Pub Date : 2025-06-01DOI: 10.3724/SP.J.1123.2024.05018
Dan-Dan Jiang, Qiong Jia
Organic synthesis experiments are often deficient and involve relatively independent experimental instrumental-analysis methods that lack integration. Accordingly， an open-instrument-analysis experiment was designed to address these shortcomings； this experiment combines organic synthesis with instrumental analysis to deliver an innovative undergraduate experiment that includes material preparation and characterization， investigating the adsorption performance of hydroxylated polychlorinated biphenyl， and exploring detection methods. First， Fe3O4 was treated with tetraethyl orthosilicate， after which 3-aminopropyltrimethoxysilane was introduced to prepare amino-modified Fe3O4. Trimesoyl chloride and p-phenylenediamine are then added as monomers to synthesize a magnetic covalent organic framework （MCOF）. The surface groups and thermal stability of the MCOF were then characterized using Fourier-transform infrared spectroscopy and thermogravimetric analysis， after which the MCOF was used to determine hydroxylated polychlorinated biphenyl in Liaohe River water samples using liquid chromatography. During this experiment， students master separation and detection methods for hydroxylated polychlorinated biphenyl， while also learning about its levels in the Liaohe River. Students will recognize the important role that instrumental analysis plays in environmental monitoring by analyzing and discussing the experimental results； they will also improve their abilities to comprehensively apply basic inorganic chemistry， organic chemistry， and instrumental-analysis knowledge， while also improving their abilities to operate， analyze， and solve problems. Implementing this open experiment will help to improve the use of laboratory equipment and fully utilize existing laboratory resources.
{"title":"[Preparation and application of magnetic covalent organic framework： open experimental teaching practice of instrumental analysis].","authors":"Dan-Dan Jiang, Qiong Jia","doi":"10.3724/SP.J.1123.2024.05018","DOIUrl":"10.3724/SP.J.1123.2024.05018","url":null,"abstract":"<p><p>Organic synthesis experiments are often deficient and involve relatively independent experimental instrumental-analysis methods that lack integration. Accordingly， an open-instrument-analysis experiment was designed to address these shortcomings； this experiment combines organic synthesis with instrumental analysis to deliver an innovative undergraduate experiment that includes material preparation and characterization， investigating the adsorption performance of hydroxylated polychlorinated biphenyl， and exploring detection methods. First， Fe<sub>3</sub>O<sub>4</sub> was treated with tetraethyl orthosilicate， after which 3-aminopropyltrimethoxysilane was introduced to prepare amino-modified Fe<sub>3</sub>O<sub>4</sub>. Trimesoyl chloride and <i>p</i>-phenylenediamine are then added as monomers to synthesize a magnetic covalent organic framework （MCOF）. The surface groups and thermal stability of the MCOF were then characterized using Fourier-transform infrared spectroscopy and thermogravimetric analysis， after which the MCOF was used to determine hydroxylated polychlorinated biphenyl in Liaohe River water samples using liquid chromatography. During this experiment， students master separation and detection methods for hydroxylated polychlorinated biphenyl， while also learning about its levels in the Liaohe River. Students will recognize the important role that instrumental analysis plays in environmental monitoring by analyzing and discussing the experimental results； they will also improve their abilities to comprehensively apply basic inorganic chemistry， organic chemistry， and instrumental-analysis knowledge， while also improving their abilities to operate， analyze， and solve problems. Implementing this open experiment will help to improve the use of laboratory equipment and fully utilize existing laboratory resources.</p>","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"705-709"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093215/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The China National Human Biomonitoring Program （CNHBP） was launched in 2016. The program aims to obtain representative exposure data of environmental pollutants in the general population by carrying out field epidemiological surveys of Chinese population and monitoring of environmental pollutants in human biological tissues. This work will provide a scientific basis for the government to formulate environmental pollution prevention and control policies. One of the objectives of human biomonitoring is to provide accurate and comparable data of chemical pollutants in human biological samples. Multi-dimensional quality control measures are implemented for the targeted quantitative analysis of chemical pollutants from the analysis method， experimental blank and analysis processes. The quality control procedures are divided into two stages： （1） focusing on the verification of biomonitoring analysis method， blank screening and control in the pre-detection stage； （2） the quality control of the large-scale sample analysis process in the detection stage. Analysis methods used in CNHBP need to be validated to evaluate the performance and practicability， with emphasis on method detection limit （MDL） and method quantification limit （MQL）， matrix effects， stability， and residue and dilution. Blank screening procedures are required for all monitoring indicators to identify， eliminate or reduce blank interference， and the blank value of each batch should be less than the MDL. The laboratory adopts a combination of internal and external quality control measures， the measures mainly include： （1） method validation and detection process of the 10 types of monitoring indicators all used biological matrix reference materials produced by the National Institute of Standards and Technology （NIST）， European Reference Materials （ERM） and China Center for Reference Materials， to ensure the accuracy and traceability of the methods； （2） commercial quality control samples and internal quality control samples were used to evaluate the stability of the testing process for the 15 types of monitoring indicators； （3） a total of 60 monitoring indicators of the nine categories participated in the German external quality assessment scheme for analyses in biological materials （G-EQUAS） and achieved satisfactory results； （4） 15 types of monitoring indicators were tested with blind samples. Overall， multi-dimensional quality control measures provide professional support for generating high-quality biomonitoring data.
{"title":"[Quality control strategy for targeted quantitative analysis of chemical pollutants in China National Human Biomonitoring Program].","authors":"Yan-Wei Yang, Xu Zhang, Xiao Lin, Qi Sun, Hui Fu, Yi-Fu Lu, Tian Qiu, Zhuo-Na Zhang, Lin-Na Xie, Hai-Jing Zhang, Miao Zhang, Xiao-Jian Hu, Ying-Li Qu, Feng Zhao, Yue-Bin Lyu, Ying Zhu, Xiao-Ming Shi","doi":"10.3724/SP.J.1123.2024.11022","DOIUrl":"10.3724/SP.J.1123.2024.11022","url":null,"abstract":"<p><p>The China National Human Biomonitoring Program （CNHBP） was launched in 2016. The program aims to obtain representative exposure data of environmental pollutants in the general population by carrying out field epidemiological surveys of Chinese population and monitoring of environmental pollutants in human biological tissues. This work will provide a scientific basis for the government to formulate environmental pollution prevention and control policies. One of the objectives of human biomonitoring is to provide accurate and comparable data of chemical pollutants in human biological samples. Multi-dimensional quality control measures are implemented for the targeted quantitative analysis of chemical pollutants from the analysis method， experimental blank and analysis processes. The quality control procedures are divided into two stages： （1） focusing on the verification of biomonitoring analysis method， blank screening and control in the pre-detection stage； （2） the quality control of the large-scale sample analysis process in the detection stage. Analysis methods used in CNHBP need to be validated to evaluate the performance and practicability， with emphasis on method detection limit （MDL） and method quantification limit （MQL）， matrix effects， stability， and residue and dilution. Blank screening procedures are required for all monitoring indicators to identify， eliminate or reduce blank interference， and the blank value of each batch should be less than the MDL. The laboratory adopts a combination of internal and external quality control measures， the measures mainly include： （1） method validation and detection process of the 10 types of monitoring indicators all used biological matrix reference materials produced by the National Institute of Standards and Technology （NIST）， European Reference Materials （ERM） and China Center for Reference Materials， to ensure the accuracy and traceability of the methods； （2） commercial quality control samples and internal quality control samples were used to evaluate the stability of the testing process for the 15 types of monitoring indicators； （3） a total of 60 monitoring indicators of the nine categories participated in the German external quality assessment scheme for analyses in biological materials （G-EQUAS） and achieved satisfactory results； （4） 15 types of monitoring indicators were tested with blind samples. Overall， multi-dimensional quality control measures provide professional support for generating high-quality biomonitoring data.</p>","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"559-570"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093211/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-01DOI: 10.3724/SP.J.1123.2024.05030
Ya-Na Luo, Jia Chen, Yu-Yu Hu, Shi-Jie Gao, Yan-Li Wang, Yan-Ming Liu, Juan-Juan Feng, Min Sun
Selecting a suitable sample preparation method is a significant step prior to chromatographic separation and detection. Directly analyzing samples instrumentally is difficult owing to the complexity of the sample matrix and the trace concentration of analytes. Most sample preparation methods have disadvantages， including complicated operating procedures， the use of large amounts of organic solvent， and ease of analyte loss during multistep processes； consequently， they do not meet the high analytical sample detection requirements of modern industry. The development of simple， environmentally friendly， efficient， and rapid preparation methods is a continuing frontier research area in the analytical chemistry field. Among the many available sample preparation techniques， in-tube solid-phase microextraction （IT-SPME） is receiving extensive attention. IT-SPME enriches the target analytes by extracting them to the inner surface of the capillary tube， and has been applied to extract various analytes in the environmental and food fields. IT-SPME is advantageous because it consumes low amounts of organic solvent and capillaries are mechanical stable； consequently， IT-SPME is a promising sample preparation technique. Magnetic field has been introduced to the IT-SPME system to further improve extraction efficiency and selectivity， leading to the development of magnetism-enhanced in-tube solid-phase microextraction （ME-IT-SPME） as a new technology. ME-IT-SPME uses magnetic field to separate and enrich targets， with different magnetic-field strengths applied to the extraction column during adsorption and elution. Diamagnetic substances in a paramagnetic medium tend to concentrate in regions where the magnetic field is weak when an external magnetic field is applied. Target analytes are detected chromatographically following elution. Conditions are optimized and an analytical method is established and used to detect targets in actual samples， leading to improved extraction sensitivity and precision compared to those obtained using IT-SPME， including shorter analysis time and superior extraction efficiency. This paper reviews the applications of ME-IT-SPME technology in combination with various analytical instruments since its inception in 2012， and analyzes its analysis and detection advantages. Based on hydrophobic interactions， hydrogen bonding， π-π and polarity interactions， coordination， and other extraction mechanisms with analytes， ME-IT-SPME uses innovative functional extraction materials， including nanomaterials， monolithic materials， and magnetic hybrid materials， all of which have high surface areas and numerous adsorption sites. Capillary microextraction columns are prepared using open-tubular capillary， particle-filling capillary， or monolithic capillaries. Diverse analytes are detected when ME-IT-SPME is combined with chromatograph， including organic pesticide residues， heavy-metal ions， herbicides， preservatives， and drug mol
{"title":"[Research progress in material preparation and application of magnetism-enhanced in-tube solid-phase microextraction].","authors":"Ya-Na Luo, Jia Chen, Yu-Yu Hu, Shi-Jie Gao, Yan-Li Wang, Yan-Ming Liu, Juan-Juan Feng, Min Sun","doi":"10.3724/SP.J.1123.2024.05030","DOIUrl":"10.3724/SP.J.1123.2024.05030","url":null,"abstract":"<p><p>Selecting a suitable sample preparation method is a significant step prior to chromatographic separation and detection. Directly analyzing samples instrumentally is difficult owing to the complexity of the sample matrix and the trace concentration of analytes. Most sample preparation methods have disadvantages， including complicated operating procedures， the use of large amounts of organic solvent， and ease of analyte loss during multistep processes； consequently， they do not meet the high analytical sample detection requirements of modern industry. The development of simple， environmentally friendly， efficient， and rapid preparation methods is a continuing frontier research area in the analytical chemistry field. Among the many available sample preparation techniques， in-tube solid-phase microextraction （IT-SPME） is receiving extensive attention. IT-SPME enriches the target analytes by extracting them to the inner surface of the capillary tube， and has been applied to extract various analytes in the environmental and food fields. IT-SPME is advantageous because it consumes low amounts of organic solvent and capillaries are mechanical stable； consequently， IT-SPME is a promising sample preparation technique. Magnetic field has been introduced to the IT-SPME system to further improve extraction efficiency and selectivity， leading to the development of magnetism-enhanced in-tube solid-phase microextraction （ME-IT-SPME） as a new technology. ME-IT-SPME uses magnetic field to separate and enrich targets， with different magnetic-field strengths applied to the extraction column during adsorption and elution. Diamagnetic substances in a paramagnetic medium tend to concentrate in regions where the magnetic field is weak when an external magnetic field is applied. Target analytes are detected chromatographically following elution. Conditions are optimized and an analytical method is established and used to detect targets in actual samples， leading to improved extraction sensitivity and precision compared to those obtained using IT-SPME， including shorter analysis time and superior extraction efficiency. This paper reviews the applications of ME-IT-SPME technology in combination with various analytical instruments since its inception in 2012， and analyzes its analysis and detection advantages. Based on hydrophobic interactions， hydrogen bonding， <i>π</i>-<i>π</i> and polarity interactions， coordination， and other extraction mechanisms with analytes， ME-IT-SPME uses innovative functional extraction materials， including nanomaterials， monolithic materials， and magnetic hybrid materials， all of which have high surface areas and numerous adsorption sites. Capillary microextraction columns are prepared using open-tubular capillary， particle-filling capillary， or monolithic capillaries. Diverse analytes are detected when ME-IT-SPME is combined with chromatograph， including organic pesticide residues， heavy-metal ions， herbicides， preservatives， and drug mol","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"606-619"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093209/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Crude oils are complex mixtures of thousands of organic compounds that differ significantly in relative molecular mass， volatility， content， and polarity. Traditional methods for analyzing crude oil often involve complicated steps， consume large amounts of organic solvents， and require long sample-preparation times. These limitations lead to inefficient and time-consuming analysis processes. Crude oil is commonly analyzed by gas chromatography-mass spectrometry （GC-MS）. However， this technique is incapable of effectively separating complex crude-oil components owing to its low resolution and peak capacity， resulting in overlapping peaks that can lead to inaccurate compound identification and quantification. These challenges highlight the need for advanced analytical techniques. Comprehensive two-dimensional gas chromatography （GC×GC） is a novel separation technique that has been widely used to analyze complex samples， such as food， environmental samples， natural products， and crude oil. GC×GC has several advantages over traditional GC. Firstly， it offers higher resolution and peak capacity， thereby improving separation efficiency. Secondly， its high separation power reduces the need for complex sample pretreatment. Thirdly， the ordered separation and "tile effect" in a GC×GC chromatogram facilitate easier compound identification and quantification in complex mixtures.In this study， we developed a gas purge microsyringe extraction （GPMSE） method for the rapid pretreatment of crude-oil samples. This method reduces sample processing time to only 10 min while minimizing organic solvent consumption. The chemical compositions of 45 crude oil samples were analyzed using GC×GC-time-of-flight mass spectrometry （GC×GC-TOFMS）， which helped to establish detailed chemical fingerprints for each sample. The GC×GC-TOFMS data were processed using multivariate statistical methods， including redundancy analysis （RDA） and Monte Carlo permutation testing， which identified 36 biomarkers that are strongly associated with the origin of the crude oil （p<0.05）. A classification model was constructed using a training set of 28 samples. Four single-source and 13 mixed-source samples were used to validate the model. The GPMSE-GC×GC-TOFMS method was demonstrated to be highly efficient and accurate. A discrimination accuracy of 97.8% was achieved during the identification of crude-oil sources. The developed method not only provides a powerful tool for tracing crude oil but also has broad applications potential， including for the detection of adulterated crude oil， tracking oil-spill sources， and monitoring oilfield development. This study offers several significant benefits. For example， it helps to address crude-oil trade fraud and supports national energy security. Additionally， it provides scientific support in relation to crude-oil quality control and risk assessment. The developed method is fast， reliable， and environmentally friendly； hence， it is expected to be a
{"title":"[Tracing the origin of crude oil based on fingerprint profiles obtained by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry].","authors":"Wei-Ya Zhang, Pin Chen, Wei-Xin Xie, Xuan-Bo Gao, Wan-Feng Zhang, Wei Dai, Si-Yuan Lin, Shu-Kui Zhu","doi":"10.3724/SP.J.1123.2025.02005","DOIUrl":"10.3724/SP.J.1123.2025.02005","url":null,"abstract":"<p><p>Crude oils are complex mixtures of thousands of organic compounds that differ significantly in relative molecular mass， volatility， content， and polarity. Traditional methods for analyzing crude oil often involve complicated steps， consume large amounts of organic solvents， and require long sample-preparation times. These limitations lead to inefficient and time-consuming analysis processes. Crude oil is commonly analyzed by gas chromatography-mass spectrometry （GC-MS）. However， this technique is incapable of effectively separating complex crude-oil components owing to its low resolution and peak capacity， resulting in overlapping peaks that can lead to inaccurate compound identification and quantification. These challenges highlight the need for advanced analytical techniques. Comprehensive two-dimensional gas chromatography （GC×GC） is a novel separation technique that has been widely used to analyze complex samples， such as food， environmental samples， natural products， and crude oil. GC×GC has several advantages over traditional GC. Firstly， it offers higher resolution and peak capacity， thereby improving separation efficiency. Secondly， its high separation power reduces the need for complex sample pretreatment. Thirdly， the ordered separation and \"tile effect\" in a GC×GC chromatogram facilitate easier compound identification and quantification in complex mixtures.In this study， we developed a gas purge microsyringe extraction （GPMSE） method for the rapid pretreatment of crude-oil samples. This method reduces sample processing time to only 10 min while minimizing organic solvent consumption. The chemical compositions of 45 crude oil samples were analyzed using GC×GC-time-of-flight mass spectrometry （GC×GC-TOFMS）， which helped to establish detailed chemical fingerprints for each sample. The GC×GC-TOFMS data were processed using multivariate statistical methods， including redundancy analysis （RDA） and Monte Carlo permutation testing， which identified 36 biomarkers that are strongly associated with the origin of the crude oil （p<0.05）. A classification model was constructed using a training set of 28 samples. Four single-source and 13 mixed-source samples were used to validate the model. The GPMSE-GC×GC-TOFMS method was demonstrated to be highly efficient and accurate. A discrimination accuracy of 97.8% was achieved during the identification of crude-oil sources. The developed method not only provides a powerful tool for tracing crude oil but also has broad applications potential， including for the detection of adulterated crude oil， tracking oil-spill sources， and monitoring oilfield development. This study offers several significant benefits. For example， it helps to address crude-oil trade fraud and supports national energy security. Additionally， it provides scientific support in relation to crude-oil quality control and risk assessment. The developed method is fast， reliable， and environmentally friendly； hence， it is expected to be a ","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"688-695"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093212/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-01DOI: 10.3724/SP.J.1123.2024.08005
Qin-Rong Nie, Ming Ni, Jiang-Yan Xu, Ying Shi, Hong-Mei Jiang
<p><p>Brominated flame retardants （BFRs） are widely used as organic flame retardants in plastic products， with most exhibiting strong biological toxicity as well as physical and chemical stability. BFRs inevitably remain in foods consumed on a daily basis through indirect or direct contact， thereby threatening human health. Therefore， establishing a fast and effective method for detecting and analyzing BFRs is imperative. Magnetic solid-phase extraction （MSPE） has been widely used in trace-analysis applications owing to advantages that include operational simplicity and rapid magnetic separability. The key to MSPE lies in the design and preparation of efficient magnetic adsorbents. In this study， a magnetic carbon aerogel （MCA） was prepared using a sol-gel method in combination with calcination. MCA was used as a magnetic solid-phase extractant to establish a new method for the analysis of four BFRs in mineral water and instant-noodle-bowl samples in combination with high performance liquid chromatography. Fourier-transform infrared （FT-IR） spectroscopy revealed peaks at 3 454， 1 590， 757， 1 349， 1 654， and 1 076 cm<sup>-1</sup> that are ascribable to -NH<sub>2</sub>， -CH， triazine-ring， C-N， C=N， and C-O-C vibrations， respectively. Brunauer-Emmett-Teller （BET） analysis revealed values of 192.16 m<sup>2</sup>/g， 0.34 cm<sup>3</sup>/g， and 7.12 nm for the surface area， pore volume and pore size of the MCA， respectively. X-ray diffractometry （XRD） revealed a characteristic peak at 2<i>θ=</i>34.90° that corresponds to the （110） crystal plane of Fe<sub>2</sub>O<sub>3</sub>， and peaks at 2<i>θ</i> values of 44.72°， 65.01° and 82.42° that are ascribable to the （110）， （200）， and （211） crystal planes of CoFe/Co<sub>3</sub>Fe<sub>7</sub>. Vibrating sample magnetometry showed that the MCA is highly magnetic （35 emu/g）， which contributes to fast magnetic solid-liquid separation. The MCA was characterized by transmission electron microscopy （TEM）， which revealed a transparent gauze-like structure with nanometer-sized squares and circular particles evenly distributed between them. High-resolution TEM （HRTEM） showed that the square particles exhibit a 0.191 nm stripe spacing that belongs to the （311） crystal plane of Fe<sub>2</sub>O<sub>3</sub>， while the 0.245 nm stripe spacing observed for the circular particles corresponds to the （110） crystal plane of the CoFe alloy， in good agreement with the XRD results. X-ray photoelectron spectroscopy （XPS） revealed the presence of Co 2<i>p</i>， Fe 2<i>p</i>， O 1<i>s</i>， N 1<i>s</i>， and C 1<i>s</i> peaks. Taken together， these results show that the MCA， which contains various functional groups， had been successfully prepared. Factors that affect MSPE， such as solution pH， amount of material， adsorption time， the concentration and volume of the elution solvent， and sample volume， were investigated using the static adsorption method. BFR adsorption by the MCA was observed to increase with time， with equilibrium eventua
{"title":"[Analysis of four brominated flame retardants in mineral water and instant-noodle-bowl samples by magnetic solid-phase extraction coupled with liquid chromatography using magnetic carbon aerogel as adsorbent].","authors":"Qin-Rong Nie, Ming Ni, Jiang-Yan Xu, Ying Shi, Hong-Mei Jiang","doi":"10.3724/SP.J.1123.2024.08005","DOIUrl":"10.3724/SP.J.1123.2024.08005","url":null,"abstract":"<p><p>Brominated flame retardants （BFRs） are widely used as organic flame retardants in plastic products， with most exhibiting strong biological toxicity as well as physical and chemical stability. BFRs inevitably remain in foods consumed on a daily basis through indirect or direct contact， thereby threatening human health. Therefore， establishing a fast and effective method for detecting and analyzing BFRs is imperative. Magnetic solid-phase extraction （MSPE） has been widely used in trace-analysis applications owing to advantages that include operational simplicity and rapid magnetic separability. The key to MSPE lies in the design and preparation of efficient magnetic adsorbents. In this study， a magnetic carbon aerogel （MCA） was prepared using a sol-gel method in combination with calcination. MCA was used as a magnetic solid-phase extractant to establish a new method for the analysis of four BFRs in mineral water and instant-noodle-bowl samples in combination with high performance liquid chromatography. Fourier-transform infrared （FT-IR） spectroscopy revealed peaks at 3 454， 1 590， 757， 1 349， 1 654， and 1 076 cm<sup>-1</sup> that are ascribable to -NH<sub>2</sub>， -CH， triazine-ring， C-N， C=N， and C-O-C vibrations， respectively. Brunauer-Emmett-Teller （BET） analysis revealed values of 192.16 m<sup>2</sup>/g， 0.34 cm<sup>3</sup>/g， and 7.12 nm for the surface area， pore volume and pore size of the MCA， respectively. X-ray diffractometry （XRD） revealed a characteristic peak at 2<i>θ=</i>34.90° that corresponds to the （110） crystal plane of Fe<sub>2</sub>O<sub>3</sub>， and peaks at 2<i>θ</i> values of 44.72°， 65.01° and 82.42° that are ascribable to the （110）， （200）， and （211） crystal planes of CoFe/Co<sub>3</sub>Fe<sub>7</sub>. Vibrating sample magnetometry showed that the MCA is highly magnetic （35 emu/g）， which contributes to fast magnetic solid-liquid separation. The MCA was characterized by transmission electron microscopy （TEM）， which revealed a transparent gauze-like structure with nanometer-sized squares and circular particles evenly distributed between them. High-resolution TEM （HRTEM） showed that the square particles exhibit a 0.191 nm stripe spacing that belongs to the （311） crystal plane of Fe<sub>2</sub>O<sub>3</sub>， while the 0.245 nm stripe spacing observed for the circular particles corresponds to the （110） crystal plane of the CoFe alloy， in good agreement with the XRD results. X-ray photoelectron spectroscopy （XPS） revealed the presence of Co 2<i>p</i>， Fe 2<i>p</i>， O 1<i>s</i>， N 1<i>s</i>， and C 1<i>s</i> peaks. Taken together， these results show that the MCA， which contains various functional groups， had been successfully prepared. Factors that affect MSPE， such as solution pH， amount of material， adsorption time， the concentration and volume of the elution solvent， and sample volume， were investigated using the static adsorption method. BFR adsorption by the MCA was observed to increase with time， with equilibrium eventua","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"659-669"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093208/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113058","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p><p>The contents of 15 organophosphate ester （OPE） metabolites in the urine of 1 869 adults residing in urban areas were quantified using ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. How gender， age， body mass index （BMI）， smoking status， exercise frequency， family income and dietary intake affected the contents of OPE metabolites in human urine were discussed. Furthermore， the daily intake （EDI） of OPEs was evaluated based on the contents of OPE metabolites in urine. The corresponding potential non-carcinogenic risks were calculated in combination with the non-carcinogenic risk reference dose （RfD）， with the health risks of individual OPE monomers and overall cumulative exposure expressed using the hazard quotient （HQ） and hazard index （HI）. Six OPE metabolites exhibited detection frequencies in excess of 60%， with bis（2-butoxyethyl） phosphate （BBOEP） and 1-hydroxy-2-propyl bis（1-chloro-2-propyl） phosphate （BCIPHIPP）， as the two main OPE metabolites， detected at levels of 0.56 and 0.36 ng/mL， respectively. Men exhibited higher urine contents of bis（1，3-dichloro-2-propyl） phosphate （BDCIPP）， BCIPHIPP， and BBOEP than women， whereas women exhibited higher urine contents of 4-hydroxyphenyl-phenylphosphate （4-HO-DPHP）. The levels of BCIPHIPP and diphenyl phosphate （DPHP） were found to correlate negatively with age， while the BCIPHIPP， and di-<i>o</i>-tolyl-phosphate （DoCP）/di-<i>p</i>-tolyl-phosphate （DpCP） levels correlated positively with family income. Higher exercise frequencies were found to be associated with significantly lower levels of BDCIPP and BCIPHIPP in urine. Furthermore， the frequency of nut consumption and the level of 4-HO-DPHP in urine were determined to be significantly negatively correlated. This study did not identify any significant associations between contents of urinary OPE metabolites and smoking or the intake of other foods， which suggests that smoking and dietary intake are not the primary OPE exposure pathways for the investigated population. Future research should have broader scope to elucidate the principal OPE exposure pathways. The overall OPE exposure levels for all participants in this study ranged between 5.60 and 2 800 ng/（kg⋅d） bw， with a median exposure level of 104 ng/（kg⋅d） bw. Among the four OPE monomers， Tris（2-butoxyethyl） phosphate （TBOEP） exhibited the highest exposure level， with a median value of 57.2 ng/（kg⋅d） bw （ranging between 1.11 and 1 330 ng/（kg⋅d） bw）， thereby contributing up to 55.6% of the total OPE exposure. Additionally， tri-<i>n</i>-butyl phosphate （TNBP） also exhibited significant exposure， with a median level of 32.4 ng/（kg⋅d） bw （ranging between 0.138 and 2 000 ng/（kg⋅d） bw）， which accounts for 31.5% of the total OPE exposure. Gender-based analysis revealed that men exhibited higher OPE exposure levels than women. Specifically， men exhibited a median exposure level of 112 ng/（kg⋅d） bw （ranging between 6.03 and 2 670 ng/（kg⋅d） bw） compared to the valu
{"title":"[Internal exposure characteristics and health risk assessment of organophosphate esters in urban residents].","authors":"Hua-Wei Wang, Shi-Yu Shi, Ling Liu, Ding Chen, Zhi-Xian Lyu, Zi-Yi Song, You-Jie Wang, Lu-Lu Song, Su-Rong Mei","doi":"10.3724/SP.J.1123.2025.01006","DOIUrl":"10.3724/SP.J.1123.2025.01006","url":null,"abstract":"<p><p>The contents of 15 organophosphate ester （OPE） metabolites in the urine of 1 869 adults residing in urban areas were quantified using ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS）. How gender， age， body mass index （BMI）， smoking status， exercise frequency， family income and dietary intake affected the contents of OPE metabolites in human urine were discussed. Furthermore， the daily intake （EDI） of OPEs was evaluated based on the contents of OPE metabolites in urine. The corresponding potential non-carcinogenic risks were calculated in combination with the non-carcinogenic risk reference dose （RfD）， with the health risks of individual OPE monomers and overall cumulative exposure expressed using the hazard quotient （HQ） and hazard index （HI）. Six OPE metabolites exhibited detection frequencies in excess of 60%， with bis（2-butoxyethyl） phosphate （BBOEP） and 1-hydroxy-2-propyl bis（1-chloro-2-propyl） phosphate （BCIPHIPP）， as the two main OPE metabolites， detected at levels of 0.56 and 0.36 ng/mL， respectively. Men exhibited higher urine contents of bis（1，3-dichloro-2-propyl） phosphate （BDCIPP）， BCIPHIPP， and BBOEP than women， whereas women exhibited higher urine contents of 4-hydroxyphenyl-phenylphosphate （4-HO-DPHP）. The levels of BCIPHIPP and diphenyl phosphate （DPHP） were found to correlate negatively with age， while the BCIPHIPP， and di-<i>o</i>-tolyl-phosphate （DoCP）/di-<i>p</i>-tolyl-phosphate （DpCP） levels correlated positively with family income. Higher exercise frequencies were found to be associated with significantly lower levels of BDCIPP and BCIPHIPP in urine. Furthermore， the frequency of nut consumption and the level of 4-HO-DPHP in urine were determined to be significantly negatively correlated. This study did not identify any significant associations between contents of urinary OPE metabolites and smoking or the intake of other foods， which suggests that smoking and dietary intake are not the primary OPE exposure pathways for the investigated population. Future research should have broader scope to elucidate the principal OPE exposure pathways. The overall OPE exposure levels for all participants in this study ranged between 5.60 and 2 800 ng/（kg⋅d） bw， with a median exposure level of 104 ng/（kg⋅d） bw. Among the four OPE monomers， Tris（2-butoxyethyl） phosphate （TBOEP） exhibited the highest exposure level， with a median value of 57.2 ng/（kg⋅d） bw （ranging between 1.11 and 1 330 ng/（kg⋅d） bw）， thereby contributing up to 55.6% of the total OPE exposure. Additionally， tri-<i>n</i>-butyl phosphate （TNBP） also exhibited significant exposure， with a median level of 32.4 ng/（kg⋅d） bw （ranging between 0.138 and 2 000 ng/（kg⋅d） bw）， which accounts for 31.5% of the total OPE exposure. Gender-based analysis revealed that men exhibited higher OPE exposure levels than women. Specifically， men exhibited a median exposure level of 112 ng/（kg⋅d） bw （ranging between 6.03 and 2 670 ng/（kg⋅d） bw） compared to the valu","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"630-639"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093206/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-01DOI: 10.3724/SP.J.1123.2024.11030
Jian-Kun Qian, Run-Ming He, Ke Fang, Chen-Long Li, Shan Bao, Wen Gu, Song Tang
<p><p>Polycyclic aromatic hydrocarbons （PAHs） are organic compounds produced primarily through the incomplete combustion of coal， petroleum， and other carbon-based materials. These compounds are environmentally ubiquitous and have attracted widespread attention because they are significantly biologically toxic and have far-reaching implications for public health and societal wellbeing. Consequently， developing a comprehensive understanding of how PAHs and their derivatives metabolically biotransform in the human body is critical for devising precise preventive strategies and targeted health interventions. PAHs and their derivatives metabolically transform <i>in vivo</i> in a complex process involving a broad variety of enzymes and pathways， and are usually divided into three distinct phases. Phase I encompasses oxidative， reductive， and hydrolytic reactions that are primarily catalyzed by cytochrome P450 （CYP） enzymes. These processes produce intermediates such as monohydroxyls， diols， diol-epoxides， and quinones， some of which （e.g.， diol-epoxides） form covalent DNA adducts， thereby contributing to their toxicities. Phase Ⅱ involves conjugation reactions， such as glucuronidation， sulfation， and glutathionylation， which enhance the water solubilities of the metabolites and facilitate their elimination. These detoxified metabolites are actively transported and excreted <i>via</i> bile or urine in phase Ⅲ， which effectively minimizes internal PAH exposure and prevents accumulation. Metabolites generated at various stages of PAH metabolism serve as crucial biomarkers for assessing human exposure levels. For example， urinary monohydroxy PAH metabolites （e.g.， 1-hydroxypyrene） have been widely adopted as reliable biomarkers for characterizing PAH exposure. However， owing to their structural diversity， PAHs metabolize via considerably different mechanisms to afford a variety of products， which highlights the need to differentiate individual PAHs and their derivatives in order to precisely assess exposure and evaluate nuanced health risks. Understanding the time-dose-effect relationships of PAH metabolites provides another major PAH-biomonitoring challenge. Investigating these dynamics is essential for revealing the cumulative and long-term health effects associated with exposure to multiple PAHs and their derivatives. Moreover， such studies provide scientific bases for formulating personalized and refined health-protection strategies. For instance， exploring how individual susceptibility， such as genetic polymorphisms in CYP enzymes or conjugation pathways， affects PAH metabolism is expected to significantly improve risk stratification and targeted interventions. PAH exposure is associated with significant health risks because they are associated with a range of diseases， including lung， pancreatic， and gastrointestinal cancers， as well as respiratory and cardiovascular diseases. The pervasive environmental presence of PAHs further complicates exposure
{"title":"[Progress in the metabolic and biotransformation of polycyclic aromatic hydrocarbons and their derivatives in humans].","authors":"Jian-Kun Qian, Run-Ming He, Ke Fang, Chen-Long Li, Shan Bao, Wen Gu, Song Tang","doi":"10.3724/SP.J.1123.2024.11030","DOIUrl":"10.3724/SP.J.1123.2024.11030","url":null,"abstract":"<p><p>Polycyclic aromatic hydrocarbons （PAHs） are organic compounds produced primarily through the incomplete combustion of coal， petroleum， and other carbon-based materials. These compounds are environmentally ubiquitous and have attracted widespread attention because they are significantly biologically toxic and have far-reaching implications for public health and societal wellbeing. Consequently， developing a comprehensive understanding of how PAHs and their derivatives metabolically biotransform in the human body is critical for devising precise preventive strategies and targeted health interventions. PAHs and their derivatives metabolically transform <i>in vivo</i> in a complex process involving a broad variety of enzymes and pathways， and are usually divided into three distinct phases. Phase I encompasses oxidative， reductive， and hydrolytic reactions that are primarily catalyzed by cytochrome P450 （CYP） enzymes. These processes produce intermediates such as monohydroxyls， diols， diol-epoxides， and quinones， some of which （e.g.， diol-epoxides） form covalent DNA adducts， thereby contributing to their toxicities. Phase Ⅱ involves conjugation reactions， such as glucuronidation， sulfation， and glutathionylation， which enhance the water solubilities of the metabolites and facilitate their elimination. These detoxified metabolites are actively transported and excreted <i>via</i> bile or urine in phase Ⅲ， which effectively minimizes internal PAH exposure and prevents accumulation. Metabolites generated at various stages of PAH metabolism serve as crucial biomarkers for assessing human exposure levels. For example， urinary monohydroxy PAH metabolites （e.g.， 1-hydroxypyrene） have been widely adopted as reliable biomarkers for characterizing PAH exposure. However， owing to their structural diversity， PAHs metabolize via considerably different mechanisms to afford a variety of products， which highlights the need to differentiate individual PAHs and their derivatives in order to precisely assess exposure and evaluate nuanced health risks. Understanding the time-dose-effect relationships of PAH metabolites provides another major PAH-biomonitoring challenge. Investigating these dynamics is essential for revealing the cumulative and long-term health effects associated with exposure to multiple PAHs and their derivatives. Moreover， such studies provide scientific bases for formulating personalized and refined health-protection strategies. For instance， exploring how individual susceptibility， such as genetic polymorphisms in CYP enzymes or conjugation pathways， affects PAH metabolism is expected to significantly improve risk stratification and targeted interventions. PAH exposure is associated with significant health risks because they are associated with a range of diseases， including lung， pancreatic， and gastrointestinal cancers， as well as respiratory and cardiovascular diseases. The pervasive environmental presence of PAHs further complicates exposure","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"571-584"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093218/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01DOI: 10.3724/SP.J.1123.2024.05003
Xian-Hui Cheng, Wen-Jing Yu, Dong-Xue Wang, Li-Yan Jiang, Liang-Hai Hu
<p><p>Exosomes are 40-160 nm vesicular nano-bodies secreted by most cells that carry large amounts of biologically active substances originating from the parent cell. Proteins in exosomes are protected by phospholipid bilayer membranes that protect them from degradation by enzymes within body fluids. Along with nucleic acid, proteins and metabolites, exosomes are biomolecules that are considered to be among the most important for discovering tumor markers. Plasma is among the most commonly used body fluids in clinical settings; it is highly complex and contains many proteins and metabolites that interfere with exosome isolation. Consequently, the development of methods for effectively isolating exosomes is a key challenge prior to their use in clinical research. In this study, we used a phosphatidylserine molecularly imprinted polymer (PS-MIP) to enrich plasma exosomes. Subsequent immunoblotting analyses for the CD9, TSG101, and CD81 exosome marker proteins showed that signals can be detected using only 5 μL of plasma, thereby demonstrating the efficiency and specificity of the enrichment protocol. Transmission electron microscope (TEM) and nanoparticle tracking analysis (NTA) data revealed that the enriched vesicles are 30-100 nm in size with elliptical or cup-shaped structures, consistent with the morphology and particle-size-distribution characteristics of the exosomes, suggesting that PS-MIP is capable of successfully isolating exosomes. Nanoflow cytometry revealed that 75.4% of the multi-angle laser scattering (MALS) signal is derived from the PS-MIP-enriched exosomes, which indicates that these enriched exosomes are highly pure and free of interference from impurities, such as aggregated protein particles that are similar in size to the exosomes themselves. This method was used to analyze the proteomes and potential exosomal protein markers of clinical plasma samples from three pancreatic-cancer patients and three healthy volunteers. A total of 1052 proteins and 4545 peptides were identified in the plasma exosomes of healthy volunteers, with a total of 972 proteins and 4096 peptides identified in the plasma exosomes of the pancreatic-cancer patients. Further bioinformatics analyses revealed that the Vesiclepedia database covered 84% of the proteins identified in the plasma exosomes isolated using the PS-MIP method; these proteins comprise 77 of the 100 most frequently identified exosomal proteins in the ExoCarta database. The identified proteins from the cellular components were subjected to gene ontology (GO) analysis, which revealed that they are mainly derived from the exosomes, thereby demonstrating the high selectivity of the PS-MIP method for enriching plasma exosomes and providing specificity for subsequent tumor-marker screening. Label-free quantitative analysis showed that 11 proteins were upregulated and 24 proteins were downregulated in the plasma exosomes of patients with pancreatic cancer compared to those of healthy volunteers
{"title":"[Enriching plasma exosomes for proteomic analysis using a phosphatidylserine-imprinted polymer].","authors":"Xian-Hui Cheng, Wen-Jing Yu, Dong-Xue Wang, Li-Yan Jiang, Liang-Hai Hu","doi":"10.3724/SP.J.1123.2024.05003","DOIUrl":"https://doi.org/10.3724/SP.J.1123.2024.05003","url":null,"abstract":"<p><p>Exosomes are 40-160 nm vesicular nano-bodies secreted by most cells that carry large amounts of biologically active substances originating from the parent cell. Proteins in exosomes are protected by phospholipid bilayer membranes that protect them from degradation by enzymes within body fluids. Along with nucleic acid, proteins and metabolites, exosomes are biomolecules that are considered to be among the most important for discovering tumor markers. Plasma is among the most commonly used body fluids in clinical settings; it is highly complex and contains many proteins and metabolites that interfere with exosome isolation. Consequently, the development of methods for effectively isolating exosomes is a key challenge prior to their use in clinical research. In this study, we used a phosphatidylserine molecularly imprinted polymer (PS-MIP) to enrich plasma exosomes. Subsequent immunoblotting analyses for the CD9, TSG101, and CD81 exosome marker proteins showed that signals can be detected using only 5 μL of plasma, thereby demonstrating the efficiency and specificity of the enrichment protocol. Transmission electron microscope (TEM) and nanoparticle tracking analysis (NTA) data revealed that the enriched vesicles are 30-100 nm in size with elliptical or cup-shaped structures, consistent with the morphology and particle-size-distribution characteristics of the exosomes, suggesting that PS-MIP is capable of successfully isolating exosomes. Nanoflow cytometry revealed that 75.4% of the multi-angle laser scattering (MALS) signal is derived from the PS-MIP-enriched exosomes, which indicates that these enriched exosomes are highly pure and free of interference from impurities, such as aggregated protein particles that are similar in size to the exosomes themselves. This method was used to analyze the proteomes and potential exosomal protein markers of clinical plasma samples from three pancreatic-cancer patients and three healthy volunteers. A total of 1052 proteins and 4545 peptides were identified in the plasma exosomes of healthy volunteers, with a total of 972 proteins and 4096 peptides identified in the plasma exosomes of the pancreatic-cancer patients. Further bioinformatics analyses revealed that the Vesiclepedia database covered 84% of the proteins identified in the plasma exosomes isolated using the PS-MIP method; these proteins comprise 77 of the 100 most frequently identified exosomal proteins in the ExoCarta database. The identified proteins from the cellular components were subjected to gene ontology (GO) analysis, which revealed that they are mainly derived from the exosomes, thereby demonstrating the high selectivity of the PS-MIP method for enriching plasma exosomes and providing specificity for subsequent tumor-marker screening. Label-free quantitative analysis showed that 11 proteins were upregulated and 24 proteins were downregulated in the plasma exosomes of patients with pancreatic cancer compared to those of healthy volunteers","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 5","pages":"539-546"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12059983/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144056809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01DOI: 10.3724/SP.J.1123.2024.10017
Jing-Yuan Song, Xiu-Lei Qi, Huai-Zhong Guo, Liang-Hai Hu
<p><p>Outer membrane vesicles (OMVs) are nanoparticles with double-phospholipid membrane structures that are secreted by gram-negative bacteria and carry a variety of bioactive substances from parental bacterial cells; consequently, OMVs serve as disease markers. Moreover, bacterial OMVs are potential anticancer- and antibacterial-drug carriers. While the addition of glycine during bacterial culturing promotes the secretion of bacterial OMVs, glycine-induced differences in the lipid compositions of such OMVs have not yet been reported. In this study, the key plasma membrane components of bacterial OMVs before and after glycine induction were analyzed using lipidomics. Bacterial OMVs were captured from bacterial-culture supernatants using an amphiphilic dendritic polymeric supramolecular probe. Two sets of enriched bacterial OMVs were characterized and their enrichment efficiencies determined, after which the numbers and purities of the OMVs within the samples were determined using a nanofluidic assay. Lipids were extracted using the methyl <i>tert</i>-butyl ether lipid-extraction method when consistent numbers were recorded. The lipid compositions of the bacterial OMVs before and after glycine induction were analyzed using an ultra-performance liquid chromatography-ion mobility spectrometry-quadrupole time-of-flight mass spectrometer (UPLC-IMS-QTOF-MS) and MS-DIAL software. Differential lipid species in the key plasma membranes of the bacterial OMVs following glycine induction were recorded along with their corresponding amounts. Detection was accomplished in positive-ion scanning mode using an ACQUITY UPLC BEH C18 column following UPLC-MS injection, and MS<sup>E</sup> mass-spectrometry data-acquisition mode. The lipid components in the two groups were determined by combining mass-spectrometric and software-analysis data, which revealed that the addition of glycine to the <i>E. coli</i> Nissle 1917 culture led to two-to-three-times higher concentrations of OMVs than observed for the untreated group under the same culturing and enrichment conditions. Particle numbers measured for the same volume revealed one-order-of-magnitude more bacterial OMVs after induction than before, with the treated group exhibiting slightly larger particles (on average); however, these particles were better dispersed and less likely to aggregate. The identified lipid components were categorized to determine the amount of each lipid type. Differentially expressed lipids were subsequently screened according to experimental conditions; significantly different expression levels were observed following glycine induction, with 820 lipids identified among the 10165 components detected. The lipid classes were ranked in order of quantity as: glycerolipids (GL), fatty acids (FA), sphingolipids (SP), glycerophospholipids (GP), saccharolipids (SL), and sterol lipids (ST), among which 463 GL lipid fractions (56.4% of all characterized lipids) were recorded. The ST lipid fraction cont
{"title":"[Lipidomics analysis of glycine-induced bacterial outer membrane vesicles].","authors":"Jing-Yuan Song, Xiu-Lei Qi, Huai-Zhong Guo, Liang-Hai Hu","doi":"10.3724/SP.J.1123.2024.10017","DOIUrl":"https://doi.org/10.3724/SP.J.1123.2024.10017","url":null,"abstract":"<p><p>Outer membrane vesicles (OMVs) are nanoparticles with double-phospholipid membrane structures that are secreted by gram-negative bacteria and carry a variety of bioactive substances from parental bacterial cells; consequently, OMVs serve as disease markers. Moreover, bacterial OMVs are potential anticancer- and antibacterial-drug carriers. While the addition of glycine during bacterial culturing promotes the secretion of bacterial OMVs, glycine-induced differences in the lipid compositions of such OMVs have not yet been reported. In this study, the key plasma membrane components of bacterial OMVs before and after glycine induction were analyzed using lipidomics. Bacterial OMVs were captured from bacterial-culture supernatants using an amphiphilic dendritic polymeric supramolecular probe. Two sets of enriched bacterial OMVs were characterized and their enrichment efficiencies determined, after which the numbers and purities of the OMVs within the samples were determined using a nanofluidic assay. Lipids were extracted using the methyl <i>tert</i>-butyl ether lipid-extraction method when consistent numbers were recorded. The lipid compositions of the bacterial OMVs before and after glycine induction were analyzed using an ultra-performance liquid chromatography-ion mobility spectrometry-quadrupole time-of-flight mass spectrometer (UPLC-IMS-QTOF-MS) and MS-DIAL software. Differential lipid species in the key plasma membranes of the bacterial OMVs following glycine induction were recorded along with their corresponding amounts. Detection was accomplished in positive-ion scanning mode using an ACQUITY UPLC BEH C18 column following UPLC-MS injection, and MS<sup>E</sup> mass-spectrometry data-acquisition mode. The lipid components in the two groups were determined by combining mass-spectrometric and software-analysis data, which revealed that the addition of glycine to the <i>E. coli</i> Nissle 1917 culture led to two-to-three-times higher concentrations of OMVs than observed for the untreated group under the same culturing and enrichment conditions. Particle numbers measured for the same volume revealed one-order-of-magnitude more bacterial OMVs after induction than before, with the treated group exhibiting slightly larger particles (on average); however, these particles were better dispersed and less likely to aggregate. The identified lipid components were categorized to determine the amount of each lipid type. Differentially expressed lipids were subsequently screened according to experimental conditions; significantly different expression levels were observed following glycine induction, with 820 lipids identified among the 10165 components detected. The lipid classes were ranked in order of quantity as: glycerolipids (GL), fatty acids (FA), sphingolipids (SP), glycerophospholipids (GP), saccharolipids (SL), and sterol lipids (ST), among which 463 GL lipid fractions (56.4% of all characterized lipids) were recorded. The ST lipid fraction cont","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 5","pages":"547-555"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12059986/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144049371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p><p>Exosomes are small extracellular vesicles 30-200 nm in diameter that contain many bioactive macromolecules, including proteins, lipids, and nucleic acids; consequently, they play important roles in many physiological and pathological processes and are classified into various property-dependent subtypes. Research into exosome heterogeneity helps broaden our understanding of the physiological and pathological mechanisms associated with exosomes. Exosomes exist in many human biological fluids, with those derived from cerebrospinal fluid (CSF) regarded as potential disease biomarkers. Despite this, few studies have focused on their proteomics, and little research into CSF-derived exosome subtypes has been reported. Traumatic brain injury (TBI) is a major public health issue characterized by a large number of patients and complex pathological processes. While a comprehensive understanding of the pathophysiological processes that underpin TBI is essential for developing therapeutic interventions, proteomic studies into CSF-derived exosomes in patients with TBI are limited. Herein, we designed a tandem size-exclusion chromatography protocol for isolating and profiling the proteins of CSF-derived exosome subtypes from patients with TBI using nanoscale liquid chromatography and trapped-ion mobility spectrometry time-of-flight mass spectrometry (nanoLC-TIMS-TOF-MS). We first centrifuged the collected CSF to remove cells and cell debris, after which it was concentrated by ultrafiltration to increase the exosome concentration and remove small proteins and peptides. A mini-size exclusion chromatography (Mini-SEC) column was then used to separate the exosomes from large amounts of interfering proteins, after which high performance liquid-SEC (HPL-SEC) was used to further separate exosomes according to size. The entire extracellular-vesicle-subset separation and purification process takes approximately 1 h for a single CSF sample. Four differently sized exosome subtypes were successfully isolated and are referred to as S1, S2, S3, and S4 in order of descending size. The S1 subtype exhibited the highest exosome purity according to the particle-to-protein ratio. Multiple characterization methods, including transmission electron microscopy (TEM), Western blotting (WB), and nanoparticle tracking analysis (NTA), confirmed that the exosome subtypes had been successfully acquired. NanoLC-TIMS-TOF-MS, combined with database searching were then used to characterize the proteins. A total of 739 proteins were identified, of which 79% and 72% matched all proteins and the top 100 proteins in the Vesiclepedia database, respectively. Moreover, gene ontology analysis revealed that the identified proteins are mainly located in extracellular exosomes, and that the isolated exosome subtypes are closely related to multiple biological processes, including cell signaling, coagulation, and immune responses. Hierarchical cluster analysis revealed that samples from the same exoso
{"title":"[Isolation and proteomics analysis of cerebrospinal fluid exosome subtypes].","authors":"Xiao-Fei Chen, Wei Liu, Wen-Jia Zhang, Yan-Peng Li, Zhi-Hua Wang, Ming-Xia Gao, Xiang-Min Zhang","doi":"10.3724/SP.J.1123.2024.10014","DOIUrl":"https://doi.org/10.3724/SP.J.1123.2024.10014","url":null,"abstract":"<p><p>Exosomes are small extracellular vesicles 30-200 nm in diameter that contain many bioactive macromolecules, including proteins, lipids, and nucleic acids; consequently, they play important roles in many physiological and pathological processes and are classified into various property-dependent subtypes. Research into exosome heterogeneity helps broaden our understanding of the physiological and pathological mechanisms associated with exosomes. Exosomes exist in many human biological fluids, with those derived from cerebrospinal fluid (CSF) regarded as potential disease biomarkers. Despite this, few studies have focused on their proteomics, and little research into CSF-derived exosome subtypes has been reported. Traumatic brain injury (TBI) is a major public health issue characterized by a large number of patients and complex pathological processes. While a comprehensive understanding of the pathophysiological processes that underpin TBI is essential for developing therapeutic interventions, proteomic studies into CSF-derived exosomes in patients with TBI are limited. Herein, we designed a tandem size-exclusion chromatography protocol for isolating and profiling the proteins of CSF-derived exosome subtypes from patients with TBI using nanoscale liquid chromatography and trapped-ion mobility spectrometry time-of-flight mass spectrometry (nanoLC-TIMS-TOF-MS). We first centrifuged the collected CSF to remove cells and cell debris, after which it was concentrated by ultrafiltration to increase the exosome concentration and remove small proteins and peptides. A mini-size exclusion chromatography (Mini-SEC) column was then used to separate the exosomes from large amounts of interfering proteins, after which high performance liquid-SEC (HPL-SEC) was used to further separate exosomes according to size. The entire extracellular-vesicle-subset separation and purification process takes approximately 1 h for a single CSF sample. Four differently sized exosome subtypes were successfully isolated and are referred to as S1, S2, S3, and S4 in order of descending size. The S1 subtype exhibited the highest exosome purity according to the particle-to-protein ratio. Multiple characterization methods, including transmission electron microscopy (TEM), Western blotting (WB), and nanoparticle tracking analysis (NTA), confirmed that the exosome subtypes had been successfully acquired. NanoLC-TIMS-TOF-MS, combined with database searching were then used to characterize the proteins. A total of 739 proteins were identified, of which 79% and 72% matched all proteins and the top 100 proteins in the Vesiclepedia database, respectively. Moreover, gene ontology analysis revealed that the identified proteins are mainly located in extracellular exosomes, and that the isolated exosome subtypes are closely related to multiple biological processes, including cell signaling, coagulation, and immune responses. Hierarchical cluster analysis revealed that samples from the same exoso","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 5","pages":"518-528"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12059988/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144049459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号