-βCD showed significantly higher removal efficiency and selective binding capacity towards BPA compared to MMIP MAA owing to its unique morphology with the presence of β-CD. The kinetics data can be well described by the pseudo second-order kinetic and Freundlich isotherm and Halsey models best fitted the isotherm data. The thermodynamic studies indicated that the adsorption reaction was a spontaneous and exothermic process. Therefore, MMIP based on the hybrid monomer of MAA-βCD shows good potential of a new monomer in molecularly imprinted polymer preparation and can be used as an effective adsorbent for the removal of BPA from aqueous solutions.
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.