Search Results (6,346)

Agricultural and agro-industrial byproducts from tropical crops represent abundant sources of structurally bound and freely extractable bioactive compounds. However, variability in feedstock composition, the incomplete characterization of microbial transformations, and limited translation beyond chemical antioxidant assays constrain their development as standardized ingredients. This review critically evaluates metabolomics-guided fermentation as a strategy for converting tropical agricultural byproducts into functional and circular products. It covers fruit-processing residues, coffee and cocoa byproducts, cereal bran, cassava-processing residues, coconut and oilseed materials, and selected medicinal-crop tissues. Solid-state, submerged, lactic-acid-bacterial, yeast, filamentous fungal, Bacillus-based, and mixed-culture fermentations are compared. Particular attention is given to cell-wall deconstruction, phenolic release, flavonoid deglycosylation, phenolic-acid conversion, carotenoid stability, peptide generation, fiber modification, organic-acid production, antinutrient reduction, and undesirable metabolite formation. Analytical strategies based on untargeted and targeted LC-MS, GC-MS, NMR, volatilomics, peptidomics, and multiomics integration are assessed, together with experimental design, quality control, annotation confidence, and statistical validation. A substrate–microorganism–process–metabolite–function framework and a six-level evidence-grading system are proposed to distinguish exploratory chemical findings from mechanistically validated and industrially translatable outcomes. Applications in functional foods, nutraceutical ingredients, natural preservatives, animal feed, active packaging, agricultural inputs, and cascade biorefineries are evaluated alongside microbial safety, mycotoxins, biogenic amines, contaminants, regulatory classification, life-cycle assessment, and techno-economic feasibility. The central conclusion is that fermentation can become a programmable platform for tropical byproduct valorization only when metabolite-resolved characterization, causal validation, process standardization, safety, and sustainability are developed as an integrated pipeline. Full article

The integrity of hollow glass microspheres (HGMs) and the association of (3-aminopropyl)triethoxysilane (APTES) with solvent-resistant organic-phase retention were examined in model butyl sealant compounds based on isobutylene–isoprene rubber (IIR), brominated IIR (BIIR), and polybutene. Within this formulation and mixing system, HGM damage is proposed as a candidate screening indicator of cumulative processing history. HGMs can reduce composite density, but they may be damaged during processing in viscous matrices. Four formulations differing in HGM content, APTES content, and APTES/HGM addition sequence, prepared in two non-randomized batch lineages, were characterized by density, consistency, flow, peel, and tack, and by double toluene extraction coupled with electron microscopy, X-ray microanalysis, infrared spectroscopy, and thermogravimetry. A two-state density balance gave apparent crushed-HGM fractions of 71–89%, depending on the matrix-density reference. A compositionally simplified BIIR/APTES model specimen showed a 65% cyclohexane-insoluble fraction and ¹H diffusion-NMR echo decays consistent with restricted proton mobility. Differences between the two same-composition formulations were associated with broader processing history, including addition sequence. APTES-containing formulations retained a solvent-resistant organic phase after extraction, including on glass surfaces, whereas the APTES-free control retained mainly glass. The specific junction chemistry, including covalent glass–silane anchoring, was not directly resolved. Cold-flow resistance and self-healing were not measured. Full article

The chemical structure of the lipooligosaccharide (LOS) from the marine bacterium Rheinheimera pacifica KMM 1406^T was investigated. Analysis by SDS-PAGE with silver staining revealed a low-molecular-weight banding pattern characteristic of R-type lipopolysaccharide (LOS). The fatty acid composition was determined by GC-MS, revealing mainly dodecanoic (12:0), 3-hydroxydodecanoic [12:0(3-OH)], and 3-hydroxytetradecanoic [14:0(3-OH)] acids. The oligosaccharide (OS) was obtained by complete deacylation of the LOS. Monosaccharide analysis indicated the presence of D-GlcN, D-Gal, D-Glc, and a phosphorylated Kdo residue. Using NMR spectroscopy, the structure of the OS was established as: α-D-Galp-(1→2)-α-D-Galp-(1→6)-α-D-Glcp-(1→5)-α-Kdop4P-(2→6)-β-D-GlcpN4P-(1→6)-α-D-GlcpN1P. Negative-ion MALDI-TOF mass spectrometry of the lipid A domain demonstrated the presence of bisphosphorylated penta-acylated and tetra-acylated molecular species. Tandem mass spectrometry determined the distribution of the acyl chains on the glucosamine disaccharide backbone. The LOS is characterized by a short carbohydrate chain and a low acylation degree of the lipid A domain. Full article

Green chemistry provides a conceptual and technological framework for redesigning agricultural inputs and analytical workflows toward safer, more efficient, and more sustainable crop production. In this review, molecular crop quality is proposed as a chemical and metabolomic endpoint of green chemistry in sustainable agriculture. Rather than evaluating agricultural interventions proposed as compatible with green chemistry only through yield, input reduction, or environmental performance, this review focuses on their capacity to reshape crop composition, including micronutrient density, primary metabolites, specialized metabolites, bioactive compounds, antioxidant potential, and bioaccessibility. Particular attention is given to nano-enabled biofortification, biogenic nanomaterials, plant-derived biostimulants, microbial consortia, and biodegradable carrier systems as tools that may modulate nutrient uptake, redox signaling, transcriptional regulation, and selected biosynthetic pathways. Representative changes in phenolics and flavonoids, carotenoids, glucosinolates, and capsaicinoids are discussed as examples of how agricultural interventions evaluated within a green chemistry framework can influence functional and nutritional traits at the molecular level. The review also considers green extraction and analytical platforms, including ultrasound-assisted extraction, microwave-assisted extraction, supercritical-fluid extraction, LC-MS, ICP-MS, NMR, and antioxidant assays, as essential tools for reliable assessment of molecular crop quality. Finally, safety-related challenges are critically examined, including nanoparticle characterization, dose-dependent phytotoxicity, environmental fate, bioaccessibility, and regulatory uncertainty. By integrating green chemistry, plant metabolism, nano-enabled biofortification, biostimulation, and analytical chemistry, this review outlines a framework for assessing crop quality beyond yield and highlights the need for standardized, mechanistically informed, and safety-oriented approaches to future agricultural innovation. Full article

Biodiesel has attracted considerable attention as a promising renewable fuel because it burns cleaner than conventional diesel and produces lower pollutant emissions. In this work, a CaO-based heterogeneous catalyst was prepared by calcining drinking water pipeline scale deposits at 900 °C for 2 h. X-ray diffraction (XRD), Fourier transforms infrared (FT-IR) spectroscopy, thermogravimetric analysis (TG-DTA), atomic emission spectrometry ICP-AES, and scanning electron microscopy SEM were used to analyze all the solids. Characterization results revealed that the raw scale deposits mainly consisted of calcite (CaCO₃) containing trace amounts of metallic impurities. Catalytic activity was performed on a high-temperature calcined scale material. The effect of catalysts quantities, methanol to oil molar ratios, and reaction periods were researched in order to enhance the biodiesel’s quality. The obtained results showed that at 60 °C, the methyl ester content was 96% under transesterification conditions utilizing a catalyst concentration of 3%, a methanol/oil molar ratio of 12, and a reaction duration of 120 min. The produced biodiesel was also analyzed using FT-IR and NMR. Their properties were recorded according to the ASTM D6751 specifications of biodiesel and were discovered to be within the parameters. Full article

Background/Objectives: Oral solid dosage (OSD) forms are historically categorized as low-risk vectors for leachables under the assumption that solid-state matrices impose severe kinetic barriers against migrant migration and reactivity. This study investigates an unexpected unknown impurity, detected as part of a routine ICH Q3B testing program to control drug product impurities in a blister-packed tablet. Since the impurity exceeded the ICH Q3B identification threshold applicable for this drug product (1.0% w/w relative to API or 5 µg total daily intake (TDI), whichever is lower), a forensic investigation into the origins and identity of the impurity was performed. Methods: Placebo and packaging line studies were performed to isolate the origin of the impurity. Systematic structure elucidation was carried out using high-resolution mass spectrometry (HRMS), isotopic fine structure analysis, and de novo chemical synthesis. To enable definitive characterization, preparative HPLC was utilized to isolate the compound for high-field 2D-NMR spectroscopy (801 MHz). Results: The impurity was proven to be independent of active pharmaceutical ingredient degradation, forming only when tablet excipients were stored in sealed PVC blister packaging. Co-incubation of the PVC heat stabilizer derivative dimethyltin bis(2-ethylhexyl mercaptoacetate) (DMTE) with pyrrolidin-2-one (a povidone excipient degradation product) generated an identical chromatographic and MS/MS spectral profile. NMR spectroscopy unambiguously identified the structure as 2-ethylhexyl 2-((5-oxopyrrolidin-2-yl)thio)acetate. Conclusions: This study provides the first direct evidence of an organotin-catalyzed solid-state reaction between a packaging leachable and a tablet excipient under 25 °C/60% RH storage conditions. While this implies that the impurity should not be evaluated under the ICH Q3B guidelines, the findings directly challenge the assumed “low-risk” status of OSD packaging regarding leachables and highlight the necessity for interaction-focused, chemistry-based risk assessments, as outlined in emerging ICH Q3E guidelines. Full article

Peganum harmala L. is a xerophytic medicinal and aromatic plant of considerable ethnopharmacological importance, characterized by a rich diversity of β-carboline alkaloids, phenolic compounds, and essential oil constituents. Despite increasing scientific interest, current knowledge remains fragmented across phytochemistry, essential oils, extraction technologies, biological activities, and safety assessments. This review provides an integrated overview of the essential oil composition, extraction methods, analytical characterization, biological properties, toxicological considerations, and emerging applications of P. harmala. Particular emphasis is given to organ-specific chemical variability, geographical and environmental influences on volatile profiles, and the importance of standardized chemical characterization for reliable bioactivity evaluation. Conventional extraction methods, including hydrodistillation and steam distillation, are critically compared with emerging green technologies such as ultrasound-assisted, microwave-assisted, and supercritical CO₂ extraction. Advanced analytical tools, including GC-MS, LC-MS/MS, NMR, and chemometric approaches, are highlighted for comprehensive phytochemical profiling. Reported biological activities include antimicrobial, antifungal, antioxidant, anti-inflammatory, antidiabetic, anticancer, and agricultural effects, although their translation requires rigorous chemical standardization, mechanistic validation, and safety evaluation. Overall, this review emphasizes that the sustainable development of P. harmala should rely on quality-by-design strategies integrating botanical authentication, chemotyping, green extraction, and regulatory-oriented toxicological assessment. Full article

Background/Objectives: Female soccer players differ from males in body composition, muscular strength, and hormonal fluctuations, which may influence performance, fatigue, recovery, and injury risk. This study aimed to characterize the time course of urinary metabolic perturbation and its persistence during a 20-day winter training season (WTS) using urinary metabolomics. Methods: Urinary metabolites in female soccer players were analyzed before (Bef) and 1 (After_1D) and 7 days after completion (After_7D) of the 20-day WTS using nuclear magnetic resonance (NMR) spectroscopy combined with multivariate analysis. Results: A total of 84 metabolites were identified in urine samples, and distinct group separation was observed by partial least squares discriminant analysis (PLS-DA) in targeted profiling. Among these, 13 metabolites, including adenine, alanine, citrate, creatine, creatine phosphate (PCr), formate, glutamine, glycine, malonate, mannitol, taurine, trimethylamine N-oxide (TMAO), and urea, showed significant changes in the three groups (Bef, After_1D and After_7D). Conclusions: Of the identified metabolites, six metabolites—alanine, PCr, formate, glutamine, glycine, and malonate—were significantly increased at 1 day post-WTS (After_1D) compared with pre-WTS (Bef) levels. These metabolites were lower at 7 days post-WTS (After_7D) than at 1 day post-WTS (After_1D). However, the metabolic profile had not fully returned to pre-WTS levels by day 7, suggesting that recovery following WTS may require longer than at least 7 days after a 20-day WTS. Full article

To develop fungicidal candidates with both high antifungal activity and phloem mobility, a total of 34 2-[2-(trifluoromethoxy)phenyl]thiazole-4-carbonyl amino acid and amino acid ester conjugates were designed and synthesized. Their structures were characterized by ¹H NMR, ¹³C NMR, and HRMS. Their in vitro antifungal activities against five phytopathogenic fungi and their phloem and xylem mobility in castor bean seedlings were subsequently evaluated. The results showed that the amino acid conjugates 9a-9p generally exhibited higher antifungal activity than the corresponding amino acid ester conjugates. Compounds 9m and 9n showed good inhibitory activity against Rhizoctonia solani, Sclerotinia sclerotiorum, Phoma citricarpa, and Phytophthora parasitica. Notably, compounds 9f, 9g, 9l, and 9n showed strong inhibitory activity against P. citricarpa at 200 μmol/L, with inhibition rates of 82.82%, 89.86%, 80.45%, and 91.55%, respectively, all higher than that of thifluzamide (29.30%). Mobility assays revealed configuration-related differences in the conjugate-derived material detected in phloem and xylem exudates, with differential hydrolysis to compound 3 contributing substantially to the observed L/D profiles In addition, some L-amino acid conjugates were hydrolyzed in castor bean seedlings to release the unconjugated carboxylic acid precursor (compound 3). These results indicate that appropriate amino acid conjugation can enhance antifungal activity and modulate systemic mobility in plants, providing a basis for the structural design of systemic fungicides. Full article

Pometia pinnata J.R. Forst. & G. Forst. is traditionally used throughout tropical Asia and the Pacific to manage diabetes-associated hyperglycemia. However, the metabolites responsible for its α-glucosidase inhibitory activity (AGI) remain poorly characterized. This study aimed to identify putative AGI-associated metabolites from P. pinnata stem bark through metabolomics-based prioritization and tentative annotation using untargeted LC–HRMS, followed by molecular docking to assess their interactions with α-glucosidase. Thirty ethyl acetate–methanol gradient fractions were analyzed by orthogonal partial least squares (OPLS) to prioritize LC–HRMS features associated with AGI activity, followed by molecular docking of the tentatively annotated metabolites against Saccharomyces cerevisiae α-glucosidase (3A4A) and human maltase-glucoamylase (3TOP). The 75% ethyl acetate in methanol fraction showed the strongest AGI, with an IC₅₀ of 5.53 μg/mL. Five AGI-associated metabolites, namely scopoletin, 3,4-dihydroxybenzaldehyde, fisetin, 4-methoxycinnamic acid, and lindetannin, were tentatively annotated in P. pinnata stem bark based on LC-HRMS/MS data. To the best of our knowledge, these annotations have not previously been reported in P. pinnata stem bark. Among these candidates, fisetin showed the most favorable binding interactions with both target enzymes. Metabolomics-guided isolation, followed by NMR analysis, confirmed the structure of scopoletin, although the isolated compound showed weak AGI activity (IC₅₀ > 200 μg/mL). The marked difference between the parent fraction and isolated scopoletin indicates that scopoletin alone is unlikely to account for the observed activity and that other constituents may contribute. Nevertheless, this study provides a promising metabolomics-guided framework for prioritizing and tentatively annotating candidate AGI-associated metabolites in the stem bark of P. pinnata. Full article

Amanita muscaria contains two structurally related neuroactive isoxazole metabolites, ibotenic acid (IA) and muscimol (MUS), which differ markedly in pharmacological activity. IA acts as an agonist at NMDA and metabotropic glutamate receptors, whereas MUS is a potent GABAergic agonist. This review critically evaluates their chemistry and biosynthesis, biological variability, post-harvest transformation, analytical determination, and toxicological significance. Direct evidence demonstrates interspecific variation within Amanita section Amanita. Developmental evidence for A. muscaria is limited but direct: an older maturation study identified tissue-dependent changes in IA and MUS, while concentrations calculated for the whole fruiting body remained comparatively stable; observations in A. subglobosa provide additional species-specific evidence. Controlled studies also demonstrate processing-related changes during drying and heating, whereas storage effects remain condition-dependent and less completely characterized. Cross-study comparison is constrained by differences in species identification, tissue selection, developmental stage, hydration, sample handling, normalization, and analytical procedure. Quantitative study-level comparison shows that LC–MS/MS and UHPLC–MS/MS, capillary electrophoresis, GC–MS, NMR, and rapid ambient-MS approaches serve different matrices and analytical purposes. Their reported sensitivity, recovery, precision, and calibration performance cannot be ranked directly across studies, and matrix-specific validation remains essential. Broader fungal research provides mechanistic context for possible environmental regulation, but direct controlled evidence for stress-dependent IA biosynthesis in A. muscaria remains sparse. The IA/MUS ratio is best treated as a secondary chemical descriptor alongside absolute concentrations and a clearly defined normalization basis. Toxicological interpretation additionally requires consideration of total dose, preparation, matrix composition, and individual susceptibility. Full article

Shale reservoirs are characterized by high tightness and strong heterogeneity; determining the lower limit of movable pore throats is a core scientific issue for reservoir evaluation and development optimization. Targeting shale in the Jiyang Depression, Bohai Bay Basin, this study employed mercury injection capillary pressure (MICP), nuclear magnetic resonance (NMR) combined with centrifugal experiments, and simulated elastic depressurization production tests to investigate the pore throat structure and fluid mobility of three types of dominant lithofacies. The dominant lithofacies in the study area are laminated cryptocrystalline argillaceous limestone, bedded cryptocrystalline argillaceous limestone, and laminated cryptocrystalline calcareous mudstone, with significant differences in mineral composition among the three lithofacies. Laminated cryptocrystalline calcareous mudstone exhibits the smallest average pore throat radius, yet possesses optimal pore throat connectivity and fluid mobilization capability, with uniform pore throat distribution concentrated in the small pore-size range. The two argillaceous limestone lithofacies develop multi-modal pore systems. Elastic depletion production simulation indicates that the lower limit of movable pore throats for the bedded cryptocrystalline argillaceous limestone lithofacies is 34.6 nm under the tested depletion conditions, demonstrating that stress sensitivity can elevate the actual lower limit of movable pore throats by approximately one order of magnitude; this threshold is lithofacies- and condition-specific and requires validation before generalization. The lower limits of movable pore throats for different lithofacies follow the order: bedded cryptocrystalline argillaceous limestone > laminated cryptocrystalline argillaceous limestone > laminated cryptocrystalline calcareous mudstone. Full article

This study investigated how high-temperature reactive atmospheres associated with underground coal gasification (UCG) differentially modify the pore system of roof sandstone. Roof sandstone from the Shanghai Miao mining area, Inner Mongolia, was conditioned to simulate formation-water saturation and heat-treated at 200 °C, 400 °C, 600 °C, and 800 °C under O₂ or CO₂ atmospheres. Low-field nuclear magnetic resonance (LF-NMR) T₂ spectra, pore-size classification, multifractal analysis, and X-ray diffraction (XRD) were combined to characterize pore-structure evolution. Thermal treatment shifted the pore composition from mesopore-dominated to micropore- and small-pore-dominated. Under O₂, NMR porosity increased continuously from 8.41% to 13.94%; the small-pore fraction increased with temperature, and the dominant T₂ components expanded into adjacent pore-size domains. Under CO₂, porosity peaked at 11.25% at 600 °C and decreased to 9.36% at 800 °C; micropores remained dominant, while medium and long T₂ components contracted markedly at high temperature. The normalized T₂ probability measures exhibited typical multifractal behavior under all treatment conditions. Under O₂, the singularity-spectrum width Δα ranged from 1.464 to 2.803 and H from 0.947 to 0.958, showing greater variability than under CO₂ (Δα = 1.627 − 1.776; H = 0.947 − 0.950). Porosity was strongly correlated with positive-order multifractal parameters and D₂ (r = 0.82 − 0.90), indicating that pore-volume expansion can be decoupled from the evolution of cross-scale heterogeneity. XRD showed that the raw sandstone was composed mainly of quartz (62.8%) and kaolinite (29.3%). Kaolinite and siderite diffraction peaks were not detected in representative samples treated at 600–800 °C, and the relative proportions of quartz and feldspar phases were reconfigured, providing mineralogical constraints on pore evolution. Two distinct thermal-damage pathways were identified: continuous pore accumulation with scale expansion under O₂ and medium-temperature pore expansion, followed by high-temperature reorganization under CO₂. These findings provide a quantitative basis for structural-state identification and risk zoning of UCG roof strata. Full article

Background: Sarcopenia is an aging-related syndrome characterized by loss of skeletal muscle mass, strength, and function, with no approved pharmacological treatment. This study aimed to design, synthesize, and evaluate novel ML-167 derivatives for sarcopenia-associated muscle wasting. Methods: ML-167 derivatives were synthesized and characterized by ¹H NMR, ¹³C NMR, and mass spectrometry. Biological activity was evaluated in C2C12 myoblasts using MTT and Western blot assays. Selected compounds were evaluated in a dexamethasone-induced muscle wasting model. Muscle strength, mass, biochemical parameters, and histopathology were assessed. Structure–activity relationships were analysed using cell viability, molecular docking, and ligand efficiency data, alongside physicochemical properties. Results: Compounds 6b (116%), 3a (115%), 8d (114%), 4c (112%), 3m (112%), and 3c (111%) showed the highest C2C12 viability at 1 μM. Compounds 3a, 3c, and 6b increased MyH3 expression by approximately 1.6–1.7-fold, while MyoG remained near basal levels. In vivo, these compounds improved muscle strength, mass, and biochemical parameters without overt hepatic or renal abnormalities based on assessed serum and histopathological findings. Among the evaluated derivatives, compound 6b emerged as the most promising overall lead candidate, showing the greatest improvement in skeletal muscle mass and metabolic parameters, whereas compound 3c demonstrated the strongest histopathological protection and favourable effects on muscle strength with favourable physicochemical properties. Molecular docking supported the SAR trends, although did not consistently correlate with cellular activity. Conclusions: The findings identify 3a, 3c, and 6b as promising lead compounds and support further investigation of ML-167 derivatives as potential pharmacological approaches for sarcopenia-associated muscle wasting. Full article

This study evaluated the anti-biofilm activity of the lipopeptide of Streptomyces lavendulae subsp. lavendulae 214 and aminoglycolipid biosurfactant of Streptomyces griseoflavus 2265 strains against biofilm formation by Xanthomonas strains. The biosurfactants of Streptomyces griseoflavus 2265 and Streptomyces lavendulae subsp. lavendulae 214 at a minimal concentration of 40 mg/L, characterized by antibiofilm activity against the development of Xanthomonas arboricola pv. juglandis 2417 strain and its mutant strains. The structure of the isolated biosurfactant was identified using Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR). The mutations in the rpfA gene of Xanthomonas arboricola pv. juglandis 8636 strain and deletions in the rpfGC genetic segment of Xanthomonas arboricola pv. juglandis 8737 strain did not ensure resistance to the effects of antimicrobial agents secreted by actinomycetes strains during the study. The concentration of aminoglycolipid biosurfactant of Streptomyces griseoflavus 2265 strain up to 20 mg/L and lipopeptide biosurfactant of Streptomyces lavendulae subsp. lavendulae 214 strain up to 10 mg/L stimulated cell motility in Xanthomonas arboricola pv. juglandis strains, while the increase in their value was accompanied by its inhibition, which was not affected by mutations in the rpfA gene of Xanthomonas arboricola pv. juglandis 8636 strain and deletions in the rpfGC genetic segment of Xanthomonas arboricola pv. juglandis 8737. These results may provide fundamental information for understanding the antagonistic effect of biological surfactants from soil microorganisms, which are dominated by actinomycetes, on the development and spread of Xanthomonas arboricola pv. juglandis strains of different genotypes on agricultural crops. Full article