Adsorption of Cationic Contaminants by Cyclodextrin Nanosponges Cross-Linked with 1,2,3,4-butanetetracarboxylic Acid and Poly(vinyl alcohol)

Cationic organic pollutants (dyes and pesticides) are mainly hydrosoluble and easily contaminate water and create a serious problem for biotic and abiotic species. The elimination of these dangerous contaminants from water was accomplished by adsorption using cyclodextrin nanosponges. These nanosponges were elaborated by the cross-linking between 1,2,3,4-butanetetracarboxylic acid and β-cyclodextrin in the presence of poly (vinyl alcohol). Their physicochemical characteristics were characterized by gravimetry, acid-base titration, TGA, 13C NMR, ATR-FTIR, Raman, X-ray diffraction, and Stereomicroscopy. The BP5 nanosponges displayed 68.4% yield, 3.31 mmol/g COOH groups, 0.16 mmol/g β-CD content, 54.2% swelling, 97.0% PQ removal, 96.7% SO removal, and 98.3% MG removal for 25 mg/L of initial concentration. The pseudo-second-order model was suitable for kinetics using 180 min of contact time. Langmuir isotherm was suitable for isotherm with the maximum adsorption of 120.5, 92.6, and 64.9 mg/g for paraquat (PQ), safranin (SO), and malachite green (MG) adsorption, respectively. Finally, the reusability performance after five regeneration times reached 94.1%, 91.6%, and 94.6% for PQ, SO, and MG adsorption, respectively.

Adsorption of Paraquat by Poly(Vinyl Alcohol)-Cyclodextrin Nanosponges

The contamination of hydrosoluble pesticides in water could generate a serious problem for biotic and abiotic components. The removal of a hazardous agrochemical (paraquat) from water was achieved by adsorption processes using poly(vinyl alcohol)-cyclodextrin nanosponges, which were prepared with various formulations via the crosslinking between citric acid and β-cyclodextrin in the presence of poly(vinyl alcohol). The physicochemical properties of nanosponges were also characterized by different techniques, such as gravimetry, thermogravimetry, microscopy (SEM and Stereo), spectroscopy (UV-visible, NMR, ATR-FTIR, and Raman), acid-base titration, BET surface area analysis, X-ray diffraction, and ion exchange capacity. The C10D-P2 nanosponges displayed 60.2% yield, 3.14 mmol/g COOH groups, 0.335 mmol/g β-CD content, 96.4% swelling, 94.5% paraquat removal, 0.1766 m2 g−1 specific surface area, and 5.2 × 10−4 cm3 g−1 pore volume. The presence of particular peaks referring to specific functional groups on spectroscopic spectra confirmed the successful polycondensation on the reticulated nanosponges. The pseudo second-order model (with R2 = 0.9998) and Langmuir isotherm (with R2 = 0.9979) was suitable for kinetics and isotherm using 180 min of contact time and a pH of 6.5. The maximum adsorption capacity was calculated at 112.2 mg/g. Finally, the recyclability of these nanosponges was 90.3% of paraquat removal after five regeneration times.

Sustainable mechanochemical synthesis of β-cyclodextrin polymers by twin screw extrusion

Cyclodextrin nanosponges (CD-NS) are cross-linked cyclodextrin polymers characterized by a nanostructured three-dimensional network. CD-NSs in the last years found many different applications in the pharmaceutical field for the controlled release of drugs and for the absorption of undesired substances from physiological media, food, and wastewater. Most of CD-NS syntheses involve the solubilization of the chosen CD in closed batch, using a suitable organic polar aprotic liquid, which may affect potential environmental or biomedical applications. Since the research is now moving towards more sustainable approaches, new and greener syntheses of CD-NS are now being developed. Here, it is reported a new eco-friendly and efficient synthesis of nanosponges through mechanochemistry. Mechanochemistry involves the application of mechanical forces to drive and control chemical reactions by transferring energy to chemical bonds. The mechanochemical approach involves the use of a twin-screw extruder (TSE) as a chemical reactor: TSE are capable of fine temperature control and, furthermore, TS Extrusion is a continuous process and not a batch process. Among the many available CD-NS syntheses, we tested our solvent-free approach on a β-CD/citric acid (CA) system. Moreover, using TSE, the same polymer was obtained in a considerably shorter time. The so obtained NSs were used for the adsorption and removal of probe molecules, in comparison with NSs prepared by cross-linking β-CD with CA in batch. Graphical Abstract

Cyclodextrin Nanosponges Inclusion Compounds Associated with Gold Nanoparticles for Potential Application in the Photothermal Release of Melphalan and Cytoxan

This article describes the synthesis and characterization of β-cyclodextrin-based nano-sponges (NS) inclusion compounds (IC) with the anti-tumor drugs melphalan (MPH) and cytoxan (CYT), and the addition of gold nanoparticles (AuNPs) onto both systems, for the potential release of the drugs by means of laser irradiation. The NS-MPH and NS-CYT inclusion compounds were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), UV–Vis, and proton nuclear magnetic resonance (1H-NMR). Thus, the inclusion of MPH and CYT inside the cavities of NSs was confirmed. The association of AuNPs with the ICs was confirmed by SEM, EDS, TEM, and UV–Vis. Drug release studies using NSs synthesized with different molar ratios of β-cyclodextrin and diphenylcarbonate (1:4 and 1:8) demonstrated that the ability of NSs to entrap and release the drug molecules depends on the crosslinking between the cyclodextrin monomers. Finally, irradiation assays using a continuous laser of 532 nm showed that photothermal drug release of both MPH and CYT from the cavities of NSs via plasmonic heating of AuNPs is possible.