基于多元活性成分同时测定结合多元统计分析评价不同干燥加工三叶青药材的质量

陈海杰¹，周永逸¹，薛佳¹，邹立思¹，吴楠¹，袁嘉欢¹，刘训红^1，2*，杨薇¹，程建明^1，2

（1．南京中医药大学  药学院，江苏  南京  210023；2．江苏省经典名方工程研究中心，江苏  南京  210023）

摘要：建立了一种超快速液相色谱－三重四极杆－线性离子阱质谱（UFLC－QTRAP－MS/MS）同时测定三叶青中黄酮类、鞣质类、酚酸类、核苷类、多酚类和氨基酸类等60种活性成分的快速分析方法，并结合多元统计分析，评价不同干燥加工三叶青的质量。采用XBridge^?C₁₈柱（4.6 mm × 100 mm，3.5 μm）以0.4%甲酸－甲醇为流动相进行梯度分离，以多反应监测模式在电喷雾正、负离子模式下进行质谱检测。基于各目标成分的质量浓度，用方差分析（ANOVA）、熵权TOPSIS法及灰色关联度分析（GRA）对不同干燥加工三叶青样品进行综合评价。结果显示，各目标成分在一定质量浓度范围内的线性关系良好，相关系数均不低于0.999 0，检出限为0.03 ~ 13.59 ng/mL，定量下限为0.09 ~ 45.30 ng/mL，平均加标回收率为96.1% ~ 102%，相对标准偏差均小于5%；不同干燥方式对三叶青的多种活性成分有影响，与传统的干燥方式相比，现代的干燥方式能明显保留三叶青的活性成分。综合分析，真空干燥的三叶青样品的综合质量较好。该研究构建的方法可为三叶青的合理干燥和加工提供实验依据，同时也为三叶青质量的综合评价和整体控制提供新的方法参考。

关键词：三叶青；不同干燥方式；多元活性成分；多元统计分析；超快速液相色谱－三重四极杆－线性离子阱质谱（UFLC－QTRAP－MS/MS）

中图分类号：O657.63；R282.4  文献标识码：A    文章编号：1004-4957（2023）03-0251-13

Quality Evaluation of Tetrastigmae Radix under Different Drying Methods Based on Simultaneous Determination of Multiple Bioactive Constituents Combined with Multivariate Statistical Analysis

CHEN Hai-jie¹，ZHOU Yong-yi¹，XUE Jia¹，ZOU Li-si¹，WU Nan¹，YUAN Jia-huan¹，LIU Xun-hong^1，2*，YANG Wei¹，CHENG Jian-ming^1，2

（1．School of Pharmacy，Nanjing University of Traditional Chinese Medicine，Nanjing  210023，China；2．Engineering Research Center for Classical Recipes of Jiangsu Province，Nanjing  210023，China）

Abstract：An ultra-fast liquid chromatography－triple quadrupole－linear ion trap mass spectrometry（UFLC－QTRAP－MS/MS） was developed for the rapid and simultaneous analysis of 60 active constituents including flavonoids，tannins，phenolic acids，nucleosides，polyphenols and amino acids in Tetrastigmae Radix，which was combined with multivariate statistical analysis to evaluate the quality of Tetrastigmae Radix dried or processed by different methods．The gradient separation was performed on an XBridge^?C₁₈ column（4.6 mm × 100 mm，3.5 μm） with 0.4% formic acid－methanol as mobile phase，and the mass spectrometric detection was carried out in electrospray positive or negative ion mode under multiple reaction monitoring（MRM） mode. The samples of differently dried and processed Tetrastigmae Radix were comprehensively evaluated by entropy weight TOPSIS，analysis of variance（ANOVA） method and gray correlation analysis（GRA） according to the contents of 60 target constituents．The results showed that there were good linear relationships for 60 target constituents in a certain mass concentration range，with their correlation coefficients（r²） not less than 0.999 0．The limits of detection（LODs） and the limits of quantitation（LOQs） were in the range of 0.03－13.59 ng/mL and 0.09－45.30 ng/mL，respectively．The average spiked recoveries for the samples ranged from 96.1% to 102%，with relative standard deviations（RSDs） less than 5%．Different drying methods have certain effects on the multiple active constituents in Tetrastigmae Radix，and modern drying methods could significantly retain the active constituents in Tetrastigmae Radix compared with the traditional drying methods．The ANOVA showed that the low temperature drying treatment had a good retention effect on flavonoids，tannins，and polyphenols．The loss of nucleosides and phenolic acids in Tetrastigmae Radix was low under vacuum drying conditions．Sun-drying or shade-drying treatment tends to cause the loss of amino acids in Tetrastigmae Radix．The results of GRA and TOPSIS analyses were the same，and the quality ranking of each group was the same，indicating that different drying methods had significant effects on the active constituents in Tetrastigmae Radix，with large differences between groups．GRA and TOPSIS analyses both indicated that the comprehensive quality of Tetrastigmae Radix samples treated by vacuum drying was better，while the overall quality of Tetrastigmae Radix treated by freeze-drying，hot-air drying，sun-drying，and shade-drying was relatively poor．TOPSIS was more suitable than GRA for distinguishing the quality of Tetrastigmae Radix samples．The comprehensive analysis showed that the comprehensive quality of the vacuum-drying treated Tetrastigmae Radix was better under the five drying and processing methods．The method developed in this study is accurate and stable，which could provide an experimental basis for the rational drying and processing of Tetrastigmae Radix，and also provide a new method reference for the comprehensive evaluation and overall control of the quality of Tetrastigmae Radix herb.

Key words：Tetrastigmae Radix；different drying methods；multiple active constituents；multivariate statistical analysis；ultra-fast liquid chromatography－triple quadrupole－linear ion trap mass spectrometry（UFLC－QTRAP－MS/MS）

分散液液微萃取/超高效液相色谱－四极杆/静电场轨道阱质谱法快速筛查化妆水中139种药物残留

容裕棠^1*，张宪臣²，邓晓莹²，吴洁珊¹，刘琼瑜²，蔡杰¹，瓮福良¹

（1．拱北海关技术中心，广东  珠海  519000；2．中山海关技术中心，广东  中山　528403）

摘要：建立了分散液液微萃取（DLLME）结合超高效液相色谱－四极杆/静电场轨道阱质谱（UPLC－Q Exactive Orbitrap MS）同时测定化妆水中抗生素、激素、禁用染料、农药以及真菌毒素5大类共139种药物残留的分析方法。考察了DLLME各条件对萃取效果的影响，确定最佳萃取条件为：取样量5.0 g，萃取剂为四氯乙烷（50 μL）、分散剂为乙腈（300 μL）、氯化钠用量为0.30 g、超声时间为8 min。样品经萃取后，采用岛津Shim-pack XR－ODS II（150 mm × 2.0 mm，2.2 μm）色谱柱分离，通过Q－Exactive Orbitrap MS以全扫描确定母离子精确质量数的离子丰度，实现多种类目标物的定量，结合保留时间和子离子数据依赖模式扫描（DD－MS²）确定子离子的精确质量数，并配合谱库检索进行快速确证与筛查。结果表明：139种化合物的质量浓度在10 ~ 1 000 ng/mL范围内与峰强度呈良好线性关系（r > 0.99），检出限为10 ~ 30 μg/kg，回收率为63.0% ~ 95.9%，相对标准偏差（RSD）为3.0% ~ 9.5%；各精确质量数偏差小于3 × 10^-6。该方法稳定、简单、快速、精确，有机试剂用量少，环境友好，适用于化妆水的快速筛查。

关键词：分散液液微萃取；超高效液相色谱－四极杆/静电场轨道阱质谱；化妆水；药物残留

中图分类号：O657.63；TQ658  文献标识码：A    文章编号：1004-4957（2023）03-0264-11

Rapid Screening of 139 Kinds of Drug Residues in Lotion by Dispersive Liquid－Liquid Microextraction/Ultra Performance Liquid Chromatography－Quadrupole/Exactive Orbitrap Mass Spectrometry

RONG Yu-tang^1*，ZHANG Xian-chen²，DENG Xiao-ying²，WU Jie-shan¹，LIU Qiong-yu²，CAI Jie¹，WENG Fu-liang¹

（1．Technology Center of Gongbei Customs，Zhuhai  519000，China；2．Technology Center of Zhongshan Customs，Zhongshan  528403，China）

Abstract：An ultra performance liquid chromatography－quadrupole/exactive orbitrap mass spectrometry（UPLC－Q Exactive Orbitrap MS） with dispersive liquid－liquid microextraction（DLLME） was established for the simultaneous determination of 139 drug residues in 5 categories，including antibiotics，hormones，prohibited dyes，pesticides and mycotoxins．The influences of various conditions on the extraction effect of DLLME were investigated．The optimal extraction conditions were as follows：5.0 g of sampling volume，50 μL of extraction agent tetrachloroethane，300 μL of dispersant acetonitrile，0.30 g of sodium chloride and 8 min of ultrasonic time．After extraction，the samples were separated on a Shimadzu Shim-pack XR－ODS II（150 mm × 2.0 mm，2.2 μm） column．By using Q－Exactive Orbitrap MS to determine the intensity of the exact mass number of precursor ion in full scan，quantitation on multi-type targets could be realized．Combined with retention time and data-dependent MS/MS（DD－MS²） scanning，the precise mass numbers of the fragment ions could be determined，followed by rapid confirmation and screening with MS/MS spectral library．The results showed that there were good linear relationships for the peak intensities of 139 compounds in mass concentration ranges of 10－1 000 ng/mL（r > 0.99）．The detection limits were 10－30 μg/kg，and the recoveries were 63.0%－95.9%，with relative standard deviations（RSDs） between 3.0% and 9.5%．The deviations for each accurate mass number were less than 3 × 10^-6．This method is stable，simple，rapid，accurate，low consumption of organic reagents and environmentally friendly，and it is suitable for rapid screening of lotion.

Key words：dispersive liquid－liquid microextraction；ultraperformance liquid chromatography－quadrupole/exactive orbitrap mass spectrometry；lotion；drug residues

基于呼气中特异性VOCs筛查的肺癌早期诊断与模型评估

茹立华¹，吕伟¹，王祥麒²，张志娟^1，3*

（1．河南中医药大学  药学院，河南  郑州  450046；2．河南中医药大学第三附属医院  肿瘤科，河南  郑州  450046；

3．暨南大学  质谱仪器与大气环境研究所，广东  广州  510632）

摘要：采用气相色谱－质谱联用仪（GC－MS）检测了180例受试者的呼出气样品，包括79名肺癌患者和101名健康志愿者。每个受试者采集3个平行样品，以及1个室内空气样品。对所有呼气样品中检测的92种挥发性有机物（VOCs）进行定量分析。结合Mann－Whitney检验和正交偏最小二乘判别分析（OPLS－DA）模型筛选出10种肺癌患者呼气特异性VOCs，包括苯甲醛、顺式-2-丁烯、2-丁酮、萘、乙酸乙烯酯、乙烯、2，2，4-三甲基戊烷、3-甲基戊烷、己醛和2-甲基戊烷。利用统计学方法研究其在不同人群中的代谢差异和可能相关的代谢机制，通过建立机器学习模型验证候选标志物对疾病的诊断性能，结果显示，随机森林模型诊断的准确度、精准率、灵敏度和特异性分别为96.25%、96.21%、95.76%、96.67%，马修斯相关系数（MCC）为0.93，曲线下面积为0.96。上述10种化合物可作为肺癌患者的潜在呼气VOCs标志物，为肺癌的早期诊断提供了丰富的基础数据。

关键词：肺癌；挥发性有机物；呼气标志物；诊断模型；气相色谱－质谱联用

中图分类号：O657.7；R318  文献标识码：A    文章编号：1004-4957（2023）03-0275-08

Early Diagnosis of Lung Cancer Based on Breath Specific VOCs Screening and Model Assessment

RU Li-hua¹，Lü Wei¹，WANG Xiang-qi²，ZHANG Zhi-juan^1，3*

（1．College of Pharmacy，Henan University of Chinese Medicine，Zhengzhou  450046，China；2．The Third Affiliated Hospital of Henan University of Chinese Medicine，Zhengzhou  450046，China；3．Institute of Mass Spectrometer and Atmospheric Environment，Jinan University，Guangzhou  510632，China）

Abstract：A gas chromatography－mass spectrometry（GC－MS） was adopted to detect the breath samples of 180 subjects in this paper，including 79 patients with lung cancer and 101 healthy controls. A total of 92 volatile organic compounds（VOCs） were detected. Furthermore，10 potential characteristic VOCs for lung cancer patients were screened out by orthogonal partial least－squares discrimination analysis（OPLS－DA） model combined with Mann－Whitney test，including benzaldehyde，cis-2-butene，2-butanone，naphthalene，vinyl acetate，ethylene，2，2，4-trimethylpentane，3-methylpentane，hexanal and 2-methylpentane. Thereafter，the metabolic differences in different populations and possible related metabolic mechanisms were analyzed using statistical method. Then，the diagnostic performance of candidate breath VOC biomarkers for lung cancer were verified by establishing machine learning models. The results showed that，the diagnostic accuracy，precision，sensitivity and specificity of random forests were 96.25%，96.21%，95.76% and 96.67%，respectively，and the Matthews correlation coefficient（MCC） was 0.93，the area under ROC curve was 0.96. All the 10 compounds could be taken as the potential breath VOC biomarkers for discriminating lung cancer and health people，which have supplied rich basic data for early diagnosis of lung cancer.

Key words：lung cancer；volatile organic compounds；breath biomarkers；diagnosis model；gas chromatography－mass spectrometry

丹江口水库土壤和水体溶解性有机质的分子结构特征分析

周雅茹¹，郝蓉^1*，伍玉鹏¹，何晨²，史权²，胡荣桂¹

（1．华中农业大学  资源与环境学院  农业部长江中下游耕地保育重点实验室，湖北  武汉  430070；

2．中国石油大学（北京）  化学工程与环境学院  重质油国家重点实验室，北京  102249）

摘要：采用傅里叶变换离子回旋共振质谱（FT－ICR MS）分析了丹江口水库土壤和水体溶解性有机质（DOM）的分子结构特征，得到土壤和水体DOM的化合物类型分布、等效双键数及碳数分布特征。结果表明：该区土壤DOM由CHO、CHOS₁、CHON₁、CHON₂、CHON₃和CHON₁S₁ 6类化合物组成，其中以CHO类为主，该类化合物的主要组分为木质素；DOM分子的芳香性结构主要与CHO和CHON₁类化合物有关；低氧原子数和高氧原子数的特征分子均含有芳香结构。该区水体DOM的化合物组成与土壤相似，但不同种类化合物的占比在两者之间表现不同；芳香类化合物的组成与土壤相似，主要也与CHO和CHON₁类物质有关；低氧原子数的特征分子大多为支链结构，从O₄分子开始含有较多的羧基和芳香结构。该研究为深入理解不同生态系统DOM的分子结构特征提供了一定的理论依据。

关键词：溶解性有机质；土壤；水体；傅里叶变换离子回旋共振质谱（FT－ICR MS）

中图分类号：O657.63；X132  文献标识码：A    文章编号：1004-4957（2023）03-0283-09

Molecular Structures Analysis of Dissolved Organic Matter in Soil and Water of Danjiangkou Reservoir

ZHOU Ya-ru¹，HAO Rong^1*，WU Yu-peng¹，HE Chen²，SHI Quan²，HU Rong-gui¹

（1．Key Laboratory of Arable Land Conservation in the Middle and Lower Reaches of Yangtze River，Ministry of Agriculture，College of Resources and Environment，Huazhong Agricultural University，Wuhan  430070，China；2．State Key Laboratory of Heavy Oil Processing，College of Chemical Engineering and Environment，China University of Petroleum，Beijing  102249，China）

Abstract：Fourier transform－ion cyclotron resonance mass spectrometry（FT－ICR MS） was applied to the analysis of the molecular structure characteristics of dissolved organic matter（DOM） in soil and water of Danjiangkou Reservoir in this paper．The compound type distribution，equivalent double bond number and carbon number distribution of soil and aquatic DOM were obtained．The results showed that the soil DOM was composed of 6 classes of compounds，i.e. CHO，CHOS₁，CHON₁，CHON₂，CHON₃ and CHON₁S₁，of which the CHO class was the most abundant，and the major part of this class was lignin．Meanwhile，the aromatic structures of soil DOM were mainly related to CHO and CHON₁ class compounds．The molecules with low and high oxygen atoms were likely to contain aromatic structures，while the constituent of aquatic DOM was similar to that of soil，but the ratio of each class among 6 classes was different between both of them．The major parts of CHO class species of aquatic DOM were also lignin．Aromatic structure was also mainly related to CHO and CHON₁ class compounds．The molecules with low oxygen atoms were likely to contain branched chain structures，while the molecules of oxygen atoms from 4 to 19 contain more carboxyl and aromatic structures．This study provided convincing evidence for better understanding the DOM molecular structure from different ecosystems．

Key words：dissolved organic matter；soil；water；Fourier transform－ion cyclotron resonance mass spectrometry（FT－ICR MS）

新型乘用车室内空气痕量组分快速检测系统的研制

燕志奇¹，汪杰¹，王慧²，王甫华¹，张立军²，谭银湘¹，吴日伟¹，黄文杰¹，黄灶田¹，谭国斌^1*

（1．广州禾信仪器股份有限公司，广东  广州  510535；2．广物汽贸股份有限公司，广东  广州  510000）

摘要：基于自主研制的真空紫外单光子电离飞行时间质谱仪和在线高精度甲醛分析仪，研制了一套新型乘用车室内空气痕量组分的快速检测系统。通过净化空气对乘用车室内空气进行置换，置换完成后，分别利用在线挥发性有机物质谱仪和在线高精度甲醛分析仪对乘用车室内空气中痕量组分和甲醛进行连续检测。结果表明，苯、甲苯、二甲苯/乙苯、苯乙烯和甲醛在对应浓度范围内具有良好的线性，相关系数（r²）均大于0.99，相对标准偏差均小于5%，检出限分别为1.3 × 10^-9、0.1 × 10^-9、0.2 × 10^-9、0.8 × 10^-9、0.1 × 10^-9 mol/mol。采用该方法测定车内空气，结果显示，在短时间内，车内VOCs可快速释放达到释放亚平衡状态，并可得到亚平衡状态下的VOCs浓度及释放速率结果。测试车辆车内空气中待测物质苯、甲苯、二甲苯/乙苯、苯乙烯和甲醛的浓度分别为0.30、8.90、25.10、21.90、15.05 μg/m³。该方法无复杂耗时的采样过程，操作简便，能够满足乘用车室内空气痕量组分的快速检测筛查需求。

关键词：乘用车；室内空气；痕量VOCs组分；快速检测

中图分类号：O657.6；O659.36  文献标识码：A    文章编号：1004-4957（2023）03-0292-07

Development of a New Rapid Detection System for Trace Components in Indoor Air of Passenger Vehicles

YAN Zhi-qi¹，WANG Jie¹，WANG Hui²，WANG Fu-hua¹，ZHANG Li-jun²，TAN Yin-xiang¹，WU Ri-wei¹，HUANG Wen-jie¹，HUANG Zao-tian¹，TAN Guo-bin^1*

（1．Guangzhou Hexin Instrument Co.，Ltd.，Guangzhou  510535，China；2．Guang Wu Automobile Co.，Ltd.，Guangzhou  510000，China）

Abstract：A novel and rapid detection system for trace components in indoor air of passenger vehicles was developed，based on the independently developed vacuum ultraviolet single photon ionization time-of-flight mass spectrometer and on-line high precision formaldehyde analyzer．Firstly，the indoor air of passenger vehicles was replaced by purified air，then the trace components of volatile organic compounds in indoor air of passenger vehicles were continuously detected with volatile organic compounds online mass spectrometer，while the formaldehyde in indoor air of passenger vehicles was continuously detected by using an online high precision formaldehyde analyzer．The results indicated that benzene，toluene，xylene/ethylbenzene，styrene and formaldehyde exhibited good linearity in the corresponding concentration ranges，with their correlation coefficients（r²） all greater than 0.99，and relative standard deviations less than 5%．The limits of detection were 1.3 × 10^-9，0.1 × 10^-9，0.2 × 10^-9，0.8 × 10^-9 and 0.1 × 10^-9 mol/mol，respectively．This method was applied to determine the indoor air of passenger vehicles．The results showed that the VOCs in indoor air of passenger vehicles could be released quickly to reach a sub-equilibrium state in a short time，and the results of VOCs concentration and release rate under the sub-equilibrium state could be obtained．The concentrations of benzene，toluene，xylene/ethylbenzene，styrene and formaldehyde in indoor air of the tested vehicle were 0.30，8.90，25.10，21.90 and 15.05 μg/m³，respectively．With no complex and time-consuming sampling process and easy to operate，this proposed method could meet the requirements for rapid detection and screening on the trace components in indoor air of passenger vehicles.

Key words：passenger vehicles；indoor air；trace components of VOCs；rapid detection

基于UiO－66－NH₂金属有机框架材料的固相萃取/高效液相色谱－串联质谱法测定饮料和配制酒中的新红

冯军军^1，3，王静²，赵连兴³，姜海云³，连雅林³，谭天宇¹，张帆¹，景正义¹，贺锋¹，李腾飞^1*

（1．河北工程大学　生命科学与食品工程学院，河北  邯郸  056038；2．河北工程大学　材料科学与工程学院，河北  邯郸  056038；

3．邯郸市食品药品检验中心，河北  邯郸  056004）

摘要：制备了一种新型固相萃取柱填料金属有机框架材料（MOFs）UiO－66－NH₂，建立了固相萃取/高效液相色谱－串联质谱（SPE/HPLC－MS/MS）测定饮料和配制酒中新红的方法。通过扫描电子显微镜、红外光谱和氮气吸附－脱附等温线等手段表征材料的结构与吸附性能。采用Waters Atlantis^TM T3（150 mm × 2.1 mm，3 μm）色谱柱，以10 mmol/L乙酸铵水溶液和甲醇为流动相进行分离，多反应监测（MRM）模式进行质谱检测。结果表明，在最佳萃取条件下，新红在0.05～10 mg/L范围内呈良好的线性关系，相关系数（r²）为0.998，检出限（LOD）和定量下限（LOQ）分别为0.05 mg/L和0.15 mg/L。回收率为87.8%～107%，相对标准偏差（RSD，n = 6）为1.9%～11%，表明该方法具有较好的准确度和精密度。开发的基于UiO－66－NH₂的固相萃取柱可作为一种高质量的吸附材料用于饮料和配制酒中新红的检测。

关键词：金属有机框架材料；固相萃取；高效液相色谱－串联质谱；新红；饮料；配制酒

中图分类号：O657.7；TS207.3  文献标识码：A    文章编号：1004-4957（2023）03-0299-08

Determination of New Red in Beverages and Prepared Wines by HPLC－MS/MS with Solid Phase Extraction Based on MetalOrganic Frameworks UiO－66－NH₂

FENG Jun-jun^1，3，WANG Jing²，ZHAO Lian-xing³，JIANG Hai-yun³，LIAN Ya-lin³，TAN Tian-yu¹，ZHANG Fan¹，JING Zheng-yi¹，HE Feng¹，LI Teng-fei^1*

（1．College of Life Science and Food Engineering， Hebei University of Engineering， Handan　056038， China；2．College of Materials Science and Engineering，Hebei University of Engineering， Handan　056038， China；3．Food and Drug Inspection Center of Handan City， Handan　056004， China）

Abstract：A new type of solid phase extraction column filler metal organic frame material（MOFs） UiO－66－NH₂ was prepared，and a solid phase extraction/high performance liquid chromatography－tandem mass spectrometry（SPE/HPLC－MS/MS） was developed for the determination of new red in beverages and prepared wines. The structure and adsorption properties of UiO－66－NH₂ were characterized by scanning electron microscopy，infrared spectroscopy and nitrogen adsorption－desorption isotherm. The samples were separated on a Waters Atlantis^TM T3（150 mm × 2.1 mm，3 μm） column with 10 mmol/L ammonium acetate aqueous solution and methanol as mobile phases，and analyzed in multiple reaction monitoring（MRM） mode. The results showed that，under the optimal extraction conditions，the calibration curves for new red showed good linearities in the range of 0.05－10 mg/L， with correlation coefficients（r²） of 0.998.The limits of detection（LODs） and limits of quantitation（LOQs） were 0.05 mg/L and 0.15 mg/L，respectively. The recoveries of this method ranged from 87.8% to 107%， with relative standard deviations（RSDs，n = 6） of 1.9%－11%， indicating that this method has good accuracy and precision. It is also proved that the UiO－66－NH₂ based solid phase extraction column could be used as a high quality adsorption material for detection of new red in beverages and prepared wines.

Key words：metalorganic frameworks；solid phase extraction；high performance liquid chromatography－tandem mass spectrometry；new red；beverage；prepared wines

基于稀疏主成分分析特征选择算法的山楂叶产地判别模型研究

梁小娟^1，2，王娅妮^1，2，4，马晋芳³，孙鹏⁵，郭拓^1*，严诗楷⁴，肖雪^2*

（1．陕西科技大学  电子信息与人工智能学院，陕西  西安  710021；2．广东药科大学  中医药研究院，广东  广州  510006；

3．暨南大学  光电工程系，广东  广州  510632；4．上海交通大学  药学院，上海  200240；5．山东中医药大学  药物研究院，山东  济南  250355）

摘要：为实现山楂叶产地的快速判别，提出一种基于稀疏主成分分析特征选择（SPCAFS）与支持向量机（SVM）建模的定性分析方法。采用近红外积分球漫反射光谱法采集6个产地共41批山楂叶123份样品的近红外光谱图，经数据预处理后，通过SPCAFS对代表性特征波段进行选择，并采用SVM建立山楂叶近红外产地判别模型。模型与连续投影（SPA），正则化自表示（RSR）和稀疏子空间聚类（SSC）3种特征选择算法进行对比，以准确率、精确度和灵敏度作为评价标准，评估所提模型的预测性能。结果显示，SPCAFS的特征波段数相比于全波长建模从1 500减少到21，预测结果的准确率和精确度分别从78%、76%提升至97%、100%。同时，相比于SPA、RSR、SSC算法，准确率分别提升了6%、3%、3%，精确度分别提升了13%、10%、5%，模型的预测能力得到显著提升，基于SPCAFS的SVM判别模型可实现山楂叶南北产地的快速判别。

关键词：近红外光谱；特征选择；山楂叶；产地判别；稀疏主成分分析特征选择算法；支持向量机

中图分类号：O657.3；TQ460.72  文献标识码：A    文章编号：1004-4957（2023）03-0307-08

Origin Discrimination Model of Crataegi Folium Based on Sparse Principal Component Analysis for Feature Selection

LIANG Xiao-juan^1，2，WANG Ya-ni^1，2，4，MA Jin-fang³，SUN Peng⁵，GUO Tuo^1*，YAN Shi-kai⁴，XIAO Xue^2*

（1．School of Electronic Information and Artificial Intelligence，Shaanxi University of Science and Technology，Xi'an  710021，China；2．Institute of Traditional Chinese Medicine，Guangdong Pharmaceutical University，Guangzhou  510006，China；3．Department of Electro-Optical Engineering，Jinan University，Guangzhou  510632，China；4．School of Pharmacy，Shanghai Jiao Tong University，Shanghai  200240，China；5．Innovative Institute of Chinese Medicine and Pharmacy，Shandong University of Traditional Chinese Medicine，Jinan  250355，China）

Abstract：A qualitative analysis method based on sparse principal component analysis feature selection（SPCAFS） and support vector machine（SVM） modeling was proposed in this paper，in order to realize the rapid discrimination on the origin of Crataegi Folium. Near infrared integrative sphere diffuse reflection spectroscopy was used to collect the near-infrared spectrograms of 123 Crataegi Folium samples from 6 regions in 41 batches. After data preprocessing，the representative characteristic bands were selected by SPCAFS，and the near infrared origin discrimination model for Crataegi Folium was established by SVM. The model was compared with three feature selection algorithms，i.e. continuous projection algorithm（SPA），regularized self representation algorithm（RSR） and sparse subspace clustering（SSC），to evaluate the prediction performance of the proposed model with accuracy，precision and sensitivity as evaluation criteria. The results showed that the numbers of characteristic band for SPCAFS were reduced from 1 500 to 21 compared with those for full wavelength modeling，but the accuracy and precision of prediction results were improved from 78% and 76% to 97% and 100%，respectively. Meanwhile，compared with those of SPA，RSR and SSC algorithms，the accuracy was improved by 6%，3% and 3%，while the precision was improved by 13%，10% and 5%，respectively. The prediction ability of the model was significantly improved. The SVM discrimination model based on SPCAFS could realize the rapid discrimination on the northern and southern geographic origins of Crataegi Folium.

Key words：near infrared spectroscopy；feature selection；Crataegi Folium；geographic origin discrimination；sparse principal component analysis for feature selection；support vector machines

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

尹学虎¹，杨新杰¹，罗丹¹，张艳丽^1*，王红斌¹，杨文荣^1，2，庞鹏飞^1*

（1．云南民族大学  化学与环境学院，云南省教育厅环境功能材料重点实验室，云南  昆明  650504；

2．迪肯大学  生命与环境科学学院，澳大利亚  维多利亚州  3217）

摘要：采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs），并将该材料与还原氧化石墨烯（rGO）复合，用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定，构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构，GOx的固定化过程，以及传感器的直接电化学和电催化性能进行表征。结果表明，HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能，该方法有效实现了对葡萄糖的高灵敏度检测，其电流响应的线性范围为0.05 ~ 7.0 mmol/L，检出限（S/N = 3）为16 μmol/L。该传感器具有良好的选择性、重现性及稳定性，对实际样品血清中血糖的测定结果令人满意，回收率为98.0% ~ 103%，相对标准偏差不大于5.0%。

关键词：葡萄糖氧化酶；中空多孔金纳米；还原氧化石墨烯；电化学传感器

中图分类号：O657.63；TS245.4  文献标识码：A    文章编号：1004-4957（2023）03-0315-08

Direct Electrochemical Behaviors of Glucose Oxidase on Hollow Porous Gold Nanoparticles/Reduced Graphene Oxide Nanocomposite and Its Biosensing Application

YIN Xue-hu¹，YANG Xin-jie¹，LUO Dan¹，ZHANG Yan-li^1*，WANG Hong-bin¹，YANG Wen-rong^1，2，PANG Peng-fei^1*

（1．Key Laboratory of Environmental Functional Materials of Yunnan Province Education Department，School of Chemistry and Environment，Yunnan Minzu University，Kunming  650504，China；2．School of Life and Environmental Sciences，Deakin University，Geelong  VIC 3217，Australia）

Abstract：Hollow porous gold nanoparticles（HPAuNPs） were prepared by a simple solution phase sacrificial template method．The hollow porous gold nanoparticles/reduced graphene oxide（HPAuNPs/rGO） nanocomposite was prepared for the effective immobilization of glucose oxidase（GOx） on the surface of glassy carbon electrode（GCE）．An electrochemical biosensor for detection of glucose was constructed based on GOx/HPAuNPs/rGO modified GCE．Scanning and transmission electron microscopy，X-ray photoelectron spectroscopy，X-ray diffraction spectroscopy，infrared spectroscopy and electrochemistry were used to characterize the morphology and structure of the nanomaterial，the immobilization process of GOx，and the direct electrochemical behaviors and the electrocatalytic properties of the biosensor．The results showed that the HPAuNPs/rGO nanocomposite could effectively accelerate the direct electron transfer（DET） between GOx and electrode due to the synergy effect of HPAuNPs and rGO．The modified electrode exhibited an excellent electrocatalytic property for glucose determination．The response current was proportional to the concentration of glucose in the range of 0.05－7.0 mmol/L，with a detection limit（S/N = 3） of 16 μmol/L．With good selectivity，reproducibility and stability，the proposed biosensor could satisfy the demands for glucose detection in real serum sample，with recoveries of 98.0%－103%，and relative standard deviations（RSDs） not more than 5.0%.

Key words：glucose oxidase；hollow porous gold nanoparticles；reduced graphene oxide；electrochemical biosensor

基于多参数融合的红外光谱对混合物的组分识别研究

陈斌^*，郑小欢，耿德春，齐文良，陆道礼

（江苏大学  食品与生物工程学院，江苏  镇江  212013）

摘要：为解决混合物组分的识别问题，该文以7种标准品以及由7种标准品配制的26种混合物为研究对象，以准确率与误判率为混合组分识别效果的评价指标，在研究谱峰匹配算法、非负最小二乘匹配算法与相关系数匹配系数算法的基础上，采用一种基于多特征融合的BP神经网络模型红外光谱技术对混合物组分进行识别，并与逻辑回归模型进行了对比。结果表明，3种单一匹配算法的识别准确率均低于76.31%，多特征融合的逻辑回归模型与多特征融合的BP神经网络模型预测集的识别准确率分别为83.33%和98.18%，误判率分别为4.76%和1.82%。研究结果表明，中红外光谱技术结合BP神经网络模型可以更好地进行混合物的组分识别。为了进一步探究模型对混合组分最低浓度的检测能力，采用香兰素和乙醇两组分溶液进行检出限的研究。结果表明混合物中香兰素的质量浓度为0.03 g/mL时准确率为100.00%，误判率为14.29%；香兰素质量浓度低于0.03 g/mL时，准确率下降20.00%，误判率上升19.04%。故可认为该研究能识别出的香兰素乙醇溶液中香兰素的最低质量浓度为0.03 g/mL。

关键词：红外光谱；混合物；多参数；BP神经网络；组分识别

中图分类号：O657.3；O642.5  文献标识码：A    文章编号：1004-4957（2023）03-0323-07

Study on Identification of Components in Mixtures Using Infrared Spectroscopy Based on Multi-parameter Fusion

CHEN Bin^*，ZHENG Xiao-huan，GENG De-chun，QI Wen-liang，LU Dao-li

（School of Food and Biological Engineering，Jiangsu University，Zhenjiang   212013，China）

Abstract：7 standard substances and 26 mixtures made from 7 standard substances were selected as the research objects in this paper， with the accuracy and misjudgment rate as the evaluation indexes for recognition effect of the components of mixtures， and spectral peak matching algorithm， non-negative least squares matching algorithm and correlation coefficient matching coefficient algorithm were studied， in order to solve the problem of identifying the components of mixtures. Furthermore， a BP neural network model infrared spectroscopy technique based on multi-feature fusion was used to identify the components of the mixture， which was compared with the logistic regression model. The results showed that the recognition accuracies of three single matching algorithms are lower than 76.31%， while the recognition accuracies of multi-feature fusion logistic regression model and multi-feature fusion BP neural network model prediction set are 83.33% and 98.18%， respectively， and the misjudgment rates are 4.76% and 1.82%. The results showed that mid-infrared spectroscopy combined with BP neural network model could better identify the components of the mixture. In order to further explore the detection ability of the model towards the lowest concentration of mixed components， the detection limit for vanillin and ethanol solution was studied. The results showed that the accuracy rate was 100.00% and the misjudgment rate was 14.29% when the concentration of vanillin was 0.03 g/mL. When the concentration of vanillin was lower than 0.03 g/mL， the accuracy decreased by 20.00% and the misjudgment rate increased by 19.04%. Therefore， it may be considered that the minimum mass concentration of vanillin in vanillin and ethanol solution identified in this study is 0.03 g/mL.

Key words：infrared spectroscopy；mixture；multi-parameters；BP neural network；component identification

超高效液相色谱－高分辨质谱法同时测定白酒中19种氨基酸

尹艳艳，杨军林，田栋伟，蒋力力，尤小龙，张健，程平言^*

（贵州茅台酒厂（集团）习酒有限责任公司，贵州省白酒制造业创新中心，贵州  遵义  564622）

摘要：建立了白酒样品中19种氨基酸的超高效液相色谱－高分辨质谱（UPLC－HRMS）检测方法。样品经烘箱干燥法除乙醇，水定容，使用水相滤膜过滤后上机检测。以甲醇-0.1%甲酸作为流动相，经Hypersil GOLD色谱柱（150 mm × 2.1 mm，1.9 μm）分离，在正离子扫描模式下，一级母离子全扫描采集化合物信息，外标法定量分析。结果表明，19种氨基酸在其线性范围内线性关系良好，相关系数（r²）不小于0.986 2，方法的检出限为0.003 ~ 0.015 μmol/L，定量下限为0.008 ~ 0.050 μmol/L，白酒样品中19种氨基酸的加标回收率为 88.2% ~ 119%，相对标准偏差为0.23% ~ 5.6%，适用于白酒样品中氨基酸分析。利用该方法分析了不同轮次酱香酒中氨基酸含量，检出L-丙氨酸、L-精氨酸、L-天冬氨酸、L-谷氨酸、甘氨酸、L-组氨酸、L-异亮氨酸、L-亮氨酸、L-赖氨酸、L-苯丙氨酸、L-脯氨酸、L-丝氨酸、L-苏氨酸、L-酪氨酸、L-缬氨酸和L-瓜氨酸共16种氨基酸。不同轮次酒中氨基酸含量的显著水平P值均小于0.05，表明不同轮次酒中氨基酸含量具有显著性差异。

关键词：氨基酸；白酒；超高效液相色谱－高分辨质谱（UPLC－HRMS）

中图分类号：O657.63；O629.7  文献标识码：A    文章编号：1004-4957（2023）03-0330-07

Determination of 19 Amino Acids in Baijiu by Ultra-high Performance Liquid Chromatography－High Resolution Mass Spectrometry

YIN Yan-yan，YANG Jun-lin，TIAN Dong-wei，JIANG Li-li，YOU Xiao-long，ZHANG Jian，CHENG Ping-yan^*

（Guizhou Baijiu Manufacturing Industry Innovation Center，Guizhou Maotai Distillery（Group） Xijiu Co.，Ltd.，Zunyi  564622，China）

Abstract：An ultra-high performance liquid chromatography－high resolution mass spectrometry（UPLC－HRMS） was established for the determination of 19 amino acids in Baijiu．The samples were firstly removed ethanol by oven-drying method，then the volume was fixed with ultrapure water，and filtered using an aqueous phase filter membrane before analysis．The samples were separated on a Hypersil GOLD column（150 mm × 2.1 mm，1.9 μm） with methanol－0.1% formic acid solution as mobile phase．The data were collected in full mass scan in positive ESI mode and the external standard method was used to achieve quantitative analysis．The results showed that the calibration curves for 19 amino acids showed good linear relationships within corresponding linear range，with  correlation coefficients（r²） not less than 0.986 2．The limits of detection and the limits of quantitation were in the range of 0.003－0.015 μmol/L and 0.008－0.050 μmol/L，respectively．The recoveries for Baijiu samples ranged from 88.2% to 119%，with relative standard deviations of 0.23%－5.6%．This method was suitable for the determination of amino acids in Baijiu samples．The contents of amino acids in different rounds base liquor of sauce-flavor Baijiu were analyzed by this method．Sixteen amino acids，i.e. L-alanine，L-arginine，L-aspartic acid，L-glutamic acid，glycine，L-histidine，L-isoleucine，L-leucine，L-lysine，L-phenylalanine，L-proline，L-serine，L-threonine，L-tyrosine，L-valine and L-citrulline were detected．The significant level P values of amino acid contents in different rounds base liquor of sauce-flavor Baijiu were all less than 0.05，indicating that amino acid contents in different rounds base liquor had significant differences.

Key words：amino acids；Baijiu；ultra-high performance liquid chromatography－high resolution mass spectrometry（UPLC－HRMS）

固相萃取净化/超高效液相色谱－串联质谱法测定养殖环境中地西泮及其代谢物

王旭峰，王强，张英侠，黄珂^*

（农业农村部渔业环境及水产品质量监督检验测试中心（广州），中国水产科学研究院南海水产研究所，广东  广州  510300）

摘要：建立了固相萃取净化/超高效液相色谱－串联质谱（SPE/UPLC－MS/MS）同时测定养殖水和沉积物样品中地西泮及其3种代谢物的分析方法。水样经0.45 μm玻璃纤维膜过滤，沉积物采用1%氨水－乙酸乙酯提取后，均通过混合型阳离子交换固相萃取（MCX SPE）柱富集净化。目标物用5%氨水－乙腈溶液洗脱后吹干，1 mL 40%乙腈水溶液溶解残渣，UPLC－MS/MS测定。经Phenomenex Kinetex C₁₈（100 mm × 2.1 mm，1.7 μm）色谱柱分离，乙腈和0.1%甲酸水溶液为流动相进行梯度洗脱。采用电喷雾正离子电离，多反应监测（MRM）模式下测定，内标法定量。4种目标物在0.1 ~ 100 μg/L范围内的线性关系良好，相关系数（r²）大于0.999。水体和沉积物中的方法检出限分别为1.0 ~ 2.0 ng/L和0.02 ~ 0.05 μg/kg，定量下限分别为2.0 ~ 5.0 ng/L和0.05 ~ 0.1 μg/kg；平均加标回收率为90.2% ~ 115%，相对标准偏差（RSD，n = 6）为2.1% ~ 9.6%。该方法灵敏度高，实用性强，可满足养殖环境中地西泮及其代谢物的测定要求。

关键词：地西泮；代谢物；固相萃取（SPE）；超高效液相色谱－串联质谱（UPLC－MS/MS）；养殖环境

中图分类号：O657.7；X132  文献标识码：A    文章编号：1004-4957（2023）03-0337-07

Determination of Diazepam and Its Metabolites in Aquaculture Environment Samples by Solid Phase Extraction Cleanup and Ultra-performance Liquid Chromatography－Tandem Mass Spectrometry

WANG Xu-feng，WANG Qiang，ZHANG Ying-xia，HUANG Ke^*

（South China Sea Fisheries Research Institute，Chinese Academy of Fishery Sciences，Fishery Environment and Aquatic Products Quality Inspection & Testing Center of the Ministry of Agriculture and Rural Affaires（Guangzhou），Guangzhou  510300，China）

Abstract：A multi-residue analytical method was developed for the simultaneous determination of diazepam and its three metabolites in aquaculture water and sediment samples based on ultra-performance liquid chromatography－tandem mass spectrometry（UPLC－MS/MS）．Water samples were filtered through 0.45 μm glass fiber membranes，and subsequently enriched with a mixed cation exchange solid phase extraction（MCX SPE） cartridge．Sediment samples were extracted with 1% ammonium hydroxide－ethyl acetate，and then cleaned up using a MCX SPE cartridge．The purified extracts were eluted with 5% ammonium hydroxide－acetonitrile solution，and then dried residues were redissolved with 1 mL 40% acetonitrile water solution for UPLC－MS/MS analysis．The chromatographic separation of four targeted analytes were performed on a Phenomenex Kinetex C₁₈（100 mm × 2.1 mm，1.7 μm） column by gradient elution，with acetonitrile and 0.1% formic acid solution as mobile phases．Targeted compounds were determined with positive electrospray ionization under multiple reaction monitoring（MRM） mode，and quantified by internal standard method．Good linear relationships for targeted analytes were obtained in the range of 0.1－100 μg/L with correlation coefficients（r²） larger than 0.999．The detection limits of the method for aquaculture water samples and sediment samples were 1.0－2.0 ng/L and 0.02－0.05 μg/kg，while the quantitation limits were 2.0－5.0 ng/L and 0.05－0.1 μg/kg，respectively．The average recoveries for spiked negative aquaculture water and spiked sediment matrix ranged from 90.2% to 115%，with relative standard deviations（RSDs，n = 6） between 2.1% and 9.6%．The proposed method is sensitive and accurate，and it is suitable for the residual determination of diazepam and its metabolites in real aquaculture water and sediment samples.

Key words：diazepam；metabolite；solid phase extraction（SPE）；ultra-performance liquid chromatography－tandem mass spectrometry（UPLC－MS/MS）；aquaculture environment

高效液相色谱－串联质谱法测定水产品中的乙氧基喹啉和乙氧基喹啉二聚体

王梦茹^1，2，殷耀^1*，宁晓盼¹，张萍¹，彭军¹，楼芸¹，丁涛¹，吴丽娜²，柳菡¹，张晓燕¹

（1．南京海关  动植物与食品检测中心，江苏  南京  210019；2．南京师范大学  食品与制药工程学院，江苏  南京  210023）

摘要：建立了检测鱼、虾、泥鳅和螃蟹等水产品中乙氧基喹啉和乙氧基喹啉二聚体残留的高效液相色谱－串联质谱（HPLC－MS/MS）方法。在样品制备时加入适量维生素C，以乙腈作为提取溶剂，正己烷进行液液萃取。上清液经Oasis PRiME HLB固相萃取柱净化后旋蒸至近干，乙腈定容后采用Agela Phenomenex Kinetex C₁₈色谱柱（100 mm × 4.6 mm × 2.6 μm）分离，在电喷雾电离源正离子模式下采用选择反应监测（SRM）模式进行检测，外标法定量。乙氧基喹啉和乙氧基喹啉二聚体在1 ~ 100 μg/L质量浓度范围内线性关系良好，相关系数（r²）均大于0.994，检出限（LOD）均为0.5 μg/kg，定量下限（LOQ）均为1.5 μg/kg。两种目标物质在1.5、5、10、100 μg/kg 4个加标浓度下的平均回收率为75.8% ~ 103%，相对标准偏差（RSD）为0.58% ~ 9.6%。该方法灵敏度高，准确度和精密度好，适用于鱼、虾、泥鳅和螃蟹等水产品中乙氧基喹啉及乙氧基喹啉二聚体的检测。

关键词：高效液相色谱－串联质谱；水产品；乙氧基喹啉；乙氧基喹啉二聚体；固相萃取

中图分类号：O657.7；TS207.3  文献标识码：A    文章编号：1004-4957（2023）03-0344-07

Determination of Ethoxyquinoline and Ethoxyquinoline Dimer in Aquatic Products by High Performance Liquid Chromatography－Tandem Mass Spectrometry

WANG Meng-ru^1，2，YIN Yao^1*，NING Xiao-pan¹，ZHANG Ping¹，PENG Jun¹，LOU Yun¹，DING Tao¹，WU Li-na²，LIU Han¹，ZHANG Xiao-yan¹

（1．Animal，Plant and Food Inspection Center，Nanjing Customs，Nanjing  210019，China；2．College of Food and Pharmaceutical Engineering，Nanjing Normal University，Nanjing  210023，China）

Abstract：An analytical method was developed for the simultaneous determination of ethoxyquinoline and ethoxyquinoline dimer residues in aquatic products such as fishes，shrimps，loaches and crabs by high performance liquid chromatography－tandem mass spectrometry（HPLC－MS/MS）．An appropriate amount of vitamin C was added in the sample preparation．Acetonitrile was used as the extraction solvent，and hexane was used for liquid－liquid extraction．The supernatant was cleaned up on an Oasis PRiME HLB solid-phase extraction column and spun to near dryness，acetonitrile was used to fix the volume．Then the sample was separated on an Agela Phenomenex Kinetex C₁₈ column（100 mm ×4.6 mm × 2.6 μm），and subsequently detected with electrospray ionization source in positive ionization mode under selected reaction monitoring（SRM） mode，and quantified by external standard method. There were good linear relationships for both ethoxyquinoline and ethoxyquinoline dimer in concentration range of 1－100 μg/L，with their correlation coefficients（r²） greater than 0.994. The limits of detection（LODs） and limits of quantitation（LOQs） of the method were 0.5 μg/kg and 1.5 μg/kg，respectively. The average recoveries for two target substances at four spiked levels of 1.5，5，10 and 100 μg/kg ranged from 75.8% to 103%，with relative standard deviations（RSDs） of 0.58%－9.6%. The developed method is sensitive，accurate and precise，and it could be applied to the determination of ethoxyquinoline and ethoxyquinoline dimer in aquatic products such as fishes，shrimps，loaches and crabs.

Key words：high performance liquid chromatography－tandem mass spectrometry；aquatic products；ethoxyquinoline；ethoxyquinoline dimer；solid-phase extraction

基于近红外光谱的塑料分选技术预处理方法的优化

李家帅¹，薛莲莲²，王凯¹，刘俊成¹，吴翰¹，李华清¹，尹凤福^1*

（1．青岛科技大学  机电工程学院，山东  青岛  266042；2．青岛工程职业学院  信息工程学院，山东  青岛  266112）

摘要：为进行不同塑料种类的识别，采集了尼龙（PA）、聚丙烯（PP）、聚苯乙烯（PS）、聚氯乙烯（PVC）4类塑料的近红外光谱数据，并针对光谱数据采集时存在的噪声、基线和光程问题，基于3点Savitzky－Golay卷积平滑（S－G）、一阶导数（FD）、二阶导数（SD）、标准正态变量变换（SNV）、多元散射校正（MSC）进行了预处理组合优化研究，以竞争性自适应重加权算法（CARS）进行特征波长提取，并运用支持向量机算法（SVM）建立模型。结果显示：所有预处理方法中，预处理组合S－G + FD + SNV获得的结果最优，S－G + FD + SNV + SVM模型的平均准确率高达96.67%，其训练集和验证集的平均准确率均为100%。上述预处理组合优化方法可为4类常见塑料的鉴别研究提供参考。

关键词：塑料分选；近红外光谱（NIR）；预处理；组合；预测分析

中图分类号：O657.3；TH145.42  文献标识码：A    文章编号：1004-4957（2023）03-0351-06

Optimization of Pretreatment Methods for Plastic Sorting Technology Based on Near-infrared Spectroscopy

LI Jia-shuai¹，XUE Lian-lian²，WANG Kai¹，LIU Jun-cheng¹，WU Han¹，LI Hua-qing¹，YIN Feng-fu^1*

（1．School of Mechanical and Electrical Engineering，Qingdao University of Science and Technology，Qingdao  266042，China；2．School of Information Engineering，Qingdao Vocational College of Engineering，Qingdao  266112，China）

Abstract：In order to identify different types of plastics，the near-infrared spectral data of four types of plastics，i.e．nylon（PA），polypropylene（PP），polystyrene（PS） and polyvinyl chloride（PVC），were collected．Meanwhile，according to the existing noise，baseline and optical path issues during spectral data acquisition，pretreatment combination optimization methods were investigated，based on 3-point Savitzky－Golay convolution smoothing（S－G），first derivative（FD），second derivative（SD），standard normal variable transformation（SNV） and multivariate scattering correction（MSC）．Furthermore，the characteristic wavelength was extracted by competitive adaptive reweighting sampling（CARS），and a model was established using support vector machine（SVM）．The results showed that among all preprocessing methods，the preprocessing combination S－G + FD + SNV obtains the best results，while the average accuracy of the S－G + FD + SNV + SVM model is as high as 96.67%，and the average accuracies of its training set and validation set are both 100%．The mentioned-above pretreatment combination optimization method could provide a reference for the identification on four common plastics.

Key words：plastic sorting；near-infrared spectroscopy（NIR）；preprocessing；combination；predictive analysis

液液萃取/气相色谱－质谱法测定氟［¹⁸F］脱氧葡糖注射液塑料生产组件浸提液中16种邻苯二甲酸酯类增塑剂

昝艳楠^1，2，张晓芸²，商少华²，陈宁²，丁逸梅^1，2*

（1．南京工业大学  药学院，江苏  南京  211816；2．江苏药物研究所有限公司  药品检测与包材研究中心，江苏  南京  210009）

摘要：建立了基于液液萃取（LLE）/气相色谱－质谱（GC－MS）检测氟［¹⁸F］脱氧葡糖注射液塑料生产组件浸提液中16种邻苯二甲酸酯类（PAEs）增塑剂的方法。根据生产工艺，采用含5%乙醇、5%乙腈的混合溶液作为模拟溶剂，在40 ℃条件下进行模拟浸提。采用Thermo TG－5 SIL MS色谱柱分离，选择离子扫描模式（SIM）进行分析。通过对仪器条件与萃取条件进行优化，确定最佳前处理方法和仪器条件。在优化实验条件下，16种PAEs在50～500 ng/mL范围内与峰面积呈良好的线性关系，相关系数（r）均不小于0.990 6，检出限（LOD）和定量下限（LOQ）分别为10、30 ng/mL。以二氯甲烷为萃取溶剂时，平均回收率为83.0%～114%，相对标准偏差（RSD，n = 6）为1.9%～4.2%。采用该方法对浸提液进行测定，16种PAEs均未超过分析评价阈值（AET）。该法操作简便，专属性强，可用于氟［¹⁸F］脱氧葡糖注射液塑料生产组件的相容性研究。

关键词：气相色谱－质谱法；液液萃取；增塑剂；氟［¹⁸F］脱氧葡糖注射液；塑料组件

中图分类号：O657.7；TS206.4  文献标识码：A    文章编号：1004-4957（2023）03-0357-06

Determination of 16 Phthalate Plasticizers in the Extracts of Plastic Components Used in the Production of Fludeoxyglucose ［¹⁸F］ Injection by Liquid－Liquid Extraction/Gas Chromatography－Mass Spectrometry

ZAN Yan-nan^1，2，ZHANG Xiao-yun²，SHANG Shao-hua²，CHEN Ning²，DING Yi-mei^1，2*

（1．School of Pharmacy， Nanjing University of Technology，Nanjing   211816，China；2．Drug Testing and Packaging Materials Research Center，Jiangsu Pharmaceutical Research Institute Co.，Ltd.，Nanjing   210009，China）

Abstract：A method based on liquid－liquid extraction（LLE）/gas chromatography－mass spectrometry（GC－MS） was developed for the determination of 16 phthalate plasticizers（PAEs） in the extracts of plastic components used in the production of fludeoxyglucose［¹⁸F］ injection. According to the production process，the simulated solvent for extraction experiments was a mixture of 5% ethanol and 5% acetonitrile，and the extraction temperature was simulated at 40 ℃. The extracts were separated on a Thermo TG－5 SIL MS column，and analyzed in selected ion scanning mode（SIM）. The instrument conditions and the extraction conditions were optimized to determine the most suitable pre-treatment method and instrument conditions. Under the optimized experimental conditions，the peak areas of 16 PAEs were linearly correlated in the range of 50－500 ng/mL，with correlation coefficients（r） not less than 0.990 6. The limits of detection（LODs） and limits of quantitation（LOQs） were 10 ng/mL and 30 ng/mL，respectively. The average recoveries ranged from 83.0% to 114% with relative standard deviations（RSDs，n = 6） of 1.9%－4.2% when dichloromethane was used as the extraction solvent. 16 PAEs did not exceed the analytical evaluation threshold（AET） when the extracts were determined by this method. The method is simple and specific，and it could be used to study the compatibility of plastic production components for fludeoxyglucose ［¹⁸F］ injection.

Key words：gas chromatography－mass spectrometry；liquid－liquid extraction；plasticizers；fludeoxyglucose ［¹⁸F］ injection；plastic components

定量核磁共振氢谱法测定枸橼酸托法替布片的有效含量

刘慢，赵阗，刘会利，陈林^*

（黄河科技学院  河南省小分子新药研发国际联合实验室，河南省食药两用植物资源综合利用工程技术研究中心，

郑州市天然产物合成生物学重点实验室，河南  郑州  450063）

摘要：建立了枸橼酸托法替布片中有效含量的定量核磁共振氢谱测定方法。以托法替布化学位移δ 7.13为定量峰，3，5-二甲基吡唑化学位移δ 5.73为内标峰，氘代二甲亚砜（DMSO－D₆）为溶剂，使用核磁共振谱仪采集混合物的氢谱，对枸橼酸托法替布片中的有效成分进行定量测定。该方法专一性强，在0.793 ~ 7.925 mg/mL范围内呈现良好的线性关系（r²= 0.998 4）。精密度、重复性和稳定性的相对标准偏差（RSD）分别为0.82%、1.7%和0.67%。该方法测得的枸橼酸托法替布片中托法替布的质量分数为2.25%，其结果与高效液相色谱法基本一致。定量核磁共振氢谱法具有操作方便简单，可同时进行定性与定量，检测时间短，无需对照品等优势，可用于枸橼酸托法替布片有效含量的测定。

关键词：定量核磁共振氢谱法；枸橼酸托法替布片；3，5-二甲基吡唑；含量测定

中图分类号：O657.7；R917  文献标识码：A    文章编号：1004-4957（2023）03-0363-05

Determination of Tofacitinib Citrate Tablets by Quantitative Proton Nuclear Magnetic Resonance

LIU Man，ZHAO Tian，LIU Hui-li，CHEN Lin^*

（Henan Joint International Research Laboratory of Drug Discovery of Small Molecules，Henan Comprehensive Utilization of Edible and Medicinal Plant Resources Engineering Technology Research Center，Zhengzhou Key Laboratory of Synthetic Biology of Natural Products，Huanghe Science and Technology College，Zhengzhou  450063，China）

Abstract：A quantitative proton nuclear magnetic resonance（qHNMR） method was developed for determination on the effective content of tofacitinib citrate tablets，with dimethyl sulfoxide（DMSO－D₆） as the solvent and 3，5-dimethylpyrazole as the internal standard．Proton signal peaks of tofacitinib at δ 7.13 and δ 5.73 of 3，5-dimethylpyrazole were selected as the quantitative signals，respectively．The spectra of the mixture complex were collected under the conditions of pulse sequence zg30，relaxation delay time（D₁） 26 s，and scanning number（NS） 16 times at 298 K on Bruker Avance Ⅲ 400 MHz NMR spectrometer．qHNMR method with high specificity showed a good linear relationship in the concentration range of 0.793－7.925 mg/mL，with linear correlation coefficient（r²） up to 0.998 4．The relative standard deviation（RSD） of precision，repeatability and stability were 0.82%，1.7% and 0.67%，respectively．The content of tofacitinib in tofacitinib citrate tablets was determined to be 2.25% by qHNMR，which was basically consistent with the results by high performance liquid chromatography（HPLC）．As a result，qHNMR method is an alternative way to determine the effective content of toacitinib cittrate tables．More importantly，it has many outstanding advantages，such as simple operation，short detection time，no requirement for reference standards，simultaneously qualitative and quantitative analysis.

Key words：quantitative proton nuclear magnetic resonance（qHNMR）；tofacitinib citrate tablets；3，5-dimethylpyrazole；content determination

适配体生物传感器在黄曲霉毒素B1检测中的应用

韩文浩^1，2，李延生^1，2*，高国伟^1，2，张学记³

（1．北京信息科技大学  传感器重点实验室，北京  100101；2．北京信息科技大学  现代测控技术教育部重点实验室，北京  100192；

3．深圳大学  生物医学工程学院，广东  深圳  518060）

摘要：该文首先对黄曲霉毒素B1（AFB1）的相关性质及其传统检测方法进行了介绍，随后概述了近年来基于光学、电化学以及微流控芯片的适配体生物传感器的构建及其在AFB1检测领域中的应用，旨为适配体生物传感器的实际应用提供参考；并通过探讨目前开发的检测方法存在的问题，对适配体生物传感器前景和未来趋势进行了展望。

关键词：黄曲霉毒素B1；适配体；生物传感器；应用

中图分类号：O657；S951.4  文献标识码：A    文章编号：1004-4957（2023）03-0368-07

Application of Aptamer Biosensor in Detection of Aflatoxin B1

HAN Wen-hao^1，2，LI Yan-sheng^1，2*，GAO Guo-wei^1，2，ZHANG Xue-ji³

（1．Key Laboratory of Sensors，Beijing Information Science and Technology University，Beijing  100101，China；2．Key Laboratory of Modern Measurement and Control Technology of Ministry of Education，Beijing Information Science and Technology University，Beijing  100192，China；3．School of Biomedical Engineering，Shenzhen University，Shenzhen  518060，China）

Abstract：Aflatoxin B1（AFB1） has strong toxicity and carcinogenicity，and its dose exceeding the standard will seriously endanger the health of organisms．The development of new AFB1 detection methods is of great significance for the prevention and control of its harm．The traditional method for AFB1 detection is mature and reliable，with low detection limit，but relying on professional equipment and professionals．It cannot meet the needs of on-site detection．Aptamer biosensors have the advantages of high sensitivity，high specificity and simple operation，which have attracted attention in the detection of AFB1．Meanwhile，researchers have developed many new methods based on different principles．The related properties of AFB1 and its traditional detection methods are firstly introduced in this paper，and then the construction of aptamer biosensors based on optical，electrochemical and microfluidic chips in recent years as well as their applications in the field of AFB1 detection are summarized．It provides a reference for the development of practical application of aptamer biosensors，and discusses the development prospects and future trends of aptamer biosensors by discussing the problems in the currently developed detection methods.

Key words：aflatoxin B1；aptamer；biosensor；application