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[Determination of 26 herbicide residues in soil， sediment， and surface water samples using modified QuEChERS method combined with ultra-high performance liquid chromatography-tandem mass spectrometry]. [采用改进的QuEChERS法结合超高效液相色谱-串联质谱法测定土壤、沉积物和地表水样品中26种除草剂残留]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.02016
Li Zhao, Lin Ma, Lan-Qi Huang, Jian-Bo Chen, Wei-Fang Zhu
<p><p>As chemical agents that selectively inhibit weed growth， herbicides play a crucial role in enhancing crop yields. With increasing weed resistance， the environmental residue problems caused by excessive application have become increasingly prominent. Studies indicate that only 20%-30% of field-applied herbicides are effectively utilized， with the remainder entering environmental media such as the atmosphere， soil， sediment， and surface water through runoff and leaching. Recent frequent occurrences of vegetable phytotoxicity incidents in Shanghai have been traced to potential associations with herbicide residues in surface water， further highlighting the urgent need to establish multi-residue analytical methods for environmental media. An analytical method was established based on ultra-high performance liquid chromatography-tandem mass spectrometry （UHPLC-MS/MS） for determining 26 herbicide residues in soil， sediment， and surface water. Instrumental detection parameters were optimized， including electrospray ionization mode， mobile phase， and chromatographic column. The mobile phase consisted of 0.1% formic acid aqueous solution （A） and acetonitrile （B） with the following gradient elution program： 0-0.5 min， 2%B； 0.5-1 min， 2%B-50%B； 1-4 min， 50%B-65%B； 4-6 min， 65%B-75%B； 6-8 min，75%B-85%B； 8-10 min， 85%B-95% B； 10-11 min， 95%B. Soil and sediment samples were extracted via acetonitrile oscillation followed by salting-out and purified using the QuEChERS method. Surface water samples were directly analyzed after acetonitrile extraction without purification. Different amounts of purification agents were investigated during sample pretreatment. Calibration curves were established by plotting the relationship between analyte concentration and measured peak area using pure solvent and matrix-matched standards. All 26 herbicides showed good linearity in the range of 0.1-50 μg/L with correlation coefficients exceeding 0.999 0. Matrix effects ranged from -35.2% to 14.6% across different matrices. Limits of quantification （LOQs） were 0.5 μg/kg for soil and sediment， 0.1 μg/L for water samples. The herbicides were spiked into soil and sediment at spiked levels of 0.5， 1， and 10 μg/kg， and into surface water at 0.1， 1， and 10 μg/L， respectively. The average recoveries for the 26 herbicides in soil， sediment， and surface water were in the ranges of 73%-108%， 73%-102%， and 74%-110%， respectively. The RSDs for the 26 herbicides were in the ranges of 4.5%-16.2%， 3.8%-19.7%， and 4.0%-15.0%， respectively. The developed method was applied to analyze the contamination status of the 26 herbicides in environmental samples collected from six vegetable cultivation zones in Shanghai. Results revealed distinct pollution patterns： In soil matrices， prometryn （PMT）， metolachlor （MTA）， and sulfometuron-methyl （SMTM） showed higher detection rates of 52.9%， 52.9%， and 29.4%， respectively， with content ranges of 0.8-490.4 μg/kg， 0.5-219.8 μg/kg， and 1.0-562.6 μg/kg. Sedim
除草剂作为一种选择性抑制杂草生长的化学药剂，在提高作物产量方面起着至关重要的作用。随着杂草抗性的增强，过量施用造成的环境残留问题日益突出。研究表明，只有20%-30%的田间除草剂被有效利用，其余除草剂通过径流和淋滤进入大气、土壤、沉积物和地表水等环境介质。近年来上海频繁发生的植物毒性事件与地表水除草剂残留有关，因此建立环境介质多残留分析方法迫在眉睫。建立了土壤、沉积物和地表水中26种除草剂残留的超高效液相色谱-串联质谱（UHPLC-MS/MS）分析方法。对电喷雾电离方式、流动相、色谱柱等仪器检测参数进行优化。流动相为0.1%甲酸水溶液(A)和乙腈(B)，梯度洗脱程序为：0-0.5 min, 2%B, 0.5-1 min, 2%B-50%B, 1-4 min, 50%B-65%B, 4-6 min, 65%B-75%B, 6-8 min,75%B-85%B, 8-10 min, 85%B-95% B, 10-11 min, 95%B。土壤和沉积物样品通过乙腈振荡提取，然后盐析，用QuEChERS法纯化。地表水样品经乙腈萃取后直接分析，无需提纯。在样品预处理过程中考察了不同量的纯化剂。采用纯溶剂和基质匹配标准，绘制分析物浓度与测峰面积的关系，建立校准曲线。26种除草剂在0.1 ~ 50 μg/L范围内线性良好，相关系数均大于0.999 0。在不同的矩阵中，矩阵效应从-35.2%到14.6%不等。土壤和沉积物的定量限为0.5 μg/kg，水样的定量限为0.1 μg/L。在土壤和底泥中分别添加0.5、1和10 μg/kg的除草剂，在地表水中添加0.1、1和10 μg/L的除草剂。26种除草剂在土壤、底泥和地表水中的平均回收率分别为73% ~ 108%、73% ~ 102%和74% ~ 110%。26种除草剂的rsd分别为4.5% ~ 16.2%、3.8% ~ 19.7%和4.0% ~ 15.0%。应用该方法对上海市6个蔬菜种植区环境样品中26种除草剂的污染状况进行了分析。结果表明：在土壤基质中，prometryn （PMT）、metolachlor （MTA）和sulfometuron-methyl （SMTM）的检出率分别为52.9%、52.9%和29.4%，含量范围为0.8 ~ 490.4 μg/kg、0.5 ~ 219.8 μg/kg和1.0 ~ 562.6 μg/kg；沉积物样品中PMT的检出率为83.3% （1.5 ~ 6.7 μg/kg）。在地表水中，SMTM、PMT和simetryne （STN）的最大含量分别为12、2.5和1.1 μg/L，显示出不同环境区室的迁移行为差异。该方法简便、快速、准确、稳定，实用性强。该方法可检测土壤、沉积物和地表水中26种除草剂的残留，为监测除草剂的残留污染和环境行为提供参考。
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引用次数: 0
[Preparation of a chiral porous organic cage-bonded silica high performance liquid chromatography stationary phase and its application to the resolution of chiral compounds]. [手性多孔有机笼键合二氧化硅高效液相色谱固定相的制备及其在手性化合物拆分中的应用]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.06014
Jia-Lei Wu, Li-Qin Yu, Bang-Jin Wang, Sheng-Ming Xie, Jun-Hui Zhang, Li-Ming Yuan
<p><p>Porous organic cages （POCs） are a new class of porous materials formed by the assembly of discrete three-dimensional cage-like molecules through intermolecular forces. They possess good solubility and well-defined intrinsic molecular cavities， making them an extremely attractive medium for chromatographic separation. In this study， a chiral porous organic cage （CC3-R， C<sub>72</sub>H<sub>84</sub>N<sub>12</sub>） was synthesized using 1，3，5-triformylbenzene and （1<i>R</i>，2<i>R</i>）-diaminocyclohexane as raw materials， and it was then reduced by NaBH<sub>4</sub> to obtain RCC3-R （C<sub>72</sub>H<sub>108</sub>N<sub>12</sub>）. After post-modification of RCC3-R with 5-bromo-1-pentene to introduce carbon-carbon double-bond functionalized linker arms， it was successfully bonded to the surface of thiolated silica via thiol-ene click reaction to prepare a chiral stationary phase （CSP） for high performance liquid chromatography （HPLC）. The successful synthesis of CC3-R， RCC3-R and CSP was confirmed by various characterization methods such as nuclear magnetic resonance （NMR）， Fourier-transform infrared spectroscopy （FT-IR）， high resolution mass spectrometry （HRMS）， thermogravimetric analysis （TGA）， and elemental analysis （EA）. The enantioseparation performance of the CSP was evaluated by separating various types of racemic compounds， including alcohols， esters， ketones， aldehydes， amines， and organic acids in both normal-phase （NP） and reversed-phase （RP） elution modes. The results demonstrate that the CSP achieved enantioseparation of 18 and 16 racemates in NP and RP modes， respectively. Among them， 12 racemates achieved baseline separation in NP elution mode， while 7 racemates achieved baseline separation in RP elution mode. Moreover， the CSP-packed column exhibited good complementarity in chiral separation with two widely used commercial columns， Chiralcel OD-H and Chiralpak AD-H， enabling the separation of some racemic compounds that cannot be separated on these two commercial columns. In NP elution mode， 7 of the 18 tested racemates could not be enantioseparated on Chiralpak AD-H column， and 4 of the 18 tested racemates could not be enantioseparated on Chiralcel OD-H column. In RP elution mode， 8 of the 16 tested racemates could not be enantioseparated on Chiralpak AD-H column， and 5 of the 16 tested racemates could not be enantioseparated on Chiralcel OD-H column. The effects of column temperature and injection mass on chiral separation performance of the RCC3-R column were investigated. In addition， the RCC3-R column exhibited excellent repeatability and stability. After hundreds of injections， no significant changes were observed in the retention times and resolution values of the analytes compared to the initial use of the column， with relative standard deviations （RSDs， <i>n</i>=5） of less than 0.50% and 1.30%， respectively. Furthermore， the RSDs （<i>n</i>=3） of retention times and resolution values of the racemates separated on RCC3-R colum
多孔有机笼（POCs）是由离散的三维笼状分子通过分子间作用力组装而成的一类新型多孔材料。它们具有良好的溶解度和良好定义的固有分子腔，使它们成为极具吸引力的色谱分离介质。本研究以1,3,5-三甲基苯和(1R,2R)-二氨基环己烷为原料合成了手性多孔有机笼（CC3-R, C72H84N12），再用NaBH4还原得到RCC3-R （C72H108N12）。用5-溴-1-戊烯修饰RCC3-R，引入碳-碳双键功能化连接臂后，通过巯基点击反应成功地与噻化二氧化硅表面结合，制备了用于高效液相色谱（HPLC）的手性固定相（CSP）。通过核磁共振（NMR）、傅里叶变换红外光谱（FT-IR）、高分辨率质谱（HRMS）、热重分析（TGA）和元素分析（EA）等表征方法证实了CC3-R、RCC3-R和CSP的成功合成。通过在正相（NP）和反相（RP）两种洗脱模式下分离各种类型的外消旋化合物，包括醇、酯、酮、醛、胺和有机酸，对CSP的对映体分离性能进行了评估。结果表明，CSP在NP和RP模式下分别实现了18和16个外消旋体的对映体分离。其中，NP洗脱模式下有12个外消旋体实现基线分离，RP洗脱模式下有7个外消旋体实现基线分离。此外，csp填充柱与Chiralcel OD-H和Chiralpak AD-H两种广泛使用的商业色谱柱在手性分离方面具有良好的互补性，可以分离一些在这两种商业色谱柱上无法分离的外消旋化合物。在NP洗脱模式下，18个外消旋体中有7个在Chiralpak AD-H柱上不能对映分离，4个在Chiralcel OD-H柱上不能对映分离。在RP洗脱模式下，16个外消旋物中有8个在Chiralpak AD-H柱上不能对映分离，有5个在Chiralcel OD-H柱上不能对映分离。考察了柱温和进样质量对RCC3-R柱手性分离性能的影响。此外，RCC3-R色谱柱具有良好的重复性和稳定性。数百次进样后，与初始使用色谱柱相比，分析物的保留时间和分辨率值无明显变化，相对标准偏差（rsd, n=5）分别小于0.50%和1.30%。不同批次制备的RCC3-R柱上分离的外消旋物的保留时间和分离值的rsd （n=3）分别小于1.89%和4.10%。本研究表明，手性POC RCC3-R是一种具有潜在应用价值的高效液相色谱手性分离材料。这对于基于手性POCs的新型高效液相色谱csp的研究也具有重要意义。
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引用次数: 0
[Simultaneous screening of pesticides and mycotoxins in dried goji berries and mulberries by QuEChERS-liquid chromatography-quadrupole-time of flight mass spectrometry]. [quechers -液相色谱-四极杆飞行时间质谱法同时筛选枸杞和桑葚干中农药和真菌毒素]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.06009
Hang Yin, Yu-Jie Xie, Meng-Jie Shi, Xing-Qiang Wu, Kai-Xuan Tong, Qiao-Ying Chang, Chun-Lin Fan, Hui Chen
<p><p>Goji berries and mulberries are susceptible to pest and pathogen invasion due to their high sugar content and the impact of growth environment. Their quality and safety are primarily influenced by pesticide residues and mycotoxins. This study has developed a simple， high-throughput， and sensitive analytical method for the simultaneous determination of 172 pesticides and 11 mycotoxins in the medicinal and edible substances of goji berries and mulberries using an improved QuEChERS method coupled with liquid chromatography-quadrupole-time of flight mass spectrometry （LC-Q-TOF/MS）. The sample was hydrated with 7 mL of purified water， and 10 mL of 5% formic acid in acetonitrile was added as the extraction solvent， along with 4 g of anhydrous MgSO<sub>4</sub> and 1 g of NaCl as extraction salts. The extract was purified using 400 mg of anhydrous MgSO<sub>4</sub>， 150 mg of primary secondary amine （PSA）， 100 mg of octadecylsilane （C<sub>18</sub>）， and 5 mg of multi walled carbon nanotubes （MWCNTs）. The supernatant was dried under nitrogen， and the residue was reconstituted in 1.0 mL of a methanol-water solution （3∶2， volume ratio）， homogenized by ultrasonication， and filtered through a 0.22 μm membrane prior to analysis. Separation was performed on a ZORBAX SB-C<sub>18</sub> column （100 mm×2.1 mm， 3.5 μm） using a mobile phase consisting of 0.1% formic acid in aqueous solution （containing 5 mmol/L ammonium acetate） and 0.1% formic acid in methanol. Detection was carried out using electrospray ionization in positive mode with full ion MS/MS （All Ions MS/MS） scanning. Quantitation was achieved using a matrix-matched external calibration method. The results showed that this method can effectively reduce matrix effects， and 183 compounds exhibited good linearity within their respective ranges， with linear correlation coefficients （<i>R</i><sup>2</sup>） greater than 0.995. The screening detection limits （SDLs） and limits of quantification （LOQs） for 172 pesticides in goji berries ranged from 1 to 50 μg/kg and 5 to 50 μg/kg， respectively. For mulberries， the SDLs and LOQs ranged from 1 to 20 μg/kg and 5 to 20 μg/kg， respectively. Additionally， the SDLs for 11 mycotoxins in goji berries were between 1 and 20 μg/kg， with corresponding LOQs of 5 to 50 μg/kg. In mulberries， the SDLs ranged from 1 to 10 μg/kg， while the LOQs were between 5 and 20 μg/kg. Overall， the LOQs of 183 compounds in mulberries were less than 20 μg/kg， and the proportions of pesticides and mycotoxins with LOQs less than 20 μg/kg in goji berries were 98.3% and 81.8%， respectively. At the spiked levels of 1， 2， and 10 times LOQs， the recoveries of 183 compounds ranged from 70.0% to 118.5%， 70.6% to 118.8%， and 71.2% to 119.0%， respectively， with relative standard deviations （RSDs） all less than 20.0%. The intra-day precision and inter-day precision of goji berries were 0.7%-9.8% and 1.0%-17.3%， respectively， whereas for mulberries were 0.8%-9.9% and 1.5%-16.0%， respectively. This method
枸杞和桑葚含糖量高，受生长环境影响，易受病虫害侵袭。它们的质量和安全主要受农药残留和真菌毒素的影响。采用改进的QuEChERS - LC-Q-TOF/MS联用技术，建立了同时测定枸杞和桑葚药用和食用物质中172种农药和11种真菌毒素的简便、高通量、灵敏的分析方法。用7 mL纯净水水化样品，加入5%甲酸乙腈溶液10 mL作为萃取溶剂，加入4 g无水MgSO4和1 g NaCl作为萃取盐。提取液采用400 mg无水MgSO4、150 mg伯仲胺（PSA）、100 mg十八烷基硅烷（C18）和5 mg多壁碳纳米管（MWCNTs）进行纯化。上清液氮气干燥后，用1.0 mL体积比为3∶2的甲醇-水溶液重组，超声均质，0.22 μm膜过滤后分析。色谱柱为ZORBAX SB-C18 (100 mm×2.1 mm, 3.5 μm)，流动相为0.1%甲酸水溶液（含5 mmol/L乙酸铵）和0.1%甲酸甲醇。采用电喷雾电离正模式，全离子MS/MS （All Ions MS/MS）扫描进行检测。采用矩阵匹配外定标法进行定量。结果表明，该方法能有效降低基质效应，183种化合物在各自的范围内呈良好的线性关系，线性相关系数（R2）均大于0.995。枸杞中172种农药的筛选检测限（sdl）和定量限（loq）分别为1 ~ 50 μg/kg和5 ~ 50 μg/kg。桑葚的sdl和loq分别为1 ~ 20 μg/kg和5 ~ 20 μg/kg。枸杞中11种真菌毒素的sdl在1 ~ 20 μg/kg之间，loq在5 ~ 50 μg/kg之间。桑葚的sdl在1 ~ 10 μg/kg之间，loq在5 ~ 20 μg/kg之间。总体而言，桑葚中183种化合物loq < 20 μg/kg，枸杞中农药和真菌毒素loq < 20 μg/kg的比例分别为98.3%和81.8%。在1倍、2倍和10倍定量限下，183个化合物的加标回收率分别为70.0% ~ 118.5%、70.6% ~ 118.8%和71.2% ~ 119.0%，相对标准偏差（rsd）均小于20.0%。枸杞日内精密度为0.7% ~ 9.8%，日内精密度为1.0% ~ 17.3%，桑葚日内精密度为0.8% ~ 9.9%，日内精密度为1.5% ~ 16.0%。将该方法应用于15批枸杞和10批桑葚的农药和真菌毒素检测，共检出16种化合物（其中农药13种，真菌毒素3种），含量范围为5.61 ~ 622.47 μg/kg。枸杞中农药和真菌毒素的检出率和平均含量均高于桑葚。此外，对检出率较高的新烟碱类农药（啶虫脒和吡虫啉）进行了初步风险评估。结果表明：枸杞中醋氨脒和吡虫啉的慢性膳食摄入风险值（%ADI）分别为0.04%和0.02%；这两个值都低于枸杞中每日推荐摄入量的100%，在可接受范围内。为保证枸杞、桑葚产品的安全和质量，有必要加强农药和真菌毒素的管理和储存条件控制。结果表明，该方法操作简便，灵敏度高，适用于枸杞和桑葚中多种农药残留和真菌毒素的高通量定性筛选和准确定量。该方法可为其他浆果药食物质中农药残留和真菌毒素的高通量筛选提供参考。通过技术创新和标准提升，间接促进产业升级，促进药食物质国际化，实现健康价值和经济效益的双赢。
{"title":"[Simultaneous screening of pesticides and mycotoxins in dried goji berries and mulberries by QuEChERS-liquid chromatography-quadrupole-time of flight mass spectrometry].","authors":"Hang Yin, Yu-Jie Xie, Meng-Jie Shi, Xing-Qiang Wu, Kai-Xuan Tong, Qiao-Ying Chang, Chun-Lin Fan, Hui Chen","doi":"10.3724/SP.J.1123.2025.06009","DOIUrl":"10.3724/SP.J.1123.2025.06009","url":null,"abstract":"&lt;p&gt;&lt;p&gt;Goji berries and mulberries are susceptible to pest and pathogen invasion due to their high sugar content and the impact of growth environment. Their quality and safety are primarily influenced by pesticide residues and mycotoxins. This study has developed a simple， high-throughput， and sensitive analytical method for the simultaneous determination of 172 pesticides and 11 mycotoxins in the medicinal and edible substances of goji berries and mulberries using an improved QuEChERS method coupled with liquid chromatography-quadrupole-time of flight mass spectrometry （LC-Q-TOF/MS）. The sample was hydrated with 7 mL of purified water， and 10 mL of 5% formic acid in acetonitrile was added as the extraction solvent， along with 4 g of anhydrous MgSO&lt;sub&gt;4&lt;/sub&gt; and 1 g of NaCl as extraction salts. The extract was purified using 400 mg of anhydrous MgSO&lt;sub&gt;4&lt;/sub&gt;， 150 mg of primary secondary amine （PSA）， 100 mg of octadecylsilane （C&lt;sub&gt;18&lt;/sub&gt;）， and 5 mg of multi walled carbon nanotubes （MWCNTs）. The supernatant was dried under nitrogen， and the residue was reconstituted in 1.0 mL of a methanol-water solution （3∶2， volume ratio）， homogenized by ultrasonication， and filtered through a 0.22 μm membrane prior to analysis. Separation was performed on a ZORBAX SB-C&lt;sub&gt;18&lt;/sub&gt; column （100 mm×2.1 mm， 3.5 μm） using a mobile phase consisting of 0.1% formic acid in aqueous solution （containing 5 mmol/L ammonium acetate） and 0.1% formic acid in methanol. Detection was carried out using electrospray ionization in positive mode with full ion MS/MS （All Ions MS/MS） scanning. Quantitation was achieved using a matrix-matched external calibration method. The results showed that this method can effectively reduce matrix effects， and 183 compounds exhibited good linearity within their respective ranges， with linear correlation coefficients （&lt;i&gt;R&lt;/i&gt;&lt;sup&gt;2&lt;/sup&gt;） greater than 0.995. The screening detection limits （SDLs） and limits of quantification （LOQs） for 172 pesticides in goji berries ranged from 1 to 50 μg/kg and 5 to 50 μg/kg， respectively. For mulberries， the SDLs and LOQs ranged from 1 to 20 μg/kg and 5 to 20 μg/kg， respectively. Additionally， the SDLs for 11 mycotoxins in goji berries were between 1 and 20 μg/kg， with corresponding LOQs of 5 to 50 μg/kg. In mulberries， the SDLs ranged from 1 to 10 μg/kg， while the LOQs were between 5 and 20 μg/kg. Overall， the LOQs of 183 compounds in mulberries were less than 20 μg/kg， and the proportions of pesticides and mycotoxins with LOQs less than 20 μg/kg in goji berries were 98.3% and 81.8%， respectively. At the spiked levels of 1， 2， and 10 times LOQs， the recoveries of 183 compounds ranged from 70.0% to 118.5%， 70.6% to 118.8%， and 71.2% to 119.0%， respectively， with relative standard deviations （RSDs） all less than 20.0%. The intra-day precision and inter-day precision of goji berries were 0.7%-9.8% and 1.0%-17.3%， respectively， whereas for mulberries were 0.8%-9.9% and 1.5%-16.0%， respectively. This method ","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 12","pages":"1327-1341"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12684016/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703608","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}
引用次数: 0
[Simultaneous determination of vitamins K1 and K2 in cosmetics by QuEChERS-high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry]. [quechers -高效液相色谱法同时测定化妆品中维生素K1和K2及高效液相色谱-串联质谱法验证]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.06011
Qian Sun, Chun-Xiao Chen
<p><p>Vitamins K<sub>1</sub> and K<sub>2</sub> are both essential fat-soluble vitamins for the human body. K<sub>1</sub> was once used in cosmetics for its efficacy in improving dark circles by promoting periorbital circulation. However， due to its potential to cause severe allergic reactions， it is now banned in cosmetics in China and the European Union. K<sub>2</sub>， particularly the MK-7 form， has a similar structure to K<sub>1</sub> but features a different side chain. It has gained attention for its skin benefits， including soothing， antioxidant， and anti-aging properties. Although there are no reports of its use in cosmetics in China yet， it has been registered three times as a new cosmetic ingredient， indicating significant market potential. Most existing methods for detecting vitamins K<sub>1</sub> and K<sub>2</sub> focus on pharmaceuticals and dietary supplements， with few studies addressing their analysis in cosmetics， especially vitamin K<sub>2</sub>. Given the structural similarity between the two compounds， a reliable method for their simultaneous determination in cosmetic products is needed. However， cosmetic matrices are complex and often interfere with analysis. Conventional sample preparation techniques， such as liquid-liquid extraction and solid-phase extraction， are time-consuming and labor-intensive. The QuEChERS method offers a faster， simpler， and more cost-effective alternative. In this study， we selected six common types of cosmetics-water-based liquids， emulsions， creams， gels， powders， and oils， to develop and validate a simultaneous quantification method for vitamins K<sub>1</sub> and K<sub>2</sub>. A QuEChERS-based sample preparation method coupled with high performance liquid chromatography （HPLC） was developed for the simultaneous quantification of vitamins K<sub>1</sub> and K<sub>2</sub> in cosmetics. To enhance specificity and confirmation capability， a complementary method using high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was also established. Samples were first pre-dispersed with saturated sodium chloride solution， extracted by <i>n</i>-hexane under ultrasonication， and purified using QuEChERS pretreatment technique （containing 150 mg MgSO<sub>4</sub>， 50 mg PSA， and 25 mg C<sub>18</sub>）. For HPLC analysis， separation was performed on a CAPCELL PAK C<sub>18</sub> AQ column （250 mm×4.6 mm， 5 µm） using methanol-isopropanol （80∶20， volume ratito） as the mobile phase， with detection at 270 nm. For HPLC-MS/MS confirmation， an ACQUITY UPLC BEH C<sub>18</sub> column （50 mm×2.1 mm， 1.7 µm） was employed， with methanol containing 0.05% （volume fraction） formic acid and 5 mmol/L ammonium formate as the mobile phase. Electrospray ionization in positive mode （ESI<sup>+</sup>） and multiple reaction monitoring （MRM） were used for detection. Both HPLC and HPLC-MS/MS methods demonstrated excellent performance for the determination of vitamins K<sub>1</sub> and K<sub>2</sub>. In the HPLC method，
维生素K1和K2都是人体必需的脂溶性维生素。K1曾被用于化妆品中，因为它能促进眼眶周围循环，改善黑眼圈。然而，由于它可能引起严重的过敏反应，它现在在中国和欧盟被禁止在化妆品中使用。K2，特别是MK-7形式，具有与K1相似的结构，但具有不同的侧链。它因其对皮肤的好处而受到关注，包括舒缓、抗氧化和抗衰老的特性。虽然在中国还没有关于其在化妆品中使用的报道，但它已经作为一种新的化妆品成分注册了三次，表明了巨大的市场潜力。大多数现有的检测维生素K1和K2的方法都集中在药物和膳食补充剂上，很少有研究涉及它们在化妆品中的分析，尤其是维生素K2。鉴于这两种化合物的结构相似，需要一种可靠的方法来同时测定它们在化妆品中的含量。然而，修饰矩阵是复杂的，经常干扰分析。传统的样品制备技术，如液-液萃取和固相萃取，既耗时又费力。QuEChERS方法提供了一种更快、更简单且更具成本效益的替代方法。在这项研究中，我们选择了六种常见的化妆品——水基液体、乳液、面霜、凝胶、粉末和油，来开发和验证维生素K1和K2的同时定量方法。建立了基于quechers的样品制备-高效液相色谱（HPLC）同时定量化妆品中维生素K1和K2的方法。为了提高特异性和确认能力，还建立了高效液相色谱-串联质谱（HPLC-MS/MS）的补充方法。样品先用饱和氯化钠溶液预分散，超声正己烷萃取，用QuEChERS预处理技术（含150mg MgSO4、50mg PSA、25mg C18）纯化。色谱柱为CAPCELL PAK C18 AQ (250 mm×4.6 mm, 5µm)，流动相为甲醇-异丙醇（体积比为80∶20），检测波长为270 nm。HPLC-MS/MS确认采用ACQUITY UPLC BEH C18色谱柱（50 mm×2.1 mm, 1.7µm），流动相为含0.05%（体积分数）甲酸的甲醇和5 mmol/L甲酸铵。采用正模式电喷雾电离法（ESI+）和多反应监测法（MRM）检测。HPLC法和HPLC-MS/MS法测定维生素K1和K2均具有良好的性能。HPLC法在0.1 ~ 50 μg/mL （r为0 0.999）范围内线性良好，检出限为0.3 μg/g，定量限为1.0 μg/g。加标回收率在93.2% ~ 104.5%之间，rsd < 5%。HPLC-MS/MS方法在0.005 ~ 0.5 μg/mL （r < 0 0.999）范围内呈良好的线性关系，定量限和定量限分别为0.02 μg/g和0.05 μg/g。加样回收率在89.4% ~ 108.2%之间，rsd < 10%。该方法成功地应用于分析30个化妆品样品跨越6种不同的矩阵类型。在任何样品中均未检测到维生素K1和K2。该方法快速、简便、灵敏、准确，适用于多种化妆品中维生素K1和K2的常规测定。它为质量控制和法规遵从性提供了可靠的技术支持，并展示了QuEChERS样品制备在其他化妆品成分分析中的实用性。
{"title":"[Simultaneous determination of vitamins K<sub>1</sub> and K<sub>2</sub> in cosmetics by QuEChERS-high performance liquid chromatography and verification by high performance liquid chromatography-tandem mass spectrometry].","authors":"Qian Sun, Chun-Xiao Chen","doi":"10.3724/SP.J.1123.2025.06011","DOIUrl":"10.3724/SP.J.1123.2025.06011","url":null,"abstract":"&lt;p&gt;&lt;p&gt;Vitamins K&lt;sub&gt;1&lt;/sub&gt; and K&lt;sub&gt;2&lt;/sub&gt; are both essential fat-soluble vitamins for the human body. K&lt;sub&gt;1&lt;/sub&gt; was once used in cosmetics for its efficacy in improving dark circles by promoting periorbital circulation. However， due to its potential to cause severe allergic reactions， it is now banned in cosmetics in China and the European Union. K&lt;sub&gt;2&lt;/sub&gt;， particularly the MK-7 form， has a similar structure to K&lt;sub&gt;1&lt;/sub&gt; but features a different side chain. It has gained attention for its skin benefits， including soothing， antioxidant， and anti-aging properties. Although there are no reports of its use in cosmetics in China yet， it has been registered three times as a new cosmetic ingredient， indicating significant market potential. Most existing methods for detecting vitamins K&lt;sub&gt;1&lt;/sub&gt; and K&lt;sub&gt;2&lt;/sub&gt; focus on pharmaceuticals and dietary supplements， with few studies addressing their analysis in cosmetics， especially vitamin K&lt;sub&gt;2&lt;/sub&gt;. Given the structural similarity between the two compounds， a reliable method for their simultaneous determination in cosmetic products is needed. However， cosmetic matrices are complex and often interfere with analysis. Conventional sample preparation techniques， such as liquid-liquid extraction and solid-phase extraction， are time-consuming and labor-intensive. The QuEChERS method offers a faster， simpler， and more cost-effective alternative. In this study， we selected six common types of cosmetics-water-based liquids， emulsions， creams， gels， powders， and oils， to develop and validate a simultaneous quantification method for vitamins K&lt;sub&gt;1&lt;/sub&gt; and K&lt;sub&gt;2&lt;/sub&gt;. A QuEChERS-based sample preparation method coupled with high performance liquid chromatography （HPLC） was developed for the simultaneous quantification of vitamins K&lt;sub&gt;1&lt;/sub&gt; and K&lt;sub&gt;2&lt;/sub&gt; in cosmetics. To enhance specificity and confirmation capability， a complementary method using high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was also established. Samples were first pre-dispersed with saturated sodium chloride solution， extracted by &lt;i&gt;n&lt;/i&gt;-hexane under ultrasonication， and purified using QuEChERS pretreatment technique （containing 150 mg MgSO&lt;sub&gt;4&lt;/sub&gt;， 50 mg PSA， and 25 mg C&lt;sub&gt;18&lt;/sub&gt;）. For HPLC analysis， separation was performed on a CAPCELL PAK C&lt;sub&gt;18&lt;/sub&gt; AQ column （250 mm×4.6 mm， 5 µm） using methanol-isopropanol （80∶20， volume ratito） as the mobile phase， with detection at 270 nm. For HPLC-MS/MS confirmation， an ACQUITY UPLC BEH C&lt;sub&gt;18&lt;/sub&gt; column （50 mm×2.1 mm， 1.7 µm） was employed， with methanol containing 0.05% （volume fraction） formic acid and 5 mmol/L ammonium formate as the mobile phase. Electrospray ionization in positive mode （ESI&lt;sup&gt;+&lt;/sup&gt;） and multiple reaction monitoring （MRM） were used for detection. Both HPLC and HPLC-MS/MS methods demonstrated excellent performance for the determination of vitamins K&lt;sub&gt;1&lt;/sub&gt; and K&lt;sub&gt;2&lt;/sub&gt;. In the HPLC method， ","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 12","pages":"1389-1396"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12684020/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703684","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}
引用次数: 0
[Research progress on the pretreatment and analysis of prohibited components of glucocorticoids in cosmetics]. [化妆品中糖皮质激素禁用成分的预处理与分析研究进展]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.01024
Lian Liu, Xiao-Hua Xiao, Ji-Hui Fang, Gong-Ke Li
<p><p>Analyzing cosmetics is particularly important from a safety perspective owing to their widespread use in modern society. A wide range of ingredients and substances are restricted and/or prohibited to ensure that cosmetics are safe， with glucocorticoids among the prohibited substances. Glucocorticoids are important hormones that regulate the body's stress response； they are also widely used as effective anti-inflammatory and immunosuppressive agents in the clinic. However， long-term topical use can lead to allergic reactions and other human-health effects； consequently， their inclusion in cosmetics formulations is prohibited. Glucocorticoids are often illegally abused in cosmetics with the aim of enhancing their anti-allergic and whitening effects. However， analyzing cosmetics is challenging owing to matrix complexity， structural diversity， and the trace-level （μg/kg） presence of glucocorticoids. Rapid and efficient sample pretreatment techniques and sensitive analytical methods are required to address these challenges， which necessitates separating/analyzing glucocorticoids and optimizing the separation/detection workflow. This review presents research progress into sample-pretreatment and analytical methods used to analyze and detect glucocorticoids in cosmetics during the 2010-2024 period. Sample preparation is a critical step when analyzing cosmetics because complex matrices can seriously interfere with the determination of target analytes； hence some separation or enrichment methods often need to be employed when analyzing glucocorticoids in cosmetics. These methods mainly include field-assisted extraction methods， such as ultrasonic-assisted， vortex-assisted， and electric-field-assisted extraction， phase-partitioning methods， such as liquid-liquid extraction and liquid-liquid microextraction， as well as phase-adsorption methods， such as solid-phase microextraction and solid-phase， dispersive-solid-phase， and magnetic-solid-phase extraction. Cosmetics are divided into three categories according to the matrix： aqueous， emulsion， and cream. Creams and emulsions contain many wax-based and lipid substances that often need to be separated and enriched by methods that involve binding field assistance or phase separation， with solid-phase extraction associated with the most （more than 40%） literature reports. Glucocorticoid dissolution is often accelerated by ultrasonic-assisted or vortex-assisted methods prior to solid-phase extraction or solid-phase microextraction. In addition， methods used to analyze and detect glucocorticoids in cosmetics mainly included liquid-chromatography， chromatography-mass spectrometry， and capillary electrophoresis in the 2010-2024 period， as well as rapid detection methods that are discussed in this review. Statistically， 64% of the reports in this timeframe use chromatography-mass spectrometry methods， with chromatography-related methods accounting for 85% of the methods used to analyze and detect glucocorticoid
由于化妆品在现代社会的广泛使用，从安全角度分析化妆品尤为重要。为了确保化妆品的安全，广泛的成分和物质受到限制和/或禁止，糖皮质激素是禁用物质之一。糖皮质激素是调节机体应激反应的重要激素，也是临床上广泛使用的有效抗炎和免疫抑制剂。然而，长期局部使用会导致过敏反应和其他人类健康影响；因此，禁止在化妆品配方中加入它们。糖皮质激素经常被非法滥用于化妆品中，目的是增强其抗过敏和美白效果。然而，由于基质复杂性、结构多样性和糖皮质激素的痕量（μg/kg）存在，分析化妆品具有挑战性。为了应对这些挑战，需要快速高效的样品前处理技术和灵敏的分析方法，这就需要分离/分析糖皮质激素并优化分离/检测工作流程。本文综述了2010-2024年化妆品中糖皮质激素的样品预处理和分析方法的研究进展。样品制备是化妆品分析的关键步骤，复杂的基质会严重干扰目标分析物的测定，因此在分析化妆品中的糖皮质激素时，往往需要采用一些分离或富集方法。这些方法主要包括场辅助提取法，如超声辅助、涡流辅助、电场辅助提取等；相分配法，如液-液萃取、液-液微萃取等；相吸附法，如固相微萃取、固相、分散-固相、磁-固相等。化妆品按基质分为水性、乳剂、乳霜三类。乳霜和乳液含有许多蜡基和脂质物质，通常需要通过结合场辅助或相分离的方法进行分离和富集，其中固相萃取与大多数（超过40%）文献报道有关。在固相萃取或固相微萃取之前，通常采用超声辅助或涡流辅助方法加速糖皮质激素的溶解。此外，2010-2024年化妆品中糖皮质激素的分析检测方法主要有液相色谱法、色谱-质谱法和毛细管电泳法，并对快速检测方法进行了讨论。据统计，在这段时间内，64%的报告使用了色谱-质谱法，色谱相关方法占化妆品中糖皮质激素分析和检测方法的85%。由于美容产品市场的庞大规模和对现场检测的高需求，本综述还介绍了快速检测化妆品中糖皮质激素的方法，包括光谱学和比色法等。在此背景下，预计化妆品中糖皮质激素的分离和分析将呈现出发展趋势。目前，固相萃取和其他预处理技术以及基于液相色谱和色谱质谱的检测技术是化妆品质量控制的主要途径。然而，一方面，糖皮质激素结构的多样性和新的糖皮质激素的不断发现和使用需要开发新的分析方法。特别是，在开发高效的定性和定量分析方法时，整合高分辨率质谱、核磁共振谱和大数据分析方法具有重要的现实意义。另一方面，开发快速、高效、通用的糖皮质激素预处理技术是有效分离和分析化妆品中糖皮质激素的关键，预计将受到越来越多的关注。此外，快速分析，特别是适用于快速现场筛选的分析技术，有望成为化妆品中糖皮质激素检测的重点，以应对化妆品市场日益增长的监管要求。整合样品预处理和分析检测方法，以及可视化、集成和自动化快速检测技术的发展，有望促进快速现场采样和高通量化妆品检测。
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引用次数: 0
[Determination of caffeine and taurine in electronic cigarette oil by high performance liquid chromatography- tandem mass spectrometry]. 高效液相色谱-串联质谱法测定电子烟油中的咖啡因和牛磺酸。
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.09003
Xiao Sun, Qi-Zhi Chang, Chang Wang, Wen-Hao Shao, Feng Feng

Electronic cigarette refers to electronic delivery systems designed to generate aerosols for human inhalation. In recent years， the global electronic cigarette market has experienced rapid expansion， drawing widespread international attention to its potential health impacts. To protect consumer health， China's mandatory National Standard for electronic cigarettes issued in 2022 explicitly prohibits the addition of additives and stimulants associated with energy and vitality in electronic cigarette oil. However， to attract consumers， many illicit manufacturers illegally incorporate various stimulating substances into e-liquids. While detection methods have been reported for some illegal additives such as industrial cannabinoids and sweeteners in electronic cigarette oil， there is no fast and reliable detection method for the determination of caffeine and taurine in electronic cigarette oil available to this day. In order to ensure human health， a method was developed for the simultaneous determination of caffeine and taurine in electronic cigarette oil using high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） with a mixed-functional column. Sample preparation involved a simple dilution and filtration step， which was optimized prior to analysis. The analytes were separated on a FMD Comixsil ACRP column （100 mm×2.1 mm， 3.0 μm）. The column temperature was maintained at 30 ℃. The mobile phase consisted of acetonitrile and a 0.1% formic acid solution containing 10 mmol/L ammonium formate with gradient elution. The flow rate was 0.2 mL/min and the injection volume was 1μL. Mass spectrometric detection was carried out using electrospray ionization in positive mode （ESI+） with multiple reaction monitoring （MRM）. Under the optimized conditions， both caffeine and taurine were well retained on the chromatographic column， exhibiting excellent， tailing-free peak shapes. The method demonstrated that the limits of detection of caffeine and taurine were 0.100 and 1.00 mg/kg， and the limits of quantification were 0.250 and 2.50 mg/kg， respectively. The linear correlation coefficient （r） was ≥0.997. The average recovery of each component was 88.2%-99.0%， with relative standard deviation （RSD， n=6） between 2.2% and 6.6%. These results indicate that the method is simple， rapid and accurate. It has been successfully applied to the detection of caffeine and taurine in real electronic cigarette oil samples.

电子烟是指设计用于产生供人体吸入的气溶胶的电子输送系统。近年来，全球电子烟市场迅速扩张，其潜在的健康影响引起了国际社会的广泛关注。为了保护消费者健康，中国于2022年发布的强制性电子烟国家标准明确禁止在电子烟油中添加与能量和活力相关的添加剂和兴奋剂。然而，为了吸引消费者，许多非法制造商非法将各种刺激物质加入电子液体中。虽然已经报道了电子烟油中一些非法添加剂（如工业大麻素和甜味剂）的检测方法，但迄今为止，还没有快速可靠的检测方法来测定电子烟油中的咖啡因和牛磺酸。为了保证人体健康，建立了混合功能柱高效液相色谱-串联质谱（HPLC-MS/MS）同时测定电子烟油中咖啡因和牛磺酸的方法。样品制备包括一个简单的稀释和过滤步骤，该步骤在分析前经过优化。色谱柱为FMD Comixsil ACRP （100 mm×2.1 mm, 3.0 μm）。柱温保持在30℃。流动相为乙腈和含10 mmol/L甲酸铵的0.1%甲酸溶液，梯度洗脱。流速0.2 mL/min，进样量1μL。质谱检测采用电喷雾电离正模式（ESI+）和多重反应监测（MRM）。在优化条件下，咖啡因和牛磺酸在色谱柱上均有较好的保留，峰形良好，无尾。结果表明，该方法对咖啡因和牛磺酸的检出限分别为0.100和1.00 mg/kg，定量限分别为0.250和2.50 mg/kg。线性相关系数(r)≥0.997。各组分的平均回收率为88.2% ~ 99.0%，相对标准偏差（RSD, n=6）在2.2% ~ 6.6%之间。结果表明，该方法简便、快速、准确。该方法已成功应用于实际电子烟油样品中咖啡因和牛磺酸的检测。
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引用次数: 0
[Determination of 35 pyrrolizidine alkaloids in dried tea by ultra-high performance liquid chromatography- triple quadrupole mass spectrometry]. 超高效液相色谱-三重四极杆质谱法测定干茶中35种吡咯利西啶类生物碱
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.01020
Lu Dong, Xiao-Lin Zhang, Chen Yang, Jing-Yan Zhao, Xue-Mei Wang, Ying-Qian Chu, Xue-Hua Li
<p><p>Pyrrolizidine alkaloids （PAs） are natural toxins widely distributed in plants， which naturally occur in about 3% of the world's flowering plants. To date， more than 660 PAs and their nitrogen oxides have been identified in over 6 000 plants. Some PAs are hepatotoxic， genotoxic and tumorigenic， posing significant health risks to humans. These alkaloids are commonly detected as contaminants in various food products， including tea， grains， milk， honey， as well as plant-derived pharmaceuticals and dietary supplements. Currently， most studies on the quantitative methods for PAs focus on a limited number of PAs and employ an additive quantification strategy， largely due to the challenges associated with chromatographic separation of isomers. These approaches limit the ability to assess exposure and health risk accurately. Herein， a method was established to quantify 35 PAs individually in dried tea samples using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry （UHPLC-MS/MS）. The 35 target compounds were divided into two groups. The first group included 30 PAs， while the second group consisted of 5 PAs. These compounds were separated on Waters Acquity BEH C18 （150 mm×2.1 mm， 1.7 μm） and Thermo Acclaim<sup>TM</sup> C30 （150 mm×2.1 mm， 3.0 μm） chromatographic columns， respectively. Mobile phases were H<sub>2</sub>O containning 5 mmol/L ammonium formate and 0.13% formic acid （pH=3） and methanol-acetonitrile （4∶6， volume raio） containing 0.1% formic acid. The 33 target compounds were separated and 2 isomers co-eluted. Under positive-ion electrospray ionization （ESI） and multiple reaction monitoring （MRM） mode， target compounds were quantified using the external standard method with the matrix-matched standard curve. The results demonstrated that all target compounds showed good linearity （<i>r</i><sup>2</sup>>0.99） in their respective mass concentration ranges. The limits of detection （LODs） and quantification （LOQs） of the method were in the range of 0.2-8.0 µg/kg and 0.5-25.0 µg/kg， respectively. The average recoveries of more than 89% compounds were in the range of 70%-130% at spiked levels of 1， 2， and 5 fold-LOQs and the relative standard deviations （RSDs） were less than 20% （RSDs of lasiocarpine and echimidine were less than 30%）. Moreover， the quantitative method of the 35 PAs was applied to 21 dark tea and 30 black tea samples from Yunnan and Fujian Province， where PAs were detected in 4 dark samples with total contents ranging from 5.07 to 15.48 µg/kg and were not detected in black tea samples. The detection rate of PAs in dark tea samples was higher than that of black tea samples. That might be because most dark tea was processed from fresh leaves picked by machines， and this attribution could be associated with the mixing of weeds containing PAs during tea harvesting. And the detected concentrations of all samples were lower than the maximum levels of tea in European Union regulations， indicating that the tea
吡咯里西啶生物碱（Pyrrolizidine alkaloids, PAs）是广泛存在于植物体内的天然毒素，世界上约3%的开花植物中天然存在吡咯里西啶生物碱。迄今为止，已在6000多种植物中鉴定出660多种PAs及其氮氧化物。一些PAs具有肝毒性、遗传毒性和致瘤性，对人类构成重大健康风险。这些生物碱通常在各种食品中被检测为污染物，包括茶、谷物、牛奶、蜂蜜，以及植物性药物和膳食补充剂。目前，大多数关于PAs定量方法的研究都集中在有限数量的PAs上，并采用加性定量策略，这主要是由于与异构体色谱分离相关的挑战。这些方法限制了准确评估接触和健康风险的能力。本文建立了一种利用超高效液相色谱-三重四极杆质谱（UHPLC-MS/MS）对干茶样品中35种PAs进行定量分析的方法。35种目标化合物被分为两组。第一组有30个PAs，第二组有5个PAs。这些化合物分别在Waters Acquity BEH C18 （150 mm×2.1 mm, 1.7 μm）和Thermo AcclaimTM C30 （150 mm×2.1 mm, 3.0 μm）色谱柱上分离。流动相为含5 mmol/L甲酸铵和0.13%甲酸（pH=3）的H2O和含0.1%甲酸的甲醇-乙腈（体积比4∶6）。分离了33个目标化合物，共洗脱了2个异构体。在正离子电喷雾电离（ESI）和多重反应监测（MRM）模式下，采用基质匹配标准曲线的外标法对目标化合物进行定量。结果表明，所有目标化合物在各自的质量浓度范围内呈良好的线性关系（r2>0.99）。方法的检出限（lod）为0.2 ~ 8.0µg/kg，定量限（loq）为0.5 ~ 25.0µg/kg。在1、2、5倍定量限的加标条件下，平均加标回收率在70% ~ 130%之间，相对标准偏差（rsd）小于20%（拉西卡平和艾希米定的rsd小于30%）。此外，将35种PAs的定量方法应用于云南和福建的21种黑茶和30种红茶样品，其中4种黑茶样品中检测到PAs，总含量在5.07 ~ 15.48µg/kg之间，红茶样品中未检测到PAs。黑茶样品中PAs的检出率高于红茶样品。这可能是因为大多数黑茶都是用机器采摘的新鲜茶叶加工而成的，而这种归因可能与茶叶收获过程中含有PAs的杂草的混合有关。所有样品的检测浓度均低于欧盟规定的茶叶最高含量，表明本研究所涉及的茶叶样品基本安全。总之，35种PAs的定量方法有助于分析茶叶样品中的存在、组成和潜在风险。
{"title":"[Determination of 35 pyrrolizidine alkaloids in dried tea by ultra-high performance liquid chromatography- triple quadrupole mass spectrometry].","authors":"Lu Dong, Xiao-Lin Zhang, Chen Yang, Jing-Yan Zhao, Xue-Mei Wang, Ying-Qian Chu, Xue-Hua Li","doi":"10.3724/SP.J.1123.2025.01020","DOIUrl":"10.3724/SP.J.1123.2025.01020","url":null,"abstract":"&lt;p&gt;&lt;p&gt;Pyrrolizidine alkaloids （PAs） are natural toxins widely distributed in plants， which naturally occur in about 3% of the world's flowering plants. To date， more than 660 PAs and their nitrogen oxides have been identified in over 6 000 plants. Some PAs are hepatotoxic， genotoxic and tumorigenic， posing significant health risks to humans. These alkaloids are commonly detected as contaminants in various food products， including tea， grains， milk， honey， as well as plant-derived pharmaceuticals and dietary supplements. Currently， most studies on the quantitative methods for PAs focus on a limited number of PAs and employ an additive quantification strategy， largely due to the challenges associated with chromatographic separation of isomers. These approaches limit the ability to assess exposure and health risk accurately. Herein， a method was established to quantify 35 PAs individually in dried tea samples using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry （UHPLC-MS/MS）. The 35 target compounds were divided into two groups. The first group included 30 PAs， while the second group consisted of 5 PAs. These compounds were separated on Waters Acquity BEH C18 （150 mm×2.1 mm， 1.7 μm） and Thermo Acclaim&lt;sup&gt;TM&lt;/sup&gt; C30 （150 mm×2.1 mm， 3.0 μm） chromatographic columns， respectively. Mobile phases were H&lt;sub&gt;2&lt;/sub&gt;O containning 5 mmol/L ammonium formate and 0.13% formic acid （pH=3） and methanol-acetonitrile （4∶6， volume raio） containing 0.1% formic acid. The 33 target compounds were separated and 2 isomers co-eluted. Under positive-ion electrospray ionization （ESI） and multiple reaction monitoring （MRM） mode， target compounds were quantified using the external standard method with the matrix-matched standard curve. The results demonstrated that all target compounds showed good linearity （&lt;i&gt;r&lt;/i&gt;&lt;sup&gt;2&lt;/sup&gt;&gt;0.99） in their respective mass concentration ranges. The limits of detection （LODs） and quantification （LOQs） of the method were in the range of 0.2-8.0 µg/kg and 0.5-25.0 µg/kg， respectively. The average recoveries of more than 89% compounds were in the range of 70%-130% at spiked levels of 1， 2， and 5 fold-LOQs and the relative standard deviations （RSDs） were less than 20% （RSDs of lasiocarpine and echimidine were less than 30%）. Moreover， the quantitative method of the 35 PAs was applied to 21 dark tea and 30 black tea samples from Yunnan and Fujian Province， where PAs were detected in 4 dark samples with total contents ranging from 5.07 to 15.48 µg/kg and were not detected in black tea samples. The detection rate of PAs in dark tea samples was higher than that of black tea samples. That might be because most dark tea was processed from fresh leaves picked by machines， and this attribution could be associated with the mixing of weeds containing PAs during tea harvesting. And the detected concentrations of all samples were lower than the maximum levels of tea in European Union regulations， indicating that the tea","PeriodicalId":101336,"journal":{"name":"Se pu = Chinese journal of chromatography","volume":"43 12","pages":"1342-1353"},"PeriodicalIF":0.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12684373/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703300","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}
引用次数: 0
[Research progress on ionic liquid-functionalized magnetic Fe3O4 nanomaterials in sample pretreatment- chromatographic analysis]. 离子液体功能化磁性Fe3O4纳米材料在样品前处理-色谱分析中的研究进展
Se pu = Chinese journal of chromatography
Pub Date : 2025-12-01 DOI: 10.3724/SP.J.1123.2025.04025
Jia-Xin Li, Li-Zhu Zhao, Xiang-Ming Sun, Zhi-Qiang He, Hui-Ling Cao, Ying-Jin Luo, Bo Yang
<p><p>The analysis of complex sample matrices， such as environmental samples， food commodities， and biological specimens， requires sophisticated pretreatment methods. These techniques are fundamentally critical for isolating and enriching analytes of interest， thereby substantially enhancing the sensitivity， accuracy， and efficiency of subsequent analytical procedures. The judicious selection of adsorbent materials represents the pivotal element in achieving effective pretreatment. In recent years， ionic liquid-functionalized magnetic Fe<sub>3</sub>O<sub>4</sub> nanoparticles （IL-Fe<sub>3</sub>O<sub>4</sub> NPs） have garnered significant attention as highly promising materials within this domain. Their potential arises from an exceptional combination of properties： outstanding chemical and colloidal stability， high adsorption capacity， abundant surface active sites， superior solvation capabilities for diverse organic and inorganic compounds， potential for regeneration and reuse， and facile magnetic separation facilitated by an external magnetic field. Ionic liquids （ILs） are characterized by their structurally tailorable nature， excellent ionic conductivity， and potent dissolution capabilities. These intrinsic attributes render ILs highly effective as modifiers for Fe<sub>3</sub>O<sub>4</sub> nanoparticles， either applied singularly or in hybrid composites with other functional materials. This surface functionalization fulfills two essential roles： firstly， it effectively mitigates the inherent tendency of nanoparticles towards agglomeration and provides a protective layer against oxidation； secondly， it circumvents well-documented limitations associated with bulk ionic liquids， notably their high viscosity （which impedes diffusion kinetics and mass transfer efficiency） and the practical difficulties often encountered in their separation from liquid phases. Consequently， IL-Fe<sub>3</sub>O<sub>4</sub> NPs demonstrate particular utility for the efficient enrichment of trace-level analytes， such as metal ions. The resulting composite material successfully retains the advantageous core properties of the magnetic Fe<sub>3</sub>O<sub>4</sub> substrate， specifically its superparamagnetic behavior （enabling rapid and efficient magnetic separation） and inherent biocompatibility. Simultaneously， it incorporates the highly desirable characteristics of ionic liquids， namely their extensive structural design flexibility and ease of chemical functionalization. The adsorption and extraction of analytes by IL-Fe<sub>3</sub>O<sub>4</sub> NPs are governed by a complex interplay of multiple intermolecular forces. These encompass <i>π</i>-<i>π</i> stacking interactions， electrostatic attractions， hydrogen bonding， hydrophobic effects， and potentially coordinative interactions. This multifaceted binding capability underpins the material's demonstrated high adsorption efficiency and selectivity towards various analytes. Currently， IL-Fe<sub>3</sub>O<sub>4</sub> NPs a
复杂样品基质的分析，如环境样品，食品商品和生物样品，需要复杂的预处理方法。这些技术对于分离和富集感兴趣的分析物至关重要，从而大大提高后续分析程序的灵敏度、准确性和效率。吸附材料的合理选择是实现有效预处理的关键因素。近年来，离子液体功能化磁性Fe3O4纳米颗粒（IL-Fe3O4 NPs）作为极具发展前景的材料受到了广泛关注。它们的潜力源于其特殊的特性组合：出色的化学和胶体稳定性，高吸附能力，丰富的表面活性位点，对各种有机和无机化合物的卓越溶剂化能力，再生和再利用的潜力，以及在外部磁场的促进下易于磁分离。离子液体具有结构适宜、离子电导率高、溶解能力强等特点。这些固有属性使得il作为Fe3O4纳米粒子的改性剂非常有效，无论是单独应用还是与其他功能材料混合复合材料。这种表面功能化实现了两个重要的作用：首先，它有效地减轻了纳米颗粒固有的团聚倾向，并提供了一个防止氧化的保护层；其次，它绕过了与大块离子液体相关的充分记录的限制，特别是它们的高粘度（这阻碍了扩散动力学和传质效率）以及它们从液相分离时经常遇到的实际困难。因此，IL-Fe3O4 NPs在有效富集痕量分析物（如金属离子）方面具有特殊的实用性。所得到的复合材料成功地保留了磁性Fe3O4衬底的优势核心特性，特别是其超顺磁性行为（实现快速有效的磁分离）和固有的生物相容性。同时，它结合了离子液体非常理想的特性，即它们广泛的结构设计灵活性和易于化学功能化。IL-Fe3O4 NPs对分析物的吸附和萃取是由多种分子间力的复杂相互作用控制的。这些包括π-π堆叠相互作用、静电吸引、氢键、疏水效应和潜在的协调相互作用。这种多方面的结合能力巩固了材料对各种分析物的高吸附效率和选择性。目前，IL-Fe3O4 NPs广泛应用于各种现代样品预处理技术。主要方法包括磁固相萃取（MSPE），管内固相微萃取（IT-SPME）和移液器尖端固相萃取（PT-SPE）。此外，这些功能化纳米颗粒表现出良好的兼容性，无论是在线还是离线配置，都可以与现有的分析检测平台集成。这包括与色谱技术的耦合，如高效液相色谱（HPLC）和气相色谱（GC），以及光谱方法，包括原子吸收光谱（AAS）和电感耦合等离子体质谱（ICP-MS）。基于IL-Fe3O4 nps的提取与这些检测系统的无缝耦合显着提高了整体方法的灵敏度和分析精度。因此，这些材料在食品安全保障、环境污染物监测和生物医学分析等关键领域显示出相当大的应用前景。本文系统综述了IL-Fe3O4 NPs的合成方法、分类、主要提取方式、在线或离线检测技术及其在样品前处理中的应用，并对该类材料未来可能的探索方向进行了展望。
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引用次数: 0
[Determination of eight per- and polyfluoroalkyl substances in seawater using dispersive membrane extraction-ultra-high performance liquid chromatography-tandem mass spectrometry]. [分散膜萃取-超高效液相色谱-串联质谱法测定海水中8种单氟烷基和多氟烷基物质]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-11-01 DOI: 10.3724/SP.J.1123.2025.04009
Zhen Ren, Ji-Ping Ma, Ya-Jing Liu, Lan Zhang, Ge-Ge Wu, Shuang Li
<p><p>Per- and polyfluoroalkyl substances （PFASs） are widely utilized in various industrial applications. Their persistence in ecosystems raises significant global environmental health concerns. Numerous studies have confirmed the toxicity of PFASs to human endocrine and immune systems. The carcinogenic risks associated with PFASs exposure increasingly alarm public health authorities worldwide. As a result， regulatory policies have been implemented to restrict both the production and environmental release of PFASs. In China， the GB 5749-2022 standard establishes stringent limits for PFASs concentrations in drinking water， capping levels of perfluorooctane sulfonic acid （PFOS） at 40 ng/L and perfluorooctanoic acid （PFOA） at 80 ng/L. Effective monitoring of PFASs requires advanced analytical techniques that exhibit exceptional sensitivity. Ultra-high performance liquid chromatography-tandem mass spectrometry （UHPLC-MS/MS） has emerged as the preferred technique for detecting these substances due to its superior selectivity and low detection limits. However， complex environmental matrices necessitate optimized sample pretreatment strategies to enhance analysis accuracy. Efficient extraction methods must effectively address matrix interference while ensuring analyte enrichment. Dispersive membrane extraction （DME） presents distinct advantages for the pretreatment of PFASs； its operational simplicity is complemented by high enrichment capabilities and efficient mass transfer. The selection of extraction materials critically influences DME performance parameters. Metal-organic frameworks （MOFs） are porous materials composed of organic ligands and metal clusters， featuring tunable pores， high surface areas， and rapid mass transfer. These unique properties enable their current use in sample pretreatment for environmental analysis. This study integrates DME with UHPLC-MS/MS utilizing cationic MOF membranes， enabling simultaneous detection of eight different PFASs within seawater matrices. Optimized parameters ensure reliable quantification of trace-level contaminants throughout this process. The experimental design assessed various parameters， including types of organic solvents （methanol and acetonitrile）， ammonium acetate concentrations in the aqueous phase （0.1， 0.5， 1.0， 2.0， and 5.0 mmol/L）， as well as ion source voltages （-2 500， -3 500， and -4 500 V）， all of which influenced detection efficacy. Chromatographic separation was performed using an ACQUITY UPLC BEH C18 column （100 mm×2.1 mm， 1.7 μm）. Gradient elution combined 1 mmol/L ammonium acetate with acetonitrile for optimal results. Detection was conducted utilizing electrospray ionization （ESI） in negative ion scanning mode coupled with multiple reaction monitoring （MRM）. The results indicated that all eight PFASs could be effectively separated within a timeframe of 12 min， exhibiting favorable peak shapes and high response values. Under optimal conditions， the eight PFASs demonstrated strong lin
全氟烷基和多氟烷基物质（PFASs）广泛应用于各种工业应用。它们在生态系统中的持续存在引起了重大的全球环境卫生关切。大量研究证实了全氟辛烷磺酸对人体内分泌和免疫系统的毒性。与全氟辛烷接触相关的致癌风险日益引起全球公共卫生当局的警惕。因此，已经实施了监管政策来限制全氟磺酸的生产和环境释放。在中国，GB 5749-2022标准对饮用水中全氟辛烷磺酸（PFOS）和全氟辛酸（PFOA）的浓度设定了严格的限值，分别为40 ng/L和80 ng/L。对全氟磺酸的有效监测需要具有特殊灵敏度的先进分析技术。超高效液相色谱-串联质谱法（UHPLC-MS/MS）因其优越的选择性和较低的检出限而成为检测这些物质的首选技术。然而，复杂的环境矩阵需要优化样品预处理策略来提高分析精度。有效的萃取方法必须在保证分析物富集的同时有效地解决基质干扰。分散膜萃取（DME）在PFASs的预处理中具有明显的优势，其操作简单，富集能力强，传质效率高。萃取材料的选择是影响二甲醚性能参数的关键因素。金属有机骨架（MOFs）是由有机配体和金属团簇组成的多孔材料，具有孔径可调、比表面积大、传质快等特点。这些独特的性质使其能够在环境分析的样品预处理中使用。本研究利用阳离子MOF膜将DME与UHPLC-MS/MS相结合，实现了海水基质中8种不同PFASs的同时检测。优化的参数确保整个过程中痕量污染物的可靠量化。实验设计评估了各种参数，包括有机溶剂类型（甲醇和乙腈），水相乙酸铵浓度（0.1,0.5,1.0,2.0和5.0 mmol/L）以及离子源电压（-2 500，-3 500和-4 500 V），所有这些参数都影响检测效果。色谱分离采用ACQUITY UPLC BEH C18色谱柱（100 mm×2.1 mm, 1.7 μm）。1 mmol/L乙酸铵与乙腈复合梯度洗脱效果最佳。利用电喷雾电离（ESI）在负离子扫描模式下结合多重反应监测（MRM）进行检测。结果表明，8种PFASs均能在12 min内有效分离，峰形良好，响应值高。在最佳条件下，8种PFASs在其浓度范围内呈较强的线性关系，相关系数（r²）均不小于0.990 7。在10、50和100 ng/L加峰条件下，PFASs的加峰回收率为50.4% ~ 116.4%，日内和日内相对标准偏差（rsd）分别为1.0% ~ 19.2%和2.2% ~ 19.5%。该方法的检测限（lod）范围约为0.07 ng/L至0.49 ng/L，而定量限（loq）范围约为0.22 ng/L至1.63 ng/L。胶州湾是太平洋沿岸典型的半封闭海湾，陆地径流将营养物质与各种有机/无机污染物聚集在一起，对生活在这些水域的水生生物构成潜在的健康风险。将该方法应用于胶州湾表层海水中8种PFASs的检测，成功鉴定出7种PFASs。其中11-氯二氟-3-草十一烷-1-磺酸钾（Minor F-53B）检测浓度最高，平均质量浓度为17.11 ng/L。与2018年胶州湾表层海水中全氟辛酸（PFOA）的检测结果相比，全氟辛酸（PFOA）的平均质量浓度明显下降。此外，在胶州湾表层海水中检测到新出现的PFASs之一9-氯十六氟-3-草氧酮-1-磺酸钾（F-53B），这可能与近期PFASs生产的转变有关。这些新型全氟磺酸的广泛使用可能会带来环境风险。这些风险与传统的全氟磺酸类似，需要紧急关注。总之，该方法操作简单、快速、灵敏度高，适用于海水中8种PFASs的分析。该方法可为环境水体中全氟辛烷磺酸的研究和分析提供有价值的数据基础和科学依据。
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引用次数: 0
[Quantitation of cow's milk allergen in hypoallergenic infant formulas using ultra-high performance liquid chromatography- tandem mass spectrometry]. [使用超高高效液相色谱-串联质谱法定量低过敏性婴儿配方奶粉中的牛奶过敏原]。
Se pu = Chinese journal of chromatography
Pub Date : 2025-11-01 DOI: 10.3724/SP.J.1123.2024.12030
Dao-Kun Xu, Yang Yang, Hao-Lun Huang, Xiao-Jie Sun, Wen-Yan Hu, Xin-Mei Liu, Jun Yang
<p><p>Cow's milk protein allergy （CMPA） has become a common public health concern and hypoallergenic formula （partially or extensively hydrolyzed formula） is considered as an alternative during infancy. Alcalase and papain are widely used in industrial production of hydrolysates， as they can modify or destroy the linear and conformational epitopes of cow's milk allergens （CMAs）， thus leading to decreased allergenicity. However， despite considerable emphasis has been laid on the manufacturing technique and nutritional value of hypoallergenic formulas， whether there are traces of CMAs in hypoallergenic formulas， remains unknown. Consequently， the need for a quantitative method of detecting multiple CMAs at a time is rising. Traditionally， enzyme-linked immunosorbent assay （ELISA）-based methods have proved to be advantageous with a wide availability of commercial kits for CMAs detection. Moreover， polymerase chain reaction （PCR）， as one of DNA-based methods， has shown exceptional specificity and high sensitivity. However， they both may encounter false-positive results and high-throughput detection is challenging. In the past two decades， mass spectrometry （MS）-based proteomic technology has advanced， including improvements in computational capability， algorithm model， as well as mass spectrometric platforms. MS is gaining more and more attention in the field of food allergen detection， allowing multiplex allergen detection with high sensitivity， accuracy and selectivity in a single run. In this study， an analytical method was developed for the simultaneous quantitation of six CMAss （namely， <i>α</i>-lactalbumin， <i>β</i>-lactoglobulin， <i>α</i>S1-casein， <i>α</i>S2-casein， <i>β</i>-casein， and <i>κ</i>-casein） in hypoallergenic formulas using ultra-high performance liquid chromatography-tandem mass spectrometry （UHPLC-MS/MS）. Proteins of spiked hypoallergenic formula were extracted with ammonium bicarbonate and digested with trypsin. After digestion， the samples were purified with a C<sub>18</sub> spin column， and analyzed by UHPLC-MS/MS （AB SCIEX Triple Quad 6500<sup>+</sup>）. Separation was achieved on a Waters ACQUITY UPLC Peptide CSH C<sub>18</sub> column （150 mm×2.1 mm， 1.7 μm）. The mobile phase consisted of 0.1% formic acid aqueous solution and 0.1% formic acid in acetonitrile， and the flow rate was 0.3 mL/min. The sample injection volume was 10 μL， and the column temperature was set to 40 ℃. Mass spectrometer was operated in positive electrospray ionization （ESI<sup>+</sup>） mode， and multiple reaction monitoring （MRM） mode was adopted. Precursor ions and product ions of marker peptides were predicted by the Skyline software. Mass spectrometric parameters such as declustering potential （DP） and collision energy （CE） were also optimized. Afterwards， by taking allergen epitopes and mass spectrometric responses into consideration， six peptides were retained for quantitative analysis. Calibration curves were constructed with good linearity in the
牛奶蛋白过敏（CMPA）已经成为一个常见的公共卫生问题，低过敏性配方奶粉（部分或广泛水解配方奶粉）被认为是婴儿时期的替代品。Alcalase和木瓜蛋白酶被广泛用于水解物的工业生产，因为它们可以修饰或破坏牛奶过敏原（CMAs）的线性和构象表位，从而降低过敏原的致敏性。然而，尽管人们对低过敏性配方奶粉的生产技术和营养价值已经相当重视，但在低过敏性配方奶粉中是否有cma的痕迹，仍然是未知的。因此，对同时检测多个cma的定量方法的需求正在上升。传统上，基于酶联免疫吸附测定（ELISA）的方法已被证明具有广泛可用的商用试剂盒用于CMAs检测的优势。此外，聚合酶链反应（PCR）作为一种基于dna的方法，具有特殊的特异性和高灵敏度。然而，它们都可能遇到假阳性结果，并且高通量检测具有挑战性。在过去的二十年中，基于质谱（MS）的蛋白质组学技术取得了进步，包括计算能力，算法模型以及质谱平台的改进。质谱法在食品过敏原检测领域受到越来越多的关注，它可以在一次运行中检测出多种过敏原，具有较高的灵敏度、准确性和选择性。本研究建立了超低敏配方中6种CMAss （α-乳清蛋白、β-乳球蛋白、α s1 -酪蛋白、α s2 -酪蛋白、β-酪蛋白、κ-酪蛋白）的同时定量分析方法。加标低过敏性配方蛋白用碳酸氢铵提取，胰蛋白酶消化。消化后，用C18自旋柱纯化，用UHPLC-MS/MS （AB SCIEX Triple Quad 6500+）分析。采用Waters ACQUITY UPLC Peptide CSH C18色谱柱（150 mm×2.1 mm, 1.7 μm）进行分离。流动相为0.1%甲酸水溶液和0.1%甲酸乙腈，流速为0.3 mL/min。进样量为10 μL，柱温为40℃。质谱仪采用正电喷雾电离（ESI+）模式，多反应监测（MRM）模式。利用Skyline软件预测标记肽的前体离子和产物离子。同时对聚类势（DP）和碰撞能（CE）等质谱参数进行了优化。然后结合过敏原表位和质谱反应，保留6个多肽进行定量分析。在0.05 ~ 500 mg/kg范围内线性良好，相关系数(r2) > 0.99。检测限（lod）为0.05 ~ 5.0 mg/kg，定量限（loq）为0.1 ~ 10.0 mg/kg。该方法在低致敏配方中的回收率为74.8% ~ 93.4%。日内、日间准确度为-25.09% ~ -6.09%，日间准确度为-24.0% ~ -5.41%，精密度分别为1.08% ~ 5.05%和1.35% ~ 4.85%。对市售低致敏配方奶粉样品的筛选证实，3种部分水解配方（pHF）和2种广泛水解配方（eHF）中存在cma，含量范围为0.48 ~ 27.36 mg/kg。本研究提出的分析方法具有高灵敏度、高通量能力，可用于监测低致敏性配方中cma的痕量。
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