The Catalytic Role of Superparamagnetic Iron Oxide Nanoparticles as a Support Material for TiO2 and ZnO on Chlorpyrifos Photodegradation in an Aqueous Solution.

Chlorpyrifos (CP) is a globally used pesticide with acute toxicity. This work studied the photocatalytic degradation of CP using TiO2, ZnO nanoparticles, and nanocomposites of TiO2 and ZnO supported on SPIONs (SPION@SiO2@TiO2 and SPION@SiO2@ZnO). The nanocomposites were synthesized by multi-step incipient wetness impregnation. The effects of the initial pH, catalyst type, and dose were evaluated. The nanocomposites of SPION@SiO2@TiO2 and SPION@SiO2@ZnO showed higher CP photodegradation levels than free nanoparticles, reaching 95.6% and 82.3%, respectively, at pH 7. The findings indicate that iron oxide, as a support material for TiO2 and ZnO, extended absorption edges and delayed the electron-hole recombination of the nanocomposites, improving their photocatalytic efficiency. At the same time, these nanocomposites, especially SPION@SiO2@TiO2, showed efficient degradation of 3,5,6-trichloropyridinol (TCP), one of the final metabolites of CP. The stability and reuse of this nanocomposite were also evaluated, with 74.6% efficiency found after six cycles. Therefore, this nanomaterial represents an eco-friendly, reusable, and effective alternative for the degradation of chlorpyrifos in wastewater treatment.

Meta-analysis of metal nanoparticles degrading pesticides: what parameters are relevant?

The rise in the global population demands an increasing food supply and methods to boost agricultural production. Pesticides are necessary for agricultural production models, avoiding losses of close to 40%. Nevertheless, the extensive use of pesticides can cause their accumulation in the environment, causing problems for human health, biota, and ecosystems. Thus, new technologies have emerged to remove these wastes efficiently. In recent years, metal and metal oxide nanoparticles (MNPs) have been reported as promising catalysts to degrade pesticides; however, a systematic understanding of their effect on pesticide degradation is still required. Therefore, this study focused on a meta-analysis of articles available in Elsevier's Scopus and Thomas Reuters Web of Science, found by searching for "nanoparticle pesticide" and "pesticide contamination." After passing different filters, the meta-analysis was performed with 408 observations from 94 reviews, which comprise insecticides, herbicides, and fungicides, including organophosphates, organochlorines, carbamates, triazines, and neonicotinoids. Herein, 14 different MNPs (Ag, Ni, Pd, Co3O4, BiOBr, Au, ZnO, Fe, TiO2, Cu, WO3, ZnS, SnO2, and Fe0), improved pesticide degradation, with the highest degradation rates achieved by Ag (85%) and Ni (82.5%). Additionally, the impact of the MNP functionalization, size, and concentration on pesticide degradation was quantified and compared. In general, the degradation rate increased when the MNPs were functionalized (~ 70%) compared to naked (~ 49%). Also, the particle size significantly affected the degradation of pesticides. To our knowledge, this study is the first meta-analysis performed about the impact of MNPs on pesticide degradation, providing an essential scientific basis for future studies.

Antioxidant Activity as an Indicator of the Efficiency of Plant Extract-Mediated Synthesis of Zinc Oxide Nanoparticles.

The green synthesis of zinc oxide nanoparticles (ZnO NPs) using a diverse range of plant species has been extensively reported. Despite the success achieved by biogenic synthesis, there are problems with the control and prediction of the properties of ZnO NPs, due to phytochemical diversity between plant species. In this sense, the main objective of our work was to investigate the effect of the antioxidant activity (AA) of plant extracts on the physicochemical characteristics of ZnO NPs (production yield, chemical composition, polydispersity index (PDI), surface charge (ζ-potential) and average particle size). In order to accomplish this objective, four plant extract with different antioxidant activities were used: Galega officinalis, Buddleja globosa, Eucalyptus globulus, and Aristotelia chilensis. Phytochemical screening, quantitative analysis of phenolic compounds and antioxidant activity determination of the different extracts were carried out. Chemical species such as catechin, malvidin, quercetin, caffeic acid, and ellagic acid were the dominant components, found in the extracts studied. The A. chilensis extract showed the highest value of total phenolic compounds (TPC) and AA, followed by E. globulus, B. globosa and G. officinalis. Zetasizer, Fourier-transform infrared (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) data show that plant extracts with lower AA leads to a decrease in the yield of ZnO NPs and an increase in the amount of residual organic extract that remains on the particles. The latter caused an increase in the average particle size, PDI and ζ-potential as a consequence of agglomeration and particle coarsening. Our result suggest that it is possible to use the AA as an indicator of the potential reducing capacity of plant extracts. In this way it is possible to guarantee the reproducibility of the synthesis process as well as ensure the formation of ZnO NPs with desired characteristics.

Synthesis of Antimicrobial Chitosan-Silver Nanoparticles Mediated by Reusable Chitosan Fungal Beads.

Nanoparticles, especially silver nanoparticles (Ag NPs), have gained significant attention in recent years as potential alternatives to traditional antibiotics for treating infectious diseases due to their ability to inhibit the growth of microorganisms effectively. Ag NPs can be synthesized using fungi extract, but the method is not practical for large-scale production due to time and biomass limitations. In this study, we explore the use of chitosan to encapsulate the mycelia of the white-rot fungus Stereum hirsutum and form chitosan fungal beads for use in multiple extractions and nanoparticle synthesis. The resulting nanoparticles were characterized using various techniques, including UV-vis spectrophotometry, transmission electron microscopy, dynamic light scattering, and X-ray diffraction analysis. The analysis revealed that the synthesized nanoparticles were composed of chitosan-silver nanoparticles (CS-Ag NPs) with a size of 25 nm. The chitosan fungal beads were reused in three extractions and nanoparticle synthesis before they lost their ability to produce CS-Ag NPs. The CS-Ag NPs showed potent antimicrobial activity against phytopathogenic and human pathogenic microorganisms, including Pseudomonas syringae, Escherichia coli, Staphylococcus aureus, and Candida albicans, with minimum inhibitory concentrations of 1.5, 1.6, 3.1, and 4 µg/mL, respectively. The antimicrobial activity of CS-Ag NPs was from 2- to 40-fold higher than Ag NPs synthesized using an aqueous extract of unencapsulated fungal biomass. The CS-Ag NPs were most effective at a pH of five regarding the antimicrobial activity. These results suggest that the chitosan fungal beads may be a promising alternative for the sustainable and cost-effective synthesis of CS-Ag NPs with improved antimicrobial activity.

Synthesis and Antibacterial Activity of Manganese-Ferrite/Silver Nanocomposite Combined with Two Essential Oils.

The antimicrobial activity of metal nanoparticles obtained by biogenic routes has been extensively reported. However, their combined use with other antimicrobial formulations, such as essential oils, remains scarcely explored. In this work, a manganese-ferrite/silver nanocomposite (MnFe2O4/Ag-NC) was synthesized in a two-step procedure: first, MnFe2O4 nanoparticles were produced by a coprecipitation method, followed by in situ biogenic reduction of silver ions using Galega officinalis. MnFe2O4/Ag-NC was characterized using transmission electron microscopy (TEM), scanning electron microscopy equipped with an energy dispersive X-ray analyzer (SEM-EDX), and a vibrating sample magnetometer (VSM-SQUID). The antibacterial activity if MnFe2O4/Ag-NC was evaluated against Pseudomonas syringae by determining its minimum inhibitory concentration (MIC) in the presence of two essential oils: eucalyptus oil (EO) and garlic oil (GO). The fractional inhibitory concentration (FIC) was also calculated to determine the interaction between MnFe2O4/Ag-NC and each oil. The MIC of MnFe2O4/Ag-NC was eightfold reduced with the two essential oils (from 20 to 2.5 µg mL-1). However, the interaction with EO was synergistic (FIC: 0.5), whereas the interaction with GO was additive (FIC: 0.75). Additionally, a time-kill curve analysis was performed, wherein the MIC of the combination of MnFe2O4/Ag-NC and EO provoked a rapid bactericidal effect, corroborating a strong synergism. These findings suggest that by combining MnFe2O4/Ag-NC with essential oils, the necessary ratio of the nanocomposite to control phytopathogens can be reduced, thus minimizing the environmental release of silver.

Molecular Weight Identification of Compounds Involved in the Fungal Synthesis of AgNPs: Effect on Antimicrobial and Photocatalytic Activity.

The biological synthesis of silver nanoparticles (AgNPs) for medical, environmental, and industrial applications is considered an alternative to chemical synthesis methods. Additionally, the reducing, capping, and stabilizing molecules produced by the organisms can play a key role in the further activity of AgNPs. In this work, we evaluated the synthesis of AgNPs by four molecular weight fractions (S1: <10 kDa, S2: 10 to 30 kDa, S3: 30 to 50 kDa, and S4: >50 kDa) of mycelia-free aqueous extract produced by the white-rot fungus Stereum hirsutum and their effect on the antimicrobial activity against Pseudomonas syringae and photocatalytic decolorization of nine synthetic dyes exposed to sunlight radiation. All synthesis assay fractions showed the characteristic surface plasmon resonance (SPR) with 403 to 421 nm peaks. TEM analysis of synthesized AgNPs showed different sizes: the whole mycelia-free extracts S0 (13.8 nm), S1 (9.06 nm), S2 (10.47 nm), S3 (22.48 nm), and S4 (16.92 nm) fractions. The results of disk diffusion assays showed an inverse relation between antimicrobial activity and the molecular weight of compounds present in the mycelia-free aqueous extract used to synthesize AgNPs. The AgNPs synthesized by S0 (14.3 mm) and S1(14.2 mm) generated the highest inhibition diameter of P. syringae growth. By contrast, in the photocatalytic assays, the AgNPs synthesized by the S2 fraction showed the highest discoloration in all the dyes tested, reaching 100% of the discoloration of basic dyes after 2 h of sunlight exposure. The maximum discoloration observed in reactive and acid dyes was 53.2% and 65.3%, respectively. This differentiation in the antimicrobial and photocatalytic activity of AgNPs could be attributed to the capping effect of the molecules present in the extract fractions. Therefore, the molecular separation of synthesis extract enables the specific activities of the AgNPs to be enhanced.

Biodegradation inducers to enhance wheat straw pretreatment by Gloeophyllum trabeum to second-generation ethanol production.

The native state of lignocellulosic biomass is highly resistant to enzymatic hydrolysis and the fermentation process of biofuel production. Brown-rot fungi use an extracellular Fenton system to degrade lignocellulosic biomass in the initial stages of decay. In this work, the combined effects of Mn2+, Fe2+, and NO3- inducers were evaluated based on the activities of hydrolytic enzymes and Fe3+ reduction as well as the catechol-type compound production during wheat straw pretreatment by the brown-rot fungus Gloeophyllum trabeum. Weight loss and chemical changes were evaluated to establish the culture conditions for stimulating wheat straw degradation using a central composite design. The results showed that weight loss and the Fe3+-reducing activity were promoted at the highest concentrations of Fe2+. A positive effect on catechol compound production by the addition of Mn2+ and NO3- was observed. Cellulase activity was increased at the highest concentration of NO3-. The multiple optimizations of G. trabeum culture conditions in wheat straw resulted in 11.3% weight loss and 0.47 total crystallinity index at 0.24 M NO3-, 0.95 mM Fe2+, and 0.85 mM Mn2+ after 40 days. The wheat straw pretreatment by G. trabeum for 10 days increased glucose recovery. The results indicated that the wheat straw pretreatment using G. trabeum with biodegradation inducers could be a complementary step to physicochemical pretreatment of lignocellulosic biomass for production of second-generation ethanol.

Sequential white-rot and brown-rot fungal pretreatment of wheat straw as a promising alternative for complementary mild treatments.

White-rot and brown-rot fungi have complementary mechanisms to selectively degrade lignin and holocellullose, respectively. Thereby, a fungal co-culture of a white-rot and a brown-rot fungal could result in efficient strategy for a mild lignocellulosic biomass pretreatment. In this work, single, sequential and co-inoculation of the selective-lignin degrading white-rot fungus Ganoderma lobatum and the brown-rot fungus Gloeophyllum trabeum were evaluated as biological pretreatments of wheat straw to enhance enzymatic hydrolysis of cellulose. The single cultures of G. lobatum and G. trabeum exhibited preferential degradation of lignin and hemicellulose, respectively. The total crystallinity index decreased in samples pretreated with G. trabeum but not with G. lobatum. The pretreatment with single cultures of G. lobatum or G. trabeum increased glucose yields by 43.6% and 26.1% respectively compared to untreated straw. Although co-inoculation resulted in higher yields of glucose when compared with single cultures, only a slight synergistic effect between fungi was observed. Contrary, the sequential inoculation of G. lobatum incubated for 10 days followed by G. trabeum incubated for 10 days more showed a strong synergic effect on enzymatic hydrolysis. This sequential culture showed the highest glucose yield (191.5 mg g-1 wheat straw), 2.8-fold higher than untreated wheat straw, and 140-150% higher than the single-cultures of G. lobatum and G. trabeum, respectively.

Combined effect of enzyme inducers and nitrate on selective lignin degradation in wheat straw by Ganoderma lobatum.

Lignin is one of the main barriers to obtaining added-value products from cellulosic fraction of lignocellulosic biomass due to its random aromatic structure and strong association with cellulose and hemicellulose. Inorganic and organic compounds have been used as enzyme inducers to increase the ligninolytic potential of white-rot fungi, without considering their effect on the selectivity of degradation. In this study, the selective lignin degradation in wheat straw by Ganoderma lobatum was optimized using a central composite design to evaluate the combined effect of Fe2+ and Mn2+ as inducers of ligninolytic enzymes and NO3- as an additional nitrogen source. Selective lignin degradation was promoted to maximize lignin degradation and minimize weight losses. The optimal conditions were 0.18 M NO3-, 0.73 mM Fe2+, and 1 mM Mn2+, which resulted in 50.0% lignin degradation and 18.5% weight loss after 40 days of fungal treatment. A decrease in absorbance at 1505 and 900 cm-1 in fungal-treated samples was observed in the FTIR spectra, indicating lignin and cellulose degradation in fungal-treated wheat straw, respectively. The main ligninolytic enzymes detected during lignin degradation were manganese-dependent and manganese-independent peroxidases. Additionally, confocal laser scanning microscopy revealed that lignin degradation in wheat straw by G. lobatum resulted in higher cellulose accessibility. We concluded that the addition of enzyme inducers and NO3- promotes selective lignin degradation in wheat straw by G. lobatum.