Efficient removal of Chromium(VI) from wastewater based on magnetic multiwalled carbon nanotubes coupled with deep eutectic solvents.

Industrial wastewater containing heavy metal Cr(VI) seriously affects the health of organisms and may even lead to cancer. Developing efficient adsorbents that can quickly separate heavy metals is crucial for treating wastewater. In this study, magnetic multiwalled carbon nanotubes (MMWCNTs) with moderate particle size and abundant surface active sites were prepared by coating multiwalled carbon nanotubes with magnetic nanoparticles. The results of FTIR, XRD, TG, VSM, BET, and EDS showed MWCNTs completely encapsulated on the surface of the magnetic nanoparticles, with a particle size of approximately 30 nm. Oxygenated groups provided abundant surface active sites and formed numerous mesopores. The response surface methodology was used to optimize the adsorbent dose, adsorption contact time and adsorption temperature, and the removal rate of Cr(VI) was more than 95%. The quasi-second order kinetics and Freundlich adsorption isotherm model explained the adsorption process to Cr(VI). MMWCNTs interacted with Cr(VI) through electrostatic attraction, reduction reactions, complexation, and other means. The extensive hydrogen bonding of the green solvent deep eutectic solvent (DES) was employed to desorb the MMWCNTs and desorption rate exceed 90%. Even after five adsorption-regeneration cycles, the adsorbent maintained a high capacity. In conclusion, these novel MMWCNTs, as efficient adsorbents paired with DES desorption, hold broad potential for application in the treatment of Cr(VI)-contaminated wastewater.

Determination of bioactive flavonoids using ß-cyclodextrin combined with chitosan-modified magnetic nanoparticles.

To accurately determine flavonoids (rutin, quercetin or kaempferol), it is necessary to extract them from complex matrices. The ultrasound-assisted magnetic dispersion microsolid phase extraction technique has been predominantly used for separation and enrichment of the target analytes. The combination of magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent (DESP) is likely to enhance the efficiency of flavonoid extraction from food. In this study, adsorbents were prepared by modifying chitosan with magnetic nanoparticles, and the eluent was a DESP derived from ß-cyclodextrin and an organic acid. The successful preparation of these materials was confirmed by FTIR, XRD, FE-SEM and 1H NMR. The extraction recovery rates exceeded 93 %, with limits of detection and quantitation ranging from 0.9 to 2.4 µg/L and 2.7 to 7.2 µg/L, respectively, and the flavonoid clearance rates for ABTS and DPPH radicals reached 100 %. Therefore, the integration of magnetic chitosan nanoparticles with the DESP provides a new and efficient method for the extraction of flavonoids while also presenting a potential application of the DESP in separations.

Adsorption of methyl orange by porous membranes prepared from deep eutectic supramolecular polymer-modified chitosan.

The fabrication of an adsorbent with excellent performance has been a focus of attention because of the toxicity, mutagenicity and carcinogenicity of methyl orange (MO)-containing wastewater discharged from the textile, tannery and pharmaceutical industries. In this study, chitosan (CS) membranes were modified with a deep eutectic supramolecular polymer (DESP), and adsorbent membranes with porous structures were prepared with polyethylene glycol (PEG). Microstructural characterization of the CS-DESP-PEG composite membranes with FT-IR, XRD and SEM showed that the membranes had amorphous crystalline structures and that hydrogen bonding interactions weakened the crystallinity and formed loose porous structures. Optimization of the chitosan to ß-cyclodextrin ratio, pH, PEG proportion, MO concentration and adsorbent dose significantly improved the adsorption efficiencies of the membranes. The adsorption behaviours of the membranes were fit with pseudo-second-order adsorption kinetics and the Freundlich adsorption isotherm model. Regeneration experiments showed that the membranes were reusable multiple times and maintained good adsorption capacities.

Determination of catechol in water with deep eutectic supramolecular solvents-assisted magnetic κ-carrageenan nanoparticles.

A combination of magnetic κ-carrageenan nanoparticles and deep eutectic supramolecular solvents used for extraction of catechol from water was evaluated by the magnetic dispersion solid phase extraction method. The magnetic κ-carrageenan nanoparticles (KC@Fe3O4MNPs) and the deep eutectic supramolecular solvent (DESP) were characterised by 1H NMR, FT-IR, XRD, SEM, VSM, TG, and BET. The adsorption kinetics, adsorption isothermal model, adsorption thermodynamics and effects of pH and salt concentration were investigated. Additionally, the factors used in the desorption process, such as the type, dosage, concentration and time, were analysed. Under the optimised conditions, the analytes were linear over the range 5-5000 ng mL-1, with a correlation coefficient greater than 0.999 and detection and quantitation limits of 1.6 and 4.7 ng mL-1, respectively. The procedure was successfully applied to determinations of the analytes of interest in spiked water samples with relative average recoveries ranging from 94.3% to 101.5%. These results indicated that the combination of functionalized magnetic nanoparticles and DESP had high specificity and extraction efficiency for catechol and will be a feasible alternative to conventional analyses of organic phenolic pollutants in water.

Ultrasonic assisted extraction of polyphenols from bayberry by deep eutectic supramolecular polymer and its application in bio-active film.

Ultrasound and deep eutectic supramolecular polymers (DESP) is a novel combination of green extraction method for phytochemicals. In this study, a new type of green extractant was developed: DESP. It is a derivative of deep eutectic solvent (DES) and was prepared by supramolecular polymer unit ß-cyclodextrin (ß-CD) as hydrogen bond acceptor (HBA) and organic acid as hydrogen bond donor (HBD). The current work focuses on the use of ultrasonic-assisted (UAE) DESP extraction of polyphenolic compounds (PCs) from bayberry. The experimental results showed that DESP synthesized with ß-CD and lactic acid (LA) in a ratio of 1:1 (w/w %) had the best extraction effect. And by using a three-level factor experiment and the response surface method, the predicted TPC content is very close to the actual content (28.85 ± 1.27 mg GAE/g). The DESP extract including PCs were further used as plasticizer for chitosan (CS) to prepare highly active green biofilms (DESP-CS). It is possible to reduce the tedious procedures for separating biologically active substances from DESP. The experiment proved that the prepared films have good mechanical properties, plastic deformation resistance, thermal stability and antioxidant activity.

Development of magnetic dispersive micro-solid phase extraction of four phenolic compounds from food samples based on magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent.

A magnetic dispersive micro-solid phase extraction technique (CS@Fe3O4-MD-µSPE-DESP) based on magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent was developed and applied to determinations of four phenolic compounds in food samples. To prevent environmental pollution and the introduction of toxic substances, deep eutectic supramolecular solvents (DESPs), which exhibited greater desorption capacities than conventional organic solvents and deep eutectic solvents, were used as novel green eluents for the first time. Some important parameters were screened by the Plackett-Burman method and then further optimized with response surface methodology (RSM). Under the optimal conditions, the proposed method showed excellent methodological indices with linearity over the range 0.1-200.0 µg·mL-1, R2 > 0.9988, extraction recoveries above 94.8 %, and precision (RSD%) below 2.9 %. The established method finishes the process of adsorption and desorption in approximately 3 min and enhances the efficiency for determination of phenolic compounds.