Ultralow Detection of Mancozeb Using Two-Dimensional Cobalt Telluride (CoTe2).

Pesticides are crucial in modern agriculture because they reduce pests and boost yield, but they also represent major risks to human health and the environment; therefore, it is important to monitor their presence in food. Reliable and precise detection techniques are possible ways to address this issue. In this work, we utilize atomically thin (two-dimensional) cobalt telluride (CoTe2) with a high surface area and charge as a template material to detect mancozeb using spectroscopic and electrochemical techniques. When mancozeb (MNZ) molecules interact with 2D CoTe2, spectroscopic analyses reveal distinctive spectral shifts that clarify the underlying chemical interactions and binding mechanisms. Furthermore, CoTe2's electroactive sites and their manipulation for improved sensitivity and selectivity toward certain MNZ molecules are investigated by electrochemical studies. The CoTe2/GCE electrode exhibits enhanced electrochemical activity toward the electrooxidation of MNZ. The developed sensing electrode shows a linear range from 0.184 mM to 18.48 µM and a limit of detection of about 0.18 µM. In addition, we employ density functional theory (DFT) first-principles calculations to validate the experimental findings and comprehend the mechanism behind the interaction between CoTe2 and MNZ molecules. The study highlights the effectiveness of 2D CoTe2 as a dual-mode sensing platform for qualitative and quantitative assessment of MNZ pollutants, demonstrated by the integration of electrochemistry and spectroscopy and the critical role that 2D CoTe2-based sensors can play in accurate and efficient pesticide detection, which is required for agricultural safety protocols and environmental monitoring.

Electrosynthesis of Cyclic Isoureas and Ureas Through Contiguous Heterofunctionalizations.

An efficient synthetic protocol for the selenylated cyclic isoureas was developed using electrochemical activation of diselenides. This sustainable approach permitted transition metal and chemical oxidant-free difunctionalization of olefins and overall access to distinct 1,2,3 triheterofunctionalized carbon skeletons. Excellent functional group tolerance was noticed, allowing the synthesis of a series of cyclic isourea derivatives. In addition, an acid-triggered skeletal isomerization facilitated the synthesis of cyclic urea derivatives from the corresponding cyclic isoureas. Mechanistic investigations, along with voltammetric studies, enabled the postulation of the reaction mechanism.

Electrosynthesis of 1,2,3-Benzotriazines through an Iodide-Catalyzed Skeletal Editing of 3-Aminoindazoles.

This report describes an environmentally benign synthesis of 1,2,3-benzotriazines through an iodide-catalyzed electro-oxidative N-centered [1,2]-rearrangement of 3-aminoindazoles. The developed method demonstrates the activation of heteroatoms via electrochemically generated reactive iodide species without using any metal catalysts and peroxides. The protocol features practical and mild reaction conditions and displays a wide substrate scope. Various mechanistic experiments and cyclic voltammetric studies have been instrumental in elucidating the reaction mechanism, operating via a skeletal rearrangement of 3-aminoindazoles.

Probing Correlation of Optical Emission and Defect Sites in Hexagonal Boron Nitride by High-Resolution STEM-EELS.

Optically bright emitters in hexagonal boron nitride (hBN) often acting as a source of a single-photon are mostly attributed to point-defect centers, featuring localized intra-bandgap electronic states. Although vacancies, anti-sites, and impurities have been proposed as candidates, the exact physical and chemical nature of most hBN single-photon emitters (SPEs) within the visible region are still up for debate. Combining site-specific high-angle annular dark-field imaging (HAADF) with electron energy loss spectroscopy (EELS), we resolve and identify a few carbon substitutions among neighboring hBN hexagons, all within the same sample region, from which typical defect emission is observed. Our experimental results are further supported by first-principles calculations, through which the stability and possible optical transitions of the proposed carbon-defect complex are assessed. The presented correlation between optical emission and defects provides valuable information toward the controlled creation of emitters in hBN, highlighting carbon complexes as another probable cause of its visible SPEs.

Growing Conditions and Varietal Ecologies Differently Regulates the Growth-regulating-factor (GRFs) Gene Family in Rice.

Background: Growth-regulating factors (GRFs) are crucial in rice for controlling plant growth and development. Among the rice cultivation practices, aerobic methods are water efficient but result in significant yield reduction relative to non-aerobic cultivation. Therefore, mechanistic insights into aerobic rice cultivation are important for improving the aerobic performance of rice. Objectives: This study aimed to examine the evolution of GRFs in different rice species, analyse the phenotypic differences between aerobic and non-aerobic conditions in three rice varieties, and assess the expression of GRFs in these varieties under both aerobic and non-aerobic conditions. Materials and Methods: This study comprehensively examined the GRFs gene family in 11 rice species (Oryza barthii, Oryza brachyantha, Oryza glaberrima, Oryza glumipatula, Oryza sativa subsp. indica, Oryza longistaminata, Oryza meridionalis, Oryza nivara, Oryza punctata, Oryza rufipogon, Oryza sativa subsp. japonica) focusing on phylogenetic analysis. Additionally, the expression patterns of 12 GRFs were investigated in three distinct genotypes of O. sativa subsp. indica rice, under both non-aerobic and aerobic conditions. Results: Three major phylogenetic clades were formed based on conserved motifs in the 123 GRFs proteins in eleven rice species. Further, novel motifs were identified especially in O. longistaminata indicative of the species level evolutionary differences in rice. Among the trait performance, the number of tillers was reduced by ~ 36% under aerobic conditions, but the reduction was found to be less in CR Dhan 201, an aerobic variety. Besides, three GRFs namely GRF3, GRF4, and GRF7 were found to be distinct in expression between aerobic and non-aerobic conditions. Conclusion: Three GRF genes namely GRF3, GRF4, and GRF7 could be associated with the aerobic adaptation in rice.

Earth-Abundant Recyclable Magnetic Iron Oxide Nanoparticles for Green-light Mediated C-H Arylation in Heterogeneous Phase.

A magnetically isolable iron oxide nanoparticles is introduced as an efficient heterogeneous photocatalyst for non-directed C-H arylation employing aryl diazonium salts as the aryl precursors. This first-row transition metal-based photocatalyst revealed versatile activities and is applicable to a wide range of substrates, demonstrating brilliant efficacy and superior recyclability. Detailed catalytic characterization describes the physical properties and redox behavior of the Fe-catalyst. Adequate control experiments helped to establish the radical-based mechanism for the C-H arylation.

Metal-Free Electrocatalytic Synthesis of Fused Azabicycles from N-Allyl Enamine Carboxylates.

An electrocatalytic approach to access structurally significant azabicyclic scaffolds from N-allyl enamine carboxylates is illustrated. This metal-free method functions exclusively with a catalytic amount of iodide, strategically employed to electrochemically generate a reactive hypervalent iodine species, which facilitates the cascade bicyclization processes with enhanced precision and efficiency. Excellent functional group compatibility was observed, enabling the synthesis of a series of azabicycle derivatives. Detailed mechanistic and electrochemical studies enhance the comprehension of the reaction sequence.

Unveiling CeZnOx Bimetallic Oxide: A Promising Material to Develop Composite SPPO Membranes for Enhanced Oxidative Stability and Fuel Cell Performance.

The incorporation of cerium-zinc bimetallic oxide (CeZnOx) nanostructures in sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) membranes holds promise in an enhanced and durable fuel cell performance. This investigation delves into the durability and efficiency of SPPO membranes intercalated with CeZnOx nanostructures by varying the filler loading of 1, 2, and 3% (w/w). The successful synthesis of CeZnOx nanostructures by the alkali-aided deposition method is confirmed by wide-angle X-ray diffraction spectroscopy (WAXS), Raman spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analyses. CeZnOx@SPPO nanocomposite membranes are fabricated using a solution casting method. The intricate interplay of interfacial adhesion and coupling configuration between three-dimensional CeZnOx and sulfonic moieties of the SPPO backbone yields an enhancement in the bound water content within the proton exchange membranes (PEMs). This constructs simultaneously an extensive hydrogen bonding network intertwined with the proton transport channels, thereby elevating the proton conductivity (Km). The orchestrated reversible redox cycling involving Ce3+/Ce4+ enhances the quenching of aggressive radicals, aided by Zn2+, promoting oxygen deficiency and Ce3+ concentration. This synergistic efficacy ultimately translates into composite PEMs characterized by a mere 4% mass loss and a nominal 6% decrease in Km after rigorous exposure to Fenton's solution. Remarkably, an improved power density of 403.2 mW/cm2 and a maximum current density of 1260.6 mA/cm2 were achieved with 2% loading of CeZnOx (SPZ-2) at 75 °C and 100% RH. The fuel cell performance of SPZ-2 is 74% higher than its corresponding pristine SPPO membrane.

Divergent Electrochemical Synthesis of Indoles through pKa Regulation of Amides: Synthetic and Mechanistic Insights.

A divergent synthetic approach to access highly substituted indole scaffolds is illustrated. By virtue of a tunable electrochemical strategy, distinct control over the C-3 substitution pattern was achieved by employing two analogous 2-styrylaniline precursors. The chemoselectivity is governed by the fine-tuning of the acidity of the amide proton, relying on the appropriate selection of N-protecting groups, and assisted by the reactivity of the electrogenerated intermediates. Detailed mechanistic investigations based on cyclic voltametric experiments and computational studies revealed the crucial role of water additive, which assists the proton-coupled electron transfer event for highly acidic amide precursors, followed by an energetically favorable intramolecular C-N coupling, causing exclusive fabrication of the C-3 unsubstituted indoles. Alternatively, the implementation of an electrogenerated cationic olefin activator delivers the C-3 substituted indoles through the preferential nucleophilic nature of the N-acyl amides. This electrochemical approach of judicious selection of N-protecting groups to regulate pKa/E° provides an expansion in the domain of switchable generation of heterocyclic derivatives in a sustainable fashion, with high regio- and chemoselectivity.

Visible-Light-Induced Hydrogen Atom Transfer En Route to Exocylic Alkenylation of Cyclic Ethers Enabled by Electron Donor-Acceptor Complex.

An electron donor-acceptor (EDA)-triggered hydrogen atom transfer (HAT) process is developed for the efficient generation of an α-alkoxy radical from cyclic ethers to synthesize exocyclic alkenylated ethers with exclusive E-selectivity. A judiciously chosen donor-acceptor pair (DABCO and maleimide) serves as the desired HAT reagent under visible light irradiation without using any photocatalyst or peroxide. A wide variety of substrates were explored to demonstrate the diverse applicability and practical viability of this cross-dehydrogenative transformation. Detailed mechanistic studies revealed a radical reaction pathway under the oxidative environment.

Electro-oxidative Synthesis of Unsymmetrical Alkyne-1,4-diones via Sequential Ring Formation and Cleavage.

Synthesis of unsymmetrical but-2-yne-1,4-diones is reported through oxidative alkyne translocation of readily accessible homopropargylic alcohols. The developed method consists of an unprecedented one-pot sequential electro-oxidative annulation-fragmentation-chemical selenoxide elimination process. Excellent functional group compatibility was observed, and an array of yne-1,4-diones were synthesized. Derivatization of the alkyne gave access to other valuable scaffolds. Detailed mechanistic studies through the isolation of key intermediates clarified the cascade transformation.

Potential soil organic carbon sequestration vis-a-vis methane emission in lowland rice agroecosystem.

Mitigating the atmospheric greenhouse effect while enhancing the inherent soil quality and productive capacity is possible through soil carbon (C) sequestration, which has a significant potential to counteract the adverse effects of agroecosystem level C emission through natural and anthropogenic means. Although rice is the most important food in India, feeding more than 60% of the country's population, it is commonly blamed for significant methane (CH4) emissions that accelerate climate change. Higher initial soil organic matter concentrations would create more CH4 under the flooded soil conditions, as reducible soil C is a prerequisite for CH4 generation. In India, rice is generally cultivated in lowlands under continuous flooding. Less extensive organic matter breakdown in lowland rice agroecosystems often significantly impacts the dynamics of soil active and passive C pools. Change from conventional to conservation agriculture might trap a significant quantity of SOC. The study aims to investigate the potential of rice-based soils to sequester C and reduce the accelerated greenhouse effects through modified farming practices, such as crop residue retention, crop rotation, organic farming, varietal selection, conservation agriculture, integrated nutrient management, and water management. Overall, lowland rice agroecosystems can sequester significant amounts of SOC, but this potential must be balanced against the potential for CH4 emissions. Management practices that reduce CH4 emissions while increasing soil C sequestration should be promoted and adopted to maximize the sustainability of rice agroecosystems. This review is important for understanding the effectiveness of the balance between SOC sequestration and CH4 emissions in lowland rice agroecosystems for adopting sustainable agricultural practices in the context of climate change.

Synthesis of Quinoxalines through Cu-electrocatalytic Azidation/Annulation Cascade at Low Catalyst Loading.

A Cu-electrocatalytic azidation of N-aryl enamines and subsequent denitrogenative annulation for the construction of quinoxaline frameworks is reported. Only 0.5 mol % of copper(II) chloride was employed for this cascade transformation displaying excellent functional-group compatibility even with complex bioactive scaffolds. The efficient electro-oxidative protocol enables the use of NaN3 as the cheapest azide source. Detailed mechanistic experiments, cyclic voltammetry, and spectroscopic studies provided strong evidence for a dual role of the Cu catalyst in azidyl and iminyl radical generation steps.

Electrochemical Organoselenium Catalysis for the Selective Activation of Alkynes: Easy Access to Carbonyl-pyrroles/oxazoles from N-Propargyl Enamines/Amides.

Intramolecular electro-oxidative addition of enamines or amides to nonactivated alkynes was attained to access carbonyl-pyrroles or -oxazoles from N-propargyl derivatives. Organoselenium was employed as the electrocatalyst, which played a crucial role as a π-Lewis acid and selectively activated the alkyne for the successful nucleophilic addition. The synthetic strategy permits a wide range of substrate scope up to 93% yield. Several mechanistic experiments, including the isolation of a selenium-incorporated intermediate adduct, enlighten the electrocatalytic pathway.

Mediator-free electrochemical trifluoromethylation: a cascade approach for the synthesis of trifluoromethylated isoxazolines.

The developed methodology describes an environmentally benign protocol for electro-oxidative CF3-radical generation, followed by cascade cyclization fabricating an isoxazoline scaffold from a ß,γ-unsaturated oxime. Consecutive C-O and C-C bond formations were achieved through this method featuring mild, robust, and scalable reaction conditions and broad substrate scope. Mechanistic studies revealed the necessity of anodic oxidation for the cascade process. Further conversion of the isoxazoline afforded other valuable derivatives.

Photoinduced Electron Donor-Acceptor Complex-Mediated Radical Cascade Involving N-(Acyloxy)phthalimides: Synthesis of Tetrahydroquinolines.

We conceptualized a novel disconnection approach for the synthesis of fused tetrahydroquinolines that exploits a visible light-mediated radical (4 + 2) annulation between alkyl N-(acyloxy)phthalimides and N-substituted maleimides in the presence of DIPEA as an additive. The reaction proceeds through the formation of a photoactivated electron donor-acceptor complex between alkyl NHPI esters and DIPEA, and the final tetrahydroquinolines were obtained in a complete regioselective fashion. The methodology features a broad scope and good functional group tolerance and operates under metal- and catalyst-free reaction conditions. Detailed mechanistic investigations including density functional theory studies provide insight into the reaction pathway.

Visible-Light-Mediated Synthesis of Phenanthrenes through Successive Photosensitization and Photoredox by a Single Organocatalyst.

An efficient approach for the synthesis of phenanthrene scaffolds by utilizing the dual catalytic activity of an organo-photocatalyst is documented. The controlled cascade transformation proceeds via in situ diazotization followed by olefin isomerization and subsequent arene radical generation through photoreduction. The overall process demonstrates both the photosensitization and photoredox properties of a single organo-photocatalyst and facilitates the desired intramolecular annulation with high precision and efficacy. In this context, the underexplored organocatalyst acridine orange base is employed and the photophysical interactions between the catalyst and the substrates along with the detailed reaction kinetics are documented.

Regioselective Synthesis of N2-Aryl 1,2,3-Triazoles via Electro-oxidative Coupling of Enamines and Aryldiazonium Salts.

An efficient synthetic route for the construction of N2-aryl 1,2,3-triazoles is reported via sequential C-N bond formation and electro-oxidative N-N coupling under metal-free conditions. Readily accessible 2-aminoacrylates and aryldiazonium salts were used as starting materials, and the developed protocol displays excellent functional group tolerance, allowing an extensive range of substrate scope up to 91% isolated yield. Various mechanistic studies, along with the isolation of an intermediate adduct, refer to successive ionic and radical reaction sequences.

Trifluoroethanol as a Unique Additive for the Chemoselective Electrooxidation of Enamines to Access Unsymmetrically Substituted NH-Pyrroles.

An electrochemical method for the synthesis of unsymmetrically substituted NH-pyrroles is described. The synthetic strategy comprises a challenging heterocoupling between two structurally diverse enamines via sequential chemoselective oxidation, addition, and cyclization processes. A series of aryl- and alkyl-substituted enamines were effectively cross-coupled from an equimolar mixture to synthesize various unsymmetrical pyrrole derivatives up to 84 % yield. The desired cross-coupling was achieved by tuning the oxidation potential of the enamines by utilizing a "magic effect" of the additive trifluoroethanol (TFE). Additionally, extensive computational studies reveal the unique role of TFE in promoting the heterocoupling process by regulating the activation energies of the reaction steps through H-bonding and C-H⋅⋅⋅π interactions. Importantly, the developed electrochemical protocol was found to be equally efficient for the homocoupling of enamines to form symmetric pyrroles up to 92 % yield.

An organophotoredox-catalyzed redox-neutral cascade involving N-(acyloxy)phthalimides and allenamides: synthesis of indoles.

An organophotoredox-catalyzed radical cascade of allenamides and alkyl N-(acyloxy)phthalimides for the synthesis of indoles is documented. The method features mild and robust reaction conditions, and exhibits broad scope. The tandem process enriches the limited repertoire of alkyl NHPI ester addition on electron-rich π-bonds as well as radical chemistry involving allenamides.