最新刊期
      卷 41 ， 期 5 ， 2022

        Scientific Paper

      • ZHANG Jing,RAO Zhu,YANG Zhi-peng,GUO Xiao-chen,LIU Chen,MENG Jian-wei,WANG Li-ping
        Vol. 41, Issue 5, Pages: 659-667(2022) DOI: 10.19969/j.fxcsxb.21080204
        摘要：A gas chromatography－mass spectrometric（GC－MS） method was developed for simultaneous and rapid determination of 102 kinds of acidic，alkaline and neutral organic pollutants in groundwater，including phenol，aniline，phenyl ether，polychlorinated naphthalene and biphenyl，etc．The simultaneous extraction condition for 102 kinds of acidic，alkaline and neutral organic pollutants in groundwater was optimized. It was confirmed that three-step liquid－liquid extraction method（first in neutral，then in acidic，finally in alkaline condition） could improve the method’s extraction recoveries，accuracy and precision.Under the optimized conditions，the linear ranges of 101 targets except pentachlorophenol were obtained within there respective mass concentration ranges，with correlation coefficients（r）of 0.995 0－0.999 9. The limits of detection were in the range of 1.8－19.7 ng/L. The spiked recoveries for groundwater samples at low，medium and high concentration levels ranged from 47.2% to 126%，43.0% to 117% and 38.8% to 120%，with the relative standard deviations（RSD，n = 7） of 1.1%－27%，2.6%－33% and 2.9%－30%，respectively（expect for pentachlorophenol，diisobutyl phthalate，dibutyl phthalate and bis（2-ethylhexyl）phthalate）．This method was used for the typical investigation on groundwater organic contamination in Shanxi and Henan．24 pollutants were detected，such as phenol，aniline，polycyclic aromatic hydrocarbons and their derivatives．The point detection rate reached 46.7%，which means the water quality presented the characteristics of point source pollution．The method is sensitive，accurate，simple and rapid，which will play an active role in the rapid screening of organic pollutants in groundwater in the future.  
        关键词：organic pollutants;simultaneous determination;groundwater pollutant;gas chromatography－mass spectrometry   
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        发布时间：2022-06-22
      • YANG Bao,LIANG Yun-xiao,HUANG Zong-sheng,TU Xing,ZHOU Chang-yuan,HU Ze-hua,WEN De-jian,ZHANG Qi-song
        Vol. 41, Issue 5, Pages: 668-674(2022) DOI: 10.19969/j.fxcsxb.21040603
        摘要：The aim of this paper is to explore the metabolic biomarkers and regulation pathways of colorectal adenoma for better understanding of its pathogenesis．The serum samples of 46 colorectal adenoma patients（age 57.8 ± 10.7） and 45 healthy controls（age 54.4 ± 8.2） were analyzed by ultra-high performance liquid chromatography－Q exactive orbitrap mass spectrometry in an untargeted metabolomic approach. The metabolomics data acquired were analyzed using an unsupervised principal component analysis to visualize the grouping trends and detect outliers．A supervised orthogonal partial least squares discriminant analysis（OPLS－DA） was subsequently utilized to maximize the discrimination．The established OPLS－DA model was validated by permutation test for 200 times．Values of variable importance for projection（VIP） were obtained from the OPLS－DA model．Volcano plots of all metabolites were constructed based on the log2-transformed fold-change and log10-transformed p-value．Then，the most altered serum metabolites responsible for the discrimination between two groups were screened based on the values of variable importance for projection（VIP > 1.50） and volcano plot analysis（p < 0.05 with fold change > 1.50 or fold change < 0.67），and further identified using the mzCloud and HMDB databases．The changed metabolic pathways were analyzed using MetaboAnalyst．ROC curves were used to verify the diagnostic ability of those metabolic biomarkers．The results showed that there were significant differences between the serum metabolic profiles of two groups．20 metabolic biomarkers were screened and identified，including essential amino acids，unsaturated fatty acids，sphingolipids，phospholipids and bile acids，and the corresponding disturbed metabolic pathways were valine，leucine and isoleucine biosynthesis，arachidonic acid metabolism，α-linolenic acid metabolism，linoleic acid metabolism，aminoacyl-tRNA biosynthesis，sphingolipid metabolism，glycerophospholipid metabolism and tryptophan metabolism．Among the 20 metabolic biomarkers，juniperic acid，arachidonic acid，creatinine，valine，leucine，tryptophan，linolenic acid，taurochodeoxycholic acid and LysoPC（20∶3） showed high specificity and sensitivity with their areas under the ROC curves（AUC）greater than 0.90，which meant strong diagnostic ability and potential clinical application in serum-based metabolomics screening for colorectal adenoma．This study provides some basic data that could be used to clarify the metabolic characteristics of colorectal adenoma．  
        关键词：colorectal adenoma;ultra-high performance liquid chromatography－Q exactive orbitrap mass spectrometry;metabolomics;serum;biomarkers   
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        发布时间：2022-06-22
      • HUANG Xiao-mei,DENG Xiang,DENG Zi-he
        Vol. 41, Issue 5, Pages: 675-681(2022) DOI: 10.19969/j.fxcsxb.21061202
        摘要：A highly sensitive "sandwich" electrochemical immunosensor was constructed for the detection of carbohydrate antigen 19－9（CA19－9），by synthesizing a unique "pearl necklace" structure of gold-silver bimetallic nanoclusters multi-walled carbon nanotubes-titanium dioxide nanocomposites（Au－Ag NCs@CNTs－TiO2 NPs） used as a signal label，carrier and signal amplifier．Firstly，the magnetic Au－Fe3O4 NPs with peroxidase mimetic properties were used to modify the electrode，then the anti－CA19－9 antibody and BSA were immobilized on the electrode surface through chemical bonding，and subsequently，the antibody was bound by specific reaction．Finally，Au－Ag NCs@CNTs－TiO2 NPs/Ab2/BSA biological coupling with redox activity and amplification was combined to form a sandwich immune structure．The experimental results showed that the response signal was effectively amplified by using double peroxide analog enzyme to catalyze H2O2 in the substrate. Under the optimal experimental conditions，CA19－9 showed a good linearity in the concentration range of 0.01－200 U/mL，with a detection limit of 0.003 U/mL．The recoveries of the immunosensor ranged from 94.6% to 105%，with relative standard deviations（RSD） of 4.3%－6.5%，indicating that the immunosensor could be used for the detection of CA19－9 in clinical serum samples.  
        关键词：bimetallic nanoclusters;synergistic effect;Au－Ag NCs@CNTs－TiO2 nanocomposites;carbohydrate antigen 19－9   
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        发布时间：2022-06-22
      • YANG Xiao,YANG Jing-ying,PAN Ming-fei,SONG Yang,WANG Shuo
        Vol. 41, Issue 5, Pages: 682-691(2022) DOI: 10.19969/j.fxcsxb.21110206
        摘要：Isorhamnetin（IS） and rutin（RU），two flavonoid compounds present in seabuckthorn，have very strong antioxidant activities for effective removal of free radicals in human body．In this paper，IS and RU of high-purity were prepared by a high-pressure liquid phase preparation method with ethanol dissolution，then their chemical structures were identified by Fourier transform infrared spectroscopy（FT－IR），ultraviolet（UV） spectroscopy，mass spectrometry（MS） and H/C－nuclear magnetic resonance（H/C－NMR）．Furthermore，a typical HPLC method was used to evaluate the obtained IS and RU products in terms of homogeneity（inter and intra-bottles） and stability（long-term：6 months，－20 ℃；short-term：1 week，4 ℃ and －20 ℃），both of them were confirmed excellent by statistical data．Finally，the purities of the prepared IS and RU reference materials were jointly determined by multiple laboratories（n = 8） to be 99.16% and 99.22%，with their extended uncertainties of 0.14% and 0.13%，respectively．The IS and RU reference materials obtained in the study could be used as reliable references in drug analysis or quality evaluation on seabuckthorn products．This study provided an effective method for the preparation and identification of IS and RU reference materials in seabuckthorn，which could be applied to the preparation of other reference materials．  
        关键词：reference materials;seabuckthorn;isorhamnetin;rutin;preparation and identification   
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        发布时间：2022-06-22
      • CUI Yuan-yuan,YANG Cheng-xiong
        Vol. 41, Issue 5, Pages: 692-700(2022) DOI: 10.19969/j.fxcsxb.21082303
        摘要：A carboxyl enriched microporous organic network（MON-2COOH） with large surface area （720.2 m2·g-1），good solvent and thermal stability（280 ℃） was synthesized with carboxyl-contained monomers for rapid adsorption and efficient removal of benzotriazoles in water．The synthesized MON-2COOH was characterized by solid-state 13C nuclear magnetic spectroscopy，N2 adsorption - desorption，Fourier transform infrared spectroscopy，thermogravimetric analysis，scanning electronic microscopy and water contact angle analysis.The adsorption isotherms，kinetics and thermodynamics，effects of ionic strength，pH and humic acid of MON-2COOH for 1H-benzotriazole （BTri） and 5-tolyltriazole （5-TTri） were also investigatied in detail.The adsorption equilibriums of BTri and 5-TTri （100 mg·L-1） were realized within 10 min on MON-2COOH，showing the extremely fast adsorption kinetics of MON-2COOH for benzotriazoles．The pseudo-second-order kinetics plots showed good linearity for all three initial concentrations of BTri and 5-TTri，and the adsorption capacity values calculated from the pseudo-second-order model were all close to the experimental ones，both suggesting the well-fitting of pseudo-second-order kinetic model for BTri and 5-TTri on MON-2COOH．The good linearity of the Langmuir adsorption plots revealed the good plotting of Langmuir adsorption model and the monolayer adsorption process for BTri and 5-TTri on MON-2COOH．The MON-2COOH gave the large maximum adsorption capacities of 251.3 and 369.0 mg·g-1 for BTri and 5-TTri，respectively，which were larger than many reported adsorbents.The MON-2COOH gave relatively stable adsorption capacity for BTri and 5-TTri in the pH range of 2.0 - 7.0，but decreased adsorption capacity of BTri and 5-TTri from 8.0 to 11.0，which suggested the alkaline condition was unfavorable for the adsorption of BTri and 5-TTri on MON-2COOH.Moreover，the adsorption capacity of BTri and 5-TTri was independent under NaCl concentration lower than 100 mg·g-1 and humic acid concentration less than 40 mg·g-1．The MON-2COOH also owned good reusability and reproducibility．In addition，MON-2COOH was successfully applied to the adsorption and removal of BTri and 5-TTri in real lake and river water samples．The mechanisms studies revealed the important roles of π - π，hydrophobic and hydrogen bonding interaction during the adsorption．This work provided a promising way to design and synthesize efficient adsorbents for benzotriazoles，which may also promote the application of functionalized MONs in environmental contaminants analysis and elimination．  
        关键词：microporous organic network;benzotriazoles;adsorption;removal;environmental contaminants   
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        发布时间：2022-06-22
      • LIU Fu-rong,YAN Li,FAN Zhe-feng,WEN Xiao-ye
        Vol. 41, Issue 5, Pages: 701-709(2022) DOI: 10.19969/j.fxcsxb.21092805
        摘要：As one endogenous gas in organisms，abnormal H2S is critically involved in various diseases and pathology research．Hence，high-sensitivity and high-selectivity methods for real-time monitoring of H2S molecule level in vivo are significantly demanded．In this paper，given the excellent performances of aggregation and enhanced fluorescence，aggregation-induced emission（AIE） fluorescence molecular in the field of biological imaging，a high-efficiency and novel probe 1 based AIE was synthesized via one-step method with 4-acetamidobenzaldehyde and carbohydrazide．The AIE characteristic，luminescence mechanism and sensing mechanism of the probe 1 were discussed by emission spectrum，ultraviolet spectrum，particle size molecules analysis，scanning electron microscopy and theoretical calculation．The AIE properties of the probe may be attributed to the effects of excited-state intramolecular proton transfer（ESIPT） and restricted intramolecular rotation（RIR）．Given the“alcohol-ketone”tautomerism，the probe molecule mainly exists in the keto form mediated by intramolecular hydrogen bonding between hydroxyl and carbonyl groups in water medium—a poor solvent，which indicates that the ESIPT process is activated．Meanwhile，the intramolecular single bond rotation is hindered and the molecular planarity is enhanced due to the orderly alignment between molecules．These two features both facilitate the radiative pathway，thus resulting in remarkable green-emissive．On the other hand，the probe 1 with Schiff base structure can specififically bind with Cu2+．The fluorescence of the probe would be essentially quenched due to the blocked ESIPT．When the probe 1 with Cu2+ is exposed to HS－，the green-emissive could be restored based on the strong binding of HS－ and Cu2+．Herein，a fast and sensitive“turn-on”H2S fluorescent probe was successfully designed．Probe 1 + Cu2+ features a high selectivity towards H2S，after adding HS－ to probe 1 + Cu2+，the fluorescence intensity at 500 nm gradually increases within 30 s and tends to stable．The detection limit of the probe 1 over H2S in containing 10% DMSO solution（PBS buffer，pH 7.4） was 0.27 µmol/L．The outstanding optical properties and biocompatibility made the probe 1 applicable to detecting exogenous H2S concentration in cells and H2S concentration in liquors．The applicability of probe 1 in detecting H2S in liquids，living cells and logic gate programs was further evaluated．The evaluation results showed that the probe is suitable for detecting the concentration of H2S in wine samples，and the probe has very low toxicity．Successfully applied to biofluorescence imaging of exogenous H2S in living cells．In addition，probe 1 was also used to construct an ultra-sensitive logic gate．Importantly，qualitative H2S detection was realized by using commercial filter paper．This research provides a new clue for exploring the functions of H2S in various physiological processes and food samples.  
        关键词：H2S;excited-state intramolecular proton transfer （ESIPT）;aggregation-induced emission （AIE）;food samples;cell imaging   
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        发布时间：2022-06-22
      • SUN Ling-bo,WU Wen-bo,WANG Qing-qing,ZHANG Yue-cheng,MA Hong-yan
        Vol. 41, Issue 5, Pages: 710-716(2022) DOI: 10.19969/j.fxcsxb.21091604
        摘要：A novel hyacinth beans carbon quantum dots（HB－CQDs） with nature hyacinth beans as the single carbon source were synthesized by hydrothermal method，which exhibit excellent fluorescent properties and water solubility．Fluorescein isothiocyanate（FITC） was composited with HB－CQDs in HAc－NaAc buffer（pH = 5.80） to form HB－CQDs/FITC composites，which could clearly show two fluorescence emission peaks at 400 nm and 510 nm under the single excitation wavelength of 326 nm，whereas both fluorescence signals were“switch off”after MnO4- was added into the system．With the addition of lornoxicam（LNXC），the fluorescence signal at 510 nm was restored，which makes the fluorescence signal“switch on”again，even though the fluorescence intensity at 400 nm was unvaried．Thus，a novel approach for the detection of LNXC based on HB－CQDs/FITC fluorescent ratiometric probe was established．The quenching mechanism of MnO4- was further explored．A good linear relationship between the concentration of LNXC and the fluorescence intensity ratio（at λem/λem = 510 nm/400 nm） of HB－CQDs/FITC probe was found under the optimized experimental conditions，with a linear range of 1.0 × 10－7－1.0 × 10－5 mol/L．The detection limit of this method was 9.0 × 10－8 mol/L. Furthermore，this probe was used in the detection of the content of LNXC in the samples with satisfactory results．  
        关键词：hyacinth beans carbon quantum dots（HB－CQDs）;fluorescein isothiocyanate（FITC）;fluorescence ratiometric probe;lornoxicam（LNXC）   
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        发布时间：2022-06-22
      • JIAO Yu-pei,WANG Xue-ying,XU Li-na,WANG Yu-song,LIU Zi-qi,LIU Xiao-hui
        Vol. 41, Issue 5, Pages: 717-723(2022) DOI: 10.19969/j.fxcsxb.21100601
        摘要：Cardiolipin is important for assembly and integrity of mitochondrial electron transfer complex．A sensitive and high throughput method via liquid chromatography - high resolution mass spectrometry was developed for the detection of low abundant cardiolipin based on methylation reaction．Unique fragmentation pattern was derived from methylated cardiolipins．Therefore，a simulated database including the featured fragments of 780 molecules was established for lipid identification．After derivatization，the signal of CL（14∶0/14∶0/14∶0/14∶0） was increased by 10 times，and 10 ng/mL of the limit of quantitation（LOQ） was achieved in the analysis．This method was applied to study the cardiolipin regulation in mouse brain during aging．A total of 43 cardiolipin molecules were identified using Tracefinder coupled with in-house MS/MS database，of which 21 cardiolipin molecules were differentially changed in aged brains．Cardiolipins with polyunsaturated acyl-component e.g. FA（20∶4） and FA（22∶6） were decreased during the aging process．The orbitrap-based platform with methylation provides a high throughput screening approach for cardiolipin analysis，which is potentially beneficial to the detection of low abundant lipids．  
        关键词：cardiolipin;methylation;high resolution mass spectrometry;high throughput   
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        发布时间：2022-06-22
      • ZHANG Quan,LIU Li-ya,ZHOU Yi-bing,WU Yu-tian,LI Lei,LIN Ye,GUO Hua,ZHOU Xue,CHEN Qing-yuan
        Vol. 41, Issue 5, Pages: 724-730(2022) DOI: 10.19969/j.fxcsxb.21100802
        摘要：A gas chromatography－tandem mass spectrometry（GC－MS/MS） with surface sampling method was established for the determination of 19 kinds of antiseptic and antifungal agents residues in wooden chopping boards．The samples were prepared by surface sampling method，followed by acidification，and then extracted with ethyl acetate－n-hexane（2∶8，volume ratio） mixed solvent．The optimized method eliminated the need for derivatization reactions and purification operations．Multi-reaction monitoring scanning mode（MRM） was used for monitoring，and the external standard method with matrix-matched solution was used for quantification．Results of the optimized analysis showed that there were good linear relationships for the 19 components in the range of 0.005－200.0 μg/mL，with their correlation coefficients（r2） larger than 0.990．The limits of detection（LODs，S/N = 3） and limits of quantitation（LOQs，S/N = 10） were in the ranges of 0.001－0.17 mg/kg and 0.003－0.55 mg/kg，respectively．The recoveries for the 19 targets at two spiked concentration levels ranged from 65.8% to 97.2%，with relative standard deviations（RSDs，n = 6） of 4.3%－13%．This method was used for special food safety risk monitoring on the bamboo and wooden products related to food in Guizhou province，and the hidden risks of high pentachlorophenol residues in non-shaped packaging wooden chopping boards were discovered，which could provide an early risk warning for relevant departments．  
        关键词：wooden chopping board;sampling in surface;antiseptic and antifungal agent;gas chromatography－tandem mass spectrometry（GC－MS/MS）;risk early warning   
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        发布时间：2022-06-22
      • GU Kun-shan,WANG Ji-fen,ZENG Xiao-hu
        Vol. 41, Issue 5, Pages: 746-753(2022) DOI: 10.19969/j.fxcsxb.21072903
        摘要：Fingernail is one of the common biological evidences on the scene of the case．The rapid inspection of fingernails found in the scene could provide direction and clues for case investigation．Meanwhile，application of machine learning for quick and nondestructive detection of the testing material is an important branch of court science．Filter could effectively remove the noise and background interference of the spectra．The dimension reduction of the spectral data could effectively reduce the dimension of the data，and improve the recognition effect of the model．In this paper，a total of 204 nail samples from the actual cases of five regions were collected．The original spectra were denoised by Hilbert transform filter（HTF），and then the principal component analysis（PCA）was used to reduce the dimension of the original data and the denoised data．Naive Bayes（NB），random forest（RF） and partial least squares discriminant analysis（PLS－DA） model were used to carry out the identification of nail area．According to the recognition rate and related indicators of the model，the optimal preprocessing method and optimal recognition model for nail area identification were selected．The results demonstrated that the recognition rate of the original spectra is significantly improved after preprocessing．HTF combined with PCA is the best preprocessing method．The recognition rate of RF for the training set of the best pretreatment method is 94.88%，while that for the test set is 93.47%．This method could effectively reduce the noise of spectra，reduce the redundancy of data，improve the recognition effect of the model，and provide some reference for the rapid identification of nail areas in forensic science．  
        关键词：spectroscopy;fingernail;Hilbert transform filter;principal component analysis（PCA）;machine learning   
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        发布时间：2022-06-22

        temperature：25 ℃；flow rate：0.1 mL·min-1；UV detection wavelength：254 nm

      • GUO Ping,XU Na-yan,CHEN Ji-kai,ZHANG Jun-hui,WANG Bang-jin,XIE Sheng-ming,YUAN Li-ming
        Vol. 41, Issue 5, Pages: 731-738(2022) DOI: 10.19969/j.fxcsxb.21091402
        摘要：In this work，a core-shell MOF@COF composite，NH2－MIL－125@TPA－COF was prepared by immobilizing the COF（TPA－COF） crystals on the surface of MOF（NH2－MIL－125） particles through in-situ growth approach．The NH2－MIL－125@TPA－COF composite was characterized by powder X-ray diffraction（PXRD），Fourier transform infrared spectroscopy（FTIR） and scanning electronic microscopy（SEM）．An HPLC column（25 cm long × 2.1 mm i.d.） was successfully prepared with NH2－MIL－125@TPA－COF composite as stationary phase．Under normal-phase（n-hexane－isopropanol（9∶1，volume ratio）） and reverse-phase（methanol－water（9∶1，volume ratio）） high performance liquid chromatographic（HPLC） conditions，the separation performance of this column for a series of positional isomers was investigated．The experimental results showed that the NH2－MIL－125@TPA－COF packed column exhibited a good separation performance toward 9 positional isomers，i.e. bromonitrobenzene，nitroaniline，chlorophenol，binitrobenzene，iodoaniline，bromaniline，phenylenediamine，toluidine and chloroaniline under a low column backpressure（60－100 kPa），among which bromonitroaniline， nitroaniline and dinitrobenzene could reach the baseline separation on this column，and the highest resolution（Rs） was 9.71．Under reverse-phase HPLC condition，the column efficiencies of o-bromonitrobenzene，m-nitroaniline and o-chlorophenol were 18 424 plates·m－1，19 053 plates·m－1 and 12 954 plates·m－1，respectively．Under normal-phase HPLC condition，the reproducibility and stability of this column was investigated using bromonitrobenzene as the analyte．The relative standard deviations（RSD） for retention time and peak area of bromonitrobenzene for five repeated injections（50th injection，100th injection，150th injection，200th injection，and 250th injection，respectively） were 0.29% and 0.89%，respectively. The retention time，selectivity and separation performance of bromonitrobenzene on this column did not change obviously，indicating that the prepared NH2－MIL－125@TPA－COF packed column exhibited good reproducibility and stability for HPLC separation of positional isomers．The results indicated that the core-shell composite NH2－MIL－125@TPA－COF as a new type of HPLC stationary phase has a good application prospect in the separation of positional isomers.  
        关键词：core-shell composites;positional isomers;high performance liquid chromatography;stationary phase;separation   
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        发布时间：2022-06-22

        Scientific Papers

      • SHI Min,BAO Chang-hao,MA Wen-wen,CHENG Han
        Vol. 41, Issue 5, Pages: 739-745(2022) DOI: 10.19969/j.fxcsxb.21082201
        摘要：An electrochemical method for the determination of luteolin（Lu） was established in this paper．Gold nanoparticles（AuNPs） were prepared by reducing chloroauric acid with trisodium citrate，which was then electrodeposited on the surface of carbon fiber microelectrode（CFME） by one-step potentiostatic deposition. A simple and sensitive electrochemical sensor for the determination of luteolin was constructed．Cyclic voltammetry（CV），electrochemical impedance spectroscopy（EIS） and differential pulse voltammetry（DPV） were used to investigate the catalytic performance of the modified electrode for the electrochemical oxidation of luteolin. The results showed that the AuNPs/CFME had an obvious electrocatalytic performance for the detection of luteolin， and the optimal modification time of AuNPs was 30 min. There were good linear relationships between peak currents and luteolin concentrations in the ranges of 0.01－0.10 μmol/L and 0.10－10 μmol/L，with their correlation coefficients（r2） of 0.994 4 and 0.995 1，respectively．The limits of detection（LODs，S/N = 3） were 1.58 nmol/L. With the advantages of simple fabrication，good stability，high sensitivity and excellent anti-interference ability，the developed sensor could be applied to the quantitative determination of luteolin in Kudo capsules．The spiked recoveries for the analyte ranged from 96.0% to 104%，with relative standard deviations（RSDs） less than 5.0%．It had a good application prospect in quantitative analysis of luteolin in biological microenvironment.  
        关键词：luteolin;gold nanoparticles（AuNPs）;electrochemical sensor   
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        发布时间：2022-06-22
      • XIA Jin-tao,WU Wan-qin,ZHU Song-song,JIANG Feng,FAN Zhi-yong,WANG Hui-xia,PENG Qing-zhi,YANG Zong
        Vol. 41, Issue 5, Pages: 754-760(2022) DOI: 10.19969/j.fxcsxb.21082001
        摘要：A high performance liquid chromatography - tandem mass spectrometry（HPLC - MS/MS）was developed for the qualitative and quantitative identification of a novel，illegally added and unknown carbadenafil analogue，N-phenylpropoxyphenyl carbadenafil in solid beverages.The sample was firstly identified by using ultra-performance liquid chromatography－quadrupole time-of-flight mass spectrometry（UPLC - Q - TOF MS） and ultra-performance liquid chromatography - linear ion trap/orbitrap high resolution mass spectrometry（UPLC－LTQ/Orbitrap MS）.Then the structure of this compound was finally determined as N-phenylpropoxyphenyl carbadenafil by one-dimensional and two-dimensional nuclear magnetic resonance（NMR） spectra and textual comparison.Quantitative analysis was carried out by the external standard method. Results showed that there was a good linear relationship for the analyte in the range of 2 - 50 ng/mL，with correlation coefficient（r2） of 0.999 1.The limit of detection（LOD） and quantification（LOQ） were 0.05 mg/kg and 0.1 mg/kg，respectively. Recoveries at low，medium and high spiked levels ranged from 89.2% to 93.1%， with relative standard deviations（RSD）of 1.8% - 3.1%. Determination on 10 batches of coffee solid beverages revealed that 5 batches of samples were found to be positive，and the contents of N-phenylpropoxyphenyl carbadenafil were between 214 mg/kg and 880 mg/kg. With high accuracy and high efficiency，this method is effective for the screening of illegally added carbadenafil analogs beyond the detection range of current standard.  
        关键词：coffee;carbadenafil analogs;illegal addition;structure identification;quantitative analysis   
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      • TANG Qing-qiang,WU Chun-deng,CAO Xiao-gang,WANG Jun,CHEN Di,YANG Fang
        Vol. 41, Issue 5, Pages: 761-767(2022) DOI: 10.19969/j.fxcsxb.21100903
        摘要：A comprehensive analytical method based on gas chromatography－mass spectrometry（GC－MS） was developed for the determination of 9 cannabinoid compounds in burnable incense smoke．The smoke of burnable incense sample was extracted with a sampling pump，then enriched into the solvent in a tube．Finally，the solvent was concentrated and centrifuged at 10 000 r/min for 5 min．The extract was purified on an HLB solid phase extraction column with water containing 10% methyl alcohol as the eluent．The sample was eluted with 6 mL methyl alcohol，and then filtered through a 0.22 μm membrane filter unit prior to GC－MS analysis．Temperature－programmed was applied at an initial temperature of 70 ℃．After 2 min，the temperature was raised to 180 ℃ at a rate of 10 ℃/min．After 18 min，the temperature was raised to 300 ℃ at a rate of 15 ℃/min．9 cannabinoid compounds were separated on an Agilent HP－5MS column（30 m × 0.25 mm × 0.25 µm）．Identification and quantification were achieved using an electrospray ionization（EI） source under the selected ion monitoring（SIM） mode．The internal standard method was used to quantify the cannabinoids．The results indicated that the 9 compounds could be analyzed within 27 min．The calibration curves showed good linearities for 9 cannabinoid compounds in the range of 0.01－4.0 mg/L， with correlation coefficients（r2） not less than 0.999 5．The limits of detection（LODs，S/N＝3） and limits of quantitation（LOQs，S/N＝10） for 9 cannabinoid compounds were in the range of 0.003－0.06 mg/L and 0.01－0.2 mg/L，respectively．The average recoveries for 9 cannabinoid compounds were in the range of 74.8%－114%，with relative standard deviations（RSDs，n＝6）of 1.6%－9.1%．This method was used to determine 10 types of burnable incense，no new psychoactive substances of cannablis were detected．The method is simple to operate，and could be used for rapid qualitative and quantitative analysis of cannabinoid compounds in burnable incense smoke.  
        关键词：burnable incense;smoke;cannabinoids;gas chromatography－mass spectrometry（GC－MS）   
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        发布时间：2022-06-22

        Experimental Techniques and Methods

      • QIN Fu,WANG Wen-long,SI Lu-lu,CAI Xiang-yu,LIANG Yu,SU Hua,WEI Tao
        Vol. 41, Issue 5, Pages: 768-773(2022) DOI: 10.19969/j.fxcsxb.21071001
        摘要：A solid phase extraction and liquid chromatography－tandem mass spectrometry was developed for the determination of iminoctadine residues in fruits and vegetables including citrus，jackfruit，apple，grape，lettuce，cucumber，tomato and asparagu．Samples were extracted with 0.2% acetic acid，and preliminarily purified with dichloromethane. The extract solution was purified using a WCX solid phase extraction column，and the target compound was eluted with 10% formic acid acetonitrile．The eluent was blown to near dryness with nitrogen，and then redissolved with 0.2% formic water．The compound was separated on a C18 column with methanol and 0.2% formic acid water as mobile phases．The double charges additive ion m/z 178.8 and its daughter ions m/z 100.0 and 187.0 from iminoctadine were selected for the multi reaction monitoring（MRM） scanning under the positive ion mode of electrospray ion source（ESI+）．The iminoctadine in the samples was quantified by the calibration curve of matrix addition standard．The correlation coefficients（r） were not less than 0.995，which indicated that the linear dependence of iminoctadine was good in the range of 0.005－0.160 mg/kg．The limits of detection（LOD） and quantitation（LOQ） for iminoctadine were 0.005 mg/kg and 0.010 mg/kg，respectively．The average recoveries at spiked levels of 0.010，0.020 and 0.050 mg/kg ranged from 88.5% to 109%，with the relative standard deviations（RSDs，n = 6） of 2.1%－8.8%．With the advantages of rapidness，accuracy and sensitivity，this method is suitable for the determination of iminoctadine in fruits and vegetables．  
        关键词：iminoctadine;iminoctadine tris（albesilate）;citrus;solid phase extraction;liquid chromatography－tandem mass spectrometry   
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        发布时间：2022-06-22
      • WEI Liang,ZHANG Chao-nan,LI Ke-yan,WEI Ting-ting,QI Shao-ke,WANG Yan-li,WANG Qiang
        Vol. 41, Issue 5, Pages: 774-780(2022) DOI: 10.19969/j.fxcsxb.21091401
        摘要：Geo-authentic Chinese medicinal materials refer to those traditional Chinese medicines that have been verified through long-term clinical application and produced in a specific region．Huai Shanyao is a class of geo-authentic Chinese medicinal materials，while Dioscorea polystachya Turczaninow cv. Tiegun is considered the best Huai Shanyao as its price is the highest. So the dealers often adulterate D.polystachya cv. Tiegun planted in other places or other yams with similar appearance as the authentic D.polystachya cv. Tiegun planted at Wenxian county，Henan Province to earn higher profits．In the previous study，it was found that D.polystachya cv. Tiegun planted at Wenxian county could be verified according to the contents of glucose and fructose，and the tetrazolium solution could be used as an identification reagent for the rapid discrimination of D.polystachya cv. Tiegun from Wenxian county based on the color reaction of glucose．In fact，not only D.polystachya cv．Tiegun from Wenxian county，but also the yams from other three counties（Mengzhou，Qinyang and Wuzhi） in Jiaozuo city，Henan Province belonged to Huai Shanyao．For the identification of Huai Shanyao，seven groups of D.polystachya Truczaninow cv. Tiegun were analyzed by NMR-based metabolomics appraoach，and 30 metabolites were identified．The metabolites of different yams were analyzed using principal component analysis（PCA） and orthogonal projections to latent structures－discriminant analysis（OPLS－DA）．Multivariate analysis revealed that yam planted in loessial soils at Wenxian county（WL） had the highest level for arginine and the lowest level for sucrose．Meanwhile，Mengzhou loessial soil yam（ML） had the highest level of threonine and glutamine，Wenxian sandy soil yam （WS） had the highest level of alanine and malate，and Wuzhi sandy soil yam（ZS） had the highest level of allantoin．The level of 2-hydroxyisobutyrate in sandy soil yams is higher than loessial soil yam．Loading plots of OPLS－DA showed the variable important projections（VIPs） for glucose and fructose were both lower than 1.0，indicating that glucose and fructose were not the principle components．Contents of citrate，malate and sucrose were determined by high performance liquid chromatography（HPLC），and the results obtained were consistent with the loading plots of OPLS－DA．Glucose and fructose were undetectable by HPLC（LOD：2.0 mg/g） in all yams．All these results showed that geo-authentic Chinese yams（Huai Shanyao） could be verified according to the contents of glucose and fructose．And the glucose chromogenic reagents could be used as an indicator for the rapid discrimination of geo-authentic Chinese yams．This study reveals the metabolites difference in Huai Shanyao planted in different counties，as well as that the characteristic metabolites are the rationale for the authentication of geo-authentic Chinese yams．  
        关键词：Dioscorea polystachya Truczaninow;authentic medicinal materials;nuclear magnetic resonance （NMR）;multivariate statistical analysis;glucose;fructose   
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        发布时间：2022-06-22
      • CUI Wan-ying,ZHAO Peng,RAO Yu-lan,YU Zhong-shan,ZHANG Yun-feng,DONG Lin-pei,WEI Chun-ming,WU Xiao-jun
        Vol. 41, Issue 5, Pages: 781-786(2022) DOI: 10.19969/j.fxcsxb.21070601
        摘要：A gas chromatography－negative chemical ionization－mass spectrometry（GC－NCI－MS） with derivatization was developed for the quantitative analysis of nitrite（NO2-） and nitrate（NO3-） in whole blood. Isotope-labeled 15NO2- and 15NO3- were used as the internal standards．After NO2- and NO3- in whole blood were extracted and derivatized，the target derivatives were analyzed by GC－NCI－MS. The target extraction solvent，derivative extraction solvent，amount of phase transfer reagent，the derivatization method，time and temperature of the derivatization reaction were optimized．The optimal pretreatment conditions were also determined．A negative chemical ionization source（NCI） was used to select ion monitor（SIM）．The quantitative ions for target NO2- and its internal standard 15NO2- were m/z 46 and 47，while those for target NO3- and its internal standard 15NO3- were m/z 62 and 63，respectively．There was a good linear relationship for NO2- in whole blood（r2 = 0.995） in the range of 0.05－5 μg/mL，with a detection limit of 0.01 μg/mL and an accuracy of 89.6%－98.0%．The extraction recoveries ranged from 99.8% to 118%，with the intra-day and inter-day relative standard deviations（RSDs） of 1.8%－9.2% and 2.1%－6.2%，respectively．There also existed a good linear relationship for NO3- in whole blood（r2 = 0.997） in the range of 1－300 μg/mL，with a detection limit of 0.2 μg/mL and an accuracy of 92.8%－112%．The extraction recoveries ranged from 80.3% to 88.4%，with the intra-day and inter-day RSDs of 0.60%－14% and 0.60%－3.7%，respectively. The endogenous NO2- and NO3- in 16 whole blood samples of healthy person were determined by this method．The results showed that the concentrations of NO2- and NO3- were in the ranges of 0.05－0.10 μg/mL and 1.70－7.70 μg/mL，respectively．In addition，the contents of two target substances in real human whole blood poisoned by nitrite were determined，and the concentrations of both substances were much higher than the endogenous concentration level in whole blood of human body，thus nitrite poisoning was determined．With the advantages of strong specificity，high sensitivity，accuracy and reliability，the method could meet the requirements for inspection and identification of nitrite poison cases．  
        关键词：nitrite;nitrate;whole blood;gas chromatography－negative chemical ionization－mass spectrometry（GC－NCI－MS）;toxicological analysis   
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        发布时间：2022-06-22
      • QI Pei-shan,ZHU Pen-sheng,XIE Tian-yao
        Vol. 41, Issue 5, Pages: 787-791(2022) DOI: 10.19969/j.fxcsxb.21102801
        摘要：A new method for the rapid separation and sensitive determination of available phosphorus in soil by capillary electrophoresis（CE） with field-amplified sample injection（FASI） and capactively coupled contactless conductivity detection（C4D） was developed．Parameters affecting the CE separation and FASI efficiency were investigated in detail，including the composition and pH value of running buffer solution，separation voltage，sample injection voltage and time．The analyte was well separated and sensitively detected within 8 min in a fused-silica capillary under the optimum conditions of 35 mmol/L acetic acid - 2 mmol/L ammonium acetate as running buffer，with separation voltage of －14 kV，electrokinetic injection of －11 kV × 10 s．The calibration curve showed good linearity in the range of 16－800 μg/L，with a limit of detection of 5 μg/L．As a result，FASI showed significant increase of sensitivity with an enhancement factor of 580．The intra- and inter-relative standard deviations（RSD） were below 5.0%．The co-existed inorganic anion（Cl－，SO42-，NO3-） and organic acid did not interfere with the detection of available phosphorus in soil．Contents of available phosphorus in soil samples could be easily determined without complex sample pretreatment．This proposed method could meet the requirements for the fast screening and sensitive detection of available phosphorus in soil samples．  
        关键词：contactless conductivity detection;field-amplified sample injection;on-line preconcentration;capillary electrophoresis;available phosphorus;soil   
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        发布时间：2022-06-22
      • YANG Guang-yuan,HAN Lei,DENG Shao-peng,LIU Qiang,WANG Wen
        Vol. 41, Issue 5, Pages: 792-796(2022) DOI: 10.19969/j.fxcsxb.21082702
        摘要：Glycerol triacetate is used as the plasticizer and hardener in molding process of cigarette filter，its content will not only affect the rigidity，resistance and filtration performance of a cigarette filter，but also have an impact on the perceived quality of cigarette smoke．In order to improve the efficiency for detection of glycerol triacetate content，a novel hand-held near-infrared spectroscopy（NIR） technique combined with particle swarm optimization－extreme learning machine（PSO－ELM） algorithm was applied to build a prediction model for glycerol triacetate content．Meanwhile，it was also compared with the traditional partial least squares（PLS） model and extreme learning machine（ELM） model．The experimental results showed that compared with PLSR model and ELMR model，the PSO－ELM model was much better with a determination coefficient（r2） of 0.921 2，which was higher than 0.860 4 for PLSR prediction model and 0.877 2 for ELMR prediction model．Besides，the root mean square error of prediction（RMSEP） for PSO－ELM model was 0.3921 2，which was smaller than 0.497 72 for PLSR model and 0.470 18 for ELMR model．The above results indicated that the established model could be applied to the rapid and accurate determination of the content of glycerol triacetate in cigarette filter，which provided a good reference for on-site rapid determination on the content of glycerol triacetate．  
        关键词：cigarette filter;glycerol triacetate;hand-held NIR;PSO－ELM   
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        发布时间：2022-06-22

        Review

      • AI Ji-xing,DU Hai-jun,HU Hua-li,ZHANG Yan,LI Yu-mei,LUO Le,WU Dan
        Vol. 41, Issue 5, Pages: 797-804(2022) DOI: 10.19969/j.fxcsxb.21072902
        摘要：Electrochemical analysis technology based on nanomaterial has become a research hotspot for rapid detection of neonicotinoid insecticides．Especially new functional materials are of great significance to broaden the applicability and enlarge detection range of pesticide sensors．In this paper，the latest advances of novel functional materials such as aptamer，molecular imprinting，photoelectric material，carbon-based nanomaterial and frameworks material are provided．The applications of novel functional materials in electroanalysis of neonicotinoid insecticides are summarized．The function，advantages and disadvantages，and the latest research progress of novel functional materials as recognition in neonicotinoid electrochemical sensor are mainly described．Furthermore，the future development of various neonicotinoid electrochemical sensors based on functional materials and their potential applications are prospected．It is anticipating to provide a reference for the further research and application of neonicotinoid insecticides．  
        关键词：neonicotinoid insecticides;electrochemical analysis;functional materials;sensor   
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        发布时间：2022-06-22
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