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Search Results (270)

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Keywords = nitrogen-15 NMR spectroscopy

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34 pages, 15641 KB  
Article
Production and Characterisation of Polyhydroxyalkanoates from Cocoa Mucilage Using a Wild-Type Priestia aryabhattai Strain
by Jimmy Núñez-Pérez, Osmar J. Cornejo-Lucero, Rosario C. Espin-Valladares, Pedro Barba, Hortensia M. Rodríguez Cabrera and José-Manuel Pais-Chanfrau
Processes 2026, 14(9), 1492; https://doi.org/10.3390/pr14091492 - 5 May 2026
Viewed by 641
Abstract
The accumulation of petroleum-based plastics demands sustainable alternatives such as polyhydroxyalkanoates (PHAs), biodegradable polyesters synthesised by numerous prokaryotes. However, high feedstock costs limit their commercialisation. This study evaluated cocoa mucilage, an underutilised by-product of the Ecuadorian cacao sector, as a low-cost carbon source [...] Read more.
The accumulation of petroleum-based plastics demands sustainable alternatives such as polyhydroxyalkanoates (PHAs), biodegradable polyesters synthesised by numerous prokaryotes. However, high feedstock costs limit their commercialisation. This study evaluated cocoa mucilage, an underutilised by-product of the Ecuadorian cacao sector, as a low-cost carbon source for PHA production by a wild-type strain isolated from cocoa fruit residues. Bacteria were recovered from cocoa mucilage and pod shell fractions and screened for PHA accumulation by Sudan Black B staining with UV–Vis spectrophotometric confirmation. A single PHA-positive isolate, designated Priestia aryabhattai strain NBP01-UTN (GenBank accession OR567321.1; 99.88% 16S rRNA gene sequence identity to the type strain B8W22T), was recovered from the cocoa shell surface—representing, to the best of our knowledge, the first report of a PHA-producing P. aryabhattai from cacao fruit residues. Fermentation conditions were optimised using the response surface methodology with a central composite design evaluating temperature, pH, and ammonium sulphate concentration. The fitted quadratic model was highly significant (R2 = 0.978, p < 0.0001), indicating that temperature and nitrogen limitation were the dominant factors. Optimal conditions (40 °C, pH 7.30, 0 g·L−1 (NH4)2SO4) yielded 0.496 g·L−1 PHA at 24 h (productivity ≈ 20.7 mg·L−1·h−1). Notably, no external nitrogen supplementation was required, as the endogenous nitrogen in cocoa mucilage sufficed to sustain growth whilst triggering the nutrient imbalance needed for PHA biosynthesis. FTIR and DSC analyses provided spectroscopic and thermal evidence consistent with poly(3-hydroxybutyrate) (PHB), although definitive monomer-level confirmation requires GC–MS or NMR spectroscopy. These results demonstrate the feasibility of coupling a locally isolated wild-type strain with cocoa mucilage to produce bioplastic within a circular bioeconomy framework. Full article
(This article belongs to the Special Issue Recent Advances in Bioprocess Engineering and Fermentation Technology)
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33 pages, 6545 KB  
Article
CuO@Pyridine Composite for Efficient Removal of Malachite Green and Cd(II) from Water: Adsorption Performance and Mechanistic Insights
by Marwa M. Abdeen, Mohamed G. Abouelenein, Marwa Abd Elfattah, Safinaz H. El-Demerdash, Marwa A. Abdelhameed, Sara M. Elnagar, Mariam T. Yasin, Donia F. Elhadad and Mohamed Mostafa A. Mohamed
Molecules 2026, 31(9), 1501; https://doi.org/10.3390/molecules31091501 - 30 Apr 2026
Cited by 1 | Viewed by 651
Abstract
A heteroatom-rich pyridine-based adsorbent (Pyridine PC) was synthesized through a multicomponent strategy and structurally confirmed by 1H/13C NMR spectroscopy and mass spectrometry. To further enhance adsorption activity and surface reactivity, waste-derived CuO nanoparticles were immobilized onto the porous [...] Read more.
A heteroatom-rich pyridine-based adsorbent (Pyridine PC) was synthesized through a multicomponent strategy and structurally confirmed by 1H/13C NMR spectroscopy and mass spectrometry. To further enhance adsorption activity and surface reactivity, waste-derived CuO nanoparticles were immobilized onto the porous heterocyclic framework, generating a sustainable CuO@Pyridine PC hybrid nanocomposite. Batch adsorption experiments demonstrate highly efficient removal of malachite green (MG) dye and Cd(II) ions from aqueous solutions. Kinetic analysis reveals that adsorption follows the pseudo-second-order model, while equilibrium data are best described by the Freundlich isotherm, indicating adsorption on heterogeneous surfaces. Thermodynamic parameters confirm that the adsorption processes are spontaneous and exothermic. Surface and structural characterization using SEM/EDX, elemental mapping analysis and FT-IR before and after adsorption verifies strong pollutant binding and highlights the role of nitrogen- and oxygen-containing functional groups as dominant interaction sites. BET measurements show that CuO incorporation increases surface area and pore volume, while zeta potential analysis indicates excellent colloidal stability of the composite in aqueous media. Consequently, the CuO-modified sorbent exhibits enhanced adsorption capacities, increasing from 169.8 to 176.13 mg g−1 for MG and from 276.5 to 368 mg g−1 for Cd(II). The adsorbent demonstrated effective pollutant removal from real wastewater. The adsorption mechanism involves synergistic interactions between functional groups in the Pyridine PC matrix and CuO nanoparticles, providing enhanced active binding sites. Full article
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19 pages, 2757 KB  
Article
Experimental and DFT Investigation of a Vitamin B6-Derived Fluorescent Probe for Detection of Al3+ and Ga3+ Ions in a Buffered Aqueous DMSO Solution
by Maksim N. Zavalishin, Artemiy A. Guschin and George A. Gamov
Sensors 2026, 26(9), 2816; https://doi.org/10.3390/s26092816 - 30 Apr 2026
Cited by 1 | Viewed by 810
Abstract
A new selective fluorescent probe based on a vitamin B6 derived hydrazone was synthesized and characterized for the detection of Al3+ and Ga3+ ions. The probe’s selectivity and sensitivity were evaluated using UV-Vis, fluorescence, and NMR spectroscopy in a buffered [...] Read more.
A new selective fluorescent probe based on a vitamin B6 derived hydrazone was synthesized and characterized for the detection of Al3+ and Ga3+ ions. The probe’s selectivity and sensitivity were evaluated using UV-Vis, fluorescence, and NMR spectroscopy in a buffered DMSO/water solution, complemented by density functional theory (DFT) calculations to elucidate the electronic structure and coordination modes of the resulting complexes. The probe exhibited a notable “turn-on” fluorescence response upon binding Al3+ and Ga3+, with emission maxima at 466 nm and 477 nm, respectively, and detection limits as low as 48 nM for Al3+ and 33 nM for Ga3+. The probe showed high selectivity for these ions over a wide range of competing cations and anions, forming stable 1:1 complexes with log β′ values of 5.98 for Al3+ and 6.28 for Ga3+. DFT calculations revealed a tridentate coordination mode via the phenolic oxygen, azomethine nitrogen, and carbonyl oxygen, with distinct electronic transitions for each complex, including a ligand-to-metal charge transfer character in the Ga3+ complex. The probe demonstrates reversibility and excellent solution stability, offering a simple and sensitive platform for the environmental and biological monitoring of aluminum(III) and gallium(III) ions. Full article
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27 pages, 2406 KB  
Article
Gold(III) Complexes with 18-Crown-6, 1-Aza-18-Crown-6, and Cryptands 22 and 222: Stability and Structure
by Daniil N. Yarullin, Olga I. Logacheva, Viktor V. Aleksandriiskii, Maksim N. Zavalishin and George A. Gamov
Inorganics 2026, 14(4), 97; https://doi.org/10.3390/inorganics14040097 - 29 Mar 2026
Viewed by 825
Abstract
The growing demand for gold in various high-technology applications necessitates the development of efficient and selective methods for its recovery and analysis, which can be achieved using such macrocyclic ligands as crown esters and their aza-substituted derivatives. The present paper reports on the [...] Read more.
The growing demand for gold in various high-technology applications necessitates the development of efficient and selective methods for its recovery and analysis, which can be achieved using such macrocyclic ligands as crown esters and their aza-substituted derivatives. The present paper reports on the equilibrium constants for the formation of gold(III) complexes with 18-crown-6, 1-aza-18-crown-6, 1,10-diaza-18-crown-6, and the cryptand 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Kryptofix 222) in aqueous solution at T = 298.2 K, p = 0.1 MPa, I → 0. The equilibrium constants (log β) for the substitution of chloride ions by macrocycles were determined to be 4.52 ± 0.04, 9.15 ± 0.03, 9.08 ± 0.07, and 11.51 ± 0.08, respectively. Equilibrium constants for protonated and polyligand species are also provided. The complexation mechanism was elucidated using a combination of spectroscopic techniques. UV-Vis and IR spectroscopy confirm the substitution of chloride ligands by the nitrogen donor atoms of the aza-macrocycles within the tetrachloroaurate(III) ion. Furthermore, 1H NMR analysis reveals that the diaza-substituted ligands can form both inclusion complexes, where the gold cation is encapsulated within the macrocyclic cavity, and exclusion complexes. These findings provide a quantitative foundation for the design of novel macrocycle-based extractants and sensors for gold(III). Full article
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21 pages, 13465 KB  
Article
Microscopic Characteristics and Development Model of Phosphatic Bioclastic Laminae in the Jurassic Lianggaoshan Formation Shale, Eastern Sichuan Basin
by Cong Zhang, Weikun Chen, Yuan Zhang, Tenger Borjigin, Boran Wang, Daojun Wang, Miaomiao Liu, Wenren Zeng, Haohan Li, Ronghui Fang and Zi Wang
Minerals 2026, 16(3), 295; https://doi.org/10.3390/min16030295 - 11 Mar 2026
Viewed by 522
Abstract
Phosphatic bioclastic laminae distributed along bedding planes have been recently discovered within the Jurassic Lianggaoshan Formation shale in the eastern Sichuan Basin. However, their characteristics and potential as shale oil and gas reservoirs remain unclear. To reveal their microscopic pore structure characteristics and [...] Read more.
Phosphatic bioclastic laminae distributed along bedding planes have been recently discovered within the Jurassic Lianggaoshan Formation shale in the eastern Sichuan Basin. However, their characteristics and potential as shale oil and gas reservoirs remain unclear. To reveal their microscopic pore structure characteristics and development model, this study focuses on samples of phosphatic bioclastic laminae obtained from drilling cores in the Fuxing area of eastern Sichuan. A multi-scale analytical approach was employed, integrating micro-X-ray fluorescence spectroscopy (μ-XRF), field emission scanning electron microscopy (FE-SEM), nitrogen adsorption, nuclear magnetic resonance (NMR), and geochemical analyses. The results indicate that the phosphatic bioclastic laminae are primarily composed of apatite and calcite and formed in a low-energy, anoxic, semi-deep to deep lacustrine environment. They exhibit an average total porosity of 4.84% and an average TOC of 1.99 mg/g. It is 14.7% and 17.8% higher than the clay laminae, and 255.9% and 109.57% higher than the calcareous bioclastic laminae. The pore system is dominated by mesopores and macropores, encompassing multiple pore types including dissolution pores, interparticle pores, interlayer pores, organic matter-hosted pores, and micro-fractures. Notably, a well-connected nanometer-scale pore network developed within fish bone fragments contributes substantially to the storage space. These intervals integrate high organic matter richness with superior reservoir properties, demonstrating typical “source-reservoir integration” characteristics. Their pore structure is synergistically regulated by sedimentary–diagenetic processes, with a core mechanism of primary biogenic pore foundation–late diagenetic dissolution enhancement–micro-fracture connectivity. This study systematically elucidates, for the first time, the reservoir formation mechanism of the phosphatic bioclast-rich laminae in the Lianggaoshan Formation. It confirms their potential as “geological-engineering” dual sweet spots for shale oil and gas exploration, providing a new basis for sweet spot prediction and exploration deployment targeting similar phosphatic bioclastic laminae in the Sichuan Basin and analogous regions. Full article
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22 pages, 1483 KB  
Article
13C-NMR Spectroscopy and Elemental Composition of Humic Acids of Brown Forest Soils and Sod-Brownzems of the Southern Vitim Plateau (Russia, Baikal Region)
by Erzhena Chimitdorzhieva, Tsypilma Korsunova, Yurii Tsybenov, Nimbu Baldanov and Elena Valova
Molecules 2026, 31(4), 606; https://doi.org/10.3390/molecules31040606 - 9 Feb 2026
Cited by 1 | Viewed by 919
Abstract
This study shows that the structural features of humic acids reflect the specific characteristics of organic matter in permafrost soils of the southern Vitim Plateau. The region’s extracontinental climate determines the rate of decomposition, the depth of humification, and the chemical structure of [...] Read more.
This study shows that the structural features of humic acids reflect the specific characteristics of organic matter in permafrost soils of the southern Vitim Plateau. The region’s extracontinental climate determines the rate of decomposition, the depth of humification, and the chemical structure of humic acids. Brown forest soils (Haplic Cambisols) and sod-brownzems (Leptic Cambisols Skeletic) contain high amounts of organic carbon and total nitrogen in their upper horizons but differ in their vertical distribution. Brown forest soils are characterized by a sharp decrease in organic carbon content with depth and the presence of humus pockets enriched in carbon and exchangeable bases. Sod-brownzems contain more organic carbon with increase in acidity and base loss with depth. Both soil types retain satisfactory natural fertility. 13C nuclear magnetic resonance spectroscopy data reveal marked differences in the structural maturity of humic acids. Humic acids from the A horizons of brown forest soils contain an equilibrium combination of aliphatic and aromatic structures, a well-developed system of oxygen-containing groups, and moderate condensation, indicating an intermediate stage of humification. Humic acids from humus pockets are more aromatic and highly humified. They reflect an advanced stage of humification and possess high chemical stability. Humic acids from sod-brownzems also exhibit high aromaticity, which facilitates the formation of stable organomineral complexes. A comparison of the samples reveals a consistent increase in aromaticity, condensation, and stability from the A horizons of brown forest soils to the A horizons of sod-brownzems and further to humus pockets. This progression corresponds to an increase in humification and a decrease in the mobility and bioavailability of organic matter. These results confirm that the structural characteristics of humic acids are determined by soil type and formation conditions. Elemental composition revealed that humic acids from brown forest soils are characterized by the highest aromaticity and maturity, while humic acids from HA-brown forest soils-A have a less condensed structure. Humic acids from sod-brownzems occupy an intermediate position, combining high aromatization with a moderate degree of humification. Overall, the obtained elemental composition data are fully consistent with the results of 13C NMR spectroscopy, mutually confirming the identified structural features and the degree of transformation of soil organic matter. Full article
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15 pages, 2181 KB  
Article
Land Use Type Affects SOM Molecular Composition in Forest Plantations by Altering Soil Nutrients and Enzyme Activities
by Anming Zhu, Jing Guo, Guguo Zhou, Naping Shen, Weilu Tang and Guibin Wang
Forests 2026, 17(2), 222; https://doi.org/10.3390/f17020222 - 6 Feb 2026
Viewed by 474
Abstract
Soil organic matter (SOM) molecular composition governs its stability and ecological functions in forest ecosystems. Nevertheless, how land-use changes (LUCs) regulate the SOM molecular composition remains poorly understood, particularly the underlying mechanisms mediated by soil properties. This study investigated the effects of LUCs [...] Read more.
Soil organic matter (SOM) molecular composition governs its stability and ecological functions in forest ecosystems. Nevertheless, how land-use changes (LUCs) regulate the SOM molecular composition remains poorly understood, particularly the underlying mechanisms mediated by soil properties. This study investigated the effects of LUCs on SOM molecular composition in a subtropical coastal region and examined the driving roles of soil nutrient availability and enzyme activities. The research was conducted in Huanghai National Forest Park, Jiangsu Province, China, focusing on four land-use types converted from historical wheat cropland (W, as control): monoculture plantations of Ginkgo biloba (G) and Metasequoia glyptostroboides (M), a ginkgo–metasequoia mixed forest (GM), and a ginkgo–wheat agroforestry system (GW). Soil samples were collected from 0 to 20 cm and 20–40 cm layers and analyzed for SOM molecular compositions using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Soil chemical properties and enzyme activity activities were also determined, with redundancy analysis (RDA) and correlation analysis applied to identify key influencing factors. Results demonstrated that LUCs significantly altered SOM molecular composition. The GW system exhibited the highest proportion of labile O-alkyl carbon (42.65%), while the M plantation accumulated greatest levels of stable aromatic carbon (up to 49.25%). During the initial decades following afforestation, soil nutrient availability and enzyme activities were confirmed as pivotal drivers of SOM molecular variation. Specifically, available potassium (AK), ammonium nitrogen (AN), and the carbon/phosphorus (C/P) ratio were significantly correlated with specific SOM components (p < 0.05). The elevated O-alkyl carbon proportion in GW was closely associated with its higher invertase activity. Notably, vertical differentiation in SOM stability was observed across land-use types, with the agroforestry system achieving the highest carbon pool management index in surface soil but showing a weakened capacity for subsoil C stabilization. RDA further confirmed that AK and AN were dominant factors shaping SOM molecular composition. In conclusion, LUCs modulate SOM chemical composition and stability primarily through altering soil nutrient availability and associated enzyme activities. Agroforestry system facilitates labile C accumulation in surface soil, whereas monoculture plantations are more conducive to stable C sequestration, especially in subsoil layers. These findings provide novel mechanistic insights into SOM dynamics following LUCs and offer a theoretical basis for formulating tailored management strategies to enhance C sequestration efficiency in subtropical coastal ecosystems. Full article
(This article belongs to the Section Forest Soil)
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23 pages, 4386 KB  
Article
Could Insect Frass Be Used as a New Organic Fertilizer in Agriculture? Nutritional Composition, Nature of Organic Matter, Ecotoxicity, and Phytotoxicity of Insect Excrement Compared to Eisenia fetida Vermicompost
by Patricia Castillo, José Antonio Sáez-Tovar, Francisco Javier Andreu-Rodríguez, Héctor Estrada-Medina, Frutos Carlos Marhuenda-Egea, María Ángeles Bustamante, Anabel Martínez-Sánchez, Encarnación Martínez-Sabater, Luciano Orden, Pablo Barranco, María José López and Raúl Moral
Insects 2026, 17(2), 142; https://doi.org/10.3390/insects17020142 - 27 Jan 2026
Cited by 5 | Viewed by 2787
Abstract
The expanding insect farming industry generates up to 67,000 tons of frass per year. Its potential use as fertilizer is promising, but has not yet been widely studied. This study aimed to characterize the chemical composition, organic matter structure, ecotoxicity, and phytotoxicity of [...] Read more.
The expanding insect farming industry generates up to 67,000 tons of frass per year. Its potential use as fertilizer is promising, but has not yet been widely studied. This study aimed to characterize the chemical composition, organic matter structure, ecotoxicity, and phytotoxicity of frass from four insect species in order to evaluate its potential as a fertilizer. We compared four types of insect frass (IF) (Tenebrio molitor, Galleria mellonella, Hermetia illucens, and Acheta domesticus) to Eisenia fetida vermicompost (EFV). We used physicochemical analyses (pH, electrical conductivity (EC), macro-micronutrients and dissolved organic carbon (DOC), spectroscopy (solid-state 13C nuclear magnetic resonance (NMR), and Fourier-transform infrared spectroscopy (FTIR)) and thermogravimetry/differential scanning calorimetry (TGA/DSC: R1, R2, Tmax), together with phytotoxicity (germination index, %GI) and ecotoxicity (toxicity units, TU) bioassays. Composition was species-dependent: A. domesticus showed the highest levels of nitrogen (N), phosphorus (P), and potassium (K); the concentration of DOC was higher in insect frass (IF) than in EFV, with the highest concentration found in IF of T. molitor. 13C NMR/FTIR profiles distinguished between frass (carbohydrates/proteins and chitin signals) and EFV (humified, oxidized matrix). Thermal stability followed: G. mellonella (R1 ≈ 0.88) ≥ A. domesticus (0.79) > H. illucens (0.73) > EFV (0.67) > T. molitor (0.50). In bioassays, T. molitor and A. domesticus exhibited phytotoxicity (%GI < 30), whereas G. mellonella and H. illucens did not. EFV exhibited the highest %GI. Dilution increased %GI in all materials, especially in T. molitor and A. domesticus, and reduced acute risk (TU). Frass is not a uniform input: its agronomic performance emerges from the interaction between EC (ionic stress), the availability of labile C (DOC, C/N and low-temperature exotherms), and structural stability (R1/R2 and aromaticity). In terms of formulation, IF can provide nutrients that mineralize rapidly, whereas EFV contributes stability. Controlling the inclusion and dilution of materials (e.g., limiting the amount of T. molitor in blends) and considering the mixing matrix helps to manage phytotoxicity and ecotoxicity, and realize the fertilizer value of the product. Full article
(This article belongs to the Section Role of Insects in Human Society)
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23 pages, 889 KB  
Article
Integrative Metabolomic and Physiological Responses of Citrus sinensis to Soil Management in a Semi-Arid Orchard
by Carlos Giménez-Valero, Dámaris Núñez-Gómez, Pilar Legua, Juan José Martínez-Nicolás, Vicente Lidón and Pablo Melgarejo
Plants 2026, 15(3), 386; https://doi.org/10.3390/plants15030386 - 27 Jan 2026
Viewed by 662
Abstract
The coordination between carbon and nitrogen metabolism is central to plant adaptation to water-limited environments. This study investigated how soil management practices modulate the metabolic and physiological performance of Citrus sinensis trees cultivated under semi-arid conditions. Six field treatments combining weed-control netting, subsurface [...] Read more.
The coordination between carbon and nitrogen metabolism is central to plant adaptation to water-limited environments. This study investigated how soil management practices modulate the metabolic and physiological performance of Citrus sinensis trees cultivated under semi-arid conditions. Six field treatments combining weed-control netting, subsurface drainage, and zeolite amendment were evaluated for their effects on vegetative growth, yield, and fruit metabolome. Using 1H-NMR spectroscopy, 23 metabolites in peel and 21 in juice were identified and quantified, revealing that sugars, organic acids, and amino acids were the most responsive compound classes. Multivariate analyses (PCA, PLS-DA) showed distinct metabolic fingerprints associated with each soil management regime. Treatments integrating netting and zeolite (T4) induced a coordinated reprogramming of carbon and nitrogen metabolism, characterized by altered levels of glucose, fructose, citrate, and proline. These changes suggest enhanced osmotic regulation and tricarboxylic acid cycle activity, supporting improved water-use efficiency and physiological stability under semi-arid stress. The results demonstrate that soil management directly influences fruit metabolic homeostasis, linking environmental modulation of root-zone conditions with whole-plant biochemical adjustment. This integrative metabolomic approach provides mechanistic insight into how soil–plant interactions shape the metabolic resilience of citrus under water-limited field environments. Full article
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20 pages, 3818 KB  
Article
Mechanistic Shifts in Organic Carbon Stabilization in a Black Soil Driven by Nitrogen Fertilization
by Yantian Cui, Qi Li, Hongyan Chang, Yanan Li, Chengyu Wang, Rong Jiang, Shuxia Liu and Wentian He
Agronomy 2026, 16(2), 268; https://doi.org/10.3390/agronomy16020268 - 22 Jan 2026
Viewed by 648
Abstract
The phaeozem in Northeast China is rich in soil organic carbon (SOC). However, the excessive and inefficient application of chemical fertilizers, particularly nitrogen fertilizers, has primarily led to a decrease in soil pH in this region. Currently, the relationship between soil pH and [...] Read more.
The phaeozem in Northeast China is rich in soil organic carbon (SOC). However, the excessive and inefficient application of chemical fertilizers, particularly nitrogen fertilizers, has primarily led to a decrease in soil pH in this region. Currently, the relationship between soil pH and the stability of soil organic carbon (SOC) remains ambiguous. This study, conducted over 13 years of field experiments, focused on soils exhibiting varying degrees of pH resulting from different nitrogen application rates. The research employed aggregate classification, 13C nuclear magnetic resonance spectroscopy, and analysis of microbial community composition to investigate the alterations in the SOC stabilization mechanisms under varying nitrogen application levels. Our results demonstrated that the decline in soil pH led to reductions in macroaggregates (>2 mm) and the soil aggregate destruction rate (PAD) by 4.8–14.6%, and in soil aggregate unstable agglomerate index (ELT) by 9.7–13.4%. The mean weight diameter (MWD) and geometric mean diameter (GMD) exhibited significant declines (p < 0.05) with decreasing pH levels. According to the 13C NMR analysis, the SOC was predominantly composed of O-alkyl carbon and aromatic carbon. At a pH of 5.32, the Alip/Arom values decreased, while the molecular structure of SOC became more complex under different levels of pH. In addition, the increase in [Fe(Al)-OC] (31.4–71.9%) complex indicates a shift in the stability of organic carbon from physical protection to organic mineral binding. Declining soil pH significantly reduced the diversity of soil microbial communities and promoted a shift toward copiotrophic microbial groups. Overall, declining soil pH resulted in a decline in soil aggregate stability and an increase in SOC aromaticity. This drove the shift in the stabilization mechanism of SOC in the black soil ecosystem of meadows in Northeast China from physical protection to chemical stability. Full article
(This article belongs to the Section Soil and Plant Nutrition)
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29 pages, 5015 KB  
Article
Synthesis and Structural Characterization of Dinitrogen Chromium Complexes with Triamidoamine Ligands Possessing Bulky Substituents, and Nitrogen Fixation by These Complexes
by Takeru Kuribayashi, Yoshiaki Kokubo, Haruki Nagai, Tomoya Furui, Tomohiro Ozawa, Hideki Masuda and Yuji Kajita
Inorganics 2026, 14(1), 24; https://doi.org/10.3390/inorganics14010024 - 7 Jan 2026
Viewed by 1130
Abstract
Chromium complexes with triamidoamine derivatives bearing bulky substituents at the terminal positions of the ligands, tris(2-(3-pentylamino)ethyl)amine (H3LPen) and tris(2-dicyclohexylmethylaminoethyl)amine (H3LCy), are prepared: [{Cr(LPen)}2(μ-N2)] (1), [...] Read more.
Chromium complexes with triamidoamine derivatives bearing bulky substituents at the terminal positions of the ligands, tris(2-(3-pentylamino)ethyl)amine (H3LPen) and tris(2-dicyclohexylmethylaminoethyl)amine (H3LCy), are prepared: [{Cr(LPen)}2(μ-N2)] (1), [{CrK(LPen)(μ-N2)(Et2O)}2] (2), [CrCl(LPen)] (3), [Cr(LCy)] (4), [CrK(LCy)(μ-N2)(18-crown-6)(THF)] (5(THF)), and [CrCl(LCy)] (6). The preparation of these complexes is confirmed by X-ray diffraction analysis. Complexes 1, 2, and 5(THF) have coordinated dinitrogen molecules, with N–N bond lengths of 1.185(3), 1.174(9), and 1.162(3) Å, respectively. These lengths are significantly elongated compared to that of a free dinitrogen molecule (1.10 Å), indicating that the N2 ligands are activated. The ν(14N–14N) values of 1, 2, and 5(THF) are 1715 cm−1 for 1 (Raman, in solution), 1787, 1743 cm−1 for 2 (IR, in solid), and 1824 cm−1 for 5(THF) (IR, in solid), respectively. These values are markedly smaller than free nitrogen (2331 cm−1), confirming that the dinitrogen is interacting with the metal ions and is activated. The structures of 2 and 5(THF) in solution are also studied by 1H NMR and solution IR spectroscopies. 1H NMR spectra of these complexes reveal that the peaks of 2 and 5(THF) are observed in the diamagnetic region, whereas those for the other complexes (1, 3, 4, and 6) exhibit paramagnetic shifts. The reactions of these complexes with K[C10H8] and HOTf under N2 in THF yield hydrazine and a small amount of ammonia; however, they are not catalytic. The 1H NMR and IR spectra of the products obtained by reacting 1 or 3 with reductant K in THF under N2 atmosphere indicate that 2 is formed based on spectral agreement. Similarly, upon examining for 4 or 6, it is confirmed that a species similar to 5(THF) is generated. Full article
(This article belongs to the Special Issue State-of-the-Art Inorganic Chemistry in Japan)
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20 pages, 2685 KB  
Article
Synthesis and Gas Permeability of Polynorbornene Dicarboximides Bearing Sulfonyl Moieties
by Alejandro Onchi, Lisandra Rubio-Rangel, Arlette A. Santiago, Brian Omar Marín-Méndez, Mar López-González and Joel Vargas
Polymers 2026, 18(1), 62; https://doi.org/10.3390/polym18010062 - 25 Dec 2025
Viewed by 1344
Abstract
This work reports on the synthesis and ring-opening metathesis polymerization (ROMP) of two novel homologous sulfonyl-containing norbornene dicarboximide monomers, specifically, N-4-(trifluoromethylsulfonyl)phenyl-norbornene-5,6-dicarboximide (1a) and N-4-(trifluoromethylsulfonyl)phenyl-7-oxanorbornene-5,6-dicarboximide (1b) using the Grubbs 2nd generation catalyst (I). The polymers are [...] Read more.
This work reports on the synthesis and ring-opening metathesis polymerization (ROMP) of two novel homologous sulfonyl-containing norbornene dicarboximide monomers, specifically, N-4-(trifluoromethylsulfonyl)phenyl-norbornene-5,6-dicarboximide (1a) and N-4-(trifluoromethylsulfonyl)phenyl-7-oxanorbornene-5,6-dicarboximide (1b) using the Grubbs 2nd generation catalyst (I). The polymers are thoroughly characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermomechanical analysis (TMA), thermogravimetric analysis (TGA), atomic force microscopy (AFM), and X-ray diffraction (XRD), among other techniques. A comparative study of gas transport in membranes based on these ROMP-prepared polymers is performed and the gases studied are hydrogen, oxygen, nitrogen, carbon dioxide, methane, ethylene and propylene. It is found that the presence of sulfonyl pendant groups in the polymer backbone increases the gas permselectivity in slight detriment of the gas permeability compared to a polynorbornene dicarboximide lacking sulfonyl groups. The membrane of the sulfonyl-containing polymer with an oxygen heteroatom in the cyclopentane ring, 2b, is also found to have one of the largest permselectivity coefficients reported to date for the separation of H2/C3H6 in glassy polynorbornene dicarboximides. Full article
(This article belongs to the Special Issue Advanced Polymeric Membranes: From Fabrication to Application)
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17 pages, 3103 KB  
Article
Multi-Analytical Insight into the Non-Volatile Phytochemical Composition of Coleus aromaticus (Roxb.) Benth.
by Chiara Toniolo, Martina Bortolami, Adriano Patriarca, Daniela De Vita, Fabio Sciubba and Luca Santi
Metabolites 2026, 16(1), 15; https://doi.org/10.3390/metabo16010015 - 23 Dec 2025
Viewed by 893
Abstract
Background/Objectives: Coleus aromaticus (Lamiaceae), also known as Cuban oregano or Indian borage, is a semi-succulent perennial species widely used in traditional medicine for its therapeutic and nutritional properties. While its essential oils and aromatic fraction have been extensively investigated, the characterization of [...] Read more.
Background/Objectives: Coleus aromaticus (Lamiaceae), also known as Cuban oregano or Indian borage, is a semi-succulent perennial species widely used in traditional medicine for its therapeutic and nutritional properties. While its essential oils and aromatic fraction have been extensively investigated, the characterization of its non-volatile metabolites remains limited. The aim of this study was to explore the chemical composition of fresh leaves with a focus on the non-volatile fraction. Methods: Fresh leaves of C. aromaticus were cryogenically treated with liquid nitrogen, ground, and subjected to three different extraction procedures: hydroalcoholic maceration, ethyl acetate maceration, and liquid–liquid partitioning to obtain a dichloromethane organic phase and a hydroalcoholic phase. Extracts and fractions were analyzed by HPTLC and HPLC for metabolic profiling. In addition, the Bligh–Dyer method was applied to separate polar and non-polar metabolites, which were subsequently characterized using NMR spectroscopy. Results: Chromatographic analyses highlighted the occurrence and distribution of organic acids, polyphenols (notably flavonoids), and proteinogenic amino acids. Spectroscopic data confirmed the presence of diverse polar and non-polar metabolites, providing a more detailed chemical fingerprint of C. aromaticus. This integrated approach broadened the phytochemical profile of the species beyond the well-documented essential oils. Conclusions: The results contribute to a better understanding of the non-volatile metabolites of C. aromaticus, offering novel insights into its chemical diversity. These findings highlight the potential of this plant as a valuable source of bioactive compounds, supporting its future application in nutraceutical and pharmaceutical research. Full article
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28 pages, 3229 KB  
Article
Studies on the Complexation of Platinum(II) by Some 4-Nitroisothiazoles and the Cytotoxic Activity of the Resulting Complexes
by Andrzej Regiec, Joanna Wietrzyk, Magdalena Milczarek, Andrzej Kochel and Henryk Mastalarz
Molecules 2026, 31(1), 34; https://doi.org/10.3390/molecules31010034 - 22 Dec 2025
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Abstract
Five novel platinum(II) complexes C1C5 were synthesized in the reaction of the appropriate substituted 4-nitroisothiazoles with K2PtCl4 and characterized with elemental analysis, ESI MS spectrometry, NMR spectroscopy, and IR spectroscopy. Also, a new methyl 3-methyl-4-nitroisothiazole-5-carboxylate (L2) [...] Read more.
Five novel platinum(II) complexes C1C5 were synthesized in the reaction of the appropriate substituted 4-nitroisothiazoles with K2PtCl4 and characterized with elemental analysis, ESI MS spectrometry, NMR spectroscopy, and IR spectroscopy. Also, a new methyl 3-methyl-4-nitroisothiazole-5-carboxylate (L2) was obtained. The structures of trans complex C4 and the new isothiazole derivative L2 were additionally confirmed by X-ray diffraction (XRD) method. The cytotoxicity of the investigated complexes was examined in vitro on three human cancer cell lines (MCF-7 breast, ES-2 ovarian, and A549 lung adenocarcinomas) in both normoxic and hypoxic conditions. The tested complexes, except for the most polar cisC5, which appeared to be the least active, showed cytotoxic activity comparable to that of the reference cisplatin. cis-complex C1, transC2, and transC3 showed slightly better cytotoxic activity than cisplatin against the MCF-7 cell line. The complexes had the weakest effect on the A549 cell line. No differences in the cytotoxic activity of the complexes were observed between normoxic and hypoxic conditions, except for the A549 cell line, where all the complexes, except for C2, were inactive in hypoxia. However, most complexes, including the reference cisplatin, were equally toxic to healthy BALB/3T3 cells and cancer cells. The trans complex C2 (isomeric to cisC1) showed even greater toxicity to healthy cells than to MCF-7 and A549 cancer cells. Some complexes were tested for stability against glutathione (GSH) solution to gain additional information that may facilitate the explanation of the pharmacological activity of the tested compounds. Additionally, some theoretical calculations on the thermochemistry of the complexation process were performed using quantum density functional theory (DFT), which indicate that complexation should occur through the coordination of the platinum cation by the nitrogen rather than the sulfur atom of the isothiazole ring. Full article
(This article belongs to the Special Issue Metal-Based Drugs: Past, Present and Future, 3rd Edition)
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18 pages, 639 KB  
Article
Synthesis, Characterization, Antimicrobial and Anticancer Evaluation of Novel Heterocyclic Diazene Compounds Derived from 8-Quinolinol
by Ion Burcă, Alexandra-Mihaela Diaconescu, Valentin Badea and Francisc Péter
Pharmaceuticals 2026, 19(1), 4; https://doi.org/10.3390/ph19010004 - 19 Dec 2025
Cited by 1 | Viewed by 1246
Abstract
Background: 8-Quinolinol and its derivatives are drawing significant attention across various disciplines due to their remarkable versatility. These compounds are well-known for their exceptional chelating ability, forming stable metal complexes via their nitrogen and oxygen electron donor atoms. This main characteristic determines [...] Read more.
Background: 8-Quinolinol and its derivatives are drawing significant attention across various disciplines due to their remarkable versatility. These compounds are well-known for their exceptional chelating ability, forming stable metal complexes via their nitrogen and oxygen electron donor atoms. This main characteristic determines their broad utility. Biological activity can also be explained by the chelating capacity, which allows 8-quinolinol to bind to essential metal ions such as Fe, Zn, Cu, and others. This chelation disrupts metal-dependent biological processes in target cells or organisms, leading to a range of effects, including antimicrobial, anticancer, antifungal, and neuroprotective activities. On the other hand, the biological activity of pyrazole derivatives is attributed to their heterocyclic structure, which allows for interactions with biological targets that can lead to enzyme inhibition, receptor antagonism, radical scavenging, and other effects. Objective: This work aimed to synthesize and characterize novel diazene compounds derived from 8-quinolinol or 2-methyl-8-quinolinol and pyrazole amines, and to evaluate their antimicrobial and anticancer activities. Methods: The compounds have been synthesized by coupling diazonium salts obtained from the diazotization of heterocyclic amines with 8-quinolinol and its derivative, 2-methyl-8-quinolinol. The careful selection of reaction conditions enabled the synthesis of high-purity products. The compounds were characterized by 1D and 2D NMR, FT-IR spectroscopy, UV-Vis spectroscopy, and LC-HRMS analysis. The biological activity of the newly synthesized compounds was evaluated following the protocols of EU-OPENSCREEN, a European Research Infrastructure Consortium (ERIC) initiative dedicated to supporting early drug discovery. Results: By combining diazonium salts obtained from 3-methyl-1H-pyrazol-5-amine and ethyl 5-amino-3-methyl-1H-pyrazole-4-carboxylate with the aforementioned coupling agents, four novel 8-quinolinol derivatives were synthesized. The further hydrolysis of the ethoxy carbonyl functional group allowed its conversion to a carboxylic functional group, thus expanding the series of new compounds to six members. Several compounds from the series have proven to be biologically active against several human pathogenic microorganisms and the Hep-G2 cancer cell line. Conclusions: The combination of two well-known biologically active scaffolds through a classic diazo coupling reaction allowed the synthesis of novel biologically active compounds, which showed promising results as possible antifungal and anticancer agents. These results represent a foundation for future studies, which will include a broader biological screening and in vivo studies. Full article
(This article belongs to the Special Issue Advances in the Synthesis and Application of Heterocyclic Compounds)
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