摘要:Porous organic framework materials,such as metal-organic frameworks(MOFs),covalent organic frameworks(COFs),hydrogen-bonded organic frameworks(HOFs) and microporous organic networks(MONs),possess notable characteristics including good chemical stability,structural diversity,tunable pore size,high specific surface area and ease of functionalization. These properties endow them with significant application potential in the field of separation and analysis. However,the extraction efficiency and selectivity of pristine porous organic framework materials for target analytes are often unsatisfactory. Aptamers are single-stranded DNA or RNA molecules that exhibit high specificity and affinity towards particular targets. Aptamer-functionalized porous organic framework materials combine the advantages of porous frameworks,such as structural diversity,large surface area and ease of functionalization with the high specificity and convenient immobilization properties of aptamers. This integration provides a powerful platform strategy for the highly efficient and selective separation and enrichment of trace targets from complex matrices. This review summarizes the selection of aptamers,the preparation of aptamer-functionalized porous organic framework materials,and their applications in various techniques,including magnetic solid-phase extraction,solid-phase microextraction,membrane separation,and magnetic separation-based detection. Finally,an outlook on future development was presented.
关键词:porous organic framework materials;aptamer;separation and enrichment;sample pretreatment;trace detection
摘要:Mycotoxins readily contaminate edible agricultural products and their processed derivatives,posing a serious threat to food safety and human health. Effective control of these toxins remains a critical challenge in the field of food safety. In recent years,porous nanomaterials have demonstrated significant potential in the detection and control of mycotoxin contamination,owing to their unique pore structures,high specific surface area,and abundant active sites. This review systematically summarizes recent advances in the application of metal-organic frameworks,covalent organic frameworks,biochar,and other porous nanomaterials in enhancing the sensitivity and selectivity of mycotoxin detection,inhibiting toxin production,and facilitating toxin removal. Furthermore,the mechanisms underlying the adsorption and degradation of mycotoxins by these materials are discussed in depth. The current challenges and future prospects for the practical application of such nanomaterials are also analyzed. This work aims to provide theoretical reference for the design and development of novel porous nanomaterials and to promote their further research and application in mycotoxin control.
摘要:Metal-organic framework(MOF) and covalent organic framework(COF) exhibit excellent material adsorption properties due to their high porosity,adjustable pore size,large specific surface area and rich modification sites. Skeleton materials have their own unique advantages and limitations in specific applications,but by combining their complementary characteristics,a new hybrid porous system with better performance than a single material can be constructed,and a variety of practical application forms can be expanded,especially in the field of sample preparation. This review first introduces a variety of design strategies for MOF and COF composites,including functional growth of COF on the surface of MOF(MOF@COF),growth of MOF on the surface of COF(COF@MOF),formation of MOF+COF by bridging reaction,growth of MOF in the pores of COF(MOF-in-COF),and MOF×COF with both coordination and covalent bond characteristics. Subsequently,the specific application and mechanism of MOF and COF composites in the fields of environment,food and biology were emphatically expounded. Finally,the development trend and existing problems of MOF and COF composites from structural design to practical application are prospected.
摘要:Molecularly imprinted covalent organic frameworks(COFs@MIPs) have become a research hotspot due to their desirable combination of the specificity and selectivity of molecularly imprinted polymers(MIPs) and the high specific surface area and designability of covalent organic frameworks(COFs). In recent years COFs@MIPs have shown great potential in analytical chemistry,environmental science,and biomedical fields. This article reviews the application of COFs@MIPs in sample pretreatment,including dispersive solid-phase extraction,magnetic solid-phase extraction,and solid-phase microextraction. The future development trends of COFs@MIPs in sample pretreatment are also discussed and prospected.
摘要:Chromatography is one of the most used techniques for complex sample analysis,and the preparation of high-performance stationary phases is the key to its advancement. Microporous organic networks(MONs) are a class of porous materials formed via Sonogashira-Hagihara coupling reactions between aromatic halides and alkynes. Owning to the high specific surface area,excellent solvent and thermal stability,tunable pore sizes,and ease of functionalization,MONs have demonstrated significant potential in chromatographic separation recently. This review first briefly outlines the development history,synthesis,and functionalization strategies of MONs,then introduces the research progress of MONs as chromatographic stationary phases in high-performance liquid chromatography,gas chromatography,and capillary electrochromatography,and finally discusses the prospects and challenges of MONs in chromatography. This review will provide valuable insights for the design and application of novel MON-based chromatographic stationary phases.
摘要:This work reports the first preparation of a crown ether-based microporous organic network coated silica gel(CE-MON@SiO2) composite stationary phase for high-performance liquid chromatography(HPLC). Multiple characterization techniques confirm that the prepared CE-MON@SiO2 exhibits a large specific surface area(476 m2·g-1) and superhydrophobicity(contact angle=150°). In reverse-phase mode,the CE-MON@SiO2 packed column demonstrates high-efficiency separation of various analytes,including alkylbenzenes,polycyclic aromatic hydrocarbons,phenols,anilines,benzenediol isomers,halogenated aromatics,and phenylurea herbicides. Additionally,this column demonstrates excellent analytical reproducibility,with relative standard deviations of retention time not more than 1.3% across five consecutive injections. The CE-MON@SiO2 column demonstrates excellent reversed-phase chromatographic separation performance and potential hydrophilic interaction separation capabilities. It was found that the column may operate through multiple chromatographic interaction mechanisms such as hydrophobic interactions,π-π interactions,and host-guest interactions. These findings reveal that the CE-MON@SiO2 stationary phase exhibits great potential in the separation and analysis of complex aromatic compounds and pharmaceutical molecules.
摘要:This study presents a green synthesis of MOF-808 using three regulators(formic acid,acetic acid,and trifluoroacetic acid) as alternatives to the conventional organic solvent N,N-dimethylformamide. Magnetic particles rich in carboxylic acid groups(Fe3O4-EDTA,FE) were then incorporated to obtain magnetic MOF-808 composites. The materials were characterized by techniques including specific surface area and porosity analyzer,transmission electron microscopy,and X-ray diffraction. The results indicated that the composite synthesized with formic acid(FA) as the regulator possessed the largest average pore diameter(12.41 nm) and was thus denoted as FE@MOF-808(FA).Adsorption experiments revealed that the uptake of DS was a spontaneous,exothermic,and entropy-increasing process,which followed a monolayer adsorption mechanism involving both physisorption and chemisorption. The Langmuir model fitted at 308 K yielded a maximum adsorption capacity of 251.57 mg/g. Furthermore,Zeta potential and Fourier transform infrared(FT-IR) spectroscopy analyses suggested that the primary mechanisms for DS adsorption involved electrostatic interactions,hydrogen bonding,and complexation. The adsorbent retained nearly 55% of its initial adsorption efficiency after four adsorption-desorption cycles. This work provides a novel strategy for the green design and recycling of efficient adsorbents,demonstrating great potential for purifying pharmaceutical-contaminated water.
摘要:In this study,terephthalic acid(H2BDC) was utilized as an organic ligand,and Cu2O nanocubes were employed to gradually release Cu+,which is subsequently oxidized by dissolved oxygen to serve as the metal center. This approach led to the synthesis of two-dimensional Cu-organic framework(2D Cu-BDC) materials,and an electrochemical sensor was developed for the simultaneous detection of bisphenol A(BPA) and 2-nitrophenol(2-NP). The results indicate that 2D Cu-BDC exhibits excellent electrocatalytic activity,selectivity,and detection performance for both phenolic compounds. The detection range for BPA is 2~50 μmol/L,with a detection limit of 0.53 μmol/L. Similarly,the detection range for 2-NP is 2-50 μmol/L,with a detection limit of 0.88 μmol/L. The recoveries of BPA and 2-NP in water samples from the Yangtze River ranged from 95.7% to 109% with RSD of 1.8%-2.1%. The electrochemical sensor developed in this study offers a simple and reliable method for the qualitative and quantitative detection of BPA and 2-NP in environmental samples.
摘要:The use of biomass raw materials for producing high-value-added chemicals is gaining significant attention in the academic community. This study used a simple,environmentally friendly microwave hydrothermal method to create a novel N-doped carbon dots (T-CDs) from Taraxacum mongolicum Hand.-Mazz..The optical properties,morphology,elemental composition,and surface functional groups of the prepared T-CDs were characterized. It exhibits excitation-dependent emission behavior and emits blue fluorescence under 365 nm UV lamp illumination. T-CDs also exhibit excellent salt resistance,light bleaching resistance,and fluorescence stability within the pH range of 4.0-8.0. The surface functional groups (—NH2,—COOH) of T-CDs specifically coordinate with Co2+ and the internal filtering synergistic effect enhanced the selectivity and sensitivity of T-CDs fluorescence probe for Co2+ recognition. The linear detection range was 0-10 μmol/L,and the detection limit (LOD) was 18 nmol/L (r2=0.999 51). With that,detection of Co2+ in the tap water sample and farmland soil sample with highly reproducible results had been successfully realized by using the present T-CDs,and the recovery is 98.1%-111% with RSD≤3.2%. Furthermore,T-CDs has good biocompatibility and exhibit significant antioxidant activity. The IC50 values for the scavenging of DPPH· and ABTS+· were 0.610 and 0.112 mg/mL,respectively,which were significantly better than those of their aqueous extract. The excellent Co2+ recognition and free radical scavenging activity of T-CDs make them promising for the simple detection of Co2+ in the complex environmental matrices,and biomedical antioxidant applications.
摘要:Herein,a novel coumarin-based fluorescent probe CAM was designed and prepared,which uses coumarin as the fluorophore and antipyrine as the recognition group. In the presence of Fe3+,the probe's fluorescence is significantly quenched,which can be attributed to the chelation fluorescence quenching (CHEQ) effect caused by the formation of the CAM-Fe3+ complex after recognizing Fe3+. The detection limit for Fe3+ by probe CAM can be as low as 5.27×10-8 mol/L. High-resolution mass spectrometry (HR-MS) was used to investigate the response mechanism of the probe to Fe3+. The probe CAM exhibits rapid response (80 s),excellent water solubility and strong interference resistance. Based on these advantages,the probe CAM“test paper”was combined with smartphone intelligent recognition to analyze and detect Fe3+ in tap water and lake water. It is worth mentioning that the probe CAM has been successfully applied to the biological imaging of cells and mice in vivo.
摘要:In this study,a method for the analysis of 34 β-lactam antibiotics in cosmetics was established based on ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). The samples were extracted with 20% acetonitrile solution,and lipophilic impurities were removed by n-hexane extraction. After centrifugation, the lower layer solution was collected and separated using an Agilent ZORBAX SB-Aq column(2.1 mm×100 mm,1.8 µm) with a mobile phase of 0.2% formic acid solution and acetonitrile in gradient elution. Analyzed by electrospray ionization source(ESI) in both positive and negative ion modes,with multiple reaction monitoring(MRM),and matrix matching curves were used for quantitative analysis.The results showed good linearity(r>0.995) for 34 β-lactam antibiotics in corresponding concentration ranges. The limits of detection(LODs) and quantitation(LOQs) were 0.03-1.5 μg∙g-1 and 0.1-5 μg∙g-1,respectively. The average recoveries of four cosmetic matrices(cream,emulsion,aqueous,gel) at three different spiked levels ranged from 85.9% to 111%,with relative standard deviations(RSDs,n=6) of 0.90%-8.0%. The method is simple,rapid,sensitive and accurate and can be used for the determination of 34 β-lactam antibiotics in cosmetics,which could provide technical support for the quality control and market supervision of cosmetics.
关键词:ultra performance liquid chromatography-tandem mass spectrometry;cosmetics;β-lactam antibiotics;cephalosporin antibiotics;penicillin antibiotics;illegal addition
摘要:To address the issues of expensive instrument dependence and insufficient sensitivity in traditional ginseng gene identification methods,the study developed a dual-mode sensor based on the autocatalytic assembly of DNAzyme for the efficient detection of ginseng-specific genes. The sensor utilized synthetic RuCOFs@EDTA material as the substrate signal material for both fluorescence(FL) and electrochemiluminescence(ECL). By integrating the catalytic hairpin assembly(CHA) strategy with the double-ended catalytic DNA molecule(DNAzyme) strategy,a“assembly-catalysis”dual signal amplification mechanism was established. Ginseng-specific genes trigger the CHA reaction,forming a dumbbell-shaped double DNAzyme structure that activates catalytic activity. This activated DNAzyme cleaves the bisferrocene-labeled substrate probe,eliminating signal quenching and enabling signal recovery. Within the target gene concentration range of 5×10⁻¹⁶ to 5×10⁻¹¹ mol/L,the limits of detection(LODs) for FL and ECL modes were as low as 0.24 fmol/L and 0.09 fmol/L,respectively,with excellent selectivity and reproducibility. In the detection of actual ginseng DNA samples,the recoveries ranged from 97.3% to 103%,demonstrating good anti-interference ability and practical application potential. This sensor,which does not rely on PCR instruments,combines high sensitivity,high specificity,and convenience,providing a novel technical approach for the molecular identification of the authenticity of ginseng and other Chinese herbal medicines.
摘要:To study the key differential smoke components in cigar filler tobacco from different domestic growing regions in China,the mainstream smoke components in 24 cigar filler tobacco from Yunnan,Sichuan,Hainan and Hubei were analyzed by middle heart-cutting two-dimensional gas chromatography-mass spectrometry. Through multivariate analysis methods,key differential components were screened out,and in combination with the environmental factors of the production area,the formation pathways of differential compounds in flue gas were preliminarily explored to further identify the key ecological factors that may cause their differences.Research results showed that a total of 337 mainstream flue gas components were identified. Cigar filler tobacco samples from Hainan exhibited significantly higher amount of nitrogen-containing compounds and phenols compared to the other three regions. Samples from Hubei contained the highest total amount of terpenes among the four regions. PCA and OPLS-DA analyses effectively differentiated the smoke components of cigar filler tobacco from four regions.Taking VIP>1,p<0.05 and |log2FC|>0.5 as the screening indicators,a total of 14 key differential compounds were screened out including 3-acetylpyridine,1,3,8-p-menthotriene,1-hydroxy-2-butanone,belolene,1,3-di-tert-butylbenzene,α-farnesene,squalene,3,4,5-trimethylphenol,2-methylresorcinol,2-methylpyrimidine,isopentenol,β-bisabolene,3-hydroxy-2-butanone,and acetonitrile.
关键词:domestic cigars;smoke components;middle heart-cutting;two-dimensional gas chromatography-mass spectrometry;growing region environment
摘要:Bio-based p-xylene(PX) is a precursor for the production of bio-based terephthalic acid(PTA),which is the core material for the manufacture of bio-based rigid cyclic polyesters such as PET,PBT and PTT. The synthesis of bio-based PX by the two-step route“cellulose→2,5-hexanedione(HDO)→PX”generates a large number of unknown volatile impurities in the process material,which seriously affects the oxidative refining and polymerization reaction in the subsequent sequence,so it is crucial to develop the separation and purification technology of bio-based PX. In this study,the volatile components in the bio-based PX feed solution were analyzed by GC-MS,and the stability of the feed solution system was evaluated by means of multivariate statistical analysis. The results showed that 100 volatile organic compounds were detected in the feed solution,including 71 hydrocarbons,4 alcohols,2 phenols,8 ketones,2 esters,7 furans and 6 other compounds. Among them,the PX content showed small inter-batch differences,and the content of the reaction substrate 2,5-hexanedione showed significant differences. According to the results of multivariate statistical analysis,the early batch(Sample #1) showed a large difference from the other batch samples(Sample #2-Sample #7),and the subsequent batches showed better stability overall. In this study,the composition of bio-based PX feed and its stability were systematically analyzed and an evaluation model was established,which can provide data support for the development of subsequent separation processes.
摘要:Different from the GB/T 16988-2013 standard“Quantitative determination for mixtures of special animal fibre and wool”which uses manual methods to distinguish and measure the fiber content of animal hair and its blended products,the fiber content analysis technology based on artificial intelligence uses a microscope to automatically scan and capture animal fiber images,integrates advanced methods such as image recognition and image processing,establishes a fiber classification model,and then completes the automatic quantitative analysis of fiber content. This paper introduces the principle of the artificial intelligence quantitative analysis method for the composition of animal hair fibers,designs a balance and uniformity level test for animal hair blended fibers with 8 laboratories and 4 types and 3 mass levels each,conducts a method validation test for the artificial intelligence quantitative analysis method,and evaluates the trueness and precision of the method. The test results show that the accuracy of the artificial intelligence quantitative analysis method is reliable and the precision meets the requirements of detection applications. It can be equivalent to replacing the manual test method of the GB/T 16988-2013 standard,and provide more efficient and stable quantitative detection results,and has broad application prospects.
摘要:Mycotoxin contamination is a significant factor affecting the quality and safety of traditional Chinese medicine(TCM). Ochratoxin A(OTA) is highly toxic and widely contaminated in TCM,so it is particularly necessary to develop rapid and accurate methods for its detection. To address interference from complex matrices in TCM,this study developed a colloidal gold strip method based on a matrix classification strategy for the rapid detection of OTA. Through systematic optimization of detection conditions and pretreatment processes,the sensitivity and matrix applicability of the method were significantly improved. Results demonstrated a cut-off value of 0.4 ng·mL-1 for OTA,with methanol tolerance up to 30%. The method exhibited excellent repeatability and stability,proving applicable to 74 kinds of TCM matrices derived from diverse medicinal parts. The detection results of 50 batches of real samples(Astragal Radix,Arecae Semen,Glycyrrhizae Radix et Rhizoma,and Zingiberis Rhizoma) indicated that OTA was detected only in the Arecae Semen samples,which was verified by the LC-MS/MS. The method developed was sensitive,rapid,and widely applicable,providing a robust platform for on-site ochratoxin screening in complex TCM matrices.
关键词:traditional Chinese medicines;ochratoxin;colloidal gold immunochromatographic assay;matrix applicability;rapid screening
摘要:Ultra-high performance liquid chromatography-high resolution mass spectrometry was applied for the analysis of 26 bile acids(BAs). Serum samples were subjected to protein precipitation,followed by centrifugation to collect the supernatant. Separation was carried out on a Phenomenex Kinetex C18 column(2.1 mm×100 mm,2.6 μm) using a gradient elution program with a mobile phase consisting of 5 mmol/L ammonium acetate in water and methanol. Detection was performed in electrospray negative ionization mode,and quantification was achieved using the external standard method. The method demonstrated excellent linearity for all analytes over the concentration range of 0.04-1 163.5 ng/mL,with correlation coefficients(r2) not less than 0.999 0. The limits of detection and limits of quantification were 0.01-0.86 ng/mL and 0.04-2.22 ng/mL,respectively. The recoveries were 68.1%-99.8%,and the relative standard deviations varied between 0.10%-10%. This validated method was successfully applied to the quantification of bile acids in serum samples from different sources,providing a reliable technical framework for investigating bile acid metabolism and screening potential disease biomarkers.
摘要:A rapid screening method for multiple pesticide residues in pears by thermal desorption low-temperature plasma time-of-flight mass spectrometry(TD-LTP-TOF MS) was developed. Pears were used as a substrate,and after a simplified QuEChERS pre-treatment,were assayed under optimized experimental conditions using a positive ion monitoring mode,and the results were compared and validated with liquid chromatography-triple quadrupole mass spectrometry(LC-TQ MS). The results showed that the correlation coefficients(r2) of the 26 pesticides were greater than 0.99 in the linear range,the spiked recoveries ranged from 72.2% to 119%,and the relative standard deviations(n=6) were less than 10% in all cases. The limits of detection(LODs) ranged from 0.1 to 184.9 μg/kg and the limits of quantification(LOQs) ranged from 5.0 to 1 000.0 μg/kg,which were in accordance with the national standards. The TD-LTP-TOF MS results of the 26 pesticides were consistent with the LC-TQ MS results after adjusting the linear ranges of pyrimethanil and pyridaben in the screening analysis of commercially available pears. The method can complete the detection of individual samples within 10 min,and has the advantages of rapidity,simplicity and broad-spectrum,which can be widely used for the rapid screening of various pesticides in fruits.
关键词:thermal desorption low-temperature plasma time-of-flight mass spectrometry;pears;pesticide residues;rapid screening;liquid chromatography-triple quadrupole mass spectrometry
摘要:An integrated strategy combining network pharmacology with high performance liquid chromatography(HPLC) fingerprint spectrum-effect correlation was developed to identify the key quality markers of Coptidis Rhizoma for type 2 diabetes mellitus. A compound-target-disease network was constructed,prioritizing six bioactive alkaloids—coptisine,jatrorrhizine,epiberberine,palmatine,obacunone and berberine—based on topological centrality. HPLC fingerprints of ten batches were established,and in vitro α-glucosidase inhibition and antioxidant assays were conducted. Grey relational and bivariate correlation analyses demonstrated significant positive associations between the hypoglycemic effect and the levels of berberine,obacunone,epiberberine and coptisine. Principal component analysis and hierarchical clustering revealed marked inter-batch compositional divergence. An activity-oriented quality evaluation paradigm was thus established,transcending traditional compound-centric approaches and definitively designating the four aforementioned constituents as core quality markers for Coptidis Rhizoma in type 2 diabetes mellitus management. These findings provide a robust scientific foundation for the standardization,quality control and precision clinical application of this botanical drug,advancing the modernization of traditional Chinese medicine and evidence-based therapeutics.
摘要:This study developed a rapid and high-throughput liquid chromatography-tandem mass spectrometry(LC-MS/MS) method for the simultaneous quantification of 10 antipsychotic drugs in human serum. The sample preparation process employed solid-phase supported liquid-liquid extraction(SLE),which offers improved reproducibility and reduced matrix effects compared to traditional liquid-liquid extraction. Methyl tert-butyl ether(MTBE) was used as the elution solvent due to its high extraction efficiency and low residue. After extraction,the eluate was concentrated under a gentle nitrogen blow-down process to ensure minimal loss of volatile analytes and then reconstituted with a 50% methanol-water solution to enhance compatibility with the LC mobile phase. The chromatographic conditions were meticulously optimized to enhance sensitivity and specificity for the target analytes. The method demonstrated excellent linearity over the tested concentration ranges,with correlation coefficients(r) greater than 0.999 for all 10 antipsychotics. The limits of detection(LOD) and quantification(LOQ) were in the ranges of 0.002-0.075 ng/mL and 0.005-0.250 ng/mL,respectively,indicating high sensitivity capable of detecting trace levels in clinical samples. The recoveries ranged from 87.3% to 112%,confirming the efficiency and consistency of the extraction process. Both intra-day and inter-day precision,expressed as relative standard deviations(RSDs),were not more than 13%,highlighting the method's reproducibility under varied conditions. Matrix effects were evaluated and found to be between 87.2% and 115% with RSD values less than 15%,demonstrating minimal impact from serum components on the accuracy of the measurements. Furthermore,the method was fully validated according to international guidelines and proven to be robust and reliable for high-throughput applications. This method offers a practical,sensitive,and reproducible approach for the simultaneous determination of multiple antipsychotic drugs in serum,supporting therapeutic drug monitoring(TDM) and clinical research in psychiatric treatment. Its high throughput capability,minimal matrix interference,and reliability at low concentrations make it an attractive and modern alternative to existing analytical methods.
摘要:A high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) method was established for the determination of spiramycin Ⅰ and its metabolite(neospiramycin Ⅰ) in livestock and poultry tissues and milk. After extraction of the samples with hydroxymethyl aminomethane(Tris) and precipitation of proteins with metaphosphoric acid,the extracts were purified with HLB columns. The extracts were separated on a reversed-phase C18 column(100 mm×2.1 mm,2.7 μm) by gradient elution with acetonitrile and 0.1% formic acid aqueous solution. Tandem mass spectrometry with electrospray ionization was used to carry out quantitative analysis in positive ion and multiple reaction monitoring(MRM) mode by external standard method. The extraction solution,the types of SPE columns,and pH of the working solutions were evaluated. The chromatographic conditions and mass spectrometric parameters were optimized. The results showed that excellent linearity was obtained in the range of 0.2-20.0 μg/L with the correlation coefficients(r) higher than 0.999. The limits of detection(LODs) were 10 μg/kg and the limits of quantification(LOQs) were 50 μg/kg for the target analytes. At spiked levels of 50-600 μg/kg,the average recoveries ranged from 71.8% to 102%,with relative standard deviations(RSDs) ranging from 1.7% to 8.5%. The method conforms to the criteria for quality control of veterinary drug residue analysis in foods and can be applied to the simultaneous detection of spiramycin Ⅰ and its metabolite in various matrices,including muscle,viscera,and milk from livestock and poultry.
摘要:A method of ultrahigh performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) was developed for the detection of butomidate,secbutomidate,and major metabolites in blood. The blood samples were extracted by precipitation protein using a mixed solution of methanol-acetonitrile(1∶3),then separated on a XSelect HSS T3 column(100 mm×2.1 mm,2.5 μm) by gradient elution,with 0.1% formic acid water and 0.1% formic acid acetonitrile as mobile phases,and electrospray ion source(ESI) in multi-response monitoring (MRM) mode. The results indicated that the linear relationship of butomidate,secbutomidate,and etomidate acid was good in the range of 0.1-100 ng/mL,with correlation coefficients(r2) not less than 0.999 1. The limits of detection(LODs) and the limits of quantitation(LOQs) were in the range of 0.001-0.01 ng/mL and 0.004-0.03 ng/mL,respectively. The matrix effects ranged from 80.1%-120%,and the recoveries ranged from 90.1%-96.9%,with the intra-day relative standard deviations(RSDs) not more than 8.3% and inter-day RSDs not more than 9.7%. The method has the advantages of simple operation,good selectivity,wide linear range,high sensitivity,and it is suitable for the identification of butomidate,secbutomidate,and etomidate acid in blood.
关键词:UPLC-MS/MS;butomidate;secbutomidate;etomidate acid;fragmentation rule;qualitative and quantitative analysis
摘要:This study developed an online aerosol thermodesorption sampling system based on an aerodynamic lens. The system primarily consists of a gas-phase denuder,a high-throughput wide-range lens,and a thermodesorption module. The lens sampling system,optimized through fluid simulation,achieves high-flow sampling at 575 mL/min and a wide particle transmission range of 0.1-13.0 μm. Experimental results demonstrate that the gas-phase denuder achieves 99.74% adsorption efficiency for volatile gases and maintains particle transmission efficiency ranging from 93.56% to 99.70% for particles within the 100-500 nm size range,effectively eliminating VOCs interference in organic aerosol samples while minimizing particle transmission losses. The lens thermodesorption sampling system was coupled with a single photon ionization time of flight mass spectrometer(SPI-MS) to conduct online detection and analysis of smoke particles from different biomass combustion sources,including cigarettes,moxa sticks,and mosquito coils. This work demonstrates the application capability of this combined system for detecting particle-phase VOCs of biomass combustion products. The aerosol sampling system can be used for a variety of traditional vacuum-ionization mass spectrometers,and has a broad application prospect.
关键词:aerosol;volatile organic compounds;aerodynamic lens;vacuum ionization source mass spectrometer
摘要:To address the problems of traditional Au/Ag particle-based SERS substrates—such as easy aggregation and deactivation,poor signal uniformity,and insufficient specificity in morphine detection,this study developed a three-dimensional SERS detection device based on Au-modified mesoporous silica nanoarrays(Au-JSiNA) for rapid identification and quantitative analysis of morphine in complex matrices. The device consists of an Au-JSiNA sensing chip and a portable Raman unit,with the chip fabricated through mesoporous array construction,gold nanolayer deposition,and functional modification. Performance tests showed that the device achieved approximately one order of magnitude signal enhancement,with a limit of detection of 0.10 nmol/L(r²=0.941) in aqueous solution and 0.13 nmol/L(r²=0.948) in ethanol solution. The device consistently identified the characteristic peaks at 623,1 254,1 367 and 1 603 cm⁻¹,demonstrating stable and sensitive detection capability;In urine samples,the device exhibited good precision and anti-interference performance,with spiked recoveries ranging from 91.8% to 104%,showing strong consistency with LC-MS/MS results(r=0.987);in blood samples,the characteristic peaks were also stably identified,demonstrating good sensitivity and applicability. Combining high sensitivity,reproducibility,and robustness against interference,this device provides novel technical support for on-site rapid screening and holds significant practical value in fields such as pharmaceutical safety and criminal investigation.
关键词:surface-enhanced Raman spectroscopy(SERS);morphine detection;Au-JSiNA 3D structured chip;mesoporous silicon nanostructure;detection device
摘要:Scanning electrochemical microscopy(SECM) is an important electrochemical characterization technique that works by measuring the current response of an ultramicroelectrode(UME) in a solution near the substrate to obtain information about the surface of a sample. Ultramicroelectrodes are available in three-dimensional sizes from nanometers(a few nanometers) to micrometers(25 micrometers). When the ultrafine electrode approaches the substrate surface,its electrochemical response can provide important information about the physical and chemical properties of the substrate,including but not limited to parameters such as surface morphology,electrochemical activity,and reaction kinetics. In this paper,the SECM redox system applied to cell analysis is systematically reviewed,focusing on the physicochemical properties of redox pairs and their interaction mechanism with cells,and divides the media into iron groups(such as ferrocenecarboxylic acid,ferrocyanide),ruthenium groups(such as hexaammineruthenium),other metals(such as cobalt complexes,hexachloroiridium),quinones(such as benzoquinone,menaquinone),amine/phenols(such as p-aminophenol) and other classes(such as thioredionone),and summarizes the hydrophilicity/lipophilicity,membrane penetration ability,and the characteristics of hydrophilic media(such as ferrocenecarboxylic acid and hexaammineruthenium) are mainly used for cell morphology imaging and membrane integrity assessment because they cannot penetrate cell membranes. Hydrophobic media(e.g.,ferrocenemethanol,benzoquinone) can enter cells across the membrane and are suitable for monitoring intracellular redox status,metabolic activity,and enzyme-catalyzed reactions. Some media achieve signal amplification through coupled strategies such as ferrocyanide and menaquinone. This paper summarizes the selection and specific application of the inductive system,in order to provide reference and guidance for the study of SECM technology in cell biology,toxicology and disease mechanism.
摘要:Tumor markers are biologically active substances abnormally produced or released by tumor cells or the host body in response to the presence of a tumor. These primarily include proteins,nucleic acids,circulating tumor cells(CTCs),small extracellular vesicles(sEVs),and metabolites,which can be detected in blood,body fluids,or tissues. The tumor markers typically exist at low concentrations,particularly during the early stages of cancer development. Therefore,highly sensitive and accurate detection technologies play a significant role in the early screening,therapeutic effect monitoring and prognosis assessment,recurrence warning,and precision medicine of cancer. RNA-cleaving DNAzyme is a bifunctional nuclease with both molecular recognition and catalytic cleavage. This unique property makes them highly promising for the precise detection of trace or ultratrace levels of tumor biomarkers. This article provides a systematic review of the working principles of RNA-cleaving DNAzyme,with a focused analysis of their applications and recent advances in tumor biomarker detection. Furthermore,it comprehensively summarizes research progress in multiplexed tumor marker detection using RNA-cleaving DNAzyme,particularly highlighting their integration with microfluidic chips,microarray platforms,and point-of-care testing(POCT) systems. Finally,the review offers perspectives on future research directions and potential clinical applications of these catalytic nucleic acids.