The Synergic Effect of h-MoO3, α-MoO3, and ß-MoO3 Phase Mixture as a Solid Catalyst to Obtain Methyl Oleate.

Extensive research in the last few decades has conclusively demonstrated the significant influence of experimental conditions, surfactants, and synthesis methods on semiconductors' properties in technological applications. Therefore, in this study, the synthesis of molybdenum oxide (MoO3) was reported by the addition of 2.5 (MoO3_2.5), 5 (MoO3_5), 7.5 (MoO3_7.5), and 10 mL (MoO3_10) of nitric acid, obtaining the respective concentrations of 0.6, 1.10, 1.6, and 0.6 mol L-1. In this study, all samples were synthesized by the hydrothermal method at 160 °C for 6 h. The materials obtained were structurally characterized by X-ray diffraction (XRD) and structural Rietveld refinement, Raman spectroscopy, and infrared spectroscopy (FTIR), confirming the presence of all crystallographic planes and bands associated with active modes for the pure hexagonal phase (h-MoO3) when the solution's concentration was 0.6 mol L-1 of nitric acid. For concentrations of 1.10, 1.60, and 2.10 mol L-1, the presence of crystallographic planes and active modes associated with the formation of mixtures of molybdenum oxide polymorphs was confirmed, in this case, the orthorhombic, monoclinic, and hexagonal phases. X-ray photoelectron spectroscopy reveals the occurrence of the states Mo4+, Mo5+, and Mo6+, which confirm the predominance of the acid Lewis sites, corroborating the analysis by adsorption of pyridine followed by characterization by infrared spectroscopy. The images collected by scanning electron microscopy confirmed the information presented in the structural characterization, where microcrystals with hexagonal morphology were obtained for the MoO3_2.5 sample. In contrast, the MoO3_5, MoO3_7.5, and MoO3_10 samples exhibited hexagonal and rod-shaped microcrystals, where the latter morphology is characteristic of the orthorhombic phase. The catalytic tests carried out in the conversion of oleic acid into methyl oleate, using the synthesized samples as a heterogeneous catalyst, resulted in conversion percentages of 52.5, 58.6, 69.1, and 97.2% applying the samples MoO3_2.5, MoO3_5, MoO3_7.5, and MoO3_10, respectively. The optimization of the catalytic tests with the MoO3_10 sample revealed that the conversion of oleic acid into methyl oleate is a thermodynamically favorable process, with a variation in the Gibbs free energy between -67.3 kJ mol-1 and 83.4 kJ mol-1 as also, the energy value of activation of 24.6 kJ mol-1, for the temperature range from 80 to 140 °C, that is, from 353.15 to 413.15 K, respectively. Meanwhile, the catalyst reuse tests resulted in percentages greater than 85%, even after the ninth catalytic cycle. Therefore, the expressive catalytic performance of the mixture of h-MoO3 and α-MoO3 (MoO3_10) phases is confirmed, associated with the synergistic effect, mainly due to the increase in the surface area and available Lewis sites of these phases.

Efficient photocatalytic degradation of diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst under UV light irradiation.

Herein, we report the efficient photocatalytic degradation of the diclofenac drug using the Zn1-x-yPrxAlyO photocatalyst [x, y] = (0.00, 0.00), (0.03, 0.01), (0.03,0.03) under UV light irradiation. The analysis of the structure reveals that the Pr3+ and Al3+ cations insertion into the ZnO lattice leads to a decrease in the lattice constant (a and c), Zn-O bond length, strain lattice, and crystallite size. These alterations are linked to the high degree of atomic disorder triggered by the dopants, which produce stress and strain in the ZnO structure. The Raman measurements confirmed the structural phase and showed changes in the position and intensity of the E2High mode, associated with oxygen vibrations and material crystallinity. The presence of the dopants reduces the concentration of VZn and VO++ type defects while increasing the levels of VO, VO+, and Oi defects, as observed from the fitting of the Photoluminescence spectra. Furthermore, it was noted that de Pr3+ and Al3+ cations insertion into ZnO increases the optical band gap, which is associated with the Moss-Burstein effect. The micrograph images show that dopants transform the morphology from quasi-spherical particles to irregular cluster structures. The textural analysis indicated that an increase in the concentration of Al3+ in the ZnO lattice led to a higher surface area, likely enhancing photocatalytic activity. The sample containing 3% Pr3+ and 3% Al3+ showed the highest photocatalytic activity and degraded up to 71.42% of diclofenac. In addition, experiments with scavengers revealed that hydroxyl radicals are the main species involved in the drug's photodegradation mechanism. Finally, the Zn1-x-yPrxAlyO compound is highly recyclable and stable.

Synthesis and Characterization of Cassava Gum Hydrogel Associated with Chlorhexidine and Evaluation of Release and Antimicrobial Activity.

Hydrogels from natural sources are attracting increasing interest due to their ability to protect biologically active molecules. Starch extracted from cassava tubers is a promising material for synthesizing these hydrogels. Copolymerization of cassava gum and incorporation of chlorhexidine digluconate (CLX) into the hydrogels is confirmed by changes in the crystallographic profile, as observed through X-ray diffraction, and a shift in the 1000 cm-1 band in the Fourier-transform infrared spectroscopy spectrum. The differential scanning calorimetry reveals changes in the decomposition temperature of the synthesized hydrogels related to CLX volatility. Micrographs illustrate the material's porosity. Release tests indicate a constant linear release over 72 h, while antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans is satisfactory, with 100% effectiveness from 0.5% CLX and the formation of inhibition halos. Toxicity and biocompatibility studies show no cytotoxicity. The continuous release of chlorhexidine is promising for components of biomedical implants and applications as it can ensure antimicrobial action according to specific therapeutic needs.

Green Synthesis of Er-Doped ZnO Nanoparticles: An Investigation on the Methylene Blue, Eosin, and Ibuprofen Removal by Photodegradation.

We present a study on the green synthesis of undoped and Er-doped ZnO compounds using Mangifera indica gum (MI). A set of tests were conducted to assess the structure of the material. The tests included X-ray diffraction, Raman, and Fourier-transform infrared spectroscopy. Optical properties were studied using diffuse reflectance and photoluminescence. Morphological and textural investigations were done using SEM images and N2 adsorption/desorption. Furthermore, photocatalytic tests were performed with methylene blue (MB), yellow eosin (EY), and the pharmaceutical drug ibuprofen (IBU) under UV irradiation. The study demonstrated that replacing the stabilizing agent with Mangifera indica gum is an effective method for obtaining ZnO nanoparticles. Additionally, the energy gap of the nanoparticles exhibits a slight reduction in value. Photoluminescence studies showed the presence of zinc vacancies and other defects in both samples. In the photocatalytic test, the sample containing Er3+ exhibited a degradation of 99.7% for methylene blue, 81.2% for yellow eosin, and 52.3% for ibuprofen over 120 min. In the presence of methyl alcohol, the degradation of MB and EY dyes is 16.7% and 55.7%, respectively. This suggests that hydroxyl radicals are responsible for the direct degradation of both dyes. In addition, after the second reuse, the degradation rate for MB was 94.08%, and for EY, it was 82.35%. For the third reuse, the degradation rate for MB was 97.15%, and for EY, it was 17%. These results indicate the significant potential of the new semiconductor in environmental remediation applications from an ecological synthesis.

Facile Synthesis of Ni-Doped ZnO Nanoparticles Using Cashew Gum: Investigation of the Structural, Optical, and Photocatalytic Properties.

This work adopted a green synthesis route using cashew tree gum as a mediating agent to obtain Ni-doped ZnO nanoparticles through the sol-gel method. Structural analysis confirmed the formation of the hexagonal wurtzite phase and distortions in the crystal lattice due to the inclusion of Ni cations, which increased the average crystallite size from 61.9 nm to 81.6 nm. These distortions resulted in the growth of point defects in the structure, which influenced the samples' optical properties, causing slight reductions in the band gaps and significant increases in the Urbach energy. The fitting of the photoluminescence spectra confirmed an increase in the concentration of zinc vacancy defects (VZn) and monovacancies (Vo) as Zn cations were replaced by Ni cations in the ZnO structure. The percentage of VZn defects for the pure compound was 11%, increasing to 40% and 47% for the samples doped with 1% and 3% of Ni cations, respectively. In contrast, the highest percentage of VO defects is recorded for the material with the lowest Ni ions concentration, comprising about 60%. The influence of dopant concentration was also reflected in the photocatalytic performance. Among the samples tested, the Zn0.99Ni0.01O compound presented the best result in MB degradation, reaching an efficiency of 98.4%. Thus, the recovered material underwent reuse tests, revealing an efficiency of 98.2% in dye degradation, confirming the stability of the photocatalyst. Furthermore, the use of different inhibitors indicated that •OH radicals are the main ones involved in removing the pollutant. This work is valuable because it presents an ecological synthesis using cashew gum, a natural polysaccharide that has been little explored in the literature.

Study of Structural and Optical Properties of Titanate Nanotubes with Erbium under Heat Treatment in Different Atmospheres.

Titanate nanotubes were synthesized and subjected to an ion exchange reaction with erbium salt aqueous solution to obtain titanate nanotubes exchanged with erbium (3+) ions. In order to evaluate the effects of the thermal treatment atmosphere on the structural and optical properties of erbium titanate nanotubes, we subjected them to heat treatment in air and argon atmospheres. For comparison, titanate nanotubes were also treated in the same conditions. A complete structural and optical characterizations of the samples was performed. The characterizations evidenced the preservation of the morphology with the presence of phases of erbium oxides decorating the surface of the nanotubes. Variations in the dimensions of the samples (diameter and interlamellar space) were promoted by the replacement of Na+ by Er3+ and the thermal treatment in different atmospheres. In addition, the optical properties were investigated by UV-Vis absorption spectroscopy and photoluminescence spectroscopy. The results revealed that the band gap of the samples depends on the variation of diameter and sodium content caused by ion exchange and thermal treatment. Furthermore, the luminescence strongly depended on vacancies, evidenced mainly by the calcined erbium titanate nanotubes in argon atmosphere. The presence of these vacancies was confirmed by the determination of Urbach energy. The results suggest the use of thermal treated erbium titanate nanotubes in argon atmosphere in optoelectronics and photonics applications, such as photoluminescent devices, displays, and lasers.

Photoresponsive Activity of the Zn0.94Er0.02Cr0.04O Compound with Hemisphere-like Structure Obtained by Co-Precipitation.

In this work, a ZnO hemisphere-like structure co-doped with Er and Cr was obtained by the co-precipitation method for photocatalytic applications. The dopant's effect on the ZnO lattice was investigated using X-ray diffraction, Raman, photoluminescence, UV-Vis and scanning electron microscopy/energy dispersive spectroscopy techniques. The photocatalytic response of the material was analyzed using methylene blue (MB) as the model pollutant under UV irradiation. The wurtzite structure of the Zn0.94Er0.02Cr0.04O compound presented distortions in the lattice due to the difference between the ionic radii of the Cr3+, Er3+ and Zn2+ cations. Oxygen vacancy defects were predominant, and the energy competition of the dopants interfered in the band gap energy of the material. In the photocatalytic test, the MB degradation rate was 42.3%. However, using optimized H2O2 concentration, the dye removal capacity reached 90.1%. Inhibitor tests showed that •OH radicals were the main species involved in MB degradation that occurred without the formation of toxic intermediates, as demonstrated in the ecotoxicity assays in Artemia salina. In short, the co-doping with Er and Cr proved to be an efficient strategy to obtain new materials for environmental remediation.

Polyurethane/Vermiculite Foam Composite as Sustainable Material for Vertical Flame Retardant.

Rigid polyurethane foams were prepared by the one-step expandable foam method using casting molding followed by forming clay-based composites. Polyurethane/vermiculite foam composites (PU/VMT) were controlled based on adding the percentage of clay in the formulation. The effects of composite modifications were evaluated by X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), and scanning electron microscopy (SEM/EDS) applied to the flame retardancy explored by the vertical burn test. The results indicated that adding clay controlled the particle size concerning polyurethane (PU) foams. However, they exhibited spherical structures with closed cells with relatively uniform distribution. XRD analysis showed the peaks defined at 2θ = 18° and 2θ = 73° relative to the crystallinity in formation and interaction of rigid segments were identified, as well as the influence of crystallinity reduction in composites. In the flame test, the flame retardant surface was successful in all composites, given the success of the dispersibility and planar orientation of the clay layers and the existence of an ideal content of vermiculite (VMT) incorporated in the foam matrix.

TiO2/Karaya Composite for Photoinactivation of Bacteria.

TiO2/Karaya composite was synthesized by the sol-gel method for the photoinactivation of pathogens. This is the first time that we have reported this composite for an antimicrobial approach. The structure, morphology, and optical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-rays (EDS), Fourier transform infrared spectroscopy (FTIR), and diffuse reflectance, and the surface area was characterized by the BET method. The XRD and EDS results showed that the TiO2/Karaya composite was successfully stabilized by the crystal structure and pore diameter distribution, indicating a composite of mesoporous nature. Furthermore, antibacterial experiments showed that the TiO2/Karaya composite under light was able to photoinactivate bacteria. Therefore, the composite is a promising candidate for inhibiting the growth of bacteria.

A Brief Photocatalytic Study of ZnO Containing Cerium towards Ibuprofen Degradation.

Ibuprofen (IBU) is one of the most-sold anti-inflammatory drugs in the world, and its residues can reach aquatic systems, causing serious health and environmental problems. Strategies are used to improve the photocatalytic activity of zinc oxide (ZnO), and thosethat involvethe inclusion of metalhave received special attention. The aim of this work was to investigate the influence of the parameters and toxicity of a photoproduct using zinc oxide that contains cerium (ZnO-Ce) for the photodegradation of ibuprofen. The parameters include the influence of the photocatalyst concentration (0.5, 0.5, and 1.5 g L-1) as well as the effects of pH (3, 7, and 10), the effect of H2O2, and radical scavengers. The photocatalyst was characterized by Scanning Electron Microscopy-Energy Dispersive Spectroscopy, Transmission electron microscopy, Raman, X-Ray Diffraction, surface area, and diffuse reflectance. The photocatalytic activity of ibuprofen was evaluated in an aqueous solution under UV light for 120 min. The structural characterization by XRD and SEM elucidated the fact that the nanoparticle ZnO contained cerium. The band gap value was 3.31 eV. The best experimental conditions for the photodegradation of IBU were 60% obtained in an acidic condition using 0.50 g L-1 of ZnO-Ce in a solution of 20 ppm of IBU. The presence of hydrogen peroxide favored the photocatalysis process. ZnO-Ce exhibited good IBU degradation activity even after three photocatalytic cycles under UV light. The hole plays akey role in the degradation process of ibuprofen. The toxicity of photolyzed products was monitored against Artemia salina (bioindicator) and did not generate toxic metabolites. Therefore, this work provides a strategic design to improve ZnO-Ce photocatalysts for environmental remediation.

Development of a semiconductor tree branch-like photoreactor for textile industry effluent treatment.

This paper aimed to develop a new photocatalytic reactor design with a rotary tree branch structure for wastewater treatment in the textile industry. The brass sheet calcined at 500 °C (B500) was used as the photocatalyst and as a substrate for ZnO nanoparticle immobilization (B500ZnO). The photoreactor performance was evaluated toward the photodegradation of an aqueous solution of Reactive Black 5 dye (AS-RB5), raw wastewater (RW), and treated wastewater (TW). X-ray diffraction (XRD) and scanning electron microscopy (SEM) results illustrated ZnO nanowire formation over B500 and B500ZnO substrates. The bandgap values of these samples were estimated by diffuse reflectance measurements. The effects of dye concentration, the type of radiation, and ZnO NP deposition on the degradation of AS-RB were evaluated. Decreases in chemical oxygen demand (COD) greater than 82% were obtained using solar irradiation and artificial light as the energy source. Regarding calcined brass sheet reutilization, a decrease of 45% in the photocatalytic activity efficiency after 5 cycles was noted due to the effect of photocorrosion of the ZnO nanowires. The photoreaction of the RW and TW effluents showed COD values of 21 and 35%, respectively, which are below the limits established by state environmental control. With respect to RB5 addition to the TW effluent (TW-RB5), a discoloration of 62% was noticed after 3 h of photodegradation. Furthermore, the toxicity tests of the AS-RB5 and TW-RB5 samples did not display toxic intermediates after the photoreaction since 80% of the seeds germinated. Finally, the photoreactor exhibited good performance regarding the decrease in effluent pollutant charge, in addition to the efficient discoloration of RB5 dye.

Survival and Proliferation under Severely Hypoxic Microenvironments Using Cell-Laden Oxygenating Hydrogels.

Different strategies have been employed to provide adequate nutrients for engineered living tissues. These have mainly revolved around providing oxygen to alleviate the effects of chronic hypoxia or anoxia that result in necrosis or weak neovascularization, leading to failure of artificial tissue implants and hence poor clinical outcome. While different biomaterials have been used as oxygen generators for in vitro as well as in vivo applications, certain problems have hampered their wide application. Among these are the generation and the rate at which oxygen is produced together with the production of the reaction intermediates in the form of reactive oxygen species (ROS). Both these factors can be detrimental for cell survival and can severely affect the outcome of such studies. Here we present calcium peroxide (CPO) encapsulated in polycaprolactone as oxygen releasing microparticles (OMPs). While CPO releases oxygen upon hydrolysis, PCL encapsulation ensures that hydrolysis takes place slowly, thereby sustaining prolonged release of oxygen without the stress the bulk release can endow on the encapsulated cells. We used gelatin methacryloyl (GelMA) hydrogels containing these OMPs to stimulate survival and proliferation of encapsulated skeletal myoblasts and optimized the OMP concentration for sustained oxygen delivery over more than a week. The oxygen releasing and delivery platform described in this study opens up opportunities for cell-based therapeutic approaches to treat diseases resulting from ischemic conditions and enhance survival of implants under severe hypoxic conditions for successful clinical translation.

Insights into the Antimicrobial Activity of Hydrated Cobaltmolybdate Doped with Copper.

Molybdates are biocidal materials that can be useful in coating surfaces that are susceptible to contamination and the spread of microorganisms. The aim of this work was to investigate the effects of copper doping of hydrated cobalt molybdate, synthesized by the co-precipitation method, on its antibacterial activity and to elucidate the structural and morphological changes caused by the dopant in the material. The synthesized materials were characterized by PXRD, Fourier Transformed Infrared (FTIR), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and SEM-Energy Dispersive Spectroscopy (SEM-EDS). The antibacterial response of the materials was verified using the Minimum Inhibitory Concentration (MIC) employing the broth microdilution method. The size of the CoMoO4·1.03H2O microparticles gradually increased as the percentage of copper increased, decreasing the energy that is needed to promote the transition from the hydrated to the beta phase and changing the color of material. CoMoO4·1.03H2O obtained better bactericidal performance against the tested strains of Staphylococcus aureus (gram-positive) than Escherichia coli (gram-negative). However, an interesting point was that the use of copper as a doping agent for hydrated cobalt molybdate caused an increase of MIC value in the presence of E. coli and S. aureus strains. The study demonstrates the need for caution in the use of copper as a doping material in biocidal matrices, such as cobalt molybdate.