最新刊期

    42 12 2023

      Scientific Papers

    • FANG Jun-lan,ZHANG Dan-yang,YI Yue-xing,LIU Ying-ying,CHAI Yun-feng,LI Zu-guang,CHEN Hong-ping
      Vol. 42, Issue 12, Pages: 1537-1546(2023) DOI: 10.19969/j.fxcsxb.23080405
      摘要:An ultra high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometric(UHPLC-Q-Exactive Orbitrap MS) method was established for the simultaneous determination of 166 pesticide residues in tea. The samples were pretreated by modified QuEChERS technology. In Full MS mode,the accurate molecular ion was employed as quantitative ion. The characteristic fragment ions and secondary mass spectrometry informations were used for qualitative analysis,and the external standard method was adopted for quantification. The accuracy and precision of the method were verified by taking green tea and black tea as sample matrices. Fifteen pesticides in green tea had good linear relationships in the range of 4-200 μg/L,and the remaining 151 pesticides had good linear relationships in the range of 2-200 μg/L. All pesticides in black tea had good linear relationships in the range of 2-200 μg/L,and the correlation coefficients(r) were all greater than 0.99. Matrix effects of green tea and black tea were -56%-63% and -19%-110%,respectively. The recoveries of 116 pesticides in both green tea and black tea were all in the range of 70%-130% at four spiked levels. The relative standard deviations(RSDs) of 99% and 87% pesticides in green tea and black tea were both less than 20%. The limits of quantitation(LOQs) were 10-25 μg/kg. The method was applied to analyze the pesticide residues in 20 real tea samples(14 green teas and 6 black teas). Nine pesticides were detected in green tea and black tea samples,and the residues were lower than the national standard maximum residue limits. This method provides a reference for high-throughput screening and detection of pesticide residues in tea.  
      关键词:tea;UHPLC-Q-Exactive Orbitrap MS;pesticide residue;QuEChERS;screening   
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    • LIU Chang,ZHOU Xi,LUO Hui-tai,HUANG Fang,WU Hui-qin
      Vol. 42, Issue 12, Pages: 1547-1557(2023) DOI: 10.19969/j.fxcsxb.23072502
      摘要:This study applied ultra performance liquid chromatography tandem quadrupole electrostatic field orbitrap high resolution mass spectrometry(UPLC-Q-Orbitrap-HRMS) to analyze and identify isoquinoline alkaloids in the roots of Corydalis suaveolens Hance. The methanol extract of Corydalis suaveolens processed with a Poroshell RRHD C18 column(150 mm×2.1 mm,1.8 μm) with acetonitrile and 0.1% formic acid water solution as the mobile phase for gradient elution. The heated electrospray ion source(HESI) was adopted to collect the data in positive ionization modes. The chemical constituents were identified and confirmed by analyzing the mass data from the reference substances and literature. A total of 62 isoquinoline alkaloids were identified in the methanol extract of Corydalis suaveolens Hance,including 15 berberine-type alkaloids,15 tetrahydro berberine-type alkaloids,14 benzylisoquinoline alkaloids,3 aporphine alkaloids,6 protamine type alkaloids,7 benzene not pyridine type alkaloids,and 2 dihydrobenzene not pyridine type alkaloids. This study comprehensively and systematically analyzed the components of isoquinoline alkaloids in the Corydalis suaveolens Hance,and provided a reference for the subsequent study of material basis and development.  
      关键词:Corydalis suaveolens Hance;UPLC-Q-Orbitrap-HRMS;isoquinoline alkaloids;component analysis   
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      发布时间:2023-12-25
    • WU Pei-shan,CHEN Yu-ping,LIANG Wei-xin,GUO Peng-ran,LEI Yong-qian,PAN Jia-chuan
      Vol. 42, Issue 12, Pages: 1558-1564(2023) DOI: 10.19969/j.fxcsxb.23091501
      摘要:An in-situ device based on fluorescence photometry for the determination of petroleum contaminants in water is developed. This device is designed as an immersion underwater probe to measure the concentration of petroleum pollutants in water based on the fluorescence intensity of aromatic components in petroleum pollutants. The influence of optimal excitation wavelength and emission wavelength and different excitation light sources on determination are investigated,and an integrated underwater detection optical path is designed. The results show that the in-situ oil measuring device has a good linear results(r2=0.999 1) in the concentration range of 0-20 mg/L oil in water. And the indication error of device is within 3% at concentration of 1 mg/L and 10 mg/L,the repeatability relative standard deviation(RSD) is 2.6% at concentration of 10 mg/L. The result determined by in-situ oil measurement device is highly consistent with laboratory measurement(n-hexane extraction-fluorescence detection)(R=0.999 8). The recoveries of real samples are between 91.2% and 114%. This device does not require the use of organic solvent extraction and has good accuracy and stability,which can be applied to the rapid and in-situ detection of oil in water.  
      关键词:petroleum pollutants;in-situ detection;fluorescence photometry;underwater detection probes   
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    • 42-) and hydrogen phosphate(HPO42-),demonstrated a pronounced decrease,indicating minimal retention,while monovalent anions underwent ion exchange retention. Optimal separation of a suite of 12 anions,including fluoride(F-),acetate(CH3COO-),chlorite(ClO2-),bromate(BrO3-),chloride(Cl-),hydrogen phosphate(HPO42-),nitrite(NO2-),sulfate(SO42-),bromide(Br-),chlorate(ClO3-),oxalate(C2O42-),and nitrate(NO3-),was achieved within a 20 mins timeframe using a 3.6 mmol/L sodium carbonate(Na2CO3) eluent. Application of the tailored ion chromatography column to the detection of these anions in real samples,such as tap water,surface water,and industrial effluents,yielded a relative standard deviation(RSD,n=3) of less than 4.0%,underscoring its formidable potential for environmental analytical applications.","issue":"12","siteId":170,"isCollected":false,"keywordExt":"","keyword":"ion chromatography;hyperbranched modification;hydrophilic stationary phase;ion chromatographic column;anion","publicationName":"","publishDate":"2023-12-25","ppubDate":"2023-12-15","oa":0,"part":"Scientific Papers","graphicAbstract":0,"referenceStatus":1,"coverId":"","pictureUrl":"","showImg":0,"showAuthor":1,"docsource":"平台生产","vasDocsource":null,"notdsjcj":true,"dsjcj":false,"showDocSource":true,"vasDownloadLink":"","vasDocLink":"","volume":"42","type":"article","coverArticle":0,"analysisStatus":null,"sequence":null,"enhance":0,"elocationId":null,"wechatRelation":0,"pageOrElocationId":"pages:1565-1572","yearAndVolumeAndIssueStr":"Vol. 42, Issue 12, Pages: 1565-1572(2023) DOI: 10.19969/j.fxcsxb.23082202","formatType":"","version":"","firstStatus":0,"articleType":null,"cstr":null,"detailUrl":"/en/article/doi/10.19969/j.fxcsxb.23082202/","referenceCount":0,"downloads":3,"articleScore":0,"score":0,"rateEnable":false})'>Synthesis and Application of Hydrophilic Anion Chromatography Column Based on Hyperbranched Modification

      MENG Su-qian,LIU Bo,LIU Wei-jun,LIU Rui,SANG Liu-bo,LAI Hua-jie
      Vol. 42, Issue 12, Pages: 1565-1572(2023) DOI: 10.19969/j.fxcsxb.23082202
      摘要:The employment of hyperbranched dendritic modification techniques,recognized for their versatile and precise structural customization,is pivotal in the hydrophobic tailoring of polymer-based stationary phases for chromatographic applications. This investigation utilized polystyrene-divinylbenzene microspheres as a foundational substrate and engaged 1,4-butanediol diglycidyl ether alongside tetraethylenepentamine as epoxy-amine grafting agents,with methylamine serving as the terminal capping agent,to synthesize a hydrophilic ion chromatography stationary phase. The developed phase's morphology,structural attributes,and surface elemental composition were systematically characterized employing techniques such as scanning electron microscopy(SEM),Brunauer Emmett Teller(BET),Fourier-transform infrared spectroscopy(FTIR),and X-ray photoelectron spectroscopy(XPS). Subsequent incorporation into a chromatographic column facilitated the assessment of its separation efficacy and retention dynamics for inorganic anions and weak organic acids. Parameters including separation degree and theoretical plate count for specified ions were quantitatively established. The retention characteristics and chromatographic resolution of the fabricated column were scrutinized under variable conditions of concentration,temperature,and eluent composition. Outcomes indicated that the integration of hydroxyl functionalities via epoxy-amine dendritic branching markedly amplified the stationary phase's hydrophilicity. The retention of divalent anions,specifically sulfate(SO42-) and hydrogen phosphate(HPO42-),demonstrated a pronounced decrease,indicating minimal retention,while monovalent anions underwent ion exchange retention. Optimal separation of a suite of 12 anions,including fluoride(F-),acetate(CH3COO-),chlorite(ClO2-),bromate(BrO3-),chloride(Cl-),hydrogen phosphate(HPO42-),nitrite(NO2-),sulfate(SO42-),bromide(Br-),chlorate(ClO3-),oxalate(C2O42-),and nitrate(NO3-),was achieved within a 20 mins timeframe using a 3.6 mmol/L sodium carbonate(Na2CO3) eluent. Application of the tailored ion chromatography column to the detection of these anions in real samples,such as tap water,surface water,and industrial effluents,yielded a relative standard deviation(RSD,n=3) of less than 4.0%,underscoring its formidable potential for environmental analytical applications.  
      关键词:ion chromatography;hyperbranched modification;hydrophilic stationary phase;ion chromatographic column;anion   
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      发布时间:2023-12-25
    • LIU Hai-xia,YANG Cai-ling,RAO Hong-hong,LIU Fang,ZHANG Li,ZHAO Guo-hu
      Vol. 42, Issue 12, Pages: 1573-1579(2023) DOI: 10.19969/j.fxcsxb.23082201
      摘要:1,3,5-Tri(4-aminophenyl) benzene(TPB) and 2,5-divinyl-1,4-phenyldiformaldehyde(DVA) were adopted as monomers to prepare a homogeneous covalent organic framework(TPB-DVA-COF) coated stir bar. The stir bar combined with high performance liquid chromatography was used for the extraction and detection of six polycyclic aromatic hydrocarbons(PAHs) in environmental water samples. Scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared spectroscopy(FTIR) were performed to characterize the material to confirm successful preparation of TPB-DVA-COF. Meanwhile,a series of experimental parameters including ion strength,extraction temperature,stirring rate,extraction time and desorption time were optimized. Under the optimized conditions,there were good linear relationships for phenanthrene(Phe),fluoranthene(Fla) and pyrene(Pyr) in the range of 0.20-200 μg/L,chrysene(Chr),benzofluoranthrene(B[b]f) and benzopyren (B[a]p) in the range of 0.05-200 μg/L,with the correlation coefficients(r) not less than 0.998 5,and enrichment factor could be reached 225 folds. The limits of detection(LODs,S/N=3) were in the range of 0.007-0.150 μg/L,and the relative standard deviations(RSDs) were in the range of 3.8%-6.1% for one bar(n=5),respectively. In the case of real samples analyses,the spiked recoveries were 87.1%-104%. The results showed that the developed method could be successfully applied to the accurate and highly sensitive detection of PAHs in actual environmental water samples.  
      关键词:covalent organic framework material;stir bar adsorption extraction;high performance liquid chromatography;polycyclic aromatic hydrocarbons;environmental water   
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    • FAN Er-le,JIANG Xing-yu,ZHANG Jia-dong,ZHANG Ming-liang,HAN Hai-feng,ZHANG Da-bing,CHEN Yi
      Vol. 42, Issue 12, Pages: 1580-1587(2023) DOI: 10.19969/j.fxcsxb.23072402
      摘要:In order to solve the variable and irreproducible issues of heterogeneously synthesized chromatographic stationary phases,a new method of homogeneous synthesis was established and used to prepare two newly designed amphiphilic stationary phases,C22-A and C22-A/U,where C22 denotes a long docosyl terminal while U and A denote the strong polar insertions of urea and amide groups at the initial end,respectively. By the means of elemental analysis and nuclear magnetic spectrum,the two new stationary phases contain nitrogen elements,and the ratio of carbon and nitrogen elements accords with the theoretical value,indicating that the amide and urea-based polar groups are successfully bonded to silica gel. Through the chromatographic separation and analysis of the standard sample and the real sample,the shielding effect on upported silicon hydroxyl,hydrophobic selectivity,shape selectivity and hydrophilicity of the two new stationary phases were investigated. It is confirmed that the two new stationary phases have amphiphilic properties as reversed-phase liquid chromatography(RPLC) and hydrophilic interaction chromatography(HILIC). Compared with C18 stationary phases,C22-A and C22-A/U own better shape selectivity,and the double embedded polar groups greatly reduce the silica hydroxyl activity of the stationary phase. C22-A and C22-A/U were used for the separation of several alkaline compounds and estrone(ketone) compounds. The C22 stationary phase solved the problem of serious tailing or insufficient retention of alkaline compounds in the traditional C18 alkyl stationary phase,and successfully realized the separation of estrone(ketone) compounds.  
      关键词:chromatographic stationary phase;amphiphilicity;homogeneous synthesis;drug analysis;liquid chromatography   
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    • JIANG Hui-jie,ZHANG Yue,SHEN Kai-fen,JIANG Yan,ZHOU Dan-ying,ZHAO Hong-jing
      Vol. 42, Issue 12, Pages: 1588-1597(2023) DOI: 10.19969/j.fxcsxb.23080304
      摘要:A multi-wavelength automatic fusion fingerprint strategy was proposed to simplify the data processing process and applied to the quality evaluation of propolis ethanol extracts. 15 batches of propolis ethanol extracts from 5 manufacturers were tested at multiple wavelengths of 220,245,270,320 nm through UPLC technology. The sample was separated on an Agilent Poroshell 120 EC-C18(3 mm×100 mm,2.7 μm) column by gradient elution,with methanol and 0.2% phosphoric acid aqueous solution as mobile phases.The multi-wavelength fusion fingerprint for each batch was generated by using the“Similarity Evaluation System for Traditional Chinese Medicine Chromatographic Fingerprint”to achieve automatic fusion of various chromatographic peaks under multiple wavelengths. The differences between multi-wavelength fusion and 270 nm single wavelength were compared in common chromatographic peaks,similarity evaluation,cluster analysis,and principal component analysis. The multi-wavelength fusion fingerprint of propolis contained 33 characteristic peaks,in which 14 characteristic peaks have been identified to be caffeic acid,ρ-coumaric acid,ferulic acid,isoferulic acid,3,4-dimethoxy group cinnamic acid,quercetin,kaempferin,apigenin,isorhamnetin,chocine,chrysin,galangin,caffeic acid,phenethyl ester. The retention time RSDs of characteristic peaks in each batch were less than 1.00% and the peak area RSDs were ranged from 14.39% to 112.02%,with an average value of 37.94%. The similarity of 15 batches of propolis fusion fingerprints ranged from 0.902 to 0.994. The samples could be divided into four categories through the principal component analysis and the clustering analysis. The 270 nm single wavelength fingerprint of propolis contained 32 characteristic peaks,of which 12 have been identified. The similarity of 270 nm single wavelength fingerprint of 15 batches of propolis ranged from 0.928 to 0.997. The samples were divided into three categories by the principal component analysis and cluster analysis. Compared to the single wavelength of 270 nm,the multi-wavelength fusion similarity evaluation was more sensitive,and its principal component analysis and cluster analysis were more accurate. The strategy of multi-wavelength automatic fusion fingerprint could process multi-wavelength data quickly and automatically,enrich the chromatographic information of different components at different wavelengths,and improve the accuracy of differential evaluation of propolis fingerprint.  
      关键词:multi-wavelength;automatic fusion;fingerprint;propolis;quality evaluation;chemical pattern recognition   
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    • HAN Jin-zhi,LI Ya-ru,LUO Lin,GUAN Tian,LEI Hong-tao,CAI Wei-yi,WANG Bing-zhi,XU Zhen-lin
      Vol. 42, Issue 12, Pages: 1598-1606(2023) DOI: 10.19969/j.fxcsxb.23062703
      摘要:The aim of this paper is to establish a rapid detection method for tetrodotoxin by colloidal gold immunochromatography assay(GICA). Monoclonal antibody specific for tetrodotoxin was labelled with colloidal gold as tracers. The effects of pH,antigen and antibody concentration,ion concentration,surfactant type and sample pretreatment on the performance of GICA were carefully investigated. The results showed that under the optimal conditions,the quantitative detection limit of the proposed assay for tetrodotoxin was 0.5 ng/mL,the linear range was 0.8-10.6 ng/mL,and the qualitative detection limit was 12.0 ng/mL. The spiked recoveries for tetrodotoxin in pufferfish、nassariidae samples ranged from 70.5%-110% with relative standard deviations of 3.7%-7.1%,and the results were similar to those of the LC-MS/MS method. Compared with the traditional analytical techniques,the proposed GICA showed better feasibility,practicality and superiority for rapid detection in the field.  
      关键词:tetrodotoxin;monoclonal antibody;colloidal gold immunochromatography assay;rapid detection;aquatic products   
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    • LI Si-yuan,CHEN An-li,ZHAO Si-wen,YAN Xiao-hong,DING Yi
      Vol. 42, Issue 12, Pages: 1607-1614(2023) DOI: 10.19969/j.fxcsxb.23091802
      摘要:A gas chromatography-tandem mass spectrometric(GC-MS/MS) method was developed for the simultaneous determination of 7 dimethylcyclosiloxanes in cosmetics. Cosmetics samples with different matrices were dispersed with isopropyl alcohol and extracted with n-hexane,then separated on a HP-5MS UI capillary column(30 m×0.25 mm×0.25 μm),and detected by GC-MS/MS in multiple reactive ion monitoring(MRM) mode. The data were processed and quantified using the matrix-matched external standard method. The results showed that the 7 dimethylcyclosiloxanes had good linear relationships in the range of 50-1 000 ng/mL,with correlation coefficients(R) of 0.996 5-0.999 9. The limits of detection(LODs) and the limits of quantitation(LOQs) were in the range of 4.0-6.1 mg/kg and 13.2-20.4 mg/kg,respectively. The average recoveries were in the range of 85.1%-115%,with relative standard deviations(RSDs) of 0.90%-7.0%. The method was applied to test 102 batches of cosmetics sold on the market,and the detected components covered D4-D9. The method is convenient,fast,sensitive and accurate,which is suitable for the determination of the 7 dimethylcyclosiloxanes in cosmetics and could provide technical support for ensuring the quality and safety of cosmetics.  
      关键词:gas chromatography-tandem mass spectrometry(GC-MS/MS);dimethylcyclosiloxanes(DMCs);cosmetics   
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    • FAN Jia-li,JI Wen-hua,WANG Xiao,GUO Lan-ping,LI Li-li
      Vol. 42, Issue 12, Pages: 1615-1622(2023) DOI: 10.19969/j.fxcsxb.23052204
      摘要:The processing technology of Salvia miltiorrhiza Bge. is closely related to its quality. Chemical components analysis was performed out on Salvia miltiorrhiza Bge. samples prepared by fresh cutting(heat dried slices after fresh cutting,sun dried slices after fresh cutting) and dry cutting method(full dried slices,traditional dried slices) based on liquid chromatography-high resolution mass spectrometry(LC-HRMS) technology. Based on accurate mass,retention time and MS/MS data,27 primary metabolites(amino acids,fatty acids,organic acids,nucleotides) and 17 secondary metabolites(salvianolic acids,tanshinones) were identified from Salvia miltiorrhiza Bge. samples. Significant differences were found between the dry cutting methods and the fresh cutting methods by principal component analysis,and the difference between the two fresh cutting methods was small. Nine tanshinones and one salvianolic acid were screened as differential secondary metabolites. The abundance of tanshinone Ⅰ,tanshinone ⅡA and miltionone Ⅰ in full dried slices were higher than those in traditional dried slices and in sun dried slices after fresh cutting. The abundance of neotanshinone B,miltionone Ⅰ,miltionone Ⅱ,methyl rosmarinate,isocryptotanshinone,cryptotanshinone and salvianolic acid B in full dried slices were higher than those in sun dried slices after fresh cutting,and higher than those in traditional dried slices. The abundance of fatty acids in full dried slices are higher than that in traditional dried slices and in the sun dried slices after fresh cutting. Aromatic amino acids(phenylalanine,tyrosine,tryptophan) were precursors of secondary metabolites,and their abundance in dry cutting slices were significantly higher than that in the sun dried slices after fresh cutting. The above results indicated that the abundance of active ingredients in the fresh cutting method were lower than that in the dry cutting method. The soaking treatment of traditional slices could cause loss of active ingredients. Fully dried slices could accumulate more secondary metabolites,which obtain the best quality. The study can provide theoretical guidance for the cutting processing method of Salvia miltiorrhiza Bge. and technical support for the quality evaluation of Salvia miltiorrhiza Bge..  
      关键词:Salvia miltiorrhiza Bge.;chemical components;processing method;liquid chromatography-high resolution mass spectrometry   
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      Experimental Techniques and Methods

    • HAN Yong,MA Yan-xin,WANG Hui,WANG Ya
      Vol. 42, Issue 12, Pages: 1623-1630(2023) DOI: 10.19969/j.fxcsxb.23070404
      摘要:In this work,blue carbon dots(B-CDs) and yellow carbon dots(Y-CDs) were synthesized through a hydrothermal method using citric acid,L-cysteine(L-Cys) and o-phenylenediamine(OPD) as precursors respectively,then hybridized dual carbon dots to form a visual ratiometric fluorescent sensor(d-CDs) for the rapid detection of Ag+ in environmental water samples. The structural and optical properties of d-CDs were characterized using transmission electron microscope(TEM),Fourier transform infrared(FTIR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),ultraviolet absorption spectroscopy and fluorescence spectroscopy. The effects of pH,reaction temperature and incubation time of the sensor were investigated and optimized. The d-CDs are spherical with an average particle size of 2.14 nm,which were well dispersed and uniformly distributed in the solution. The d-CDs contain mercapto and aromatic ring structures and a large number of hydroxyl and carboxyl groups,which can induce d-CDs/Ag+ complexes in the presence of Ag+ and quenched the blue fluorescence of d-CDs by photoinduced energy transfer(PET). As the blue fluorescence decreases,yellow fluorescence significant increases in the ratiometric fluorescent system. The sensor showed good linear response in the range of Ag+ concentration 0-40 µmol/L with the r2 of 0.996 7 and the limit of detection(LOD) of 1.26 µmol/L. The spiked recoveries were 98.2%-105% with the relative standard deviations of 0.49%-3.8% in practical test. The method is rapid,simple,sensitive and reliable,and can realize the visual semi-quantitative detection of Ag+ in environmental water samples.  
      关键词:carbon dots;ratiometric fluorescent;visual detection;silver ions;water   
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    • QU De-ye,WANG Cai-hong,CHEN Jing,ZHU Meng-chen,YANG Ming-yue,XIA Bo,CHAI Wen-bo,YANG Shan-quan
      Vol. 42, Issue 12, Pages: 1631-1638(2023) DOI: 10.19969/j.fxcsxb.23072101
      摘要:An optimized solvent-induced extraction pretreatment method combined with ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) was established for the simultaneous and rapid determination of 20 herbicides in agricultural soil. In the experiment,1.5 mL of dichloromethane was used as extractant,5 mL of acetonitrile as extractant,and 8 min vortex time were used for extraction,and ZORBAX Eclipse Plus C18 column(100 mm×2.1 mm,1.8 μm) were used for separation,0.1% formic acid water and acetonitrile were used as mobile phase,and scanned with ESI mode. The results showed that 20 herbicides had good linearity in the corresponding mass concentration ranges with correlation coefficients not less than 0.999 0. The detection limit of the method ranged from 0.1-1.0 μg/kg,the average recoveries were 77.6%-115%,and the relative standard deviations were between 0.40%-3.8%. This method is simple,fast,sensitive,and requires less organic solvent,which is suitable for high-throughput detection of 20 herbicides in actual samples.  
      关键词:solvent-induced extraction;UPLC-MS/MS;herbicide;agricultural soil   
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    • ZOU Hai-fei,LI Min,DENG Shun-yan,XIA Bing,ZHOU Yan
      Vol. 42, Issue 12, Pages: 1639-1644(2023) DOI: 10.19969/j.fxcsxb.23071501
      摘要:A method was developed for high throughput and high sensitive detection of free triiodothyronine(FT3) and free thyroxine(FT4) in serum using gel filtration chromatography(GFC) and liquid chromatography-tandem mass spectrometry(LC-MS/MS). The hydroxypropyl cellulose gel Sephadex LH-20 column was used to filter and separate 150 μL serum samples. First of all,the thyroid hormones bound to binding proteins were removed by washing with tri(hydroxymethyl) aminomethane hydrochloride(Tris-HCl) buffer solution(0.1 mol/L,pH 7.4). Following that,the free thyroid hormones were eluted using methanol. The established LC-MS/MS analysis method was employed for detection and quantification. The results of the methodological validation showed that the correlation coefficient(r2) was not less than 0.999 5. The precision ranges from 1.8% to 10%,accuracy ranges from 85.4% to 110%,matrix effect ranges from 85.8% to 114%,and recoveries from 85.8% to 107%. According to the CLSI EP09-A3 method comparison guidelines,this method was further applied to the detection of 95 serum samples and compared with the equilibrium dialysis(ED),to evaluate the accuracy and applicability of the established GFC/LC-MS/MS method. The statistical analysis was performed using IBM SPSS Statistics 26 and MedCalc statistical software(v.20.0.0) for paired t-test analysis,Passing-Bablok regression analysis,and Bland-Altman agreement analysis. The statistical analysis results indicated that there was no significant difference(P>0.05) between the detection results of FT3 and FT4 in the serum measured by the developed GFC/LC-MS/MS method and the ED/LC-MS/MS method. The developed method can provide a reference method for rapid,efficient,and accurate detection of free thyroid hormones in clinical laboratories,as well as offering a new approach for the detection of other free hormones such as cortisol and testosterone.  
      关键词:liquid chromatography-tandem mass spectrometry;free thyroid hormones;gel filtration chromatography;serum   
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    • LANG Yu-bo,LI Hong-da,YAN Shi,LIU Chun-qing
      Vol. 42, Issue 12, Pages: 1645-1651(2023) DOI: 10.19969/j.fxcsxb.23071802
      摘要:This paper synthesized five carbon quantum dots based on the structures and properties of 2,4,6-trinitrotoluene(TNT),2,4,6-trinitrophenol(PA),tetryl,cyclotrimethylenetrinitramine(RDX),and pentaerythritol tetranitrate (PETN). A fluorescence colorimetric sensing array was constructed,and the fingerprints of TNT,PA,Tetryl,RDX and PETN were obtained using the data collected by microplate reader. The fluorescence colorimetric sensing array has good selectivity and anti-interference ability,which is basically unaffected by other common explosive ions. Finally,the correct classification of the above five explosives was further achieved with an accuracy rate of 100% by using principal component analysis(PCA) and Q-type hierarchical clustering analysis(Q-HCA). The established method has been successfully applied to the determination of explosive concentration in simulated samples.  
      关键词:carbon quantum dots;fluorescence colorimetric sensing arrays;metrology;explosive residue detection;public safety   
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    • HE Zhong-hai,CAO Gong-wei,JIA Qiong,ZHANG Xiao-fang
      Vol. 42, Issue 12, Pages: 1652-1658(2023) DOI: 10.19969/j.fxcsxb.23070901
      摘要:The predictive ability of the partial least squares(PLS) model established by near-infrared spectroscopy is often limited when there are changes in the composition of the test sample or environmental conditions,making it difficult to predict new samples accurately. In this case,the labeled samples containing the new changes need to be added to the calibration set for model update. However,the large size of the old calibration set combined with the limited number of new samples can make it difficult for the new changes to be reflected in the model. To be able to update the model quickly,this paper proposes a method to reduce the number of samples by selecting important old samples using kernel coefficients(KCS). A kernel model is built for the old samples to obtain the coefficients of each sample in the model,larger coefficients correspond to greater sample importance. Thus,samples with higher coefficients are chosen to reduce the sample size,and new samples are added to the part of old samples to update the model. The experiment compared the model updates of KCS by including a portion of old samples with the model updates by including all old samples with the new samples. The experiments were conducted on simulated and soybean meal datasets. Using a portion of old samples for model updates in KCS decreased the root mean square errors(RMSE) of the predictions from 1.165 and 0.730 before the update to 0.961 and 0.654 after the update,which represents a decrease of 17.5% and 10.4%,respectively. Using all old samples for model updates in KCS decreased the RMSE of the predictions from 1.110 and 0.720 before the update to 0.980 and 0.662 after the update,which represents a decrease of 11.7% and 8.1%,respectively.The results show that this method of selecting some important old samples for model updating solves the imbalance of the number of new and old samples,thereby accelerating the update speed of models.  
      关键词:PLS;kernel coefficients;model update;selection of significant samples   
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    • PAN Zheng-hao,WANG Peng,CHEN Kun-yan,LI Qiu-tong,TANG Jie,YANG Jun,SHAO Li-min
      Vol. 42, Issue 12, Pages: 1659-1665(2023) DOI: 10.19969/j.fxcsxb.23082802
      摘要:Variable selection is often used to optimize linear calibration models for NIR spectroscopy,eliminating redundant information and improving the accuracy and interpretability of regression. In this paper,a Monte Carlo-based method is studied and designed to find the optimal limit of variable selection for linear calibration models,and can evaluate the optimal degree that different linear calibration methods(such as partial least squares regression PLSR) can achieve in the subspace of variable selection. In this study,the distribution plot of the root mean square error prediction(RMSEP) of the validation metric is obtained,and the optimization effect and optimization limit of the variable selection methods on the dataset are revealed. The method was applied to the near-infrared spectroscopy modeling of three datasets,and the results showed that the optimizable rate on the tobacco-pectin dataset was about 24.98%,and the prediction error RMSEP was reduced by 15.2%. The optimizable rate on the wheat-protein dataset is about 13.90%,and the prediction error RMSEP is reduced by 9.5%. The optimizable on the corn-starch dataset is about 14.05%,and the prediction error RMSEP is reduced by 57.1%. The application of this method can quickly obtain the optimization limit of the variable selection methods on the model,and provide reference for the design,application and evaluation of the variable selection methods.  
      关键词:chemometrics;near-infrared spectroscopy;chemical calibration;linear model;variable selection;Monte Carlo method   
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      Review

    • LIU Nan,XU Li-li,ZHANG Xiao-mei,ZONG Ai-zhen,XU Tong-cheng,YOU Yan-li,ZHANG Hong-wei,XIAO Jing
      Vol. 42, Issue 12, Pages: 1666-1672(2023) DOI: 10.19969/j.fxcsxb.23053003
      摘要:Food allergen is tightly related to food safety,and technological progresses on the issue are realistically valuable to food allergy risk assessment. Compared with conventional immunological technique such as enzyme-linked immunosorbent assay(ELISA),high-resolution mass spectrometry(HRMS) is burgeoning in recent years for food allergic protein with its high-throughput characterization. In this paper,the research progress of HRMS technology for allergic protein detection is mainly reviewed,and extraction,purification and enzymatic hydrolysis of allergic protein,as well as HRMS-based analysis strategy and data acquisition is emphatically highlighted. Additionally,the challenges in the detection of allergic protein were also analyzed.  
      关键词:high-resolution mass spectrometry;food allergic protein;detection   
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