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Controlling ion-specific interactions in organic mixed ionic-electronic conductors (OMIECs) remains a major challenge for high-gain electrochemical sensors, particularly in aqueous environments where detection of emerging contaminants such as perchlorate (ClO4 -) is limited by ion hydration dynamics and sluggish volumetric electrochemical doping. Herein, we report a membrane-free organic electrochemical transistor (OECT) platform based on a fully methoxylated diketopyrrolopyrrole (DPP)-based amphiphilic copolymer. Backbone methoxylation promotes preferential volumetric electrochemical doping by perchlorate ions, enabling efficient bulk polaron stabilization. Consequently, the fully methoxylated polymer exhibits a five-fold increase in volumetric charge (QV = 32 C cm- 3) and a four-fold enhancement in doping level (y = 0.38) relative to its non-methoxylated analogue. Integrated into OECTs, the material delivers a 300-fold improvement in detectivity, achieving detection limits of 22 ± 1 ppb in pristine electrolyte and 37 ± 2 ppb in a mixed-ion background containing 5 mM each of F-, Cl-, NO3 -, SO4 2-, and ClO3 -. Mixed-interference studies demonstrate ∼12-fold selectivity for perchlorate with 83% signal recovery, while control experiments and impedance spectroscopy reveal an auxiliary glycol effect, in which backbone methoxylation and glycol side chains cooperatively facilitate efficient bulk doping. These findings establish backbone functionalization as an effective strategy for realizing selective, membrane-free OMIEC-based chemical sensors.
As the most prospective cathode material for sodium-ion batteries (SIBs), layered oxides persistently suffer from detrimental phase transitions, irreversible oxygen loss, and severe interfacial degradation during cycling. Herein, utilizing O3-NaNi1/3Fe1/3Mn1/3O2 cathode as prototype, we propose an integrated modification strategy beyond conventional chemical modulation to simultaneously boost the bulk, surface and interfacial properties. The Y-enriched NaYO2 (NYO) coating derived via surface reconstruction facilitates site-selective bulk substitution whilst inducing suitably quantized local oxygen vacancy (OV) defects through charge balancing. The synergistic interaction between Y─O─TM strong bond and the OV's charge-buffering effect jointly modulates O 2p orbital electronic band configuration, preventing excessive O oxidation and formation of O─O dimers arising from charge concentration. Moreover, the perovskite-phase NYO surface serves as an inherent fast Na+ conductor ensuring efficient ion transport at interface, whilst also providing a robust rigid mechanical barrier that effectively suppresses interfacial side reactions and dissolution of transition metals. As a result, anion redox reversibility and local chemical environment stability are elevated, thereby comprehensively boosting electrochemical reaction kinetics and charge transfer efficiency, as confirmed by theoretical calculations and advanced synchrotron characterization. This research establishes a novel paradigm for the advancement of high-performance Na-layered oxide cathodes incorporating synergistic multi-mechanism modification.
This study investigated the chemical composition, safety profile, and pharmacological activities of a decocted extract from the aerial parts of Mentha aquatica (MA-DE). High-performance liquid chromatography with diode-array detection (HPLC-DAD) identified several phenolic constituents, mainly hydroxycinnamic and hydroxybenzoic acids. Safety was evaluated through acute and subacute toxicity studies in albino mice. Acute toxicity testing involved oral and intraperitoneal administration of MA-DE at doses up to 8 g/kg body weight (BW). Oral administration produced no mortality or observable toxic effects, whereas intraperitoneal administration induced dose-dependent toxicity, with an LD50 of 5.975 g/kg BW; the NOAEL and LOAEL were determined as 0.5 and 1 g/kg BW, respectively. In the subacute study, mice received daily oral doses of 0.1, 0.5, or 1 g/kg BW for 28 days, with no significant changes observed in hematological, biochemical, or histopathological parameters compared with controls. The anti-inflammatory activity of MA-DE was assessed using the carrageenan-induced paw edema model in Wistar rats, while analgesic activity was evaluated using the writhing test. MA-DE exhibited significant, dose-dependent anti-inflammatory and analgesic effects at 200 and 400 mg/kg BW. Overall, MA-DE appears safe when administered orally and demonstrates promising pharmacological properties, supporting its traditional use and potential phytotherapeutic application.
Planting altitude is a critical environmental factor shaping the flavor quality of Coffea arabica. However, how altitude influences flavor through microbial dynamics and chemical transformations during wet processing remains poorly understood. This study systematically investigates microbial diversity during wet processing and the corresponding changes in non-volatile and volatile compounds in coffee beans from four elevations: 1000 m (A1), 1200 m (A2), 1400 m (A3), and 1600 m (A4). The results showed that fermentation significantly altered the dominant bacterial genera from Sphingomonas and Pleomorphomonas (before fermentation) to Weissella and Lactobacillus (after fermentation), while Cladosporium and Fusarium remained the dominant fungal genera. Notably, non-volatile compounds in de-pulping coffee beans and volatile compounds of roasted coffee beans showed significant differences. Among them, 57 (1000 m), 218 (1200 m), 133 (1400 m), and 173 (1600 m) differentially changed non-volatile compounds (DCn-VCs) belonging to lipids and lipid-like molecules, organic acids and derivatives, organoheterocyclic compounds, organic oxygen, phenylpropanoids and polyketides, benzenoids, and other classes were identified. The cupping score of roasted coffee beans increased with increasing planting altitude, and A4 exhibited a long-lasting aftertaste, mellow and full body with high sweetness, nutty, and flowery with 42 (A4 vs. A1), 27 (A4 vs. A2), and 26 (A4 vs. A3) volatile compounds showing significant variation across altitudes. Therefore, planting altitude significantly influences coffee flavor by reshaping microbial diversity and chemical composition during wet processing. High-altitude cultivation promotes desirable sensory characteristics, highlighting its potential for producing specialty-grade coffee.
We report a quantum chemical theoretical study on the structural, electronic, and chemical bonding properties of Ge3C3 -/0 and Ge3C4 -/0 clusters. We find that Ge3C3 - and Ge3C4 - contain one CCC and one CCCC unit, with one C terminal bonding with a Ge atom and another C terminal interacting with two additional Ge atoms forming a Ge2C three-membered ring, respectively. Ge3C3 has a GeC3 trigonal pyramidal and two Ge2C2 tetrahedral units. Ge3C4 possesses a hexagonal pyramidal structure containing a Ge2C4 six-membered ring. The vertical detachment energies (VDEs) are predicted to be 2.10 eV for Ge3C3 - and 2.40 eV for Ge3C4 - at the CCSD-(T) level, and the theoretical photoelectron spectra are simulated. Adaptive natural density partitioning (AdNDP) analyses indicate that the top C atom of the CCC unit in Ge3C3 - bonds with a Ge atom via a Ge-C σ bond, while another C terminal interacts with two Ge atoms via a 3c-2e σ bond, and there are two 6c-2e π bonds and one 6c-1e π bond delocalizing all atoms. The CCCC unit in Ge3C4 - bonds with the top Ge atom forming a Ge-C σ bond, two 5c-2e π bonds, and one 5c-1e π bond, with another two Ge atoms resulting in one Ge-C σ bond and one 3c-2e π bond.
To validate moderate chemical aggregation of flame-retardant groups as an effective strategy for obtaining advanced flame-retardant molecules, moderate-aggregated linear oligomer B-PDHQ (trimer-dominant) and high-aggregated crosslinked macromolecule C-PDHQ were synthesized via the polymerization between the 10-(2,5-Dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) monomer and formaldehyde. By propagating linear polymerization aggregation of phenolated phosphaphenanthrene (PDOPO) groups, the moderate-aggregated B-PDHQ exhibits outstanding superiority in combustibility suppression efficiency and toughness enhancement effectiveness of epoxy thermoset (EP), compared with the highly aggregated C-PDHQ and non-aggregated monomer DOPO-HQ. Especially, 3%B-PDHQ/EP passed UL94 V-0 rating, 3%DOPO-HQ/EP only passed UL94 V-2 rating, while 3%C-PDHQ/EP failed to pass any rating of UL94 vertical burning test. Furthermore, moderate-aggregated B-PDHQ also showed leading efficiency in the limited oxygen index, combustion heat inhibition, smoke emission reduction, and char formation enhancement of EP. The behavior of linear oligomer B-PDHQ that triggers the flame-retardant groups aggregation effect was revealed from the condensed-phased char-forming behavior, char layer morphology investigation, and the gas-phased thermal decomposition volatile tracing. In addition, the moderate polymerization aggregation of PDOPO groups in linear oligomer B-PDHQ still enable EP matrix with a higher glass transition temperature and impact toughness. The superiority of moderate-aggregated B-PDHQ provides a practical and efficient route for designing and manufacturing high-performance reactive flame-retardant molecules.
Protein kinase A (PKA) is a key cellular signaling enzyme that transfers phosphate groups from adenosine triphosphate (ATP) to serine or threonine residues to regulate activity and downstream processes. This work presents a highly sensitive and selective electrochemical biosensor for PKA activity detection. Peptide and DNA are self-assembled on Au nanoparticles (Au NPs) via AuS bonds to form DNA-Au NPs-peptide complexes. The peptide is phosphorylated in the presence of PKA. Moreover, zirconium-metal organic framework (Zr-MOF) acts as an electrode substrate to facilitate charge transfer and molecular capture. Critically, phosphorylation allows complex immobilization on the electrode through ZrOP bonds between phosphorylated peptide and Zr-MOF. [Ru(NH3)6]3+ is electrostatically bound to DNA as an electroactive species for signal amplification. PKA activity regulates the amount of immobilized DNA, which determines the loading amount of [Ru(NH3)6]3+, and quantitative analysis is achieved by monitoring signal changes. The response signal of the biosensor exhibits a linear relationship with the logarithm of PKA concentration in the range of 0.05 to 100 U mL-1, and the limit of detection is 0.016 U mL-1. This biosensor can discriminate PKA from interferents, and allow inhibitor screening and cellular sample detection, providing a promising approach for PKA determination and inhibitor research.
Machine learning accelerates molecular discovery and relies heavily on standardised benchmark datasets to evaluate computational performance. To learn transferable structure-activity relationships (SARs), models must be trained on datasets that accurately reflect chemical and biological realities without introducing artificial redundancies. Although standardised benchmarks are ubiquitous, the integrity of their underlying data is often assumed rather than rigorously verified. Currently, there is a lack of systematic and quantitative assessments of hidden data leakage and structural inconsistencies across widely used biomolecular benchmarks. Here, we demonstrate that several prominent chemical and biochemical benchmarking suites have pervasive cross-split contamination, unresolved label conflicts, and severe structural redundancies. By auditing over fifty dataset configurations, we reveal that tasks previously considered robust evaluation environments often have hidden flaws, particularly in drug-target interaction datasets with extensive protein overlap. Controlled noise-injection experiments show that these artefacts can systematically bias benchmark metrics. A complementary counterfactual leaderboard analysis further shows that leading-model conclusions can change when the audited composition of the test set is altered, particularly when label conflicts are enriched. These findings suggest that many leaderboard and leading-model conclusions should be interpreted in light of benchmark composition and data quality, rather than as automatic evidence of robust methodological superiority. Our findings highlight the importance of auditing evaluations, reporting chemically meaningful test-set composition, and using leakage-resistant data splits to accurately measure model generalisability. Moving from uncritical leaderboard optimisation to rigorous dataset auditing will yield more reliable computational tools. Ultimately, this will ensure that artificial intelligence models can be reliably translated into real-world applications in therapeutic design.
Ozonated water is increasingly being explored as a gentler alternative to chlorhexidine for chemical plaque control because of its antimicrobial and anti-inflammatory properties and the absence of common side effects such as staining or altered taste. However, the evidence on its effectiveness-especially in healthy individuals-remains unclear. This systematic review and meta-analysis aimed to determine whether ozonated water is more effective than placebo or chlorhexidine mouthwash in reducing dental plaque. An extensive literature search was carried out across PubMed, Cochrane Library, Scopus, Web of Science, LILACS, ScienceDirect, EBSCOhost, and Google Scholar up to August 5, 2025. Randomized controlled trials involving healthy participants and comparing ozonated water with placebo or chlorhexidine were included. In total, five studies were selected for qualitative synthesis, of which four were included in the meta-analysis. Risk of bias was assessed using the RoB 2 tool, and the certainty of evidence was evaluated using the GRADE approach. A random-effects model was applied to calculate standardized mean differences (SMDs) with 95% confidence intervals. The meta-analysis suggested that ozonated water may provide slightly better short-term plaque reduction than placebo or chlorhexidine (SMD = -1.35; 95% CI: -2.77 to 0.06). However, as the confidence interval crossed the line of no effect, this difference was not statistically significant. Risk of bias was high in one study, unclear in three studies, and low in one study. The overall certainty for plaque reduction was rated as "low". While ozonated water appears to be a promising short-term option for plaque control-especially for individuals unable to tolerate chlorhexidine-the current evidence is not strong enough to confirm that it works better than standard rinses or even plain water. Well-designed, longer-term clinical trials are needed before ozonated water can be recommended for routine daily use.
Superparamagnetic iron oxide nanoparticles (SPIONs-Fe3O4) functionalized with l-cysteine (SPIONs-l-Cys) were evaluated as a biocompatible, magnetically responsive nanosystem in an Ehrlich solid tumor model. The formulation was obtained by chemical coprecipitation, and its complementary physicochemical characterization is provided in the Supporting Information and supported by our previous report on the same l-cysteine-functionalized magnetite system, including X-ray diffraction, FTIR, hydrodynamic size, polydispersity index, ζ-potential, surface thiol quantification by DTNB, magnetic measurements, and complementary in vitro data. The supplementary characterization supports the preservation of the magnetite crystalline structure after functionalization and confirms the presence of free thiol groups in an aqueous dispersion. In vitro cytotoxicity assays using human mononuclear cells and Ehrlich tumor cells indicated low toxicity under selected experimental conditions and biologically relevant redox-associated activities. In vivo evaluation demonstrated preserved hematological and biochemical parameters, the absence of overt systemic toxicity, and reduced tumor burden in groups treated with SPIONs-l-Cys under magnetic targeting conditions. These findings support the biological compatibility of SPIONs-l-Cys and indicate antitumor-associated effects under localized magnetic field conditions, while not establishing intratumoral accumulation, drug delivery, or a definitive mechanism of action.
To systematically evaluate the biomechanical, optical, and clinical outcomes of crosslinking (CXL) applied to corneal stromal lenticules derived from keratorefractive lenticular extraction, and to assess the rationale and efficacy of this approach for therapeutic re-implantation in corneal disease. A systematic review with exploratory pooled analysis was conducted following PRISMA and MOOSE guidelines. Literature searches across five databases identified studies reporting outcomes following crosslinking of SMILE-derived lenticules. Risk of bias was assessed using appropriate tools for study design. Random-effects pooled analyses were performed for clinical outcomes where appropriate, with careful consideration of study heterogeneity. Nine studies met inclusion criteria (5 in vitro, 4 clinical). In vitro studies consistently demonstrated that both ultraviolet A (UVA)-riboflavin and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) chemical CXL enhanced lenticule stiffness, enzymatic resistance, and transparency, with chemical CXL showing superior mechanical performance. Because of the limited sample size and substantial between-study heterogeneity, pooled estimates should be interpreted as exploratory and hypothesis-generating rather than definitive evidence. Clinical data from 26 eyes across three heterogeneous studies showed variable outcomes. Maximum keratometry showed a non-significant trend toward improvement (random-effects weighted mean difference: -2.94 D; 95% CI: -6.24 to 0.35 D; P = 0.08), though this finding was limited by substantial heterogeneity (I² = 87.7%). No serious complications were reported in the limited follow-up periods available. In vitro experimental studies consistently demonstrate that crosslinking enhances the structural resilience and therapeutic potential of SMILE-derived lenticules. Chemical CXL, particularly EDC/NHS protocols, provides superior biomechanical reinforcement while preserving transparency in experimental settings. Preliminary clinical data suggest possible benefit in selected advanced keratoconus cases. However, current evidence remains insufficient to establish efficacy. Controlled trials are warranted to standardize protocols and validate long-term safety and efficacy.
The pervasive accumulation of micro(nano)plastics (MNPs) in the environment establishes them as persistent contaminants, posing a significant threat to ecosystem integrity and human health. This review synthesizes the environmental journey of MNPs by framing them as dynamic colloidal particles and mechanistically tracing their pathway from source to biological uptake. We discuss fundamental interfacial processes, including DLVO and non-DLVO interactions, straining, and air-water interface capture, governing MNP mobility and retention in porous media. These processes control MNP dispersal and potential to contaminate groundwater and agricultural systems. The interplay of colloidal properties (size, shape, surface chemistry) with environmental parameters is examined to explain exposure routes. We also detail how this colloidal behavior dictates bioavailability, facilitating MNP uptake in plants and soil fauna and amplifying their role as vectors for co-contaminants and antibiotic resistance genes. Human biomonitoring studies reveal MNPs in blood, stool, placenta, and bronchoalveolar lavage fluid. Systematic review evidence indicates associations with cardiovascular inflammation, endothelial dysfunction, and fibrosis; in vitro studies demonstrate PS MP-induced reductions in human sperm motility, vitality, and fertility-related gene expression; and cross-sectional studies link higher fecal MNP concentrations to gut microbiota dysbiosis, including increased abundance of harmful bacteria and decreased beneficial taxa. However, causation remains unestablished due to methodological heterogeneity and the predominance of cross-sectional designs. By integrating colloid science with ecotoxicology and exposure science, this review bridges the gap between MNP physical transport and adverse health outcomes, provides a framework for risk assessment, and highlights urgent research priorities, including standardized methods, longitudinal studies, and human-relevant models.
Polymer composites are the result of reinforcing a polymeric matrix with other materials. For example, the reinforcement of polyurethanes (PU) with natural fibers is a popular combination because of the great chemical compatibility between the two materials. This work investigates the production of composites using a polyurethane matrix synthesized from macaúba kernel oil and glycerol, reinforced with beech, fir, and carvoeiro. A thermal treatment was applied to the wood reinforcements, and the impact of the thermal treatment on chemical, thermal, and water sorption properties was extensively investigated. The composites prepared exhibited negligible differences in Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) when compared to the starting PU, showing that the addition of both thermally treated and untreated wood resulted in similar products, with comparable functional groups and thermal stabilities. However, the addition of 2 wt % of thermally treated wood drastically influences the water sorption properties and maximum water uptake under DVS, reaching values several times higher than the unreinforced samples.
The comprehensive quality control of chiral pharmaceuticals like mitiglinide necessitates simultaneous assessment of chemical impurities and enantiomeric purity, yet conventional workflows address these separately, leading to inefficiency. This study develops a comprehensive analytical strategy to overcome this challenge for the anti-diabetic drug mitiglinide. For chiral analysis, an online heart-cutting two-dimensional liquid chromatography-high-resolution mass spectrometry (2D-LC-HRMS) method was developed. First, impurity profiling of mitiglinide was accomplished using a one-dimensional reversed-phase LC-HRMS (1D-LC-HRMS) method. Subsequently, the 2D-LC-HRMS system achieved enantiomer separation by online coupling of a C18 column (first dimension) with a polysaccharide-based chiral column (second dimension), with the separated analytes detected by an Orbitrap mass spectrometer. 1D-LC-HRMS identified five major impurities, structurally characterizing four, with the main component accounting for only 49.12% of the total integrated peak area (relative abundance by EIC peak area normalization, not absolute purity). The 2D-LC-HRMS method achieved effective enantiomer separation. A consistent third minor chromatographic peak was observed across six replicate analyses, which is tentatively assigned as a potential diastereomeric impurity based on stereochemical interpretation of the chromatographic behavior; confirmatory evidence is required for definitive identification. This work successfully establishes a comprehensive strategy that efficiently consolidates impurity profiling and chiral purity assessment for mitiglinide. It provides a reliable, more informative approach for the quality control of complex chiral pharmaceuticals.
Type 2 diabetes mellitus (T2DM) is a complex metabolic disorder requiring multi-target therapeutic strategies. Traditional Chinese medicine offers potential multi-component interventions, yet the material basis and molecular mechanisms of novel formulations often remain incompletely defined. This study developed an integrated formula (FSV) combining a modified Baihu Jia Renshen Decoction with Sanghuangporus vaninii extract and explored its anti-hyperglycemic potential using chemical profiling, network pharmacology, in vitro α-glucosidase inhibition, and an STZ/HSHFD-induced hyperglycemic mouse model. A total of 2,413 database-matched features were annotated, most of which should be regarded as putative rather than standard-confirmed identifications. Mangiferin and several flavonoids were retained as plant/fungus-compatible candidate constituents, whereas implausible xenobiotic matches were excluded from biological interpretation. Network pharmacology predicted the involvement of inflammation- and insulin-resistance-related targets, including TNF, AKT1, IL6, NFKB1, and MAPK3 (also known as ERK1), whereas ALB was treated as a high-connectivity carrier protein rather than a direct druggable mediator. FSV inhibited α-glucosidase in vitro and was associated with improvements in hyperglycemia, insulin-sensitivity indices, dyslipidemia, and tissue morphology in the mouse model. These phenotypic findings are presented as experimental support accompanying the pathway predictions, while direct pathway validation is left for future mechanistic studies. Overall, the results provide a preliminary basis for further chemical validation and mechanistic investigation of FSV in diabetes-related metabolic dysfunction.
Deep‑subwavelength confinement and strong coupling at visible frequencies are central to scalable nanophotonic and quantum technologies. While transition metal dichalcogenides are promising candidates for such confinement, achieving tunable strong coupling often relies on patterned plasmonic nanostructures or chemical modification of the excitonic material. Furthermore, in metal-coupled systems, the distinct role of metallic mirror-induced electromagnetic confinement is often experimentally obscured by exciton-plasmon energy hybridization. Here we introduce a vdW-integrated, chemically non-invasive WS2/h-BN/Au heterostructure in which the h-BN spacer forms a controllable nanogap that tunes image-charge confinement while preserving the excitonic material. Scattering‑type near‑field microscopy directly maps propagating interference fringes and reveals a collapse of the TM‑polariton wavelength to ∼172 nm under 633‑nm excitation as the spacer is reduced to 5 nm (λ0/λp≈3.7, corresponding to ∼71% wavelength reduction), which is one of the highest degrees of optical confinement reported for room-temperature TMDC polaritons. Full‑wave simulations and transfer‑matrix analysis, aided by boundary‑condition engineering from an ideal conductor to real Au, separate a purely geometric mirror mode from plasmon‑assisted hybridization. This platform establishes a deterministic route to deeply subwavelength field control, offering a scalable architecture for nonlinear optical enhancement and integrated quantum devices.
Domoic acid (DA)-producing Pseudo-nitzschia and the heterotrophic dinoflagellate Noctiluca scintillans frequently co-occur during coastal harmful algal blooms, yet their interactions and consequences for toxin cycling remain poorly understood. Here, controlled co-cultures were conducted to examine grazer-induced defense, grazing dynamics, and DA accumulation-depuration. Sustained 3-d exposure stimulated a 3-4-fold increase in cellular DA production, without detectable changes in cell size or frustule silicification, indicating a primarily chemical defense response. Cellular DA induction exceeded dissolved-pool enhancement during sustained co-culture. Conversely, short-term 24-h exposure increased dissolved DA concentrations by 1.73-fold relative to grazer-free controls, whereas cellular DA was not significantly induced. Mass-balance calculations revealed that grazer excretion accounted for only 15.4% of this dissolved surplus, indicating grazer-induced extracellular DA release by P. fukuyoi. These patterns suggest a potential shift from early extracellular chemical deterrence to sustained intracellular toxin-based defense. N. scintillans ingested all prey strains, but prey toxicity suppressed ingestion rates and drove negative grazer growth via post-ingestive toxin accumulation. Feeding on P. fukuyoi generated high cellular DA burdens in the grazer, with an apparent accumulation efficiency ∼300%, but depuration was rapid, removing ∼90% of accumulated DA within 6 h. This rapid clearance resulted in a low trophic transfer efficiency (3.69%), with only 12.52% released as dissolved DA, while most parent toxin became undetectable, suggesting internal transformation or degradation. These findings characterize N. scintillans as a transient DA reservoir and active toxin recycler that substantially modifies DA partitioning and dampens its upward trophic transfer potential in marine food webs.
Gravimetric quantification of atmospheric particulate matter (PM) can be biased by particle-bound water persisting after filter conditioning, with magnitude depending on chemical composition, mixing state, and the protocol's operational definition of "water." Here, particle-bound water was measured by Karl Fischer (KF) coulometric titration with stepwise heating to distinguish weakly adsorbed from strongly retained fractions. Thirty-five single-component chemicals and certified reference materials were analyzed at two loadings (0.6 and 2.0 mg; summer and winter loads), alongside a powder mixture imitating PM (artificial PM, aPM), examined as sequential-addition and bulk systems of relevant composition. Bulk KF measurements showed class-dependent differences: deliquescent inorganic salts retained most water, whereas most metals, metal oxides, PAHs, and graphitic carbons approached background. Water-to-solute molar ratios (W/S) enabled cross-compound comparison and scaled non-linearly with loading-absolute water rose with mass, but W/S fell, consistent with reduced vapor accessibility in compacted powders. Clustering of temperature-resolved release signatures resolved three material groups differing chiefly in strongly bound (250 °C) water. Sequential aPM experiments showed secondary inorganic species dominate retained water; bulk aPM release profiles matched ambient PM₁ filters. PM-bound water releases across a continuum of thermal fractions, governed by composition, modulated by loading-informing mitigation of humidity-related gravimetric uncertainty.
Bangladesh's fisheries sector, central to national nutrition, food security, and rural livelihoods, is increasingly threatened by the convergence of zoonotic pathogens, antimicrobial resistance (AMR), and environmental degradation. Using a One Health framework, this review synthesizes evidence from 87 peer-reviewed articles, institutional reports, and regional studies to demonstrate how interactions among aquatic ecosystems, farmed and wild fish populations, and human communities drive the emergence and transmission of disease. Zoonotic parasites including trematodes, cestodes, nematodes, and protozoa persist through contaminated water, inadequate market hygiene, and exposure to domestic and wild animals. Aquaculture systems are further burdened by zoonotic bacteria (e.g., Vibrio spp., Aeromonas spp., and Mycobacterium spp.) and microsporidian parasites (e.g., Enterocytozoon spp.), together posing significant occupational and foodborne risks. Emerging fungal pathogens, notably Saprolegnia spp. and Aphanomyces invadans, intensify disease burdens under poor farm management and environmentally stressed conditions. Critical contamination pathways, industrial and agricultural runoff, cross-contamination in fish markets, unregulated chemical use, and weak biosecurity link aquatic pollution with human and animal health outcomes. The introduction of non-native fish species (e.g., tilapia, pangas, carp) and the expanding ornamental fish trade further amplify pathogen risks, facilitating the silent spread of bacterial, parasitic, and fungal agents with zoonotic potential. Climate change, biodiversity loss, and socioeconomic vulnerabilities exacerbate these pressures by destabilizing aquatic ecosystems, reducing resilience, and accelerating AMR dissemination across aquatic, human, and livestock interfaces. By integrating insights from parasitology, microbiology, epidemiology, and environmental science, this review underscores the urgent need for coordinated surveillance, diagnostic capacity, regulatory enforcement, and risk communication strategies. Embedding One Health and climate-smart approaches into fisheries governance is essential to mitigate zoonotic hazards, safeguard food safety, and ensure the long-term sustainability of Bangladesh's aquaculture sector under accelerating environmental change.
Centella asiatica contains pharmacologically important pentacyclic triterpenes that are commonly used as chemical markers for quality evaluation of herbal preparations. However, accurate quantification remains challenging because some analytes are structurally related and chromatographically difficult to resolve. In this study, a validated high-performance liquid chromatography (HPLC) method was developed for the simultaneous separation and quantification of six major triterpenes in C. asiatica products, namely, asiaticoside B (ASB), madecassoside (MS), asiaticoside (AS), terminolic acid (TA), madecassic acid (MA), and asiatic acid (AA). Because β-cyclodextrin (β-CD) is inexpensive, it was thus selected as a mobile-phase modifier to improve discrimination of closely related triterpene isomers. Baseline separation of the two critical isomeric pairs, ASB/MS and TA/MA, was achieved within 15 min with a total chromatographic run time of 25 min on an ACE Excel C18 column (5 μm, 4.6 × 250 mm) using gradient elution with acetonitrile and 0.2% (v/v) phosphoric acid containing β-CD. Unlike previous CD-assisted HPLC methods that focused on the separation of five triterpenes or selected isomeric pairs, the present method enables, for the first time, simultaneous identification and quantification of six triterpenes, including both ASB/MS and TA/MA isomeric pairs. The method was fully validated according to ICH, Eurachem, and AOAC guidelines. The method showed good linearity, acceptable limits of detection and quantification, satisfactory repeatability and intermediate precision, suitable recovery, and good selectivity. The validated method was successfully applied to commercial C. asiatica products, demonstrating its suitability for routine quality control and phytochemical assessment of herbal raw materials and preparations. Analytical greenness assessment using the Analytical GREEnness (AGREE) metric gave a score of 0.50, indicating a moderate greenness profile, while holistic assessment using the Mosaic-White Analytical Chemistry (WAC) tool gave a Whiteness Index of 68.6, suggesting satisfactory overall method quality based on analytical reliability, environmental impact, and practical applicability. This method provides a practical and reliable approach for the simultaneous determination of six triterpenes in C. asiatica matrices.