摘要:Current ecological risk assessments of microplastics predominantly use spherical particles as models,paying insufficient attention to ubiquitous non-spherical microplastics,such as fibers. This oversight may lead to an underestimation of their migration and accumulation risks in benthic environments. This study employed rare-earth upconversion nanoparticles(UCNPs) tracer technology,combined with ICP-MS quantification and time-gated imaging(TGI),to compare the environmental fate and bioaccumulation characteristics of spherical PS and fibrous PAN during a 30-day exposure period within a multi-trophic estuarine intertidal mesocosm. The results indicate that PAN rapidly settles and accumulates in sediments,reaching a concentration of(30.94±5.52) μg·g-1 after 30 days;in contrast,PS remains suspended in the water column for a longer period. The accumulation concentration of PS in the biofilmed leaves of eelgrass(Zostera asiatica) reached as high as(511.69±108.16) μg·g-1,with a BCF of 11 449. The concentration of PS in the digestive gland of Crassostrea gigas((15.26±1.12) μg·g-1) was significantly higher than the PAN concentration. In contrast,Rapana venosa and Sebastes schlegelii exhibited a higher tendency to accumulate PAN in the sedimentary phase,with the material primarily retained in metabolic organs such as the digestive gland and liver. This study demonstrates that the physical characteristics of microplastics,including density,morphology,and their derived effective hydrodynamic size,are critical factors regulating their environmental fate and biological exposure pathways,providing a scientific basis for the precise control and risk prediction of microplastic pollution in estuaries.
摘要:To reveal the accumulation characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs) in coastal shellfish from Shenzhen and assess the associated dietary exposure risk for the local population,a total of 79 shellfish samples covering 8 species were collected. 17 kinds of PCDD/Fs congeners were determined by isotope dilution high-resolution gas chromatography coupled with high-resolution double-focusing magnetic mass spectrometry(HRGC-HRMS),and an exposure assessment was conducted. The detection rate of PCDD/Fs in all samples was found to be 100%. The total mass concentration ranged from 0.37 to 535 pg/g wet weight,and the total toxic equivalent concentration(TEQ) ranged from 0.003 9 to 0.55 pg TEQ/g wet weight. The most dominant congener was OCDD,while 1,2,3,7,8-PeCDD contributed the most to the TEQ. In terms of mass concentration ranking from highest to lowest,it followed the order:clam,mussel,corbicula,pearl shell,scallop,oyster,oriental snail and abalone. In terms of TEQ ranking from highest to lowest,it followed the order:mussel,clam,oyster,oriental snail,pearl shell,corbicula,scallop and abalone. Furthermore,fat content in shellfish samples showed a positive correlation with both PCDD/Fs mass concentration and TEQ. The estimated daily intake of PCDD/Fs from consuming these eight shellfish species was 0.006-0.811 pg WHO-TEQ/kg b.w./day for adult males and 0.007-0.956 pg WHO-TEQ/kg b.w./day for adult females,with median values of 0.136 and 0.161 pg WHO-TEQ/kg b.w./day,respectively. The contamination levels of PCDD/Fs in coastal shellfish from Shenzhen were relatively low,all below the European TEQ limit standards. The total estimated intake of PCDD/Fs from shellfish species for residents was below the permissible maximum tolerable intake level established by the Joint FAO/WHO Expert Committee on Food Additives.
关键词:shellfish;polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs);accumulation characteristics;dietary exposure;HRGC-HRMS
摘要:An analytical method was established for the determination of 101 emerging contaminants(ECs) in human serum using high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Serum samples were treated with acetonitrile to precipitate proteins. After thorough mixing,vortexing,and centrifugation,the supernatant was purified using phospholipid removal columns. Separation was achieved on an ACQUITY HSS T3 column(100 mm×2.1 mm,1.8 μm) with a mobile phase consisting of 0.02% formic acid aqueous solution and acetonitrile-methanol(1∶1,volume ratio). The ion source for the tandem mass spectrometry was an electrospray ionization source(ESI),mass spectrometric data acquisition was performed in multiple reaction monitoring(MRM) mode,and quantification was carried out using matrix-matched external standards. The results demonstrated good linearity for all 101 contaminants within their respective concentration ranges,with correlation coefficients(r2) ranging from 0.993 3 to 0.999 9. The limits of detection(LODs) and limits of quantification(LOQs) were 0.01-0.94 ng/mL and 0.03-3.20 ng/mL,respectively. At three spiked levels(5,20,and 50 ng/mL),the recoveries ranged from 75.0% to 122%,with relative standard deviations(RSDs,n=6) of 1.0%-9.8%. The method was applied to analyze 17 human serum samples,detecting 43 pollutants at concentrations ranging from 0.01 to 48.1 ng/mL. This method features efficient sample preparation,high sensitivity,and good stability,making it suitable for the rapid screening of multiple emerging pollutants in human serum.
关键词:high performance liquid chromatography-tandem mass spectrometry;serum;emerging contaminants;phospholipid removal column
摘要:Cr(Ⅵ) is a significant target in the control of water pollution because of its high toxicity and severe carcinogenicity,which makes the development of inexpensive,quick,and simple detection techniques extremely pertinent. In this work,red-fluorescent BSA-gold nanoclusters(BSA-AuNCs) were synthesized using bovine serum albumin(BSA) as a template and L-ascorbic acid as a reducing agent. A new analytical technique for identifying Cr(Ⅵ) in water was developed using these BSA-AuNCs as a fluorescent probe. The resulting assay showed high selectivity,a linear range of 9.00×10-7 to 1.00×10-5 mol/L,and a limit of detection(S/N=3) of 4.90 nmol/L. Mechanistic investigations revealed that static quenching and inner filter effect work together to quench the fluorescence of BSA-AuNCs by Cr(Ⅵ). Method validation using real water samples(tap water,the water of Yanhe River,and chromium-containing laboratory wastewater) yielded spike recoveries of 95.8%-101%,demonstrating high accuracy and reliability. Furthermore,a portable test strip based on BSA-AuNCs was fabricated,which enabled the rapid and visual detection of Cr(Ⅵ). Collectively,this study provides a practical and effective strategy for on-site screening and monitoring of Cr(Ⅵ) pollution in water environments.
摘要:An analytical method was developed for the determination of 11 neonicotinoid pesticides in drinking water and surface water by automatic solid-phase extraction combined with ultra performance liquid chromatography-tandem mass spectrometry. The samples were purified and concentrated using an HLB solid-phase extraction column,separated on an AccucoreTM aQ C18 column(2.1 mm ×100 mm,2.6 μm),and then detected using positive‑ion electrospray ionization coupled with multiple reaction monitoring mode. Quantification was achieved using internal standard calibration. The results showed that 11 neonicotinoid pesticides exhibited excellent linearity,with all correlation coefficients(r) above 0.999 5. The detection limits of the method were 0.015 0-1.50 ng/L,and the limits of quantitation were 0.050 0-5.00 ng/L. At different spiked levels,the average recoveries in drinking water were 83.2%-117%,with relative standard deviations(RSDs) ranging from 3.9% to 13%,and the average recoveries in surface water were 92.4%-111%,with RSDs ranging from 3.5% to 14%. The method was successfully applied to the quantitative analysis of 11 neonicotinoid pesticides in drinking water and surface water samples collected from Chengdu. Thiamethoxam,imidacloprid,clothianidin,acetamiprid,and dinotefuran were detected at varying levels,with concentrations ranging from 1.18 to 148 ng/L.
关键词:neonicotinoid pesticides;automatic solid-phase extraction;ultra performance liquid chromatography-tandem mass spectrometry;drinking water;surface water
摘要:In this study,a sensitive and reliable analytical method was established for the simultaneous determination of gaseous and particulate benzotriazole ultraviolet absorbers(BUVs) in ambient air. The target analytes included four common BUVs:UV-320,UV-326,UV-327,and UV-328. Specifically,a high-volume air sampler was used to collect gaseous and particulate BUVs separately,with quartz fiber filters(QFF) for particulate phase and polyurethane foam(PUF)/XAD-2 resin for gaseous phase. Air samples were extracted by accelerated solvent extraction,purified by silica cartridges,and analyzed by gas chromatography-triple quadrupole mass spectrometry. Method validation experiments were carried out to evaluate the performance of the established method,and the results showed that the four target compounds exhibited a good linear relationship in the concentration range of 1-200 ng/mL,with correlation coefficients(r) all greater than 0.999. The method detection limits ranged from 0.4 to 0.5 pg/m³,and the quantitation limits ranged from 1.6 to 2.0 ng/m3,which was sufficiently low to detect trace levels of BUVs in ambient air. The recoveries of the target analytes in QFF,PUF,and XAD-2 samples were 83.0%-103%,74.9%-108%,83.4%-96.0%,and the relative standard deviations(RSDs) were less than 10% for all target analytes,respectively. The method was used to monitor BUVs in ambient air samples of Beijing,and UV-326 and UV-328 were detected with concentration range of 0.9-6.8 pg/m3,while UV-320 and UV-327 were not detected in any samples.The established method is highly sensitive and accurate,which can fully meet the monitoring requirements for trace BUVs in the ambient atmosphere. It not only provides a reliable analytical tool for further in-depth research on the environmental behavior and ecological risks of BUVs in the atmospheric environment but also lays a solid foundation for the environmental monitoring and risk control of BUVs.
关键词:benzotriazole;ultraviolet absorbers;air monitoring;gas chromatography-triple quadrupole mass spectrometry;accelerated solvent extraction
摘要:In this study,a method for simultaneous determination of 12 phthalate esters(PAEs) in wastewater using gas chromatography-mass spectrometry(GC-MS) was established. For each sample,100 mg/L of ascorbic acid was added to reduce matrix interference;then,liquid-liquid extraction was performed using n-hexane(n-hexane∶sample=250∶1,volume ratio). The n-hexane extract was determined via GC-MS and quantified using the internal standard method. The results revealed good linearity for the 12 PAEs in the concentration range of 10 to 1 000 µg/L,with correlation coefficients(r2)>0.99. The limits of detection and limits of quantification were in the ranges of 0.004 to 0.068 μg/L and 0.013 to 0.227 μg/L,respectively. The average spiked recoveries ranged from 79.5% to 122%,and the relative standard deviations were between 0.23% and 19%;these results indicate that the proposed method has good accuracy and stability. This method was used to determine PAEs in real influent samples from five wastewater treatment plants in the Pearl River Delta,where each plant employs different treatment processes. In addition to the common phthalates such as diisobutyl phthalate,dibutyl phthalate,and bis(2-ethylhexyl) phthalate,dioctyl phthalate was also detected. Thus,the proposed method is suitable for the accurate analysis and determination of trace PAEs in real wastewater samples.
摘要:Early and accurate diagnosis of pancreatic cancer represents a pivotal breakthrough for improving patient survival. Although exosome-based liquid biopsy has demonstrated immense promise and attracted widespread attention,existing methods for isolating pancreatic cancer exosomes from blood still face two major bottlenecks:low reaction efficiency within laminar-flow microchips and the lack of tumor-specific exosomal protein markers,which severely compromise both separation specificity and efficiency. To tackle these limitations,this study developed a phenylboronic acid-functionalized three-dimensional nano-herringbone microfluidic chip. By exploiting the covalent binding between phenylboronic acid and the aberrantly overexpressed glycosylated cis-diol structures on tumor exosome surfaces,the chip achieves broad-spectrum,high-affinity recognition of tumor-derived exosomes. Simultaneously,the periodically ordered nano-herringbone array induces microvortices that disrupt the laminar diffusion boundary layer,substantially enhancing the collision and binding efficiency between exosomes and the chip interface. The results demonstrated that the chip achieved a capture efficiency of approximately 85% for exosomes derived from three pancreatic cancer cell lines,PANC-1,SW1990,and PACA-2. In stark contrast,exosomes from normal pancreatic hTERT-HPNE cells exhibited minimal binding,and tumor exosomes subjected to PNGase F-mediated N-glycan cleavage lost nearly all ability to be captured,definitively confirming that the chip's specific capture is dependent on glycan recognition. Building upon this capability,the chip further integrates in situ enzymatic fluorescence signal amplification,successfully enabling simultaneous molecular profiling of six pancreatic cancer-associated membrane protein markers prostate-specific membrane antigen(PSMA),carcinoembryonic antigen(CEA),mucin 1(MUC-1),nucleolin (NCL),protein tyrosine kinase 7(PTK7),and epithelial cell adhesion molecule(EpCAM)within a single sample. All six markers were significantly overexpressed in tumor-derived exosomes,and distinct cell lines displayed characteristic expression signatures,demonstrating the chip's capacity to distinguish tumor-derived from normal exosomes and to identify pancreatic cancer molecular subtypes. By integrating glycan-based chemical recognition,efficient fluidic mass transport,and multiplexed molecular profiling into a unified platform,this study provides a novel,antibody-independent separation,highly specific,and multi-dimensional information-enriched technology for early pancreatic cancer liquid biopsy,exhibiting significant application prospects in the clinical accurate diagnosis and molecular subtyping of pancreatic cancer.
关键词:microfluidic chip;exosome;Liquid biopsy;Biomarker;Pancreatic Cancer
摘要:In this study,an analytical method based on headspace-gas chromatography-mass spectrometry(HS-GC-MS) was established for the simultaneous determination of 33 harmful volatile organic solvents(VOCs) in cosmetics. The sample was prepared by dispersion in methanol followed by dilution with water,and equilibrated at 65 ℃ for 30 min. The separation was performed on a VF-1301 capillary column(30 m×0.25 mm×1 μm),and detection was carried out in selected ion monitoring(SIM) mode. Quantification was performed using toluene-D8 or 1,2-dichlorobenzene-D4 as internal standards. The selection of solvent calibration curves or matrix-matched calibration curves was based on the properties of each matrix.The results showed good linearity of 33 VOCs in corresponding concentration ranges,with the correlation coefficients(r) ranging from 0.995 1 to 0.999 8. The limits of detection(LODs) ranged from 0.02 to 0.40 mg·kg-1,and the limits of quantification(LOQs) ranged from 0.05 to 1.0 mg∙kg-1. At three spiked levels,the average recoveries of the five matrices(aqueous,cream,gel,lotion and powder) ranged from 85.1% to 119%,with relative standard deviations(RSDs) between 0.20% and 8.4%. The method was used to analyze 169 commercially available cosmetic products,and 78 batches were found to contain the target compounds. Among them,toluene,o-xylene,ethylbenzene,m-xylene & p-xylene,and benzene showed relatively high detection rates of 34.9%,20.1%,20.1%,17.8% and 10.1%,respectively. Positive samples were mainly concentrated in sunscreen and hair dye cosmetics. The content of benzene exceeded the limit(2.0 mg∙kg-1) in 11 batches of hair dye cosmetics,and prohibited raw materials such as dichloromethane and trichloromethane were detected in 3 batches of other product types. The method is simple,rapid,sensitive,and accurate,making it suitable for high-throughput detection of various harmful VOCs in cosmetics.
关键词:headspace-gas chromatography-mass spectrometry;cosmetics;volatile organic solvents;benzene series;prohibited raw materials
摘要:Ultra-fast liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry(UFLC-Q-TOF-MS/MS) was employed to analyze the prototype compounds and metabolites of Zhangyanming Tablet extract in the urine and feces of Beagle dogs. The mobile phase consisted of water and acetonitrile,both containing 0.1% formic acid(volume fraction). Gradient elution was performed on a Kinetex C18(2.1 mm×100 mm,2.6 μm) column,with a flow rate of 0.3 mL/min and the column temperature maintained at 40 ℃. An electrospray ionization(ESI) source was used to scan the m/z range from 50 to 1 500 in both positive and negative ion modes. A total of 36 prototype compounds and 13 derived metabolites in Beagle dog urine and feces were characterized by analyzing retention time,MS fragments,reference standards,database,and literature data. The main metabolic reactions included phase I(hydrogenation,deglucosylation) and phase Ⅱ reactions(glucosylation,methylation,xylosylation,glucuronidation,sulfation). This study revealed the in vivo metabolic biotransformation of Zhangyanming Tablet extract in Beagle dogs,providing scientific evidence and references for elucidating the pharmacologically active substances and facilitating clinical application of Zhangyanming Tablet.
关键词:Zhangyanming Tablet extract;UFLC-Q-TOF-MS/MS;Beagle dog;urine;feces;metabolism in vivo
摘要:The mercury sulfide(HgS) content is the core indicator for the quality eval uation of cinnabar. To address the limitations of traditional determination methods,which are time-consuming,destructive,and inadequate for rapid quality control,this study combined X-ray diffraction(XRD) with multiple machine learning algorithms to develop a predictive modeling system comprising partial least squares regression(PLSR),random forest(RF),particle swarm optimization-support vector regression(PSO-SVR),long short-term memory(LSTM),and convolutional neural network(CNN). Various spectral preprocessing methods and feature selection algorithms were systematically investigated,and the shapley additive explanations(SHAP) framework was introduced to elucidate the decision-making logic of the models. The results indicated that after applying standard normal variate(SNV) preprocessing coupled with competitive adaptive reweighted sampling(CARS) for feature selection,the PSO-SVR and LSTM models exhibited the best overall performance. For the LSTM model,the coefficients of determination for the calibration and validation sets(R²C,R²V) were 0.992 6 and 0.879 4,respectively,with root mean square errors(RMSEC,RMSEV) of 0.120 5 and 0.411 5,and a residual predictive deviation(RPD) of 2.879 7. The PSO-SVR model achieved an R²V of 0.865 0,an RMSEV of 0.435 4,and an RPD of 2.721 4. External validation on 10 independent sample batches yielded R² values all exceeding 0.80,confirming the models' strong generalization ability and robustness. SHAP analysis further revealed that the diffraction intensities within the 2θ ranges of 24°-35° and 50°-60° were the core features driving model decisions. Specifically,the features corresponding to key diffraction angles identified by the models,such as 27.92° and 45.59°,showed a significant positive correlation with HgS content,demonstrating a high consistency between algorithmic decision-making and the crystal diffraction characteristics of HgS. The integration of XRD with intelligent algorithms enables non-destructive,rapid,and accurate prediction of HgS content in cinnabar,providing methodological support for the rapid quality evaluation of mineral medicines and the construction of intelligent quality control systems.
摘要:This study established a green analytical strategy using direct analysis in real time(DART) coupled with orbitrap high-resolution mass spectrometry(HRMS) for the rapid screening and confirmation of 21 whitening functional ingredients in cosmetics. Samples were ultrasonically extracted with 50% methanol aqueous solution and diluted,then 3 μL was introduced via a 12-Dip-It module into a DART ion source. Mass spectrometric detection was performed in positive/negative switching full-scan mode with data-dependent MS² triggered by an inclusion list,enabling acquisition of accurate mass and characteristic fragment ions for definitive structural confirmation. Under optimized conditions of 350 ℃ ionization temperature,400 V grid voltage and 0.4 mm/s sample transfer rate,the compounds showed good response and the method exhibited excellent specificity,with limits of detection of 0.15-3 ng. Application of the method to 20 batches of commercially available whitening cosmetics showed that 19 batches were tested positive,collectively containing 6 whitening agents,Notably,5 batches exhibited discrepancies where detected whitening agents contradicted product label declarations. This method eliminates the chromatographic step,features simple operation and low solvent consumption,and is suitable for rapid screening,confirmation,and risk warning of whitening ingredients in cosmetics.
关键词:direct analysis in real time(DART);electrostatic field orbitrap high-resolution mass spectrometry(Orbitrap HRMS);whitening functional ingredients;cosmetics;green analysis;niacinamide;resorcinol derivatives
摘要:To address decision-making bottlenecks caused by scarce standard reference materials and limited sample sizes during near-infrared spectroscopy(NIRS) equipment trials in the pharmaceutical industry,this study proposes a dual evaluation strategy combining“absorbance dynamic repeatability”and“small-sample modeling potential”.This strategy is based on the“4S principles”for material screening and a multicriteria decision analysis(MCDA) model. Three NIRS instruments with different spectroscopic principles—Fourier transform(A) and grating-based(E and Ⅰ)—were selected to evaluate absorbance precision using three nonstandard materials(mannitol,stearic acid,and polyethylene) as carriers. Simultaneously,targeting the moisture quantification of Guizhi Fuling Capsules soft material,small-sample partial least-squares models were constructed via leave-one-out cross-validation to compare the application modeling potential of each instrument. The results revealed significant performance disparities:Instrument A exhibited optimal absorbance precision and modeling accuracy(RMSECV=0.192 3,R2CV=0.946 9),with its integrated MCDA score(92.93) leading significantly,thereby reflecting the hardware advantages of a high signal-to-noise ratio. Instrument E exhibited significantly inferior absorbance repeatability compared with the other devices,with its inherent hardware instability constraining its modeling potential. Instrument I revealed significant defects in its temperature control system during tests on a thermosensitive sample(stearic acid),thus resulting in measurement failure. This strategy requires no expensive standard reference materials and accurately identifies hardware risks using small sample sizes,thus providing an economical,efficient,and metrologically credible decision-making reference for equipment selection and risk assessment in pharmaceutical enterprises.
关键词:near-infrared spectroscopy;instrument evaluation and selection;absorbance repeatability;partial least squares;leave-one-out cross-validation
摘要:The escalating abuse of synthetic cannabinoids poses a significant threat to public safety and human health. This study focuses on the synthetic cannabinoid methyl 2-(1-(5-fluoropentyl)-1H-indole-3-carboxamido)-3,3-dimethylbutanoate(5F-MDMB-PICA) as the target analyte. A novel portable electrochemical sensor was developed by innovatively combining cerium-based metal-organic framework(Ce-BTC) with reduced graphene oxide(rGO) and integrating molecular imprinting technology. This design leverages the synergistic effects of the high specific surface area of Ce-BTC and the excellent electrical conductivity of rGO,effectively mitigating rGO agglomeration. A molecularly imprinted polymer membrane was constructed using L-arginine as the functional monomer,enabling highly sensitive and selective trace detection of 5F-MDMB-PICA. Under optimal conditions,the sensor exhibited a good linear response within the concentration range of 1.0×10-9-1.0×10-7 mol·L⁻¹ and 1.0×10-7-4.0×10⁻⁶ mol·L⁻¹,with a detection limit as low as 3.5×10⁻¹⁰ mol·L⁻¹. Furthermore,the sensor enabled the detection of the target analyte in actual e-liquid samples without the need for complex sample pretreatment,providing a reliable new approach for the on-site rapid screening of synthetic cannabinoids.
摘要:In this study,an efficient quencher was prepared by loading branched-Au nanoparticles(BA) onto graphene oxide(GO). Based on the quenching of the fluorescent signal from red aggregation-induced emission fluorescent microspheres(RAIEFM),a lateral flow immunoassay(LFIA) method for the semi-quantitative detection of isocarbophos was established. GO@BA exhibited a high molar extinction coefficient of 2.376×10⁹ L·mol⁻¹·cm⁻¹ at 640 nm,and its fluorescence quenching constant(Kn) against RAIEFM in aqueous solution reached 4.076×10⁹ L·mol⁻¹. By measuring the changes in fluorescence lifetime,the quenching mechanism of GO@BA was confirmed to be the inner filter effect. The fluorescence quenching LFIA based on GO@BA enabled highly sensitive detection of ICP,with a limit of detection as low as 0.006 3 ng/mL,which represented a 7.5-fold improvement in sensitivity compared with traditional AuNPs-LFIA,and the linear range was 0.20-6.25 ng/mL. When this method is applied to the detection of isocarbophos in cucumbers,green vegetables,and wolfberries,the spiked recovery rate ranges from 82.2% to 104%,the relative standard deviation does not exceed 20%,and it shows good consistency with the detection results of the liquid chromatography-tandem mass spectrometry method. The established method has good specificity and high sensitivity,providing a new idea for the on-site rapid detection of isocarbophos.
摘要:This study was aimed at comprehensively analyzing the chemical components of the decocted liquid obtained by honey-processing of Glycyrrhiza uralensis. using ultra-performance liquid chromatography-quadrupole/time-of-flight tandem mass spectrometry(UPLC-Q-TOF-MS/MS),and exploring the changes and rules of its components in compatibility with compound prescriptions(Sini Decoction and Pogejuxin Decoction). Based on the accurate mass,fragment ions,literature and network database,102 components were successfully identified in the decocted liquid of honey-processing of Glycyrrhiza uralensis,including 52 flavonoids,28 triterpenes and their saponins,15 phenols,6 coumarins,and 1 other compound. Among these compounds,triterpene saponins included 4 potentially new compounds. Comparative analysis of the components of single-ingredient herbs,Sini Decoction,and Pogejuxin Decoction revealed that compound formulations significantly reduce the amounts of compounds,such as flavonoids,triterpene saponins,and phenolic compounds obtained by honey-processing of Glycyrrhiza uralensis. The phenolic components are affected by the combination of Cornus officinalis and mineral herbs,decreasing the types of dissolved components. This study provides better understanding of the chemical substance basis of roasted licorice and its compounds,thus laying a foundation for subsequent quality research.
关键词:UPLC-Q-TOF-MS/MS;honey-processing of Glycyrrhiza uralensis;chemical component analysis;triterpene saponins;Sini Decoction;Pogejuxin Decoction
摘要:The in vivo antioxidant efficacy of nanomaterial-based scavengers for reactive oxygen species(ROS)is governed by both their intrinsic ROS-scavenging capacity and biological factors,including cellular interactions,internalization efficiency,and intracellular distribution. Currently,cell-free chemical assays and cellular-level evaluation methods for assessing the antioxidant properties of nanomaterials are conducted independently,precluding the differentiation of their intrinsic ROS-scavenging activity from their targeting efficiency. Manganese-doped hollow mesoporous silica nanoparticles(MSNs)were first prepared by a sol-gel method followed by hydrothermal treatment. After modification with polyallylamine hydrochloride(PAH),the MSNs were sequentially covalently conjugated with 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl(Tempol) and the RAGE-targeting aptamer(Apt),successfully yielding aptamer-functionalized reactive oxygen species(ROS)-scavenging composite nanomaterials,denoted as TMSN@Apt. TMSN@Apt was comprehensively characterized using transmission electron microscopy(TEM),scanning TEM-energy-dispersive X-ray spectroscopy(STEM-EDS),and dynamic light scattering-based zeta potential analysis. TEM observations revealed spherical hollow architectures with a diameter of (87.94±11.14) nm and mesoporous channels in the shell walls. STEM-EDS elemental mapping confirmed the uniform distribution of Mn,Si,and O throughout the silica framework,without phase segregation. Zeta potential measurements revealed a stepwise surface charge reversal from negative(-20.0±1.4) mV to positive(23.0±0.3) mV after PAH coating, a further increase in the surface charge to(30.3±1.1) mV upon Tempol grafting,and an eventual reversal to(-2.1±0.3) mV following aptamer conjugation,thereby verifying the successful layer-by-layer functionalization of the MSN.The targeted recognition and antioxidant efficacy of TMSN@Apt were evaluated from four perspectives:molecular binding to purified RAGE protein,cellular uptake by H2O2-stimulated MLE-12 alveolar epithelial cells,intrinsic ROS-scavenging capacity in cell-free systems,and cytoprotection against oxidative stress-induced apoptosis. Flow cytometric analysis revealed that TMSN@Apt exhibits approximately 12.4-fold higher binding affinity to immobilized RAGE protein compared with that of the random sequence control. Concentration-dependent cellular association was observed at 12.5,25,and 50 μg/mL,with the mean fluorescence intensity increasing proportionally. Laser confocal scanning microscopy further revealed notable intracellular colocalization of TMSN@Apt with RAGE,confirming receptor-mediated internalization,whereas no significant intracellular fluorescence was detected in the random sequence control group. In cell-free assays,TMSN@Apt displayed broad-spectrum ROS-scavenging activity against superoxide anion(O2·⁻),hydroxyl radical(·OH),and hydrogen peroxide(H2O2) in a dose-dependent manner,achieving scavenging efficiencies of 75.6%,76.7%,and 80.1%,respectively,at 0.2 mg/mL. Remarkably,at the cellular level,only 0.05 mg/mL of TMSN@Apt was required to reduce intracellular ROS levels from(82.30±1.91)% to (13.93±1.33)% and to attenuate total apoptotic rates from(20.94±2.18)% to(7.85±0.61)% in H2O2-challenged cells. This substantial concentration-efficacy discrepancy between the cell-free and cell-based systems highlights the critical contribution of aptamer-mediated targeted enrichment and intracellular accumulation. The established methodology enables quantitative differentiation between the intrinsic antioxidant capacity and the targeting-enhanced biological efficacy of aptamer-functionalized nanomaterials,providing a robust framework for their precise performance evaluation and rational dosage optimization in therapeutic applications.
关键词:aptamer;nanomaterial;targeted recognition;antioxidant activity;reactive oxygen species scavenging
摘要:An analytical method based on liquid-liquid extraction coupled with gas chromatography-triple quadrupole mass spectrometry(GC-MS/MS) was developed and validated for the determination of 13 polychlorinated biphenyls(PCBs) congeners in honey. The honey samples were extracted with n-hexane and cleaned up by dispersive solid phase extraction with primary secondary amine(PSA) powder. After filtration through an organic membrane,the extracts were analyzed by GC-MS/MS. Separation was performed on a DB-5HT capillary column(15 m×250 μm×0.10 μm),detection was carried out in multiple reaction monitoring(MRM) mode,and quantification was achieved using the external standard method. Under optimized conditions,good linearity was observed for all 13 PCBs in the concentration range of 0.1-100 μg/L,with correlation coefficients greater than 0.99. The method detection limits were 0.37-0.93 μg/kg,and the quantification limits were 1.17-2.97 μg/kg. The average recoveries at spiked levels of 5,10,50 μg/kg ranged from 82.3% to 106%,with relative standard deviations between 3.0% and 10%. The proposed method is simple and rapid in sample pretreatment,exhibits high analytical efficiency,and demonstrates good accuracy and precision,making it suitable for the routine detection of PCBs in honey samples.
关键词:honey;polychlorinated biphenyls;liquid-liquid extraction;gas chromatography-triple quadrupole mass spectrometry
摘要:MicroRNA-21(miR-21),one of the earliest discovered miRNAs in the human genome,provides crucial information for the early diagnosis,drug treatment,and prognosis assessment of cancer. To address the issues of low miRNA abundance and complex background interference,this study developed a light-controlled,cascade amplification sensor(CHA-DNAzyme) by combining ultraviolet light-triggered DNA strand cleavage with catalytic hairpin assembly(CHA) and deoxyribozyme(DNAzyme) amplification techniques. The initiation strand of CHA was initially blocked by a hairpin strand containing a photolysis bond. Only under the combined action of ultraviolet light and target miR-21 could the initiation strand be released and the CHA reaction initiated. Meanwhile,inactive DNAzyme fragments were integrated into the metastable CHA hairpin reactants,forming active DNAzyme during the CHA process. The active DNAzyme cyclically cleaved the substrate strand S,achieving signal amplification. Under optimal conditions,the platform exhibited a good linear relationship within the range of 0.3-10 nmol/L,with a detection limit of 189 pmol/L. Additionally,the platform demonstrated high specificity for different base-mismatched sequences and was successfully applied to the detection of miR-21 in diluted serum samples. In conclusion,this platform holds great potential for high-sensitivity miRNA analysis.
摘要:An analytical method based on liquid-phase microextraction coupled with portable ion trap mass spectrometry was developed for the determination of fentanyl,alfentanil,sufentanil,α-methylfentanyl,and acetylfentanyl in urine. Samples were extracted using a menthol-thymol natural deep eutectic solvent(NADES) supported on polypropylene fibers and subsequently analyzed by portable mass spectrometry for rapid detection. The five fentanyl analogues exhibited good linearity within the concentration range of 50-400 ng/mL,with correlation coefficients(r2) all greater than 0.99. The limits of detection(LODs) and limits of quantification(LOQs) were 5-20 ng/mL and 10-50 ng/mL,respectively. Using blank urine as the matrix,at low,medium,and high spiked concentration levels,the intra-day spiked recoveries of the five fentanyl analogues ranged from 84.1% to 119%,with relative standard deviations(RSDs) of 2.6%-9.9%. The inter-day spiked recoveries ranged from 87.7% to 116%,with RSDs of 5.5%-9.7%. The method was applied to the analysis of five random urine samples,and fentanyl and sufentanil were detected in two of them. The results demonstrate that the proposed method is suitable for the rapid monitoring and analysis of fentanyl analogues in urine matrices,and can effectively facilitate on-site investigation and support anti-drug enforcement efforts.
关键词:fentanyl;portable mass spectrometry;polypropylene fiber;Liquid-phase microextraction;natural deep eutectic solvent
摘要:Iron tetracarboxyphenylporphyrin was used as a precursor to prepare an iron-porphyrin-based hydrogen-bonded organic framework that was further modified with gold nanoparticles and a tetracycline-specific aptamer. Relying on the peroxidase-like nanozyme activity of this material,3,3',5,5'-tetramethylbenzidine(TMB)was catalytically oxidized to produce a color response in the presence of H2O2. The modification of the aptamer enhanced both the catalytic activity of the nanozyme and the selectivity of the assay,enabling highly sensitive and selective detection of tetracycline. The experimental results showed that rapid colorimetric detection of the target analyte could be achieved using ultraviolet-visible spectrophotometry and smartphone-based color acquisition. Smartphone-assisted color reading enabled intelligent visual detection of tetracycline. The developed method exhibited a good linear relationship with tetracycline concentrations in the range of 0.000 5-800 μmol/L,with a regression coefficient(r2) of 0.996 and a limit of detection(S/N=3) of 0.49 nmol/L. Moreover,it demonstrated favorable selectivity,with spiked recoveries ranging from 85.3% to 100%. Owing to its simple operation and low cost,this method provides a novel strategy for rapid visual detection of tetracycline in feed,demonstrating potential for practical applications.
摘要:High-molecular-weight oxygen-containing compounds were detected in the Fischer-Tropsch synthetic oil-decanol/dodecane mixture during processing,and their generation is closely related to the catalyst used as well as the alcohols and aldehydes present in the high temperature Fischer-Tropsch synthetic oil. By using the combined technology of gas chromatography-mass spectrometry(GC-MS) and positive ion electrospray ionization Orbitrap high-resolution mass spectrometry(ESI(+) Orbitrap MS),these compounds were identified as acetals formed via the condensation reaction between aldehydes and alcohols in the desorbent,while their characteristic ion is m/z 141 and m/z 327 and the general molecular formula is CxH2x+2O2. The EI mass spectral characteristics of the acetals confirm their correlation with the precursor aldehydes,and their carbon number distribution is comparable to that of the raw Fischer-Tropsch synthetic oil. This study provides theoretical guidance for the development and process optimization of synthetic oil refining.
关键词:Fischer-Tropsch oil;acetal formation;GC-MS;high-resolution mass spectrometry
摘要:A size exclusion chromatography(SEC) analysis method was developed for determination of polyacrylic acid(PAA) concentrations in aqueous solutions containing ethanolamine(ETA) and hydrazine. Furthermore,we discussed the interaction between PAA and anions test method inthe secondary water chemistry system of pressurized water reactor nuclear power plant. The results showed that under the coexistence of conventional additives such as hydrazine,ethanolamine and ammonia,the PAA concentration in the range of 27.25-1 090 μg/L were accurately determined with limits of detection(LOD) of 1.368 μg/L and limits of quantification(LOQ) of 4.561 μg/L,while spiked recoveries fully met analytical requirements. Other coexisting substances such as F-,Cl-,NO3-,SO42-,PO43- and other anions and small organic acids such as formic acid and acetic acid had almost no effect on the determination of PAA content. The presence of PAA also did not affect the accuracy of test results of above five anions. The PAA test method in this paper was accurate and useful,and itwas an effective method for determining PAA content in the secondary water chemistry system of pressurized water reactor nuclear power plant.
关键词:polyacrylic acid dispersant;test method;size exclusion chromatography;pressurized water reactor nuclear power plant
摘要:Accurate analysis of the mutation status of the HRAS gene fragment is closely related to the early screening and treatment of various human cancers. Herein,we report the simultaneous detection and analysis of DNA fragments encompassing HRAS codons 11 and 12,utilizing a custom-built high-performance capillary electrophoresis(HPCE) system coupled with a spatial internal standard method(SDIS). Following rigorous validation of the platform's reliability,stability,and accuracy,optimal baseline separation was achieved within just 6 minutes using a 1.0% hydroxyethyl cellulose(HEC,1 300 K) sieving matrix and a 100 V/cm electric field. The analytical performance proved highly robust:relative standard deviations(RSDs) remained below 2.5%. Both target fragments exhibited excellent quantitative linearity(r²>0.95),achieving limits of detection(LOD) as low as 0.059 ng/μL and 0.061 ng/μL. Compared to conventional quantitative polymerase chain reaction(qPCR) and sequencing technologies,this custom-built system exhibits significant advantages in cost,analysis time,and device portability. By integrating the SDIS method,it achieves highly sensitive targeted analysis of HRAS gene fragments.
摘要:Emerging contaminants(ECs) pose significant risks to the ecological environment and biological health due to their diverse types,trace-level presence,complex structures,inherent bioaccumulation,and biotoxicity. Therefore,the development of functional materials that can afford highly sensitive detection and efficient removal is crucial for achieving accurate detection and in-depth remediation of these contaminants. Currently available detection technologies and removal materials are characterized by facile operation,sensitive response,low cost,and environment-friendliness. These techniques and materials effectively address the problems of conventional detection techniques—including reliance on large-scale precision instruments,cumbersome sample pretreatment processes,high costs,requirement for professional operation,and insufficient removal efficiency to meet industrial application standards. Metal-organic framework(MOF) materials,by virtue of their high specific surface areas,tunable pore structures,and facile surface functionalization,exhibit excellent selective enrichment capacities,high-sensitivity detection performance,and efficient catalytic degradation potential for contaminants in complex matrices. Based on these observations,in this study,we systematically collate the categories and regulatory status of emerging contaminants,elaborate on the synthesis methods and classification systems of MOF materials,and focus on reviewing the latest progress of research on functionalized MOF materials in the high-sensitivity detection and efficient removal of typical emerging contaminants,such as antibiotics,persistent organic pollutants,and endocrine-disrupting chemicals.
摘要:Time-resolved luminescence detection can eliminate scattered light and distinguish luminescence signals with different lifetimes,enabling important applications in biological detection and imaging. However,conventional time-resolved luminescence instruments typically require sophisticated and complex lasers as excitation sources and ultrafast photodetectors to capture delayed fluorescence,resulting in bulky,complex,and expensive instruments that limit the application of related technologies. In recent years,the application of long-lived luminescent materials such as phosphorescent and delayed fluorescent materials has significantly reduced the requirement for instrumental temporal resolution. Low-cost light sources and shutters have been used for time-resolved luminescence detection,significantly reducing instrument costs. The application of miniaturized detectors,such as complementary metal-oxide-semiconductor(CMOS )image sensors and photodiodes,has significantly improved integration level and realized the miniaturization of instruments. This review introduces the principles,development,and applications of time-resolved luminescence detection technology and focuses on research progress of miniaturized time-resolved luminescence devices and their applications in biological detection.