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.
The increase in new cases of drug resistance to first-line drugs such as ethambutol (ETB) makes it necessary to develop improvements for antituberculosis drugs. A new method for improving the bioavailability of active pharmaceutical ingredient (API) was investigated for preventing drug resistance and side-effects of antituberculosis drugs. In this study, an antituberculosis drug delivery system using β-cyclodextrin (β-CD) as the supramolecular carrier of ETB was prepared using the kneading method. The inclusion behaviour of β-CD/ETB inclusion complex in solid and liquid state was investigated. The inclusion complex was characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, nuclear magnetic resonance (NMR) spectroscopy, and UV-visible spectroscopy. The 1H and nuclear Overhauser effect spectroscopy NMR results indicated the hydrophobic interaction between β-CD and ETB. Meanwhile, the Benesi-Hildebrand equation was used to calculate the formation constant (K) of β-CD/ETB complex in natural condition, pH4, and pH9, which were 105.43, 107.06, and 119.11, respectively. The stoichiometry ratio of β-CD/ETB complex was proven to be 1:1.
In this study, mannitol-functionalized magnetic nanoparticles (MMNPs) as a unique nanosorbent and N-doped fluorescent carbon dots (N-CDs) as a cost-effective nanosensor were created and utilized, for the first time, for dispersive micro-solid-phase extraction (Dµ-SPE) to determine carmine (E120) dye in water samples and juices. The modification of the magnetic nanoparticles with mannitol was designed to enhance the responsive potential for adsorption of the polar E120 dye from complex sample matrices through electrostatic interaction. The as-fabricated N-CDs fluorescent probe exhibited a high fluorescence quantum yield (Φs) of 43.1 %, allowing for accurate fluorometric detection of E120 dye. The as-synthesized MMNPs nanosorbent and fluorescent N-CDs nanoprobe were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), thermogravimetric analysis (TGA), and vibrating-sample magnetometer (VSM). Density functional theory (DFT) studied the E120 dye structure using Gaussian 09 to explore the interactions between E 120 dye molecules and MMNPs/N-CDs. The impact of the critical adsorption and detection experimental factors was investigated and adjusted. A minimal amount of MMNPs nanosorbent (150 mg) is sufficient for E120 extraction in an acceptable time of 15 min. Furthermore, with a high determination coefficient, the adsorption characteristics fit with the models of Langmuir isotherm and first-order kinetics. The maximum adsorption capacity (qm) of the as-fabricated MMNPs was 87.7 mg.g-1. After adsorption, E120 dye was fluorometrically analyzed using nitrogen-doped carbon dots as a fluorescent nanosensor via the inner filter effect (IFE) mechanism. Under the optimized conditions, the proposed fluorometric procedures showed a linear increase in the fluorescence ratio with increasing the E120 concentration in the range of 1.0 - 160.0 μg.mL-1 with detection (LOD) and quantitation (LOQ) limits of 0.27 and 0.83 μg.mL-1, respectively. The relative standard deviation (%RSD) did not exceed 2.34 %. The proposed methodology was successfully applied to determine E120 dye in juice and environmental water samples with % recovery ranged from 89.2-106.1 % and 92.9-107.2 %, respectively offering a reliable and environmentally friendly alternative to traditional detection methods with potential applications across various industries.
The behavior of the inclusion behavior of guanosine (GU) with beta-cyclodextrin (β-CD) in the liquid, solid and virtual state were investigated. The absorption and fluorescence spectral were used to determine the inclusion behavior in liquid state. FT-IR, NMR, TGA, DSC, PXRD and FESEM techniques were used to investigate the inclusion behavior in solid-state, meanwhile the virtual state studies are done by molecular docking. The solid inclusion complex (GU: β-CD) was prepared by using the co-precipitation method. The binding constant (K) of (GU: β-CD) was calculated by using Benesi-Hildebrand. Besides that, the 1:1 stoichiometric ratio of inclusion complex was confirmed by using the Benesi-Hildebrand plot and Job's plot of continuous variation method. The most preferable model of GU: β-CD that suggested via molecular docking studies was in good agreement with experimental results. The inclusion complex of GU: β-CD exerted its toxicity effects towards HepG2 cell lines based on the reduced number of cell viability and lowest IC50 value compared to the GU and β-CD viability.
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.
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.
An emulsification liquid-liquid microextraction (ELLME) method was successfully developed using phenolic-based deep eutectic solvent (DES) as an extraction solvent for the determination of phenoxy acid herbicides, 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in environmental water samples. Five different phenolics-based DESs were successfully synthesized by using phenol (DES 1), 2-chlorophenol (DES 2), 3-chlorophenol (DES 3), 4-chlorophenol (DES 4) and 3,4-dichlorophenol (DES 6) as the hydrogen-bond donor (HBD) and choline chloride as the hydrogen-bond acceptor (HBA). The DESs were mixed at 1 : 2 ratio. A homogeneous solution (clear solution) was observed upon the completion of successful synthesis. The synthesized DESs were characterized by using Fourier transform infrared and nuclear magnetic resonance (NMR). Under optimum ELLME conditions (50 µl of DES 2 as extraction solvent; 100 µl of THF as emulsifier solvent; pH 2; extraction time 5 min), enrichment factor obtained for dicamba and MCPA were 43.1 and 59.7, respectively. The limit of detection and limit of quantification obtained for dicamba were 1.66 and 5.03 µg l-1, respectively, meanwhile for MCPA were 1.69 and 5.12 µg l-1, respectively. The developed ELLME-DES method was applied on paddy field water samples, with extraction recoveries in the range of 79-91% for dicamba and 82-96% for MCPA.
One of the world's challenging energy issues is introducing practical and affordable technology for organosulfur removal in fuel. Adsorptive desulfurization (ADS) can address this issue if highly effective activated carbon (AC) derived from industrial waste with excellent textural properties is used. In this study, the derived ACs from glycerin pitch loaded with P and Fe (AC/P and AC/Fe) were used as adsorbents for the ADS of model fuel oils, such as dibenzothiophene (DBT) at mild operating conditions. Under the optimized experimental conditions, 0.3 g of adsorbent dosage, 60 min reaction time, 30 °C temperature, and pH 4, the maximal DBT removal of 96.28 and 43.64%, respectively, for AC/P and AC/Fe was realized. The results indicated that the phosphorus-doped AC/P increases the selectivity of the ADS mechanism for DBT removal. Kinetic investigations disclosed that the adsorption process follows second-pseudo-order kinetics and the Langmuir adsorption isotherm model. The adsorbents remained active for five successive reuses, indicating their robust real-world applications. The electrochemical properties of the fabricated carbon electrodes were analyzed via cyclic voltammetry by coating the ACs with polytetrafluoroethylene (PTFE) as a binder. The transition-metal-doped AC/Fe, though exhibiting 5 times lower surface area, showed the highest specific capacitance at a scan rate of 5 mVs-1 (0.65 μF cm-2). Similarly, the extended AC:PTFE capacitor at a 10% binder ratio offered the maximum capacitance value (1.13 μF cm-2). The synthesized ACs demonstrated potential application as an electrode material, and hence glycerin pitch could be a low-cost precursor to improve the feasibility of commercial production of AC.