Preparation of low-cost sludge-based highly porous biochar for efficient removal of refractory pollutants from agrochemical and pharmaceutical wastewater.

Producing a high-performance sludge biochar through a feasible method is a great challenge and is crucial for practicability. Herein, we reported a highly porous sludge biochar synthesized from agrochemical-pharmaceutical and municipal sludge blends through a novel pyrolysis-acid treatment-post pyrolysis method. The optimized biochar named ASMS91 obtained interconnected pores with a total pore volume of 0.894 cm3/g and a surface area of 691.4 m2/g through extended acid wash and subsequent post-pyrolysis, which is superior to non-activated sludge biochar. ASMS91 removed 45.3 % of wastewater COD (156 mg/L) in 24 h, which was rapid and higher performance than commercial activated carbon (1000 iodine number). This outstanding performance is due to its high adsorption ability of long-chain aliphatic compounds (e.g., 2,4-Di-tert-butylphenol, neophytadiene and eicosane) into mesopores, which accounts for 71.8 % of pore filling. ASMS91 was highly recyclable, and adsorption was reduced by only 5.3 % after the 4th cycle. It also outperformed other sludge biochar in literature in removing perfluorooctanoic acid (PFOA), 6:2 fluorotelomer sulfonate (6:2 FTS), sulfamethoxazole, methylene blue, and methylene orange. Finally, the feasibility of our proposed method was validated by a brief techno-economic analysis. This feasible approach may support future research regarding sludge valorization and low-cost chemical wastewater treatment.

Is bismuth(III) able to inhibit the activity of urease? Puzzling results in the quest for soluble urease complexes for agrochemical and medicinal applications.

Bismuth(III) complexes have been reported to act as inhibitors of the enzyme urease, ubiquitously present in soils and implicated in the pathogenesis of several microorganisms. The general insolubility of Bi(III) complexes in water at neutral pH, however, is an obstacle to their utilization. In our quest to improve the solubility of Bi(III) complexes, we selected a compound reported to inhibit urease, namely [Bi(HEDTA)]·2H2O, and co-crystallized it with (i) racemic DL-histidine to obtain the conglomerate [Bi2(HEDTA)2(µ-D-His)2]·6H2O + [Bi2(HEDTA)2(µ-L-His)2]·6H2O, (ii) enantiopure L-histidine to yield [Bi2(HEDTA)2(µ-L-His)2]·6H2O, and (iii) cytosine to obtain [Bi(HEDTA)]·Cyt·2H2O. All compounds, synthesised by mechanochemical methods and by slurry, were characterized in the solid state by calorimetric (DSC and TGA) and spectroscopic (IR) methods, and their structures were determined using powder X-ray diffraction (PXRD) data. All compounds show an appreciable solubility in water, with values ranging from 6.8 mg mL-1 for the starting compound [Bi(HEDTA)]·2H2O to 36 mg mL-1 for [Bi2(HEDTA)2(µ-L-His)2]·6H2O. The three synthesized compounds as well as [Bi(HEDTA)]·2H2O were then tested for inhibition activity against urease. Surprisingly, no enzymatic inhibition was observed during in vitro assays using Canavalia ensiformis urease and in vivo assays using cultures of Helicobacter pylori, raising questions on the efficacy of Bi(III) compounds to counteract the negative effects of urease activity in the agro-environment and in human health.

Recent Advances and Outlook of Benzopyran Derivatives in the Discovery of Agricultural Chemicals.

Scaffold structures, new mechanisms of action, and targets present enormous challenges in the discovery of novel pesticides. The discovery of new scaffolds is the basis for the continuous development of modern agrochemicals. Identification of a good scaffold such as triazole, carbamate, methoxy acrylate, pyrazolamide, pyrido-pyrimidinone mesoionic, and bisamide often leads to the development of a new series of pesticides. In addition, pesticides with the same target, including the inhibitors of succinate dehydrogenase (SDH), oxysterol-binding-protein, and p-hydroxyphenyl pyruvate dioxygenase (HPPD), may have the same or similar scaffold structure. Recent years have witnessed significant progress in the discovery of new pesticides using natural products as scaffolds or bridges. In recent years, there have been increasing reports on the application of natural benzopyran compounds in the discovery of new pesticides, especially osthole and coumarin. A systematic and comprehensive review of benzopyran active compounds in the discovery of new agricultural chemicals is helpful to promote the discussion and development of benzopyran active compounds. Therefore, this work systematically reviewed the research and application of benzopyran derivatives in the discovery of agricultural chemicals, summarized the antiviral, herbicidal, antibacterial, fungicidal, insecticidal, nematicidal and acaricidal activities of benzopyran active compounds, and discussed the structural-activity relationship and mechanism of action. In addition, some active fragments were recommended to further optimize the chemical structure of benzopyran active compounds based on reference information.

ZIF-8@Hydroxyapatite Composite as a High Potential Material for Prolonged Delivery of Agrochemicals.

Although agrochemical practices can enhance agricultural productivity, their intensive application has resulted in the deterioration of ecosystems. Therefore, it is necessary to develop more efficient and less toxic methods against pests and infections while improving crop productivity. Moving toward sustainable development, in this work, we originally described the preparation of a composite (ZIF-8@HA) consisting of the coating of zeolitic-like metal-organic framework (MOF) ZIF-8 (based on Zn, an essential micronutrient in plants with antibacterial, antifungal, and antifouling properties) with hydroxyapatite (HA) nanoparticles (i.e., nanofertilizer). The interaction between the HA and ZIF-8 has been characterized through a combination of techniques, such as microscopic techniques, where the presence of a HA coating is demonstrated; or by analysis of the surface charge with a dramatic change in the Z-potential (from +18.7 ± 0.8 to -27.6 ± 0.7 mV for ZIF-8 and ZIF-8@HA, respectively). Interestingly, the interaction of HA with ZIF-8 delays the MOF degradation (from 4 h for pristine ZIF-8 to 168 h for HA-coated material), providing a slower and gradual release of zinc. After a comprehensive characterization, the potential combined fertilizer and bactericidal effect of ZIF-8@HA was investigated in wheat (Triticum aestivum) seeds and Pseudomonas syringae (Ps). ZIF-8@HA (7.3 ppm) demonstrated a great fertilizer effect, increasing shoot (9.4 %) and root length (27.1 %) of wheat seeds after 11 days at 25 °C under dark conditions, improving the results obtained with HA, ZIF-8, or ZnSO4 or even physically mixed constituents (HA + ZIF-8). It was also effective in the growth inhibition (>80 % of growth inhibition) of Ps, a vegetal pathogen causing considerable crop decline. Therefore, this work demonstrates the potential of MOF@HA composites and paves the way as a promising agrochemical with improved fertilizer and antibacterial properties.

Oxime chemistry in crop protection.

An overview is given on the significance of the oxime moiety in crop protection chemistry. This review focuses on the two most important aspects of agrochemical oximes, which are the occurrence and role of oxime groups in compounds with herbicidal, fungicidal and insecticidal activity, as well as the application of oxime derivatives as intermediates in the synthesis of crop protection agents not bearing any oxime function. Especially noteworthy is the fact, that in the synthesis of agrochemicals, oximes can be cyclized to isooxazoline, isoxazole, oxadiazole, oxazine, pyrrole, isothiazole and imidazole rings. © 2024 Society of Chemical Industry.

Modification of physicochemical properties of chitosan to improve its pharmaceutical and agrochemical potential applications.

Chitosan has received much more attention as a functional biopolymer with applications in pharmaceuticals, agricultural, drug delivery systems and cosmetics. The objectives of present investigation were to carry out modification of chitosan for enhancement of aqueous solubility, which will impart increased solubility and dissolution rate of poorly soluble drug itraconazole (ITZ) and also evaluate the modified chitosan for soyabean seed germination studies. The modification of chitosan was accomplished through the antisolvent precipitation method; employing five carboxylic acids. The resulting products were assessed for changes in molecular weight, degree of deacetylation, solubility and solid state characterization. Subsequently, the modified chitosan was complexed with itraconazole using the co-grinding technique. The prepared formulations were evaluated for solubility, FTIR (Fourier-transform infrared spectroscopy), PXRD (Powder X-ray diffraction), in-vitro dissolution studies. Furthermore the effect of modified chitosan has been evaluated on soybean seed germination. Results demonstrated that, modified chitosan improves self and solubility of itraconazole by six folds. As there was increased degree of deacetylation of chitosan leads to improvement in solubility. The results of FTIR showed the slight shifting of peaks in co-grind formulations of itraconazole. Formulations showed reduction in crystallinity of drug which leads to enhancement in dissolution rate as compared to pure itraconazole. Retention of property of seed germination was observed with modified chitosan at optimum concentration of 3 % w/v, with benefit of enhanced aqueous solubility of chitosan. This positive result paves the way for the advancement of pharmaceutical and agrochemical products employing derivatives of chitosan.

Transport of polyethylene and polypropylene microplastics under the action of agricultural chemicals: Role of pesticide adjuvants and neonicotinoid active ingredients.

Understanding the impact of various agricultural chemical components on the fate and transport of microplastics (MPs) in the subsurface is essential. In this study, column experiments on saturated porous media were conducted to explore the influence of the coexistence environment of pesticide adjuvants (surfactants) and active ingredients (neonicotinoids) on the transport of polyethylene (PE) and polypropylene (PP) MPs. An anionic surfactant (sodium dodecyl sulfate (SDS)), a nonionic surfactant (nonylphenol ethoxylate (NP-40)), and three neonicotinoid insecticides (acetamiprid, dinotefuran, and nitenpyram) could independently increase MP migration by 9.31%-61.01% by improving the hydrophilicity. Acetamiprid or dinotefuran reduced the adhesion work of the binary system by competing with SDS for adsorption sites, thereby inhibiting PE mobility. However, nitenpyram in the mixture was not easily adsorbed on the surface of PE MPs together with SDS because of nitenpyram's high hydrophilicity. Neonicotinoid molecules could not reduce the hydrophilic modification of SDS on PP MPs by competing for adsorption sites. Owing to their weak charge and adhesion work of nonionic surfactants (-4.80 mV and 28.45 kT for PE and -8.21 mV and 17.64 kT for PP), neonicotinoids tended to occupy the adsorption sites originally belonging to NP-40. The long molecular chain of NP-40 made it difficult for high-concentration neonicotinoids to affect the adhesion on MPs. In addition, NP-40 was harder to peel off from the MP surface than SDS, leading to a larger MP transport ability in the sand column.

Spatial and Depth Profiling of Agricultural Formulations in Leaf Tissue Using LAESI Mass Spectrometry.

Formulating agrochemical products involves combining several chemical components, including the active ingredient(s), to obtain a final product with desirable efficacy. A formulated product incorporates additional components to modulate properties that enhance the efficacy of the active(s) by modifying physical properties such as viscosity, hydrophobicity, miscibility, and others. In plants, understanding the formulation's ability to spread on tissues and penetrate through the outer layer is critical in evaluating the efficacy of the final product. We have previously demonstrated the use of mass spectrometry imaging to determine spreadability. In this study, we show that laser ablation electrospray mass spectrometry (LAESI-MS) can be a valuable tool to assess the penetrability of formulations into the leaf tissues by selectively sampling various layers of leaf tissue by manipulating the laser intensity and analyzing the ablated material using a mass spectrometer. Using this technique, we were able to identify a formulation composition that can improve the penetration and uptake of active ingredients.

GARD™skin and GARD™potency: A proof-of-concept study investigating applicability domain for agrochemical formulations.

Several New Approach Methodologies (NAMs) for hazard assessment of skin sensitisers have been formally validated. However, data regarding their applicability on certain product classes are limited. The purpose of this project was to provide initial evidence on the applicability domain of GARD™skin and GARD™potency for the product class of agrochemical formulations. For this proof of concept, 30 liquid and 12 solid agrochemical formulations were tested in GARDskin for hazard predictions. Formulations predicted as sensitisers were further evaluated in the GARDpotency assay to determine GHS skin sensitisation category. The selected formulations were of product types, efficacy groups and sensitisation hazard classes representative of the industry's products. The performance of GARDskin was estimated by comparing results to existing in vivo animal data. The overall accuracy, sensitivity, and specificity were 76.2% (32/42), 85.0% (17/20), and 68.2% (15/22), respectively, with the predictivity for liquid formulations being slightly higher compared to the solid formulations. GARDpotency correctly subcategorized 14 out of the 17 correctly predicted sensitisers. Lack of concordance was justifiable by compositional or borderline response analysis. In conclusion, GARDskin and GARDpotency showed satisfactory performance in this initial proof-of-concept study, which supports consideration of agrochemical formulations being within the applicability domain of the test methods.

Nanotechnology in sustainable agriculture: A double-edged sword.

Nanotechnology is a rapidly developing discipline that has the potential to transform the way we approach problems in a variety of fields, including agriculture. The use of nanotechnology in sustainable agriculture has gained popularity in recent years. It has various applications in agriculture, such as the development of nanoscale materials and devices to boost agricultural productivity, enhance food quality and safety, improve the efficiency of water and nutrient usage, and reduce environmental pollution. Nanotechnology has proven to be very beneficial in this field, particularly in the development of nanoscale delivery systems for agrochemicals such as pesticides, fertilizers, and growth regulators. These nanoscale delivery technologies offer various benefits over conventional delivery systems, including better penetration and distribution, enhanced efficacy, and lower environmental impact. Encapsulating agrochemicals in nanoscale particles enables direct delivery to the targeted site in the plant, thereby reducing waste and minimizing off-target effects. Plants are fundamental building blocks of all ecosystems and evaluating the interaction between nanoparticles (NPs) and plants is a crucial aspect of risk assessment. This critical review therefore aims to provide an overview of the latest advances regarding the positive and negative effects of nanotechnology in agriculture. It also explores potential future research directions focused on ensuring the safe utilization of NPs in this field, which could lead to sustainable development. © 2024 Society of Chemical Industry.

Multiple amino acid transporters as carriers load L-valine-phenazine-1-carboxylic acid conjugate into Ricinus sieve tubes for the phloem translocation.

Some transporters play important roles in the uptake and acropetal xylem translocation of vectorized agrochemicals. However, it is poorly understood the basipetally phloem-loading functions of transporters toward vectorized agrochemicals. Here, L-Val-PCA (L-valine-phenazine-1-carboxylic acid conjugate) uptake was demonstrated carrier-mediated. RcAAP2, RcANT7, and RcLHT1 showed a similarly up-regulated expression pattern from 62 transporter coding genes in Ricinus at 1 h after L-Val or L-Val-PCA treatment. Subcellular localization revealed that fusion RcAAP2-eGFP, RcANT7-eGFP and RcLHT1-eGFP proteins were expressed in the plasma membrane of mesophyll and phloem cells. Yeast assays found that RcAAP2, RcANT7, and RcLHT1 facilitated L-Val-PCA uptake. To further demonstrate the phloem-loading functions, using vacuum infiltration strategy, an Agrobacterium-mediated RNA interference (RNAi) protocol was constructed in seedlings. HPLC detection indicated that L-Val-PCA phloem sap concentrations were significantly decreased 54.5 %, 27.6 %, and 41.6 % after silencing for 72 h and increased 48.3 %, 52.6 %, and 52.4 % after overexpression, respectively. In conclusion, the plasma membrane-located RcAAP2, RcANT7, and RcLHT1 can loaded L-Val-PCA into Ricinus sieve tubes for the phloem translocation, which may aid in the utilization of transporters and molecular design of phloem-mobile fungicides target root or vascular pathogens.

Retrospective evaluation of the eye irritation potential of agrochemical formulations.

Multiple in vitro eye irritation methods have been developed and adopted as OECD health effects test guidelines. However, for predicting the ocular irritation/damage potential of agrochemical formulations there is an applicability domain knowledge gap for most of the methods. To overcome this gap, a retrospective evaluation of 192 agrochemical formulations with in vivo (OECD TG 405) and in vitro (OECD TG 437, 438, and/or 492) data was conducted to determine if the in vitro methods could accurately assign United Nations Globally Harmonized System for Classification and Labelling of Chemicals (GHS) eye irritation hazard classifications. In addition, for each formulation the eye irritation classification was derived from the classification of the contained hazardous ingredients and their respective concentration in the product using the GHS concentration threshold (CT) approach. The results herein suggest that the three in vitro methods and the GHS CT approach were highly predictive of formulations that would not require GHS classification for eye irritation. Given most agrochemical formulations fall into this category, methods that accurately identify non-classified agrochemical formulations could significantly reduce the use of animals for this endpoint.

Resolving binding pathways and solvation thermodynamics of plant hormone receptors.

Plant hormones are small molecules that regulate plant growth, development, and responses to biotic and abiotic stresses. They are specifically recognized by the binding site of their receptors. In this work, we resolved the binding pathways for eight classes of phytohormones (auxin, jasmonate, gibberellin, strigolactone, brassinosteroid, cytokinin, salicylic acid, and abscisic acid) to their canonical receptors using extensive molecular dynamics simulations. Furthermore, we investigated the role of water displacement and reorganization at the binding site of the plant receptors through inhomogeneous solvation theory. Our findings predict that displacement of water molecules by phytohormones contributes to free energy of binding via entropy gain and is associated with significant free energy barriers for most systems analyzed. Also, our results indicate that displacement of unfavorable water molecules in the binding site can be exploited in rational agrochemical design. Overall, this study uncovers the mechanism of ligand binding and the role of water molecules in plant hormone perception, which creates new avenues for agrochemical design to target plant growth and development.

Morpholine Derivatives in Agrochemical Discovery and Development.

Derivatives of morpholine are biologically active organic compounds with special structures discovered in multiple drugs. As a result of the terminal pharmacophore of action and extraordinary activity, they attracted fair attention with regard to pesticide innovation and development. Analysis of brief structure-activity relationships and the summarization of the characteristics of pesticides containing morpholine fragments with efficient activity are key steps in the development of novel pesticides. This review primarily overviews morpholine compounds with insecticidal, fungicidal, herbicidal, antiviral, and plant growth regulation properties to provide educational insight for the creation of new morpholine-containing compounds.

Pursuing Green and Efficient Agriculture from Molecular Assembly: A Review of Solid-State Forms on Agrochemicals.

Achieving rapid global agricultural development while maintaining ecological harmony is a major challenge of the new millennium. Meeting this challenge requires the development of efficient and environmentally friendly agrochemicals, including pesticides and fertilizers. Molecular assembly, as a promising strategy, has garnered significant attention in recent years for the development of advanced solid-state forms of agrochemicals. In this review, we present the potential and recent advancements of solid-state forms, such as polymorphs, cocrystals/salts, solvates, inclusion compounds, and the amorphous state, for the production of high-efficiency and low-polluting agrochemical products. We provide an overview of the concepts and preparation methods of these solid-state forms, followed by an exploration of their applications in sustainable agriculture. Specifically, we highlight their value in enhancing pesticide solubility, enabling controlled release of chemical fertilizers, and reducing off-target risks. Lastly, we discuss the challenges and prospects associated with the utilization of solid-state forms for the advancement of environmentally friendly and efficient agriculture.

Design, synthesis, insecticidal activities and translocation of amino acid-tralopyril conjugates as vectorizing agrochemicals.

BACKGROUND: Conjugating amino acid moieties to active ingredients has been recognized as an effective method for improving the precise targeting of the active form to the specific site. Based on the vectorization strategy, a series of amino acid-tralopyril conjugates were designed and synthesized as novel proinsecticide candidates, with the potential capability of root uptake and translocation to the foliage of crops. RESULTS: Bioassay results showed excellent insecticidal activities of some conjugates, in particular, the conjugates 6b, 6e, and 7e, against the diamondback moth (Plutella xylostella), with equivalent insecticidal activity to chlorfenapyr (CFP). Importantly, conjugate 6e exhibited significantly higher in vivo insecticidal activity against P. xylostella than CFP. Furthermore, the systemic test experiments with Brassica chinensis demonstrated that conjugates 6e and 7e could be transported to the leaves, in contrast to CFP, which remained in the root. CONCLUSION: This study demonstrated the feasibility of amino acid fragment conjugation as a vectorization strategy for transporting non-systemic insecticides into the leaves of B. chinensis while maintaining in vivo insecticidal activity. The findings also provide insights for subsequent mechanism studies on the uptake and transport of amino acid-insecticide conjugates in plants. © 2023 Society of Chemical Industry.

Sulfur-based functional groups in agrochemistry.

The element sulfur has an outstanding role in the crop protection chemistry because it is used in its elemental form as a multisite fungicide, but is also part of agrochemicals in the form of aromatic or aliphatic sulfur-containing rings or sulfur-based functional groups. This review gives an exhaustive overview over the latter category. Several fundamental agrochemical compound classes are named after a sulfur-based functionality, such as the dithiocarbamate fungicides and sulfonylurea herbicides. Altogether, 16 different sulfur-based functional groups are presented with their typical synthesis approaches and most important representatives in crop protection. © 2023 Society of Chemical Industry.

Ring Closure and Ring Opening as Useful Scaffold Hopping Tools in Agrochemistry.

Ring closing acyclic parts of a molecular scaffold or the opposite manipulation, opening rings to produce pseudo-ring structures, is an important scaffold hopping manipulation. Analogues derived from biologically active compounds through the utilization of such strategies are often similar in shape and physicochemical properties and, therefore, likely to exhibit similar potency. This review will demonstrate how several different ring closure techniques, such as replacing carboxylic functions by cyclic peptide mimics, incorporating double bonds into aromatic rings, tying back ring substituents to a bicyclic structure, cyclizing adjacent ring substituents to an annulated ring, bridging annulated ring systems to tricyclic scaffolds, and exchanging gem-dimethyl groups by cycloalkyl rings, but also ring opening led to the discovery of highly active agrochemicals.

Isosteric Ring Exchange as a Useful Scaffold Hopping Tool in Agrochemistry.

Replacing one ring in a molecule by a different carba- or heterocycle is an important scaffold hopping manipulation, because biologically active compounds and their analogues, which underwent such a transformation, are often similar in size, shape, and physicochemical properties and, therefore, likely in their potency as well. This review will demonstrate, how isosteric ring exchange led to the discovery of highly active agrochemicals and which ring interchanges have proven to be most successful.

Nanopesticides in comparison with agrochemicals: Outlook and future prospects for sustainable agriculture.

Agrochemicals are products of advanced technologies that use inorganic pesticides and fertilizers. Widespread use of these compounds has adverse environmental effects, leading to acute and chronic exposure. Globally, scientists are adopting numerous green technologies to ensure a healthy and safe food supply and a livelihood for everyone. Nanotechnologies significantly impact all aspects of human activity, including agriculture, even if synthesizing certain nanomaterials is not environmentally friendly. Numerous nanomaterials may therefore make it easier to create natural insecticides, which are more effective and environmentally friendly. Nanoformulations can improve efficacy, reduce effective doses, and extend shelf life, while controlled-release products can improve the delivery of pesticides. Nanotechnology platforms enhance the bioavailability of conventional pesticides by changing kinetics, mechanisms, and pathways. This allows them to bypass biological and other undesirable resistance mechanisms, increasing their efficacy. The development of nanomaterials is expected to lead to a new generation of pesticides that are more effective and safer for life, humans, and the environment. This article aims to express at how nanopesticides are being used in crop protection now and in the future. This review aims to shed some light on the various impacts of agrochemicals, their benefits, and the function of nanopesticide formulations in agriculture.