Wen-Ding Nie, Si-Jie Shuai, Ke Hu, Xiao-Lei Cui, Teng-Fei Li
{"title":"[Determination of 18 polychlorinated biphenyls in milk by dispersive solid-phase extraction based on zeolitic- imidazolate-framework composite microspheres prior to gas chromatography-mass spectrometry].","authors":"Wen-Ding Nie, Si-Jie Shuai, Ke Hu, Xiao-Lei Cui, Teng-Fei Li","doi":"10.3724/SP.J.1123.2024.07005","DOIUrl":"10.3724/SP.J.1123.2024.07005","url":null,"abstract":"<p><p>Polychlorinated biphenyls (PCBs) are hazardous, persistent organic pollutants that are widely used industrially. Although the use of PCBs is banned in many countries, they are still present at trace levels in food and the environment. PCBs are highly chemically stable and lipophilic; hence, they are easily enriched and accumulate in the human body through milk and dairy products. PCBs residues pose serious threats to human health; therefore establishing a reliable enrichment method is an important objective. Sample pretreatment is required to efficiently extract target PCBs owing to sample-matrix complexity and their low contents. Efficient adsorbents form the cores of novel sample-pretreatment technologies, and designing new stable adsorbents is crucial for the further development of pretreatment techniques. Zeolitic imidazolate frameworks (ZIFs) are a family of metal-organic frameworks composed of imidazole linkers and metal ions. Their large surface areas, good stabilities, high porosities, and ease of modification are distinct advantages; consequently, ZIFs are widely used to adsorb organic pollutants. However, powdered ZIFs are difficult to separate and collect, which provides reuse challenges; hence, preparing ZIF composites with other functional materials is a highly effective way of addressing this challenge. Chitosan (CS) is an inexpensive and biodegradable natural polysaccharide that gelates easily. The structure of CS contains many free amino and hydroxyl groups that facilitate chemical modification and hybridization; consequently, CS is a matrix commonly used in composite materials. In this study, we prepared CS@ZIF-8 composite beads by the in-situ synthesis of ZIF-8 on chitosan through acid-solubilization/base-fixation. An analytical method for determining 18 PCBs in milk was developed using CS@ZIF-8 composite microspheres as the adsorbent for dispersive solid-phase extraction (DSPE) coupled with gas chromatography-mass spectrometry (GC-MS).The CS@ZIF-8 composite microspheres were characterized by scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD), and nitrogen-adsorption-desorption experiments, which confirmed that the material had been successfully prepared. How adsorbent dosage, extraction and desorption times, and type and volume of the desorption solvent affect the extraction efficiency were investigated, with the following optimal extraction conditions determined: 20 mg of CS@ZIF-8 as the adsorbent, 30 min of extraction by shaking, and 8 min of ultrasonic desorption with 1 mL of <i>n</i>-hexane. The 18 PCBs exhibited good linearities in the 1-200 μg/L under these optimal conditions, with coefficients of determination (<i>r</i><sup>2</sup>) exceeding 0.999. Detection limits (<i>S/N</i>=3) ranged between 0.06 and 0.24 μg/L, with quantification limits (<i>S/N</i>=10) of 0.19-0.79 μg/L. Repeatability experiments were performed by the addition of 100 μg/L of the 18 P","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"678-687"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093210/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113066","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}
{"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}
Wei-Chen Ji, You-Li Tian, Hao-Dong Fu, Gen-Han Zha, Cheng-Xi Cao, Li Wei, Qiang Zhang
{"title":"[Rapid identification and analysis of hemoglobin isoelectric focusing electrophoresis images based on deep learning].","authors":"Wei-Chen Ji, You-Li Tian, Hao-Dong Fu, Gen-Han Zha, Cheng-Xi Cao, Li Wei, Qiang Zhang","doi":"10.3724/SP.J.1123.2024.05012","DOIUrl":"10.3724/SP.J.1123.2024.05012","url":null,"abstract":"<p><p>Gel electrophoresis is used to separate and analyze macromolecules (such as DNA, RNA, and proteins) and their fragments, and highly reproducible and efficient automatic band-detection methods have been developed to analyze gel images. Uneven background, low contrast, lane distortion, blurred band edges, and geometric deformation pose detection-accuracy challenges during automatic band detection. In order to address these issues, various correction algorithms have been proposed; however, these algorithms rely on researcher experience to adjust and optimize parameters based on image characteristics, which introduces human error while qualitatively and quantitatively processing bands. Isoelectric focusing (IEF) gel electrophoresis separates proteins with high-resolution based on isoelectric point (pI) differences. Microarray IEF (mIEF) is used for the auxiliary diagnosis of diabetes and adult <i>β</i>-thalassemia owing to operational ease, low sample consumption, and high throughout. This diagnostic method relies on accurately positioning and precisely determining protein bands. To avoid errors associated with correction algorithms during band analysis, this paper introduces a method for rapidly recognizing bands in gel electrophoresis patterns that relies on a deep learning object detection algorithm, and uses it to quantify and classify the IEF electrophoresis pattern of hemoglobin (Hb). We used mIEF experiments to collect 1 665 pI-marker-free Hb IEF images as a model dataset to train the YOLOv8 model. The trained model accepts a Hb IEF image as input and infers band bounding boxes and classification results. Using inference data, the gray intensities of the pixels in each band area are summed to determine the content of each protein. The background and foreground of the image need to be separated prior to summing the abovementioned gray intensities, and the threshold method is used to achieve this. The threshold is defined as the average intensity of the background area, which is obtained by summing and averaging the background intensities of gel areas between the detection bounding boxes of each protein band. The baseline band areas are unified after removing the background. This method only requires the input image, directly outputs the corresponding electrophoretic band information, and does not rely on the experience of professionals nor is it affected by factors such as lane distortion or band deformation. In addition, the developed method does not depend on pI markers for qualitatively determining bands, thereby reducing experimental costs and improving detection efficiency. YOLOv8n delivered a detection accuracy of 92.9% and an inference time of 0.6 ms while using limited computing resources. Using Hb A2 as an example, we compared its content measured using the developed method with clinical data. The quantitative results were subjected to regression analysis, which delivered a linearity of 0.981 2 and a correlation coefficient of 0.","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 6","pages":"696-704"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12093207/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113165","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}
{"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}
Ya-Na Luo, Jia Chen, Yu-Yu Hu, Shi-Jie Gao, Yan-Li Wang, Yan-Ming Liu, Juan-Juan Feng, Min Sun
{"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}
{"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}
Qin-Rong Nie, Ming Ni, Jiang-Yan Xu, Ying Shi, Hong-Mei Jiang
{"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}
{"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}
Jian-Kun Qian, Run-Ming He, Ke Fang, Chen-Long Li, Shan Bao, Wen Gu, Song Tang
{"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}
Xian-Hui Cheng, Wen-Jing Yu, Dong-Xue Wang, Li-Yan Jiang, Liang-Hai Hu
{"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}