Anderson do Espirito Santo Pereira

Chitosan/tripolyphosphate nanoparticles loaded with paraquat herbicide: An environmentally safer alternative for weed control

Paraquat is a fast acting nonselective contact herbicide that is extensively used worldwide. However, the aqueous solubility and soil sorption of this compound can cause problems of toxicity in nontarget organisms. This work investigates the preparation and characterization of nanoparticles composed of chitosan and sodium tripolyphosphate (TPP) to produce an efficient herbicidal formulation that was less toxic and could be used for safer control of weeds in agriculture. The toxicities of the formulations were evaluated using cell culture viability assays and the Allium cepa chromosome aberration test. The herbicidal activity was investigated in cultivations of maize (Zea mays) and mustard (Brassica sp.), and soil sorption of the nanoencapsulated herbicide was measured. The efficiency association of paraquat with the nanoparticles was 62.6 ± 0.7%. Encapsulation of the herbicide resulted in changes in its diffusion and release as well as its sorption by soil. Cytotoxicity and genotoxicity assays showed that the nanoencapsulated herbicide was less toxic than the pure compound, indicating its potential to control weeds while at the same time reducing environmental impacts. Measurements of herbicidal activity showed that the effectiveness of paraquat was preserved after encapsulation. It was concluded that the encapsulation of paraquat in nanoparticles can provide a useful means of reducing adverse impacts on human health and the environment, and that the formulation therefore has potential for use in agriculture.

Controlled release system for ametryn using polymer microspheres: preparation, characterization and release kinetics in water.

The purpose of this work was to develop a modified release system for the herbicide ametryn by encapsulating the active substance in biodegradable polymer microparticles produced using the polymers poly(hydroxybutyrate) (PHB) or poly(hydroxybutyrate-valerate) (PHBV), in order to both improve the herbicidal action and reduce environmental toxicity. PHB or PHBV microparticles containing ametryn were prepared and the efficiencies of herbicide association and loading were evaluated, presenting similar values of approximately 40%. The microparticles were characterized by scanning electron microscopy (SEM), which showed that the average sizes of the PHB and PHBV microparticles were 5.92±0.74 μm and 5.63±0.68 μm, respectively. The ametryn release profile was modified when it was encapsulated in the microparticles, with slower and more sustained release compared to the release profile of pure ametryn. When ametryn was associated with the PHB and PHBV microparticles, the amount of herbicide released in the same period of time was significantly reduced, declining to 75% and 87%, respectively. For both types of microparticle (PHB and PHBV) the release of ametryn was by diffusion processes due to anomalous transport (governed by diffusion and relaxation of the polymer chains), which did not follow Ficks laws of diffusion. The results presented in this paper are promising, in view of the successful encapsulation of ametryn in PHB or PHBV polymer microparticles, and indications that this system may help reduce the impacts caused by the herbicide, making it an environmentally safer alternative.

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

A method was developed to attach 4-amino-2-mercaptopyrimidine (AMP) onto silica gel surface and to determine trace metals. The surface functionalization reaction was performed with a silylant agent, chloropropyltrimethoxysilane (Si-CPTS), and the product, Si-AMP, was characterized by FT-IR and elemental analysis to evaluate the surface modification. The functionalized silica was applied in the sorption of Cu(II) ions from an aqueous medium. The series of adsorption isotherms were adjusted to a modified Langmuir equation and the maximum number of moles of adsorbed copper was 0.447 mmol g(-1). The modified material was placed in a preconcentration system, where it reached an approximately 20-fold enrichment factor using 5mg of Si-AMP. The proposed method was applied in the preconcentration and determination of Cu(II) in a fresh water sample from the Paraná river and was validated through a comparative analysis of a standard reference material (1643e).

Application of poly(epsilon-caprolactone) nanoparticles containing atrazine herbicide as an alternative technique to control weeds and reduce damage to the environment.

Nanoparticles of poly(epsilon-caprolactone) containing the herbicide atrazine were prepared, characterized, and evaluated in terms of their herbicidal activity and genotoxicity. The stability of the nanoparticles was evaluated over a period of three months, considering the variables: size, polydispersion index, pH, and encapsulation efficiency. Tests on plants were performed with target (Brassica sp.) and non-target (Zea mays) organisms, and the nanoparticle formulations were shown to be effective for the control of the target species. Experiments using soil columns revealed that the use of nanoparticles reduced the mobility of atrazine in the soil. Application of the Allium cepa chromosome aberration assay demonstrated that the nanoparticle systems were able to reduce the genotoxicity of the herbicide. The formulations developed offer a useful means of controlling agricultural weeds, while at the same time reducing the risk of harm to the environment and human health.

Evaluation of the Genotoxicity of Chitosan Nanoparticles for Use in Food Packaging Films

The use of nanoparticles in food packaging has been proposed on the basis that it could improve protection of foods by, for example, reducing permeation of gases, minimizing odor loss, and increasing mechanical strength and thermal stability. Consequently, the impacts of such nanoparticles on organisms and on the environment need to be investigated to ensure their safe use. In an earlier study, Moura and others (2008a) described the effect of addition of chitosan (CS) and poly(methacrylic acid) (PMAA) nanoparticles on the mechanical properties, water vapor, and oxygen permeability of hydroxypropyl methylcellulose films used in food packaging. Here, the genotoxicity of different polymeric CS/PMAA nanoparticles (size 60, 82, and 111 nm) was evaluated at different concentration levels, using the Allium cepa chromosome damage test as well as cytogenetic tests employing human lymphocyte cultures. Test substrates were exposed to solutions containing nanoparticles at polymer mass concentrations of 1.8, 18, and 180 mg/L. Results showed no evidence of DNA damage caused by the nanoparticles (no significant numerical or structural changes were observed), however the 82 and 111 nm nanoparticles reduced mitotic index values at the highest concentration tested (180 mg/L), indicating that the nanoparticles were toxic to the cells used at this concentration. In the case of the 60 nm CS/PMAA nanoparticles, no significant changes in the mitotic index were observed at the concentration levels tested, indicating that these particles were not toxic. The techniques used show promising potential for application in tests of nanoparticle safety envisaging the future use of these materials in food packaging.

Chitosan nanoparticles as carrier systems for the plant growth hormone gibberellic acid

This work concerns the development of nanocarriers composed of alginate/chitosan (ALG/CS) and chitosan/tripolyphosphate (CS/TPP) for the plant growth regulator gibberellic acid (GA3). ALG/CS nanoparticles with and without GA3 presented mean size of 450±10nm, polydispersity index (PDI) of 0.3, zeta potential of -29±0.5mV, concentrations of 1.52×1011 and 1.92×1011 nanoparticles mL-1, respectively, and 100% encapsulation efficiency. CS/TPP nanoparticles with and without GA3 presented mean size of 195±1nm, PDI of 0.3, zeta potential of +27±3mV, concentrations of 1.92×1012 and 3.54×1012 nanoparticles mL-1, respectively, and 90% encapsulation efficiency. The nanoparticles were stable during 60days and the two systems differed in terms of the release mechanism, with the release depending on factors such as pH and temperature. Bioactivity assays using Phaseolus vulgaris showed that the ALG/CS-GA3 nanoparticles were most effective in increasing leaf area and the levels of chlorophylls and carotenoids. The systems developed showed good potential, providing greater stability and efficiency of this plant hormone in agricultural applications.

γ-Polyglutamic acid/chitosan nanoparticles for the plant growth regulator gibberellic acid: Characterization and evaluation of biological activity

The growth regulator gibberellic acid (GA3) has several uses in the field, improving germination, plant development, productivity, and the quality of food. This work describes the development of a nanocarrier system for GA3, based on the poly(γ-glutamic acid) (γ-PGA) and chitosan (CS) polymers, Nanoparticles without GA3 (nano-γPGA/CS-GA3) showed colloidal characteristics, with an average size of 117±9nm, PDI of 0.43±0.07, and zeta potential of -29±0.5mV. The encapsulated nanoparticles (nano-γPGA/CS-GA3) presented an average size of 134±9nm, PDI of 0.35±0.05, zeta potential of 27.9±0.5mV, and 61% encapsulation. The images of nanoparticles observed by Transmission and scanning electron microscopy (TEM and SEM) showed a spherical shape of the nanoparticles. The system showed sustained release, with 58% release after 48h. Evaluation of thermal properties using DSC and TGA analyses indicated that there was an interaction between the CS and γ-PGA polymers. In tests using Phaseolus vulgaris seeds, nano-γPGA/CS-GA3 showed high biological activity, enhancing the rate of germination in the first day (50-70%) when compared with free GA3 (10-16%). Encapsulated GA3 was also more efficient than the free hormone in the increase of leaf area and the induction of root development (including the formation of lateral roots). These effects were not observed when seeds were treated with nano-γPGA/CS without GA3. The results demonstrated the considerable potential of nano-γPGA/CS-GA3 for use in agriculture.

Evaluation of the effects of polymeric chitosan/tripolyphosphate and solid lipid nanoparticles on germination of Zea mays, Brassica rapa and Pisum sativum

Although the potential toxicity of many metallic and carbon nanoparticles to plants has been reported, few studies have evaluated the phytotoxic effects of polymeric and solid lipid nanoparticles. The present work described the preparation and characterization of chitosan/tripolyphosphate (CS/TPP) nanoparticles and solid lipid nanoparticles (SLN) and evaluated the effects of different concentrations of these nanoparticles on germination of Zea mays, Brassica rapa, and Pisum sativum. CS/TPP nanoparticles presented an average size of 233.6±12.1nm, polydispersity index (PDI) of 0.30±0.02, and zeta potential of +21.4±1.7mV. SLN showed an average size of 323.25±41.4nm, PDI of 0.23±0.103, and zeta potential of -13.25±3.2mV. Nanotracking analysis enabled determination of concentrations of 1.33×1010 (CS/TPP) and 3.64×1012 (SLN) nanoparticles per mL. At high concentrations, CS/TPP nanoparticles caused complete inhibition of germination, and thus negatively affected the initial growth of all tested species. Differently, SLN presented no phytotoxic effects. The different size and composition and the opposite charges of SLN and CS/TPP nanoparticles could be associated with the differential phytotoxicity of these nanomaterials. The present study reports the phytotoxic potential of polymeric CS/TPP nanoparticles towards plants, indicating that further investigation is needed on the effects of such formulations intended for future use in agricultural systems, in order to avoid damage to the environment.

Evaluation of the effects of nitric oxide-releasing nanoparticles on plants

Nowadays, there are several commercially available products containing nanostructured materials. Meanwhile, despite the many benefits that can be obtained from nanotechnology, it is still necessary to understand the mechanisms in which nanomaterials interact with the environment, and to obtain information concerning their possible toxic effects. In agriculture, nanotechnology has been used in different applications, such as nanosensors to detect pathogens, nanoparticles as controlled release systems for pesticides, and biofilms to deliver nutrients to plants and to protect food products against degradation. Moreover, plants can be used as models to study the toxicity of nanoparticles. Indeed, phytotoxicity assays are required to identify possible negative effects of nanostructured systems, prior to their implementation in agriculture. Nitric oxide (NO) plays a key role in plant growth and defense, and recently, several papers described the beneficial effects due to application of exogenous NO donors in plants. The tripeptide glutathione (GSH) is an important anti-oxidant molecule and is the precursor of the NO donor, S-nitrosoglutathione (GSNO). In this context, the present work investigates the effects of different concentrations of alginate/chitosan nanoparticles, containing either GSH or GSNO, on the development of two test species (Zea mays and Glycine sp.). The results showed that the alginate/chitosan nanoparticles present a size average range from 300 to 550 nm with a polydispersity index of 0.35, and encapsulation efficiency of GSH between 45 - 56%. The NO release kinetics from the alginate/chitosan nanoparticles containing GSNO showed sustained and controlled NO release over several hours. Plant assays showed that at the concentrations tested (1, 5 and 10 mM of GSH or GSNO), polymeric nanoparticles showed no significant inhibitory effects on the development of the species Zea mays and Glycine sp., considering the variables shoot height, root length, and dry mass. Therefore, these nanoparticles seem to have promissing uses in agriculture, and might be potencially used as controlled release systems applied by the foliar route.

Zein Nanoparticles as Eco-Friendly Carrier Systems for Botanical Repellents Aiming Sustainable Agriculture

Botanical repellents represent one of the main ways of reducing the use of synthetic pesticides and the contamination of soil and hydric resources. However, the poor stability and rapid degradation of these compounds in the environment hinder their effective application in the field. Zein nanoparticles can be used as eco-friendly carrier systems to protect these substances against premature degradation, provide desirable release characteristics, and reduce toxicity in the environment and to humans. In this study, we describe the preparation and characterization of zein nanoparticles loaded with the main constituents of the essential oil of citronella (geraniol and R-citronellal). The phytotoxicity, cytotoxicity, and insect activity of the nanoparticles toward target and nontarget organisms were also evaluated. The botanical formulations showed high encapsulation efficiency (>90%) in the nanoparticles, good physicochemical stability, and effective protection of the repellents against UV degradation. Cytotoxicity and phytotoxicity assays showed that encapsulation of the botanical repellents decreased their toxicity. Repellent activity tests showed that nanoparticles containing the botanical repellents were highly repellent against the Tetranychus urticae Koch mite. This nanotechnological formulation offers a new option for the effective use of botanical repellents in agriculture, reducing toxicity, protecting against premature degradation, and providing effective pest control.