An All-Green Photo-Electrochemical Biosensor Using Microalgae Immobilized on Eco-Designed Lignin-Based Screen-Printed Electrodes to Detect Sustainable Nanoherbicides.

Herein, a novel completely green biosensor was designed exploiting both the biological and instrumental components made of eco-friendly materials for the detection of herbicides encapsulated into biodegradable nanoparticles for a sustainable agriculture. Similar nanocarriers, indeed, can deliver herbicides to the correct location, reducing the amount of active chemicals deposited in the plant, impacting the agricultural and food industries less. However, handling measurements of nanoherbicides is crucial to provide comprehensive information about their status in the agricultural fields to support farmers in decision-making. In detail, whole cells of the unicellular green photosynthetic alga Chlamydomonas reinhardtii UV180 mutant were immobilized by a green protocol on carbonized lignin screen-printed electrodes and integrated into a photo-electrochemical transductor for the detection of nanoformulated atrazine. Specifically, atrazine encapsulated into zein and chitosan doped poly-ε-caprolactone nanoparticles (atrazine-zein and atrazine-PCL-Ch) were analyzed following the current signals at a fixed applied potential of 0.8 V, in a range between 0.1 and 5 µM, indicating a linear relationship in the measured dose-response curves and a detection limit of 0.9 and 1.1 nM, respectively. Interference studies resulted in no interference from 10 ppb bisphenol A, 1 ppb paraoxon, 100 ppb arsenic, 20 ppb copper, 5 ppb cadmium, and 10 ppb lead at safety limits. Finally, no matrix effect was observed on the biosensor response from wastewater samples and satisfactory recovery values of 106 ± 8% and 93 ± 7% were obtained for atrazine-zein and atrazine-PCL-Ch, respectively. A working stability of 10 h was achieved.

Adsorption studies of the hybrid material obtained from the functionalization of silica with alfa and gamma cyclodextrins.

The generation of residues containing dyes by industrial sectors has been mobilizing scientists to develop methodologies capable of treating water containing these contaminants. Adsorption is an option to remove these molecules from the aqueous medium and, for this study, the composites between silica and cyclodextrins alpha (α-CDSI) and gamma (γ-CDSI) were used to capture methylene blue. Adsorption was spontaneous for both composites (ΔG < 0) and characterized as exothermic and of a physical nature, with ΔH of -17.68 and -12.13 kJ mol-1 for α-CDSI and γ-CDSI, respectively. Adsorption took place over a wide pH range, with an efficiency of approximately 96%, reaching equilibrium at 5 minutes. The adsorption kinetics was described by the pseudo-second-order model (R2 > 0.999) and the adsorption isotherms showed that the process must occur mainly by dye complexation in the cyclodextrins cavities. The qm values obtained were 210.8 and 205.2 mg g-1 for α-CDSI and γ-CDSI, respectively; the Sips and Temkin models were the ones that best fit the experimental data. The deposition and interactions of the dye with the adsorbent surface were confirmed by the analysis of the IR spectra. Desorption studies showed that the material maintained its adsorption capacity of around 90% until the fourth adsorption/desorption cycle. Thus, the materials produced showed to efficiently remove methylene blue and that composite reuse is a viable process for application in dye removal.

Interaction of Nanoatrazine and Target Organism: Evaluation of Fate and Photosystem II Inhibition in Hydroponically Grown Mustard (Brassica juncea) Plants.

Poly(epsilon-caprolactone) nanoparticles are an efficient carrier system for atrazine. However, there is a gap regarding the effects of nanoencapsulation on herbicide-plant interactions. Here, we evaluate the fate and photosystem II inhibition of nano and commercial atrazine in hydroponically grown mustard (Brassica juncea) plants whose roots were exposed to the formulations. In addition, to quantify the endogenous levels of atrazine in plant organs, we measured the inhibition of photosystem II activity by both formulations. Moreover, the fluorescently labeled nanoatrazine was tracked in plant tissues using confocal microscopy. The nanoencapsulation induced greater inhibition of photosystem II activity as well as higher accumulation of atrazine in roots and leaves. The nanoparticles were quickly absorbed by the roots, being detected in the vascular tissues and the leaves. Overall, these results provide insights into the mechanisms involved in the enhanced preemergent herbicidal activity of nanoatrazine against target plants.

Development of a Preemergent Nanoherbicide: From Efficiency Evaluation to the Assessment of Environmental Fate and Risks to Soil Microorganisms.

Nanoparticles based on biodegradable polymers have been shown to be excellent herbicide carriers, improving weed control and protecting the active ingredient in the crop fields. Metribuzin is often found in natural waters, which raises environmental concerns. Nanoencapsulation of this herbicide could be an alternative to reduce its losses to the environment and improve gains in its efficiency. However, there is a paucity of information about the behavior of nanoformulations of herbicides in environmental matrices. In this study, the stability of nanoencapsulated metribuzin in polymeric nanoparticles (nanoMTZ) was verified over time, as well as its dissipation in different soils, followed by the effects on soil enzymatic activity. The physiological parameters and control effects of nanoMTZ on Ipomoea grandifolia plants were investigated. No differences were verified in the half-life of nanoencapsulated metribuzin compared to a commercial formulation of the herbicide. Moreover, no suppressive effects on soil enzymatic activities were observed. The retention of nanoMTZ in the tested soils was lower compared to its commercial analogue. However, the mobility of nanoencapsulated metribuzin was not greatly increased, reflecting a low risk of groundwater contamination. Weed control was effective even at the lowest dose of nanoMTZ (48 g a.i. ha-1), which was consistent with the higher efficiency of nanoMTZ compared to the conventional herbicide in inhibiting PSII activity and decreasing pigment levels. Overall, we verified that nanoMTZ presented a low environmental risk, with increased weed control.

Foliar absorption and field herbicidal studies of atrazine-loaded polymeric nanoparticles.

Nanoparticles loaded with atrazine show weed control efficacy even with lower application doses of the active ingredient. Changes in the mode of action of the herbicide through the nanoformulation are key to understanding the efficiency of post-emergence activity of nanoatrazine. Here, we report the leaf absorption and translocation of nanoatrazine and atrazine employing radiometric techniques and compare their herbicidal effects in greenhouse and field conditions. Compared to the commercial formulation, nanoatrazine showed greater and faster absorption rates in mustard leaves (40% increment in the absorbed herbicide 24 h after application), inducing higher inhibition of photosystem II activity. Assays with fusicoccin-treated leaves indicated that the stomatal uptake of nanoparticles might be involved in the improved activity of nanoatrazine. Nanoencapsulation potentiated the post-emergent herbicidal activity of atrazine and the gain provided by nanoencapsulation was higher in the field compared to greenhouse conditions. Regardless of the dose, nanoatrazine provided two-fold higher weed control in the field compared to commercial atrazine. Thus, the design of this carrier system enables improvements in the performance of the herbicide in the field with less risk of environmental losses of the active ingredients due to faster absorption.

Zein based-nanoparticles loaded botanical pesticides in pest control: An enzyme stimuli-responsive approach aiming sustainable agriculture.

Nanoencapsulation of biopesticides is an important strategy to increase the efficiency of these compounds, reducing losses and adverse effects on non-target organisms. This study describes the preparation and characterisation of zein nanoparticles containing the botanical compounds limonene and carvacrol, responsive to proteolytic enzymes present in the insects guts. The spherical nanoparticles, prepared by the anti-solvent precipitation method, presented in the nanoparticle tracking analysis (NTA) a concentration of 4.7 × 1012 ± 1.3 × 1011 particles.mL-1 and an average size of 125 ± 2 nm. The formulations showed stability over time, in addition to not being phytotoxic to Phaseolus vulgaris plants. In vivo tests demonstrated that formulations of zein nanoparticles containing botanical compounds showed higher mortality to Spodoptera frugiperda larvae. In addition, the FTIC probe (fluorescein isothiocyanate) showed wide distribution in the larvae midgut, as well as being identified in the feces. The trypsin enzyme, as well as the enzymatic extract from insects midgut, was effective in the degradation of nanoparticles containing the mixture of botanical compounds, significantly reducing the concentration of nanoparticles and the changes in size distribution. The zein degradation was confirmed by the disappearance of the protein band in the electrophoresis gel, by the formation of the lower molecular weight fragments and also by the greater release of FTIC after enzymes incubation. In this context, the synthesis of responsive nanoparticles has great potential for application in pest management, increasing the selectivity and specificity of the system and contributing to a more sustainable agriculture.

How can nanotechnology help to combat COVID-19? Opportunities and urgent need.

Incidents of viral outbreaks have increased at an alarming rate over the past decades. The most recent human coronavirus known as COVID-19 (SARS-CoV-2) has already spread around the world and shown R0 values from 2.2 to 2.68. However, the ratio between mortality and number of infections seems to be lower in this case in comparison to other human coronaviruses (such as severe acute respiratory syndrome coronavirus (SARS-CoV) and Middle East respiratory syndrome coronavirus (MERS-CoV)). These outbreaks have tested the limits of healthcare systems and have posed serious questions about management using conventional therapies and diagnostic tools. In this regard, the use of nanotechnology offers new opportunities for the development of novel strategies in terms of prevention, diagnosis and treatment of COVID-19 and other viral infections. In this review, we discuss the use of nanotechnology for COVID-19 virus management by the development of nano-based materials, such as disinfectants, personal protective equipment, diagnostic systems and nanocarrier systems, for treatments and vaccine development, as well as the challenges and drawbacks that need addressing.

Chitosan-based delivery systems for plants: A brief overview of recent advances and future directions.

Chitosan has been termed as the most well-known among biopolymers, receiving widespread attention from researchers in various fields mainly, agriculture, food, and health. Chitosan is a deacetylated derivative of chitin, mainly isolated from waste shells of the phylum Arthropoda after their consumption as food. Chitosan molecules can be easily modified for adsorption and slow release of plant growth regulators, herbicides, pesticides, and fertilizers, etc. Chitosan as a carrier and control release matrix that offers many benefits including; protection of biomolecules from harsh environmental conditions such as pH, light, temperatures and prolonged release of active ingredients from its matrix consequently protecting the plant's cells from the hazardous effects of burst release. In the current review, tends to discuss the recent advances in the area of chitosan application as a control release system. Also, future recommendations will be made in light of current advancements and major gaps.

Interaction with Modified Cyclodextrin as a Way to Increase the Antimalarial Activity of Primaquine.

BACKGROUND: Malaria is still a dangerous disease that impacts specifically Africa, Asia, and Latin America. The development of therapies to overcome the parasite infection is an important challenge nowadays. The medicine primaquine (PQ) is used in the treatment, although several side effects and low oral bioavailability are reported. OBJECTIVE: This work focused on the preparation and characterization of a complex between PQ and 2- hydroxypropyl-ß-cyclodextrin (HPCD), besides performing release tests of this formulation. METHODS: PQ:HPCD complexes were prepared at 1:1 and 1:2 molar ratios, by the lyophilization method. The association between PQ and HPCD was tested using UV-vis, infrared (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy and NMR techniques (chemical shift, Job Plot, DOSY, and ROESY). Tests were also conducted to evaluate drug release before and after complexation with HPCD. RESULTS: Results showed that there was a weak interaction of PQ with HPCD, forming non-inclusion complexes. These results were supported by FTIR results and spatial correlations between hydrogens from PQ with the external HPCD hydrogens. A 1:2 PQ:HPCD preferred molar ratio was determined by DSC and Job Plot experiments and the time to release 96% of the drug was 21.2 h slower after complexation. CONCLUSION: Conclusion indicate that PQ interacts poorly with HPCD, probably due to its hydrophilic character, as well as to its interaction with the external rim of HPCD. Our results demonstrate that there was a significant improvement in the release time after the complexation process, which could lead to an increase in the activity of the drug.

Complexes between methyltestosterone and ß-cyclodextrin for application in aquaculture production.

The inclusion complexes between 17-α-methyltestosterone (MT) and ß-cyclodextrin (bCD) were prepared and characterized in dissolution and solid phase. The complex promoted a sixfold increment in solubility of the hormone. It has a limited solubility and stoichiometry of 2:1 (bCD:MT) determined by DSC, NMR and solubility experiments, the association constant Ka=2846Lmol-1 and complex fraction of 76% (assessed by DOSY-NMR, in (1:3) DMSO/D2O). The association constant obtained in water by the solubility isotherms is 7540Lmol-1. 2D-ROESY experiments indicate the intermolecular orientation (complete inclusion of the hormone in the cavity). Simulations by molecular dynamics agreed with the formation of the inclusion complex 2:1. Release tests showed the slower release for the complexes, with 50% for lyophilization and 56% for malaxation. These results clearly demonstrate the complexation of MT in bCD, which formulations are promising for further applications involving this steroid in aquaculture, both for sexual reversal and in technologies of hormone in water sequestration.