Bioinspired smart microcarriers precisely deliver agrochemicals in plants.

Precise agrochemical delivery to crops is vital for sustainable agricultural productivity. Recently, Liu et al. developed highly biocompatible smart microcarriers for precise agrochemical delivery to plants that can effectively provide nutrition while reducing runoff. This innovative and precise agrochemical delivery system represents a significant advancement in efficient and eco-friendly crop cultivation practices.

Valorization of lignin from aqueous-based lignocellulosic biorefineries.

An additional 100 million tons/year of lignin coproduct will result when lignocellulosic biomass is processed in biorefineries to fiber, sugars, biofuels, and bioproducts. This will double the amount of lignin already generated from pulping and paper production. Unlike pulping that results in lignosulphonate (88% of total) or Kraft lignin (9%), aqueous-based biorefining leaves behind non-sulfonated lignin and aromatic molecules. This new type of lignin provides opportunities for large volume agricultural uses such as controlled-release carriers and soil amendments as well as feedstocks for new chemistries that lead to molecular building blocks for the chemical industry and to precursors for sustainable aviation biofuels.

Investigation of 2,4-Dihydroxylaryl-Substituted Heterocycles as Inhibitors of the Growth and Development of Biotrophic Fungal Pathogens Associated with the Most Common Cereal Diseases.

Climate change forces agriculture to face the rapidly growing virulence of biotrophic fungal pathogens, which in turn drives researchers to seek new ways of combatting or limiting the spread of diseases caused by the same. While the use of agrochemicals may be the most efficient strategy in this context, it is important to ensure that such chemicals are safe for the natural environment. Heterocyclic compounds have enormous biological potential. A series of heterocyclic scaffolds (1,3,4-thiadiazole, 1,3-thiazole, 1,2,4-triazole, benzothiazine, benzothiadiazine, and quinazoline) containing 2,4-dihydroxylaryl substituents were investigated for their ability to inhibit the growth and development of biotrophic fungal pathogens associated with several important cereal diseases. Of the 33 analysed compounds, 3 were identified as having high inhibitory potential against Blumeria and Puccinia fungi. The conducted research indicated that the analysed compounds can be used to reduce the incidence of fungal diseases in cereals; however, further thorough research is required to investigate their effects on plant-pathogen systems, including molecular studies to determine the exact mechanism of their activity.

Examining the interaction between pesticides and bioindicator plants: an in-depth analysis of their cytotoxicity.

Agrochemicals are substances used to prevent, destroy, or mitigate any pest. Their indiscriminate use can cause serious problems in ecosystems, contaminating surface and groundwater and affecting surrounding biota. However, in the environment, various natural processes such as biological degradation and photodegradation can mitigate their persistence and, consequently, their ecotoxicological impact. In this regard, this study aimed to obtain relevant data on the cytotoxic effects produced by pesticides on bioindicator plants. As observed in the literature review, cellular inhibition, nuclear anomalies, and micronucleus index are some of the different impacts commonly known from pesticides. These chemical substances can cause cytogenetic alterations in a plant bioassay. Plant bioindicators such as Allium cepa L, Vicia faba L, Pisum sativum L, Lactuca sativa L, and Lens culinaris Med are very important and effective experimental models for identifying the cytogenotoxicity of pesticides. These have been available for many years. However, they are still used today for their effectiveness in detecting and monitoring chemical substances such as agrochemicals.

Shadow prices of agrochemicals in the Chinese farming sector: A convex expectile regression approach.

The use of agrochemical inputs has significantly enhanced agricultural yields in China; however, their excessive utilization has also caused a range of environmental issues. This paper examines the costs associated with reducing agrochemicals by employing shadow prices, which represent the value of the marginal product of agrochemicals, to further develop cost-effective environmental policy measures for reducing their usage. To this end, the shadow prices of agrochemicals have been assessed by adopting a newly developed convex expectile regression approach and using statistical data from 31 provinces in China spanning from 2005 to 2020. Furthermore, the present study investigates the disparities between shadow prices and market prices for different agrochemicals across various regions in China. The findings suggest that the costs of reducing chemical fertilizers are higher than those of reducing pesticides and plastic films. Moreover, the results indicate that central China exhibits relatively high potential for decreasing agrochemical usage. Finally, these findings can inform the Chinese government's restructuring of producer support and environmental policy in a cost-effective way to mitigate agrochemicals use in the future. Additionally, the research method employed in this study holds potential for extension to other agrochemicals-dependent countries.

New Insights into Materials for Pesticide and Other Agricultural Pollutant Remediation.

The increase in the world population and the intensification of agricultural practices have resulted in the release of several contaminants into the environment, especially pesticides and heavy metals. This article reviews recent advances in using adsorbent and catalytic materials for environmental decontamination. Different materials, including clays, carbonaceous, metallic, polymeric, and hybrid materials, are evaluated for their effectiveness in pollutant removal. Adsorption is an effective technique due to its low cost, operational simplicity, and possibility of adsorbent regeneration. Catalytic processes, especially those using metallic nanoparticles, offer high efficiency in degrading complex pesticides. Combining these technologies can enhance the efficiency of remediation processes, promoting a more sustainable and practical approach to mitigate the impacts of pesticides and other agricultural pollutants on the environment. Therefore, this review article aims to present several types of materials used as adsorbents and catalysts for decontaminating ecosystems affected by agricultural pollutants. It discusses recent works in literature and future perspectives on using these materials in environmental remediation. Additionally, it explores the possibilities of using green chemistry principles in producing sustainable materials and using agro-industrial waste as precursors of new materials to remove contaminants from the environment.

Ethnobotanical insights on the management of plant pests and diseases by smallholder farmers in Mpumalanga Province of South Africa.

BACKGROUND: Pests and diseases are a major contributor to yield losses in sub-Saharan Africa, prompting smallholder farmers to seek cost-effective, accessible and ecologically friendly alternatives for crop protection. This study explored the management of pests and diseases affecting crops across eight selected villages in Ehlanzeni District, Mpumalanga Province, South Africa. METHODS: A total of 120 smallholder farmers were purposefully selected utilising the snowball technique. Information on the management of plant pests and diseases was collected through interviews and focus group discussions using semi-structured interview schedules. Ethnobotanical indices, including relative frequency of citation (RFC), use-value (UV) and informant consensus factor (Fic), were used to quantify and rank the plants used for crop protection in the study area. RESULTS: Twenty-three plant species (16 naturalised exotics and seven indigenous plants) belonging to 16 families were used for managing pests (vertebrates and invertebrates) and diseases (fungal and bacterial related) affecting crops in the study area. The dominant (100%) crops cultivated by the participants were Allium cepa L., Mangifera indica L., Solanum lycopersicum L. and Zea mays L. The RFC value ranged from 0.08 to 0.83 and the three most popular plants for crop protection were Capsium annuum L. (0.83), A. cepa (0.63) and Dichrostachys cinerea (L.) Wight & Arn. (0.43). In terms of the UV, the five most promising plants used as biocontrol were Tulbaghia violacea (0.13), A. cepa (0.12), C. annuum L. (0.09), Solanum campylacanthum Hochst. Ex A.Rich.(0.09) and Pinus pinaster (0.08). Based on the Fic, four categories were established and dominated by fungal diseases (0.64). Furthermore, T. violacea and A. cepa were the most often mentioned plants used against fungal conditions. Other categories cited were bacterial diseases (0.3), invertebrate pests (0.11) and vertebrate pests (0.14), an indication that smallholder farmers had limited agreement or common knowledge about the plants used for their management. The preparation methods included maceration (38%), decoction (38%) and burning (24%). Foliar application (67%) and soil drenching (33%) were used for administering plant extracts during the management of crop pests and diseases. CONCLUSION: The study highlights the importance of botanicals and associated indigenous knowledge among smallholder farmers in Mpumalanga Province, South Africa. It is pertinent to explore the valorisation of these botanicals by generating empirical data on their biological efficacies and phytochemical profiles.

Application of Asymmetric Catalysis in Chiral Pesticide Active Molecule Synthesis.

The different configurations of chiral pesticides generally have significant influence on their biological activities. Chiral agrochemicals with high optical purities have become a prominent topic in the research field of new pesticides due to their advantages including lower toxicity, higher efficiency, and reduced residue levels. However, most commercially available pesticides that possess chiral elements are still used in their racemic forms. To date, asymmetric catalysis has emerged as a versatile tool for the enantioselective synthesis of various chiral agrochemicals and novel chiral pesticide active molecules. This perspective provides a comprehensive overview of the applications of diverse asymmetric catalytic approaches in the facile preparation of numerous novel pesticide active molecules, and our own outlook on the future development of this highly active research direction is also presented at the end of this review.

Diverse role, structural trends, and applications of fluorinated sulphonamide compounds in agrochemical and pharmaceutical fields.

Our knowledge of fluorine's unique and complex properties has significantly increased over the past 20 years. Consequently, more sophisticated and innovative techniques have emerged to incorporate this feature into the design of potential drug candidates. In recent years, researchers have become interested in synthesizing fluoro-sulphonamide compounds to discover new chemical entities with distinct and unexpected physical, chemical, and biological characteristics. The fluorinated sulphonamide molecules have shown significant biomedical importance. Their potential is not limited to biomedical applications but also includes crop protection. The discovery of novel fluorine and Sulfur compounds has highlighted their importance in the chemical sector, particularly in the agrochemical and medicinal fields. Recently, several fluorinated sulphonamide derivatives have been developed and frequently used by agriculturalists to produce food for the growing global population. These molecules have also exhibited their potential in health by inhibiting various human diseases. In today's world, it is crucial to have a steady supply of innovative pharmaceutical and agrochemical molecules that are highly effective, less harmful to the environment, and affordable. This review summarizes the available information on the activity of Fluorine and Sulphonamide compounds, which have proven active in pharmaceuticals and agrochemicals with excellent environmental and human health approaches. Moreover, it focuses on the current literature on the chemical structures, the application of fluorinated sulphonamide compounds against various pathological conditions, and their effectiveness in crop protection.

Uso de agrotóxicos em canaviais de Pernambuco e danos à saúde do trabalhador / Use of pesticides in Pernambuco sugarcane fields and damage to workers' health

RESUMO O presente estudo teve por objetivo analisar a exposição aos agrotóxicos e os danos à saúde dos trabalhadores das plantações de cana-de-açúcar em Pernambuco. Trata-se de pesquisa participante desenvolvida em territórios rurais de cinco municípios com forte expressão em área plantada de cana-de-açúcar. Os dados primários foram produzidos em oficinas com trabalhadores rurais para construção de diagnóstico rural participativo, analisados mediante condensação de significados e interpretados à luz do referencial teórico da epidemiologia crítico latino-americana. Os resultados estão apresentados em três seções: i) Fluxograma do trabalho nas plantações de cana-de-açúcar; ii) Exposição aos agrotóxicos utilizados nas lavouras; iii) Danos à saúde do trabalhador. Conclui-se que a exposição permanente aos agrotóxicos envolve o trabalho nas plantações de cana-de-açúcar e emerge de um construto histórico e socioambiental, em que se encontram subsumidos os modos de vida dos territórios sob o domínio do agronegócio canavieiro. Recomendam-se políticas públicas de fomento à agricultura familiar com diversificação, escoamento e distribuição da produção agroecológica, além do fortalecimento da Atenção Primária à Saúde e de ações integradas de vigilância epidemiológica, sanitária, ambiental e do trabalhador.

ABSTRACT This study aims to analyze exposure to pesticides and harm to the health of workers on sugarcane plantations in Pernambuco. This participatory research was conducted in rural territories of five municipalities with a strong presence in sugarcane-planted areas. The primary data were produced in workshops with rural workers to construct a participatory rural diagnosis, analyzed through condensation of meanings, and interpreted in light of the theoretical framework of Latin American critical epidemiology. The results are presented in three sections: i) Flowchart of work on sugarcane plantations; ii) Exposure to pesticides used on crops; iii) Harm to worker's health. We conclude that permanent exposure to pesticides involves working on sugarcane plantations and emerges from a historical and socio-environmental construct in which the ways of life of the territories under the control of sugarcane agribusiness are subsumed. Public policies are recommended to promote family farming with diversification, flow, distribution of agroecological production, and strengthening primary health care and integrated epidemiological, health, environmental, and worker surveillance actions.

Compound-Specific Isotope Analysis Provides Direct Evidence for Identifying the Source of Residual Pesticides Diazinon and Procymidone in the Soil-Plant System.

Compound-specific isotope analysis stands as a promising tool for unveiling the behavior of pesticides in agricultural environments. Using the commercial formulations of persistent fungicide procymidone (PRO) and less persistent insecticide diazinon (DIA), respectively, we analyzed the concentration and carbon isotope composition (δ13C) of the residual pesticides through soil incubation experiments in a greenhouse (for 150 days) and lab conditions (for 50-70 days). Our results showed that the magnitude of δ13C variation depends on pesticide specificity, in which PRO in the soil exhibited little variation in δ13C values over the entire incubation times, while DIA demonstrated an increased δ13C value, with the extent of δ13C variability affected by different spiking concentrations, plant presence, and light conditions. Moreover, the pesticides extracted from soils were isotopically overlapped with those from crop lettuce. Ultimately, the isotope composition of pesticides could infer the degradation and translocation processes and might contribute to identifying the source(s) of pesticide formulation in agricultural fields.

Making the Complicated Simple: A Minimizing Carrier Strategy on Innovative Nanopesticides.

The flourishing progress in nanotechnology offers boundless opportunities for agriculture, particularly in the realm of nanopesticides research and development. However, concerns have been raised regarding the human and environmental safety issues stemming from the unrestrained use of non-therapeutic nanomaterials in nanopesticides. It is also important to consider whether the current development strategy of nanopesticides based on nanocarriers can strike a balance between investment and return, and if the complex material composition genuinely improves the efficiency, safety, and circularity of nanopesticides. Herein, we introduced the concept of nanopesticides with minimizing carriers (NMC) prepared through prodrug design and molecular self-assembly emerging as practical tools to address the current limitations, and compared it with nanopesticides employing non-therapeutic nanomaterials as carriers (NNC). We further summarized the current development strategy of NMC and examined potential challenges in its preparation, performance, and production. Overall, we asserted that the development of NMC systems can serve as the innovative driving force catalyzing a green and efficient revolution in nanopesticides, offering a way out of the current predicament.

From Pipeline to Plant Protection Products: Using New Approach Methodologies (NAMs) in Agrochemical Safety Assessment.

The human population will be approximately 9.7 billion by 2050, and food security has been identified as one of the key issues facing the global population. Agrochemicals are an important tool available to farmers that enable high crop yields and continued access to healthy foods, but the average new agrochemical active ingredient takes more than ten years, 350 million dollars, and 20,000 animals to develop and register. The time, monetary, and animal costs incentivize the use of New Approach Methodologies (NAMs) in early-stage screening to prioritize chemical candidates. This review outlines NAMs that are currently available or can be adapted for use in early-stage screening agrochemical programs. It covers new in vitro screens that are on the horizon in key areas of regulatory concern. Overall, early-stage screening with NAMs enables the prioritization of development for agrochemicals without human and environmental health concerns through a more directed, agile, and iterative development program before animal-based regulatory testing is even considered.

Relationship between stream size, watershed land use, and pesticide concentrations in headwater streams.

A quantitative multiresidue study of current-use pesticides in multiple matrices was undertaken with field sampling at 32 headwater streams near Lac Saint-Pierre in Québec, Canada. A total of 232 samples were collected in five campaigns of stream waters and streambed sediments from streams varying in size and watershed land use. Novel multiresidue analytical methods from previous work were successfully applied for the extraction of pesticide residues from sediments via pressurized liquid extraction (PLE) and quantitative analysis using ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) with online sample preparation on a hydrophilic-lipophilic balance (HLB) column. Of the 31 target compounds, including 29 pesticides and two degradation products of atrazine, 29 compounds were detected at least once. Consistent with other studies, atrazine and metolachlor were the most widely-detected herbicides. Detections were generally higher in water than sediment samples and the influence of land use on pesticide concentrations was only detectable in water samples. Small streams with a high proportion of agricultural land use in their watershed were generally found to have the highest pesticide concentrations. Corn and soybean monoculture crops, specifically, were found to cause the greatest impact on pesticide concentration in headwater streams and correlated strongly with many of the most frequently detected pesticides. This study highlights the importance of performing multiresidue pesticide monitoring programs in headwater streams in order to capture the impacts of agricultural intensification on freshwater ecosystems.

Agrochemical-free genetically modified and genome-edited crops: Towards achieving the United Nations sustainable development goals and a 'greener' green revolution.

Sustainable farming on ever-shrinking agricultural land and declining water resources for the growing human population is one of the greatest environmental and food security challenges of the 21st century. Conventional, age-old organic farming practices alone, and foods based on costly cellular agriculture, do not have the potential to be upscaled to meet the food supply challenges for feeding large populations. Additionally, agricultural practices relying on chemical inputs have a well-documented detrimental impact on human health and the environment. As the available farming methods have reached their productivity limits, new approaches to agriculture, combining friendly, age-old farming practices with modern technologies that exclude chemical interventions, are necessary to address the food production challenges. Growing genetically modified (GM) crops without chemical inputs can allow agricultural intensification with reduced adverse health and environmental impacts. Additionally, integrating high-value pleiotropic genes in their genetic improvement coupled with the use of modern agricultural technologies, like robotics and artificial intelligence (AI), will further improve productivity. Such 'organic-GM' crops will offer consumers healthy, agrochemical-free GM produce. We believe these agricultural practices will lead to the beginning of a potentially new chemical-free GM agricultural revolution in the era of Agriculture 4.0 and help meet the targets of the United Nations Sustainable Development Goals (SDGs). Furthermore, given the advancement in the genome editing (GE) toolbox, we ought to develop a new category of 'trait-reversible GM crops' to avert the fears of those who believe in ecological damage by GM crops. Thus, in this article, we advocate farming with no or minimal chemical use by combining chemical-free organic farming with the existing biofortified and multiple stress tolerant GM crops, while focusing on the development of novel 'biofertilizer-responsive GE crops' and 'trait-reversible GE crops' for the future.

Potential of Chitosan for the Control of Powdery Mildew (Leveillula taurica (Lév.) Arnaud) in a Jalapeño Pepper (Capsicum annuum L.) Cultivar.

One of the phytopathogens that cause severe damage to jalapeño pepper is Leveillula taurica (Lév.) Arnaud, the causative agent of powdery mildew. Synthetic fungicides are currently employed for its control, contributing to adverse effects on human health and the environment. The main objective of this research was to identify the causal agent of powdery mildew and assess the efficacy of chitosan in powdery mildew control on jalapeño pepper. The following treatments were evaluated in laboratory and greenhouse conditions: T1 = 0.0125% chitosan, T2 = 0.0025% chitosan, T3 = 0.05% chitosan, T4 = 0.1% chitosan, T5 = 0.2% chitosan, T6 = tebuconazole 25% (1.8 mL/L water), and T7 = control (water). Symptomatology results indicated that L. taurica is indeed the causative agent of powdery mildew. Treatments T4 and T5 exhibited the lowest percentages of incidences and severity, hence achieving higher control efficacy in the laboratory (57.70 ± 3.85 and 65.39 ± 3.85) and greenhouse (56.67 ± 4.08 and 70 ± 8.16%) compared to T6 (control efficacy, 38.46 ± 0.00% in the laboratory and 50 ± 0.00% in the greenhouse). The chitosan derived from shrimp had a significant impact on the cell walls of L. taurica spores and mycelium. Consequently, chitosan emerges as a viable organic alternative to fungicides for controlling powdery mildew in jalapeño pepper.

Attenuation photochemical potential of Pontal of Paranapanema river waters (Brazil) from agrochemicals: geographical and temporal assessment.

Knowledge of the environmental photochemical fate of pesticides is essential to assess their potential impacts. However, there are few studies in the literature focused on the photochemical attenuation of micropollutants in Brazilian rivers. In this context, this study characterized the surface waters of the Pontal of Paranapanema region (region which concentrates more than 80% of Brazilian sugarcane cultivations), in order to determine its photochemical attenuation potential against micropollutants in different seasons. Thus, the steady-state concentrations of the photochemically produced reactive intermediates (PPRIs) (hydroxyl radical, HO•; singlet oxygen, 1O2, and triplet-excited state chromophoric dissolved organic matter, 3CDOM*), formed in the rivers, were simulated by using the APEX model (Aquatic Photochemistry of Environmentally-occurring Xenobiotics), considering the sunlight irradiance, water chemistry, and depth. Based on our simulations, these concentrations vary between 0.35 × 10-15 and 4.52 × 10-14 mol L-1 for HO•, 1.3 × 10-15 and 1.2 × 10--14 mol L-1 for 3CDOM*, and 2.5 × 10-15 and 2.5 × 10-14 mol L-1 for 1O2. Finally, mathematical simulations were used for predicting persistence of pesticides atrazine (ATZ) and diuron (DIR) in Pontal of Paranapanema surface waters and the half-life times (t1/2) of the pollutants ranged from a few hours to one week.

Assessing glyphosate and AMPA pesticides in the Ofanto River waters and sediments.

In the present study, we determined glyphosate (GPS) and aminomethylphosphonic acid (AMPA) in the water and sediments of the Ofanto River (Italy), evaluating their transport from the mouth to the sea. Sediments were collected twice in 2021 during low and high tide; waters were sampled on a seasonal basis. The results showed the prevalence of GPS and AMPA in the water with concentrations equal to 190 and 3053 ng/l, respectively. We also found GPS and AMPA in the sediments with values of 0.95 and 11.34 ng/g. In water, pesticides were detected in all seasons with peaks in concentrations during summer and spring. A significant positive correlation between the pesticides in the sediments and the water pH and a negative correlation with salinity was observed. An estimation of the average loads revealed a discharge of 64.11 kg/yr. of GPS and 958.37 kg/yr. of AMPA from the river to the marine environment.

Synthesis and antifungal activity of hexahydropyrrolidoindole alkaloids.

Twenty-one hexahydropyrrolidoindole alkaloids were designed and synthesised via acylation reaction at the 3-N position from the commercially available indole-3-acetonitrile as the starting material in excellent yields. The effects of all target compounds against Verticillium dahlia, Fusarium oxysperium sp., Cytospora juglandis, Aspergillu sflavu, Aspergillus niger and Fusarium oxysporum were determined. The results of bioassays indicated that the majority of tested compounds displayed comparable or better in vitro bioactivity than the positive control. Notably, compounds 8 and 17 revealed potent activity against C. juglandis and A. sflavu, both with the same minimum inhibitory concentration value of 1.9 µg mL-1, which has fungicidal activity far exceeded that of amphotericin B and chlorothalonil.

Impact of seed priming with Selenium nanoparticles on germination and seedlings growth of tomato.

Poor germination and seedlings growth can lead to significant economic losses for farmers, therefore, sustainable agricultural strategies to improve germination and early growth of crops are urgently needed. The objective of this work was to evaluate selenium nanoparticles (Se NPs) as nanopriming agents for tomato (Solanum lycopersicum) seeds germinated without stress conditions in both trays and Petri dishes. Germination quality, seedlings growth, synergism-antagonism of Se with other elements, and fate of Se NPs, were determined as function of different Se NPs concentrations (1, 10 and 50 ppm). Results indicated that the germination rate in Petri dishes improved with 10 ppm, while germination trays presented the best results at 1 ppm, increasing by 10 and 32.5%, respectively. Therefore, seedlings growth was measured only in germination trays. Proline content decreased up to 22.19% with 10 ppm, while for same treatment, the total antioxidant capacity (TAC) and total chlorophyll content increased up to 38.97% and 21.28%, respectively. Antagonisms between Se with Mg, K, Mn, Zn, Fe, Cu and Mo in the seed were confirmed. In the case of seedlings, the N content decreased as the Se content increased. Transmission Electron Microscopy (TEM) imaging confirmed that Se NPs surrounded the plastids of the seed cells. By this finding, it can be inferred that Se NPs can reach the embryo, which is supported by the antagonism of Se with important nutrients involved in embryogenesis, such as K, Mg and Fe, and resulted in a better germination quality. Moreover, the positive effect of Se NPs on total chlorophyll and TAC, and the negative correlation with proline content with Se content in the seed, can be explained by Se NPs interactions with proplastids and other organelles within the cells, resulting with the highest length and fresh weight when seeds were exposed to 1 ppm.