Search Results (164)

The introduction of cyano groups into aza-heterocyclic compounds plays a pivotal role in accessing diverse derivatives that are essential for the development of natural products, pharmaceuticals, and agrochemicals. Herein, we report a unified strategy for the direct ortho-C-H cyanation of a broad range of heterocyclic N-oxides, including pyridine, quinoline, isoquinoline, and pyrimidine derivatives. This transformation proceeds under mild conditions without the need for external activating agents or catalysts, and has been successfully applied to structurally complex, biologically relevant molecules. Compared to existing methodologies, our approach offers several distinct advantages: the use of non-prefunctionalized heteroarene substrates, environmentally benign reaction solvents, operational simplicity, broad substrate scope, and high efficiency in generating diverse ortho-cyanated heterocyclic compounds. Moreover, the method demonstrates considerable potential for scalable synthesis. Full article

The photochemical behavior of substituted pyridine N-Oxides is characterized by complex rearrangements culminating in the formation of valuable photoproducts. The CAS(10,8)/cc-pVDZ approach with NEVPT2 corrections is applied to investigate geometric distortions associated with the $S_1$ excited state, conical intersections, and the ultimate transformation of pyridine N-Oxides into oxaziridine-like derivative formations. Our results reveal that the deactivation of the $S_1$ excited state is driven by an out-of-plane rotation of the N-O oxygen atom, resulting in the formation of a lone pair over the nitrogen atom. Along this excited-state reaction pathway, the N-O bond undergoes significant weakening, while a C=C double bond emerges mainly in the excited state. The deactivation at the minimum-energy conical intersection leading to the ground state reveals the formation of an oxaziridine-like intermediate, which subsequently converts into a 1,2-oxazepine derivative. Full article

Tea plantations are a hot-spot source of nitrous oxide (N₂O) emissions in the agricultural system. Using nitrification inhibitors (NIs) is a promising way to mitigate agricultural N₂O emissions and has been widely tested in many croplands. However, the efficiency of different NIs and whether there are soil-specific effects are still unclear in tea plantations with typical acidic soil conditions. This study evaluated the effects of three widely used NIs, i.e., dicyandiamide (DCD), 3,4-dimethylpyrazole phosphate (DMPP), and 2-chloro-6-(trichloromethyl) pyridine (Nitrapyrin), through a lab incubation trial, on the nitrification suppression, N₂O emissions, and ammonia-oxidizing microbial communities in two tea plantation soils with contrasting physicochemical properties (pH and texture). During the 50-day incubation, the soil with a higher pH and coarse texture (TA) exhibited a four-times-higher apparent nitrification ratio (ANR) than the more acidic and clay soil (HZ). Nitrification inhibitor addition resulted in about a 60% and 80% reduction in the ANR in HZ and TA soils, respectively. During the entire incubation, ammonium sulfate (N) addition without NIs emitted N₂O at 64.1 ± 1.2 and 61.5 ± 0.4 μg N kg⁻¹ (mean ± standard deviation, and the same in the following text) in the HZ and TA soils, respectively. Compared with the N alone, the N₂O mitigation efficiency of DCD, DMPP, and Nitrapyrin was 38.3% ± 0.4% (standard deviation), 33.8% ± 0.99%, and 36.5% ± 0.59% in the HZ soil and 94.1% ± 0.39%, 52.8% ± 1.05%, and 95.6% ± 0.65% in the TA soil, respectively. Nitrapyrin more effectively suppressed both ammonia-oxidizing archaeal (AOA) and ammonia-oxidizing bacterial (AOB) abundance, particularly in the acidic soil (HZ), where ammonia-oxidizing archaea dominate nitrification. These results revealed the pivotal role of soil properties in controlling NI efficiency and highlighted Nitrapyrin as a potential superior nitrification inhibitor for N₂O mitigation under the tested conditions in this study. Full article

Based on comprehensive experimental datasets—proximate/ultimate analyses, XPS, solid-state ¹³C NMR, and Raman spectroscopy—we constructed and optimized a compositionally faithful macromolecular model of SG coking coal. Using density-functional theory (DFT) calculations, we simulated electrostatic-potential (ESP) fields and frontier molecular orbitals (FMO) to probe elementary oxidation steps relevant to combustion, and focused on how heteroatom speciation and carbon ordering govern site-selective reactivity. Employing multi-peak deconvolution and parameter synthesis, we obtained an aromatic fraction f_a = 76.56%, a bridgehead-to-periphery ratio X_BP = 0.215, and Raman indices I_D1/I_G ≈ 1.45 (area) with FWHM(G) ≈ 86.7 cm⁻¹; the model composition C₁₉₀H₁₄₄N₂O₂₁S and its predicted ¹³C NMR envelope validated the structural assignment against experiment. ESP–FMO synergy revealed electron-rich hotspots at phenolic/ether/carboxyl and thiophenic domains and electron-poor belts at H-terminated edges/aliphatic bridges, rationalizing carbon-end oxidation of CO, weak electrostatic steering by O₂/CO₂, and a benzylic H-abstraction → edge addition → O-insertion/charge-transfer sequence toward CO₂/H₂O, with thiophenic sulfur comparatively robust. We quantified surface functionalities (C–O 65.46%, O–C=O 24.51%, C=O 10.03%; pyrrolic/pyridinic N dominant; thiophenic-S with minor oxidized S) and determined a naphthalene-dominant, stacked-polyaromatic architecture with sparse alkyl side chains after Materials Studio optimization. The findings are significant for mechanistic understanding and control of coking-coal oxidation, providing actionable hotspots and a reproducible workflow (multi-probe constraints → model building/optimization → DFT reactivity mapping → spectral back-validation) for blend design and targeted oxidation-inhibition strategies. Full article

This study reports the design of N- and S-doped ordered mesoporous carbon hollow spheres (OMCHS) as metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. Three electrocatalysts were synthesized using molecular precursors: (i) 2-thiophenemethanol (S-OMCHS), (ii) 2-pyridinecarboxaldehyde/2-thiophenemethanol (N1-S-OMCHS), and (iii) pyrrole/2-thiophenemethanol (N2-S-OMCHS). Among them, S-OMCHS exhibited the best activity (E_onset = 0.88 V, E_½ = 0.81 V, n ≈ 3.95), surpassing both co-doped analogs. After conducting an accelerated degradation test (ADT), S-OMCHS and N1-S-OMCHS showed improved catalytic behavior and outstanding long-term stability. Surface analysis confirmed that performance evolution correlates with heteroatom reorganization: S-OMCHS retained and regenerated thiophene-S and C=O/quinone species, while N1-S-OMCHS converted N-quaternary into N-pyridinic/pyrrolic, both enhancing O₂ adsorption and *OOH reduction through synergistic spin–charge coupling. Conversely, oxidation of N and loss of thiophene-S in N2-S-OMCHS led to partial deactivation. These results establish a direct link between surface chemistry evolution and electrocatalytic durability, demonstrating that controlled heteroatom doping stabilizes active sites and sustains the four-electron ORR pathway. The approach provides a rational design framework for next-generation, metal-free carbon electrocatalysts in alkaline fuel cells and energy conversion technologies. Full article

Nitrogen-modified atmosphere technology, due to its effectiveness in pest control, is widely used in grain storage as an eco-friendly preservation method. This study compared the quality changes in unhulled rough rice (paddy) stored under nitrogen-modified atmosphere and conventional conditions. Fatty acid value (FAV), reactive oxygen species (ROS) content, coenzyme levels, antioxidant enzyme activities, and concentrations of central carbon metabolism-related metabolites of paddy were monitored during storage under different storage conditions. The results revealed that compared to conventional storage, nitrogen-modified atmosphere resulted in lower FAV and ROS levels, as well as higher pyridine nucleotides contents and antioxidant enzyme activities, including superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), and glutathione reductase (GR). Metabolomic profiling demonstrated that N₂-MAS induced metabolic changes characterized by the down-regulation of 2-hydroxyglutaric acid and the up-regulation of fructose 6-phosphate, glucose 1-phosphate, glycerol 3-phosphate, gluconic acid, fumaric acid, and malic acid, which collectively contribute to reduced oxidative damage and enhanced preservation quality. These findings elucidated the mechanism of N₂-MAS-delayed quality deterioration and revealed the regulatory role of the antioxidant system and central carbon metabolism. Full article

Although spontaneous or complexation-induced reductions of Cu^II to Cu^I have occasionally been observed, controlling these processes remains a challenge. Herein, we report the synthesis of Cu^I complexes via the complexation-induced reduction of Cu^II complexes with pyridine-containing N₄ Schiff-base ligand L incorporating a biphenyl unit (L = N,N’-([1,1′-biphenyl]-2,2′-diyl)bis(1-(6-methylpyridin-2-yl)methanimine)). Such a reduction has not yet been observed in previously reported Cu^II complexes with pyridine-containing N₄ Schiff-base ligands, strongly suggesting that the torsional distortion of the ligand framework induced by the biphenyl moiety effectively promotes the complexation-induced reduction of Cu^II to Cu^I. The Cu^I complexes were thoroughly characterized by ¹H NMR spectroscopy, UV–vis–NIR spectroscopy, and single-crystal X-ray diffraction analyses. The [Cu^I(L)]⁺ complex undergoes a reversible redox process with its oxidized species, which was identified as a Cu^II complex based on spectroelectrochemical measurements and theoretical calculations. Full article

Through atomic-scale characterization of a single cobalt atom anchored in a pyridinic N₃ vacancy of graphene (Co-N₃-gra), this study computationally explores three interconnected functionalities mediated by cobalt’s electronic configuration. Quantum-confined molecular prototypes extend prior bulk models, achieving a competitive catalytic activity for CO oxidation via Langmuir–Hinshelwood pathways with a 0.85 eV barrier. These molecular prototypes’ discrete energy states facilitate single-electron transistor operation, enabling sensitive detection of NO, NO₂, SO₂, and CO₂ through adsorption-induced conductance modulation. When applied to lithium–sulfur batteries using periodic Co-N₃-gra, cobalt sites enhance polysulfide conversion kinetics and suppress the shuttle effect, with the Li₂S₂→Li₂S step identified as the rate-limiting process. Density functional simulations provide atomic-scale physicochemical characterization of Co-N₃-gra, revealing how defect engineering in 2D materials modulates electronic structures for multifunctional applications. Full article

The continuous increase in solid waste poses a significant environmental challenge. Pyrolysis represents a crucial technology for the valorization of solid waste. As the primary product, biochar has found applications in numerous fields and garnered significant scientific interest. This study investigated the potential of NH₄Cl and FeCl₃ for modifying biochar. The resultant modified biochar achieved over 70% sulfamethoxazole (SMX) degradation within 30 min. The incorporation of NH₄Cl and FeCl₃ facilitated the formation of pyridinic nitrogen (N), graphitic nitrogen (N), and Fe(II) 1/2p, while the concomitant increase in persistent free radicals facilitated enhanced electron transfer rates. Notably, NH₄Cl/FeCl₃-modified biochar demonstrated superior efficacy compared with alternative activation techniques for real wastewater treatment. This study presents a novel material for persulfate (PDS)-based advanced oxidation processes, while also offering a cost-effective strategy for solid waste disposal. Full article

Pyridine is a recalcitrant organic compound present in industrial wastewater that causes severe effects on the environment and the health of living beings, as it is considered a toxic, mutagenic, teratogenic, and carcinogenic agent. Therefore, this research explored the efficacy of a zinc oxide catalyst, doped with platinum nanoparticles and supported alumina through the precipitation method, for the photocatalytic degradation of pyridine using a fluidized bed reactor. A Box–Behnken experimental design was used to analyze the effect of the pH (4–10), the pyridine concentration (20–300 ppm), and the amount of catalyst (20–100 g). The X-ray diffraction (XRD) characterization results confirmed the hexagonal structure of the zinc oxide and the successful incorporation of platinum. Scanning electron microscopy (SEM) revealed a nano-bar morphology upon catalyst doping, favoring the photocatalytic activity. Pyridine removal of 57.7% was achieved under the following conditions: a pH of 4, 160 ppm of pyridine, and 100 g of catalyst. The process followed a pseudo-first-order model, obtaining the reaction constant k₁ = 1.943 × 10⁻³ min⁻¹ and the adsorption constant k₂ = 1.527 × 10⁻³ L/mg. The results showed high efficiency and stability of the catalyst in the fluidized bed reactor for pyridine degradation, especially under acidic conditions, representing a promising technological alternative for treating industrial wastewater contaminated with N-heterocycles such as pyridine. Full article

Nitrogen-doped carbon dots (NCDs) exhibiting superior fluorescence characteristics were synthesized employing o-phenylenediamine and 2-methylimidazole as precursors. The synthesized NCDs exhibited yellow photoluminescence with an excitation/emission maxima of 410/554 nm with a quantum yield of 28.41%. The presence of pyridinic N, pyrrolic N, graphitic N, and amino N functionalities on the NCDs’ surface provided strong evidence for the successful nitrogen doping of the carbon dots. Upon exposure to hydrogen peroxide (H₂O₂), the NCDs exhibited a significant reduction in fluorescence intensity, which could be restored by the addition of ascorbic acid (AA), demonstrating a quantitative relationship between ascorbic acid and fluorescence efficiency. A novel fluorescence “off–on” system utilizing these NCDs was developed for the quantification of AA. The sensing mechanism relies on H₂O₂-induced fluorescence quenching via the selective oxidation of the NCDs’ surface, followed by fluorescence restoration upon AA addition due to the reduction in surface defects. Meanwhile, further experiments confirmed that the quenching mechanism was static quenching. The NCDs demonstrated a limit of detection (LOD) of 0.605 μM for AA detection. The use of NCDs for AA sensing was validated through the analysis of commercially available beverages. This study aimed to establish a simplified method for ascorbic acid detection. The experimental findings indicated that the developed technique exhibited high accuracy in quantifying ascorbic acid. These findings suggest that the developed NCDs possess considerable potential as a multifunctional sensing tool for various analytical applications. Full article

N-(2-chloro-5-(3-(pyridin-4-yl)-1H-pyrazolo [3,4-b]pyridin-5-yl)pyridin-3-yl)-4-fluorobenzenesulfonamide, namely, FD274, is a promising 7-azaindazole-based PI3K inhibitor candidate with high antitumor efficacy against acute myeloid leukemia and reduced cardiotoxicity in the zebrafish model. To advance its clinical translation, in this work, we conducted comprehensive assessments of the cardiotoxicity of FD274 and preliminarily investigated its synergistic antitumor effects with an FLT3 inhibitor, Gilteritinib. The cardiotoxicity profile of FD274, as well as its bioisostere FD268 (positive control), was evaluated using the C57BL/6 mouse model and the H9C2 cell line. The cardiotoxicity of FD274 after a consecutive 20-day treatment period was further assessed in an HL-60 xenograft mouse model. The synergistic cytotoxicity of FD274 with Gilteritinib was evaluated in the HL-60 cell line and the FLT3-ITD cell line MV-4-11. FD274 demonstrated lower adverse effects associated with cardiac dysfunction, oxidative stress, and myocardial injury in the C57BL/6 mouse model and in the H9C2 cell line as compared with FD268. Its negligible adverse effect was further validated in the HL-60 xenograft mice after the 20-day treatment process. Moreover, FD274 demonstrated a synergistic pro-apoptotic effect with Gilteritinib in both HL-60 and MV-4-11 cells. Our findings confirmed the low cardiotoxicity of FD274 and its great potential for combination therapy with Gilteritinib, warranting further development. Full article

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

To comparatively study the effects of cold plasma activation and chemical treatment on the adsorption capacities of biomass carbon nanofiber membranes (BCNMs), microcrystalline cellulose (MCC) and chitosan (CS) were used to fabricate porous BCNMs by electrospinning and carbonization. Two modification methods, including oxygen (O₂) plasma activation and chemical treatment using nitric acid (HNO₃), sulfuric acid (H₂SO₄), hydrogen peroxide (H₂O₂), and urea, were further employed to enhance their adsorption performance. Various carbonyl group (C=O), ether bond (C-O), carboxyl group (O-C=O) and pyridinic nitrogen (N), pyrrolic N, and quaternary N functional groups were successfully introduced onto the surface of the BCNMs by the two methods. The BCNM-O₂ showed optimal formaldehyde absorption capacity (120.67 mg g⁻¹), corresponding to its highest contents of N, O-containing functional groups, and intact network structure. However, chemical treatment in strong acid or oxidative solutions destructed the microporous structures and changed the size uniformity of fibers in the BCNMs, resulting in a decline in formaldehyde adsorption capacity. A synergistically physical–chemical adsorption took place during formaldehyde adsorption by the modified biomass nanofiber membranes, due to the coexistence of suitable functional groups and porous structures in the membranes. Full article

In this study, catalytically active coatings on titanium were synthesized by plasma electrolytic oxidation (PEO) in aqueous electrolytes based on sodium tungstate with the addition of sodium phosphate or sodium borate and chelate complexes of iron, cobalt or nickel. Taking into account the EDX, XPS and XRD data, the oxide–phosphate coatings (PWFe, PWCo, PWNi) contained crystalline titanium oxide and amorphous tungstates and/or phosphates of iron triad metals. Amorphization was facilitated by high phosphorus concentrations (up to 6 at.%). Replacing phosphate with borate in the electrolyte with Ni(II)-EDTA complexes led to the crystallization of WO₃ and NiWO₄ in the PEO coatings (BWNi). All formed PEO coatings were active in reactions of the oxidative desulfurization (ODS) of thiophene and dibenzothiophene and oxidative denitrogenation (ODN) of pyridine, as well as in the simultaneous removal of S- and N-containing substrates from their mixture. The stability of samples with MWO₄ increased in the following series: PWNi < PWCo < PW < PWFe < BWNi. Replacing phosphate with borate in the electrolyte resulted in the preparation of catalysts with enhanced stability and activity. In contrast to PWM catalysts, the BWNi catalyst had selectivity toward the oxidation of pyridine in its mixture with thiophene. Full article