Removal of doxorubicin hydrochloride and crystal violet from aqueous solutions using spray-dried niobium oxide coated with chitosan-activated carbon: Experimental and DFT calculations.

Spray-dried niobium oxide coated with chitosan-activated carbon (NIC) was synthesized and used to remove doxorubicin hydrochloride and crystal violet from aqueous solutions under different parameters such as solution pH (2, 4, 6, and 8), contact time (1 to 9 h), initial concentration (20 to 200 mg L-1), and competing ions (0.1 M of CaCl2 and NaCl). The addition of 5 % chitosan-activated carbon to the matrix of niobium oxide slightly increased the specific surface area from 26 to 30 m2 g-1, with the introduction of a carboxylic functional group. This led to an increase in the amount of adsorbed doxorubicin hydrochloride (DOH) from 30 to 44 mg g-1 and that of crystal violet (CV) from 15 to 32 mg g-1 from the initial respective 100 mg L-1 at pH 8. The data from the concentration study fitted into Liu isotherm having adsorption capacity of 128 and 57 mg g-1 for DOH and CV respectively, while pseudo first and second order are more suitable for adsorption kinetics. The additional functional groups on the IR spectrum of NIC after the adsorption of DOH and CV confirmed the interaction between NIC and the adsorbates' molecules. The mechanism of adsorption was supported by DFT calculations.

Removal and environmentally safe disposal of As(III) and As(V)-loaded ferrihydrite/biosilica composites.

Pure ferrihydrite and ferrihydrite-biosilica composite were synthesized and studied for the removal of As(III) and As(V). The synthesized materials have an adsorption capacity higher than some reported materials in the literature - 140 and 90 mg g-1 for As(III) and As(V), respectively. The pH of the solution was shown to impact greatly on As(V) adsorption, but not on As (III), which is stable as a protonated, uncharged oxyanion, at pH < 9.2. The adsorption products were subjected to thermal treatment (500 °C for 2 h), promoting ferric arsenate formation. The adsorbed As on ferrihydrite (Fh) was shown to inhibit the phase transformation of Fh to hematite. More so, thermal treatment was shown to oxidize As(III) to As (V). The changes in the adsorption residues after thermal treatment also had an impact on As mobility. The As (III) associated with the Fh phase increased from 42 to 95%, according to a sequential extraction protocol. Therefore, this work presents a process for As removal, followed by thermal treatment of arsenic-loaded ferrihydrites which enables environmentally safe disposal of As residues.

Reducing the negative impact of ceftriaxone and doxycycline in aqueous solutions using ferrihydrite/plant-based composites: mechanism pathway.

The adsorption of ceftriaxone (CET) and doxycycline (DOX) from aqueous solution using ferrihydrite/plant-based composites (silica rice husk) to reduce their negative impact on the ecosystem was adequately studied. On the other hand, phosphate and humic acid are often found in water and soil; in view of this, their effects on the adsorption of CET and DOX were investigated. The results showed that the removal of ceftriaxone decreased with an increase in pH, while that of doxycycline did not. Ferrihydrite with 10% silica rice husk (Fh-10%SRH) has the highest maximum adsorption capacity of 139 and 178 mg g-1 for CET and DOX, respectively, at room temperature based on Liu's adsorption isotherm. This implies that the presence of silica rice husk increases CET and DOX uptake due to an increase in the pore volume of FH-10%SRH. The results showed that phosphate had a significant inhibition role on CET adsorption and minor on DOX, whereas humic acid salt affected neither case. Increase in temperature up to 333 K favored the adsorption of both contaminants. The proposed adsorption mechanisms of ceftriaxone are electrostatic interaction, n-π interaction, and hydrogen bond, while that of DOX entails n-π interaction and hydrogen bond.

Defects induced by Al substitution enhance As(V) adsorption on ferrihydrites.

An original rationale is proposed to explain the controversial role of aluminum, a common substitutive element in ferrihydrite (Fh), on arsenic adsorption. The adsorption of arsenic on synthetic Al-for-Fe substituted Fh (AlFh) with up to 20 mol% Al was investigated at pH 5 and 8. The reduced interplanar spacings observed by selected area electron diffraction show that all AlFh samples are isomorphically substituted up to 20 mol% Al. A 15 mol% Al incorporation increases the arsenic uptake by 28%. In contrast, the Langmuir binding constants decrease, suggesting weaker bonds. Arsenic uptake reduces by 50% as pH rises from 5 to 8. The Al-for-Fe substitution in ferrihydrite causes structural defects, proton-compensated by OH groups, as indicated by the Vegard rule deviation. X-ray photoelectron spectroscopy demonstrates the increase in the relative amount of surface M-OH sites (45% to 77%) with Al concentration (AlFh-0 to AlFh-20), respectively. The enhanced As(V) uptake was ascribed to the insertion of hydroxyls on the Fh structural defects. Fourier-transformed-infrared spectroscopy showed that the sites modified by Al introduction are involved in As adsorption. These findings help to understand aluminum's role in arsenic adsorption, fixation, and fate in the environment.

Investigation of phase transition employing strain mapping in TT- and T-Nb2O5 obtained by HRTEM micrographs.

This work aimed to study the crystalline structure of TT-,T-phases of Nb2O5 nanoparticles through XRD, Rietveld refinement, and HRTEM, using geometric phase analysis (GPA). The results show the presence of distorted NbO6 and NbO7 polyhedral, producing strain effects, mainly in the plane boundaries and along the b-c plane. XRD and HRTEM analyses show the TT→T transition at 700 °C, with increased particle size and increased strain in the boundaries between nanoparticles. The sample calcinated at 700 °C presents segregation of the TT-(001), (100), and T-(130) planes, where the strain effect is more relevant along the [100] zone axis and between phases.

Synergistic effect of a spinel ferrite on the adsorption capacity of nano bio-silica for the removal of methylene blue.

The synergistic effect of CoFe2O4 on the capacity of bio-silica extracted from rice husk for the removal of methylene blue (MB) was investigated. The novel composite of cobalt ferrite/nano bio-silica was prepared by dispersing cobalt and iron salt in ratio 1:2 in a solution containing bio-silica, calcined at 700°C and characterized. The adsorption capacity of the composite (253.6 mg g-1) was higher than that of bio-silica (52.6 mg g-1), and the process was exothermic and spontaneous. Langmuir and Freundlich models were applicable to explain the adsorption isotherm, while pseudo-second-order and Elovich are best applicable for the kinetics mechanism. The amount of MB that was removed, increased with an increase in ionic strength due to dimerization of MB. Regeneration and reusability of the adsorbents showed that they are economically viable. Energy-filtered transmission electron microscopy (EFTEM) and Fourier transformed infrared (FTIR) analysis of MB-loaded adsorbent confirmed the adsorption of MB.

Adsorption of Methylene blue and Congo red from aqueous solution using synthesized alumina-zirconia composite.

Alumina-zirconia (Al2O3-ZrO2) composite was prepared by combustion method and used to remove Congo red and Methylene blue from aqueous solutions. It was characterized using SEM-EDS, XRD and gas adsorption techniques. The results obtained from gas adsorption and SEM agree with each other, showing meso- and macro-porosity of inter-agglomerate pores. The removal of the two dyes was pH dependent, acidic pH favoured Congo red removal, while basic pH favoured Methylene blue. The, mechanism of adsorption was not limited to electrostatic attraction between the adsorbent and the dye molecules. Adsorption kinetic of both dyes was consistent with Pseudo-second-order model. The data obtained fitted to Langmuir and Liu isotherm models, with the maximum adsorption capacity of 57. 50 and 53.44 mg g-1 for Congo red and Methylene blue, respectively. The thermodynamic parameters indicated that the adsorption is spontaneous and exothermic. The mechanism of adsorption was elucidated using XRD and FTIR techniques.

Comparative adsorption mechanism of doxycycline and Congo red using synthesized kaolinite supported CoFe2O4 nanoparticles.

Kaolinite supported CoFe2O4 (KCF) was synthesized and employed to adsorb doxycycline (DOX), an antibiotic and Congo red (CR), a dye from aqueous solution. The prepared KCF nanocomposite was treated in a muffle furnace at 300, 500 and 700 °C, and thereafter characterized. X-ray diffractogram revealed structural damage of kaolinite and appearance of distinct peaks of CoFe2O4 with an increase in calcination temperature, while transmission electron microscopy (TEM) images showed that CoFe2O4 nanoparticles were supported on the lamellar surface of kaolinites. Comparative adsorption mechanism of the two targeted contaminants showed that adsorption of DOX was influenced by hydrogen bond and n-π interaction, while that of CR was due to hydrophobic interaction and hydrogen bond. However, the adsorption of the two contaminants was best fitted to the isotherm that was proposed by Langmuir, with a monolayer maximum adsorption capacity of 400 mg g-1 at 333 K for DOX, and 547 mg g-1 at 298 K for CR. The removal of DOX from aqueous solution was favored by an increase in temperature (endothermic), while that of CR was exothermic. Thermodynamics studies confirmed that the adsorption of the two contaminants is feasible and spontaneous. The presence of natural organic matter (NOM) did not affect the removal of the two contaminants. Regeneration and reusability study showed that KCF is economically viable. Therefore, introducing inorganic particles like cobalt ferrite into the matrix of kaolinites provides a composite with promising adsorption capacity.

Influence of oxidized starch on physicomechanical, thermal properties, and atomic force micrographs of cassava starch bioplastic film.

Oxidized starch was produced and its effect on starch-based bioplastic film has been evaluated. The produced oxidized starch was coarse, brownish with 15.68% carbonyl content, insoluble in cold water and has a positive influence on bioplastic films. The film thickness increased with increase in the amount of added oxidized starch from 0.21% (filmO) to 0.23% (film6O). The film moisture content dropped from 7.93% (filmO) to 5.36% (film6O), likewise the film water solubility decreased from 13.48% (filmO) to 5.75% (film6O). Addition of oxidized starch led to longer biodegradability and enduring water absorption kinetics. The mechanical property was improved by the addition of oxidized starch. The derivative thermogravimetry analysis indicates five degradation stages for all the bioplastic films, while films surface roughness was shown by AFM. The research has revealed that oxidized starch can be used to improve the physicomechanical properties of starch based bioplastic film.

Self-assembled organic-inorganic magnetic hybrid adsorbent ferrite based on cyclodextrin nanoparticles.

Organic-inorganic magnetic hybrid materials (MHMs) combine a nonmagnetic and a magnetic component by means of electrostatic interactions or covalent bonds, and notable features can be achieved. Herein, we describe an application of a self-assembled material based on ferrite associated with ß-cyclodextrin (Fe-Ni/Zn/ßCD) at the nanoscale level. This MHM and pure ferrite (Fe-Ni/Zn) were used as an adsorbent system for Cr(3+) and Cr(2)O(7) (2-) ions in aqueous solutions. Prior to the adsorption studies, both ferrites were characterized in order to determine the particle size distribution, morphology and available binding sites on the surface of the materials. Microscopy analysis demonstrated that both ferrites present two different size domains, at the micro- and nanoscale level, with the latter being able to self-assemble into larger particles. Fe-Ni/Zn/ßCD presented smaller particles and a more homogeneous particle size distribution. Higher porosity for this MHM compared to Fe-Ni/Zn was observed by Brunauer-Emmett-Teller isotherms and positron-annihilation-lifetime spectroscopy. Based on the pKa values, potentiometric titrations demonstrated the presence of ßCD in the inorganic matrix, indicating that the lamellar structures verified by transmission electronic microscopy can be associated with ßCD assembled structures. Colloidal stability was inferred as a function of time at different pH values, indicating the sedimentation rate as a function of pH. Zeta potential measurements identified an amphoteric behavior for the Fe-Ni/Zn/ßCD, suggesting its better capability to remove ions (cations and anions) from aqueous solutions compared to that of Fe-Ni/Zn.

Xerogel from N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide: a nanohybrid material displaying efficient tryptophan photooxidation.

A nanohybrid xerogel (XDPN) was obtained from a tetraethyl orthosilicate (TEOS) condensation reaction in the presence of N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (DPN). Physical and chemical characterization of the materials revealed that the XDPN morphology is quite different from that of xerogel without DPN (X). Photochemical and photophysical studies of the hybrid material showed that XDPN is efficient in promoting the photosensitization of tryptophan radical formation, and the radical species are stabilized due to the presence of DPN aggregates in the material. Radical stabilization can also be observed for DPN in solution but only for concentrations in the millimolar range.