行業(yè)資訊
《分析測(cè)試學(xué)報(bào)》2023年3月第42卷第3期中英文摘要
基于多元活性成分同時(shí)測(cè)定結(jié)合多元統(tǒng)計(jì)分析評(píng)價(jià)不同干燥加工三葉青藥材的質(zhì)量
陳海杰1，周永逸1，薛佳1，鄒立思1，吳楠1，袁嘉歡1，劉訓(xùn)紅1，2*，楊薇1，程建明1，2
（1．南京中醫(yī)藥大學(xué) 藥學(xué)院，江蘇 南京 210023；2．江蘇省經(jīng)典名方工程研究中心，江蘇 南京 210023）
摘要：建立了一種超快速液相色譜－三重四極桿－線性離子阱質(zhì)譜（UFLC－QTRAP－MS/MS）同時(shí)測(cè)定三葉青中黃酮類、鞣質(zhì)類、酚酸類、核苷類、多酚類和氨基酸類等60種活性成分的快速分析方法，并結(jié)合多元統(tǒng)計(jì)分析，評(píng)價(jià)不同干燥加工三葉青的質(zhì)量。采用XBridge?C18柱（4.6 mm × 100 mm，3.5 μm）以0.4%甲酸－甲醇為流動(dòng)相進(jìn)行梯度分離，以多反應(yīng)監(jiān)測(cè)模式在電噴霧正、負(fù)離子模式下進(jìn)行質(zhì)譜檢測(cè)。基于各目標(biāo)成分的質(zhì)量濃度，用方差分析（ANOVA）、熵權(quán)TOPSIS法及灰色關(guān)聯(lián)度分析（GRA）對(duì)不同干燥加工三葉青樣品進(jìn)行綜合評(píng)價(jià)。結(jié)果顯示，各目標(biāo)成分在一定質(zhì)量濃度范圍內(nèi)的線性關(guān)系良好，相關(guān)系數(shù)均不低于0.999 0，檢出限為0.03 ~ 13.59 ng/mL，定量下限為0.09 ~ 45.30 ng/mL，平均加標(biāo)回收率為96.1% ~ 102%，相對(duì)標(biāo)準(zhǔn)偏差均小于5%；不同干燥方式對(duì)三葉青的多種活性成分有影響，與傳統(tǒng)的干燥方式相比，現(xiàn)代的干燥方式能明顯保留三葉青的活性成分。綜合分析，真空干燥的三葉青樣品的綜合質(zhì)量較好。該研究構(gòu)建的方法可為三葉青的合理干燥和加工提供實(shí)驗(yàn)依據(jù)，同時(shí)也為三葉青質(zhì)量的綜合評(píng)價(jià)和整體控制提供新的方法參考。
關(guān)鍵詞：三葉青；不同干燥方式；多元活性成分；多元統(tǒng)計(jì)分析；超快速液相色譜－三重四極桿－線性離子阱質(zhì)譜（UFLC－QTRAP－MS/MS）
中圖分類號(hào)：O657.63；R282.4 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-hong1，2*，YANG Wei1，CHENG Jian-ming1，2
（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/超高效液相色譜－四極桿/靜電場(chǎng)軌道阱質(zhì)譜法快速篩查化妝水中139種藥物殘留
容裕棠1*，張憲臣2，鄧曉瑩2，吳潔珊1，劉瓊瑜2，蔡杰1，甕福良1
（1．拱北海關(guān)技術(shù)中心，廣東 珠海 519000；2．中山海關(guān)技術(shù)中心，廣東 中山 528403）
摘要：建立了分散液液微萃取（DLLME）結(jié)合超高效液相色譜－四極桿/靜電場(chǎng)軌道阱質(zhì)譜（UPLC－Q Exactive Orbitrap MS）同時(shí)測(cè)定化妝水中抗生素、激素、禁用染料、農(nóng)藥以及真菌毒素5大類共139種藥物殘留的分析方法。考察了DLLME各條件對(duì)萃取效果的影響，確定最佳萃取條件為：取樣量5.0 g，萃取劑為四氯乙烷（50 μL）、分散劑為乙腈（300 μL）、氯化鈉用量為0.30 g、超聲時(shí)間為8 min。樣品經(jīng)萃取后，采用島津Shim-pack XR－ODS II（150 mm × 2.0 mm，2.2 μm）色譜柱分離，通過Q－Exactive Orbitrap MS以全掃描確定母離子精確質(zhì)量數(shù)的離子豐度，實(shí)現(xiàn)多種類目標(biāo)物的定量，結(jié)合保留時(shí)間和子離子數(shù)據(jù)依賴模式掃描（DD－MS2）確定子離子的精確質(zhì)量數(shù)，并配合譜庫(kù)檢索進(jìn)行快速確證與篩查。結(jié)果表明：139種化合物的質(zhì)量濃度在10 ~ 1 000 ng/mL范圍內(nèi)與峰強(qiáng)度呈良好線性關(guān)系（r > 0.99），檢出限為10 ~ 30 μg/kg，回收率為63.0% ~ 95.9%，相對(duì)標(biāo)準(zhǔn)偏差（RSD）為3.0% ~ 9.5%；各精確質(zhì)量數(shù)偏差小于3 × 10-6。該方法穩(wěn)定、簡(jiǎn)單、快速、精確，有機(jī)試劑用量少，環(huán)境友好，適用于化妝水的快速篩查。
關(guān)鍵詞：分散液液微萃取；超高效液相色譜－四極桿/靜電場(chǎng)軌道阱質(zhì)譜；化妝水；藥物殘留
中圖分類號(hào)：O657.63；TQ658 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-tang1*，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
基于呼氣中特異性VOCs篩查的肺癌早期診斷與模型評(píng)估
茹立華1，呂偉1，王祥麒2，張志娟1，3*
（1．河南中醫(yī)藥大學(xué) 藥學(xué)院，河南 鄭州 450046；2．河南中醫(yī)藥大學(xué)第三附屬醫(yī)院 腫瘤科，河南 鄭州 450046；
3．暨南大學(xué) 質(zhì)譜儀器與大氣環(huán)境研究所，廣東 廣州 510632）
摘要：采用氣相色譜－質(zhì)譜聯(lián)用儀（GC－MS）檢測(cè)了180例受試者的呼出氣樣品，包括79名肺癌患者和101名健康志愿者。每個(gè)受試者采集3個(gè)平行樣品，以及1個(gè)室內(nèi)空氣樣品。對(duì)所有呼氣樣品中檢測(cè)的92種揮發(fā)性有機(jī)物（VOCs）進(jìn)行定量分析。結(jié)合Mann－Whitney檢驗(yàn)和正交偏最小二乘判別分析（OPLS－DA）模型篩選出10種肺癌患者呼氣特異性VOCs，包括苯甲醛、順式-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。利用統(tǒng)計(jì)學(xué)方法研究其在不同人群中的代謝差異和可能相關(guān)的代謝機(jī)制，通過建立機(jī)器學(xué)習(xí)模型驗(yàn)證候選標(biāo)志物對(duì)疾病的診斷性能，結(jié)果顯示，隨機(jī)森林模型診斷的準(zhǔn)確度、精準(zhǔn)率、靈敏度和特異性分別為96.25%、96.21%、95.76%、96.67%，馬修斯相關(guān)系數(shù)（MCC）為0.93，曲線下面積為0.96。上述10種化合物可作為肺癌患者的潛在呼氣VOCs標(biāo)志物，為肺癌的早期診斷提供了豐富的基礎(chǔ)數(shù)據(jù)。
關(guān)鍵詞：肺癌；揮發(fā)性有機(jī)物；呼氣標(biāo)志物；診斷模型；氣相色譜－質(zhì)譜聯(lián)用
中圖分類號(hào)：O657.7；R318 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-juan1，3*
（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
丹江口水庫(kù)土壤和水體溶解性有機(jī)質(zhì)的分子結(jié)構(gòu)特征分析
周雅茹1，郝蓉1*，伍玉鵬1，何晨2，史權(quán)2，胡榮桂1
（1．華中農(nóng)業(yè)大學(xué) 資源與環(huán)境學(xué)院 農(nóng)業(yè)部長(zhǎng)江中下游耕地保育重點(diǎn)實(shí)驗(yàn)室，湖北 武漢 430070；
2．中國(guó)石油大學(xué)（北京） 化學(xué)工程與環(huán)境學(xué)院 重質(zhì)油國(guó)家重點(diǎn)實(shí)驗(yàn)室，北京 102249）
摘要：采用傅里葉變換離子回旋共振質(zhì)譜（FT－ICR MS）分析了丹江口水庫(kù)土壤和水體溶解性有機(jī)質(zhì)（DOM）的分子結(jié)構(gòu)特征，得到土壤和水體DOM的化合物類型分布、等效雙鍵數(shù)及碳數(shù)分布特征。結(jié)果表明：該區(qū)土壤DOM由CHO、CHOS1、CHON1、CHON2、CHON3和CHON1S1 6類化合物組成，其中以CHO類為主，該類化合物的主要組分為木質(zhì)素；DOM分子的芳香性結(jié)構(gòu)主要與CHO和CHON1類化合物有關(guān)；低氧原子數(shù)和高氧原子數(shù)的特征分子均含有芳香結(jié)構(gòu)。該區(qū)水體DOM的化合物組成與土壤相似，但不同種類化合物的占比在兩者之間表現(xiàn)不同；芳香類化合物的組成與土壤相似，主要也與CHO和CHON1類物質(zhì)有關(guān)；低氧原子數(shù)的特征分子大多為支鏈結(jié)構(gòu)，從O4分子開始含有較多的羧基和芳香結(jié)構(gòu)。該研究為深入理解不同生態(tài)系統(tǒng)DOM的分子結(jié)構(gòu)特征提供了一定的理論依據(jù)。
關(guān)鍵詞：溶解性有機(jī)質(zhì)；土壤；水體；傅里葉變換離子回旋共振質(zhì)譜（FT－ICR MS）
中圖分類號(hào)：O657.63；X132 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1004-4957（2023）03-0283-09
Molecular Structures Analysis of Dissolved Organic Matter in Soil and Water of Danjiangkou Reservoir
ZHOU Ya-ru1，HAO Rong1*，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）
新型乘用車室內(nèi)空氣痕量組分快速檢測(cè)系統(tǒng)的研制
燕志奇1，汪杰1，王慧2，王甫華1，張立軍2，譚銀湘1，吳日偉1，黃文杰1，黃灶田1，譚國(guó)斌1*
（1．廣州禾信儀器股份有限公司，廣東 廣州 510535；2．廣物汽貿(mào)股份有限公司，廣東 廣州 510000）
摘要：基于自主研制的真空紫外單光子電離飛行時(shí)間質(zhì)譜儀和在線高精度甲醛分析儀，研制了一套新型乘用車室內(nèi)空氣痕量組分的快速檢測(cè)系統(tǒng)。通過凈化空氣對(duì)乘用車室內(nèi)空氣進(jìn)行置換，置換完成后，分別利用在線揮發(fā)性有機(jī)物質(zhì)譜儀和在線高精度甲醛分析儀對(duì)乘用車室內(nèi)空氣中痕量組分和甲醛進(jìn)行連續(xù)檢測(cè)。結(jié)果表明，苯、甲苯、二甲苯/乙苯、苯乙烯和甲醛在對(duì)應(yīng)濃度范圍內(nèi)具有良好的線性，相關(guān)系數(shù)（r2）均大于0.99，相對(duì)標(biāo)準(zhǔn)偏差均小于5%，檢出限分別為1.3 × 10-9、0.1 × 10-9、0.2 × 10-9、0.8 × 10-9、0.1 × 10-9 mol/mol。采用該方法測(cè)定車內(nèi)空氣，結(jié)果顯示，在短時(shí)間內(nèi)，車內(nèi)VOCs可快速釋放達(dá)到釋放亞平衡狀態(tài)，并可得到亞平衡狀態(tài)下的VOCs濃度及釋放速率結(jié)果。測(cè)試車輛車內(nèi)空氣中待測(cè)物質(zhì)苯、甲苯、二甲苯/乙苯、苯乙烯和甲醛的濃度分別為0.30、8.90、25.10、21.90、15.05 μg/m3。該方法無復(fù)雜耗時(shí)的采樣過程，操作簡(jiǎn)便，能夠滿足乘用車室內(nèi)空氣痕量組分的快速檢測(cè)篩查需求。
關(guān)鍵詞：乘用車；室內(nèi)空氣；痕量VOCs組分；快速檢測(cè)
中圖分類號(hào)：O657.6；O659.36 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-bin1*
（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金屬有機(jī)框架材料的固相萃取/高效液相色譜－串聯(lián)質(zhì)譜法測(cè)定飲料和配制酒中的新紅
馮軍軍1，3，王靜2，趙連興3，姜海云3，連雅林3，譚天宇1，張帆1，景正義1，賀鋒1，李騰飛1*
（1．河北工程大學(xué) 生命科學(xué)與食品工程學(xué)院，河北 邯鄲 056038；2．河北工程大學(xué) 材料科學(xué)與工程學(xué)院，河北 邯鄲 056038；
3．邯鄲市食品藥品檢驗(yàn)中心，河北 邯鄲 056004）
摘要：制備了一種新型固相萃取柱填料金屬有機(jī)框架材料（MOFs）UiO－66－NH2，建立了固相萃取/高效液相色譜－串聯(lián)質(zhì)譜（SPE/HPLC－MS/MS）測(cè)定飲料和配制酒中新紅的方法。通過掃描電子顯微鏡、紅外光譜和氮?dú)馕?/span>－脫附等溫線等手段表征材料的結(jié)構(gòu)與吸附性能。采用Waters AtlantisTM T3（150 mm × 2.1 mm，3 μm）色譜柱，以10 mmol/L乙酸銨水溶液和甲醇為流動(dòng)相進(jìn)行分離，多反應(yīng)監(jiān)測(cè)（MRM）模式進(jìn)行質(zhì)譜檢測(cè)。結(jié)果表明，在最佳萃取條件下，新紅在0.05～10 mg/L范圍內(nèi)呈良好的線性關(guān)系，相關(guān)系數(shù)（r2）為0.998，檢出限（LOD）和定量下限（LOQ）分別為0.05 mg/L和0.15 mg/L。回收率為87.8%～107%，相對(duì)標(biāo)準(zhǔn)偏差（RSD，n = 6）為1.9%～11%，表明該方法具有較好的準(zhǔn)確度和精密度。開發(fā)的基于UiO－66－NH2的固相萃取柱可作為一種高質(zhì)量的吸附材料用于飲料和配制酒中新紅的檢測(cè)。
關(guān)鍵詞：金屬有機(jī)框架材料；固相萃取；高效液相色譜－串聯(lián)質(zhì)譜；新紅；飲料；配制酒
中圖分類號(hào)：O657.7；TS207.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-jun1，3，WANG Jing2，ZHAO Lian-xing3，JIANG Hai-yun3，LIAN Ya-lin3，TAN Tian-yu1，ZHANG Fan1，JING Zheng-yi1，HE Feng1，LI Teng-fei1*
（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 AtlantisTM 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選擇算法的山楂葉產(chǎn)地判別模型研究
梁小娟1，2，王婭妮1，2，4，馬晉芳3，孫鵬5，郭拓1*，嚴(yán)詩(shī)楷4，肖雪2*
（1．陜西科技大學(xué) 電子信息與人工智能學(xué)院，陜西 西安 710021；2．廣東藥科大學(xué) 中醫(yī)藥研究院，廣東 廣州 510006；
3．暨南大學(xué) 光電工程系，廣東 廣州 510632；4．上海交通大學(xué) 藥學(xué)院，上海 200240；5．山東中醫(yī)藥大學(xué) 藥物研究院，山東 濟(jì)南 250355）
摘要：為實(shí)現(xiàn)山楂葉產(chǎn)地的快速判別，提出一種基于稀疏主成分分析特征選擇（SPCAFS）與支持向量機(jī)（SVM）建模的定性分析方法。采用近紅外積分球漫反射光譜法采集6個(gè)產(chǎn)地共41批山楂葉123份樣品的近紅外光譜圖，經(jīng)數(shù)據(jù)預(yù)處理后，通過SPCAFS對(duì)代表性特征波段進(jìn)行選擇，并采用SVM建立山楂葉近紅外產(chǎn)地判別模型。模型與連續(xù)投影（SPA），正則化自表示（RSR）和稀疏子空間聚類（SSC）3種特征選擇算法進(jìn)行對(duì)比，以準(zhǔn)確率、精確度和靈敏度作為評(píng)價(jià)標(biāo)準(zhǔn)，評(píng)估所提模型的預(yù)測(cè)性能。結(jié)果顯示，SPCAFS的特征波段數(shù)相比于全波長(zhǎng)建模從1 500減少到21，預(yù)測(cè)結(jié)果的準(zhǔn)確率和精確度分別從78%、76%提升至97%、100%。同時(shí)，相比于SPA、RSR、SSC算法，準(zhǔn)確率分別提升了6%、3%、3%，精確度分別提升了13%、10%、5%，模型的預(yù)測(cè)能力得到顯著提升，基于SPCAFS的SVM判別模型可實(shí)現(xiàn)山楂葉南北產(chǎn)地的快速判別。
關(guān)鍵詞：近紅外光譜；特征選擇；山楂葉；產(chǎn)地判別；稀疏主成分分析特征選擇算法；支持向量機(jī)
中圖分類號(hào)：O657.3；TQ460.72 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1004-4957（2023）03-0307-08
Origin Discrimination Model of Crataegi Folium Based on Sparse Principal Component Analysis for Feature Selection
LIANG Xiao-juan1，2，WANG Ya-ni1，2，4，MA Jin-fang3，SUN Peng5，GUO Tuo1*，YAN Shi-kai4，XIAO Xue2*
（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
基于中空多孔金納米/石墨烯復(fù)合納米材料的葡萄糖氧化酶直接電化學(xué)及其生物傳感研究
尹學(xué)虎1，楊新杰1，羅丹1，張艷麗1*，王紅斌1，楊文榮1，2，龐鵬飛1*
（1．云南民族大學(xué) 化學(xué)與環(huán)境學(xué)院，云南省教育廳環(huán)境功能材料重點(diǎn)實(shí)驗(yàn)室，云南 昆明 650504；
2．迪肯大學(xué) 生命與環(huán)境科學(xué)學(xué)院，澳大利亞 維多利亞州 3217）
摘要：采用溶液相犧牲模板法制備中空多孔金納米粒子（HPAuNPs），并將該材料與還原氧化石墨烯（rGO）復(fù)合，用于葡萄糖氧化酶（GOx）在玻碳電極（GCE）表面的有效固定，構(gòu)建GOx/HPAuNPs/rGO/GCE傳感界面。利用掃描和透射電鏡、X射線光電子能譜、X射線衍射譜、紅外光譜及電化學(xué)等方法對(duì)材料的形貌與結(jié)構(gòu)，GOx的固定化過程，以及傳感器的直接電化學(xué)和電催化性能進(jìn)行表征。結(jié)果表明，HPAuNPs和rGO的協(xié)同作用能有效促進(jìn)GOx與電極之間的直接電子轉(zhuǎn)移（DET）。基于GOx/HPAuNPs/rGO/GCE對(duì)葡萄糖的良好電催化性能，該方法有效實(shí)現(xiàn)了對(duì)葡萄糖的高靈敏度檢測(cè)，其電流響應(yīng)的線性范圍為0.05 ~ 7.0 mmol/L，檢出限（S/N = 3）為16 μmol/L。該傳感器具有良好的選擇性、重現(xiàn)性及穩(wěn)定性，對(duì)實(shí)際樣品血清中血糖的測(cè)定結(jié)果令人滿意，回收率為98.0% ~ 103%，相對(duì)標(biāo)準(zhǔn)偏差不大于5.0%。
關(guān)鍵詞：葡萄糖氧化酶；中空多孔金納米；還原氧化石墨烯；電化學(xué)傳感器
中圖分類號(hào)：O657.63；TS245.4 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-li1*，WANG Hong-bin1，YANG Wen-rong1，2，PANG Peng-fei1*
（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
基于多參數(shù)融合的紅外光譜對(duì)混合物的組分識(shí)別研究
陳斌*，鄭小歡，耿德春，齊文良，陸道禮
（江蘇大學(xué) 食品與生物工程學(xué)院，江蘇 鎮(zhèn)江 212013）
摘要：為解決混合物組分的識(shí)別問題，該文以7種標(biāo)準(zhǔn)品以及由7種標(biāo)準(zhǔn)品配制的26種混合物為研究對(duì)象，以準(zhǔn)確率與誤判率為混合組分識(shí)別效果的評(píng)價(jià)指標(biāo)，在研究譜峰匹配算法、非負(fù)最小二乘匹配算法與相關(guān)系數(shù)匹配系數(shù)算法的基礎(chǔ)上，采用一種基于多特征融合的BP神經(jīng)網(wǎng)絡(luò)模型紅外光譜技術(shù)對(duì)混合物組分進(jìn)行識(shí)別，并與邏輯回歸模型進(jìn)行了對(duì)比。結(jié)果表明，3種單一匹配算法的識(shí)別準(zhǔn)確率均低于76.31%，多特征融合的邏輯回歸模型與多特征融合的BP神經(jīng)網(wǎng)絡(luò)模型預(yù)測(cè)集的識(shí)別準(zhǔn)確率分別為83.33%和98.18%，誤判率分別為4.76%和1.82%。研究結(jié)果表明，中紅外光譜技術(shù)結(jié)合BP神經(jīng)網(wǎng)絡(luò)模型可以更好地進(jìn)行混合物的組分識(shí)別。為了進(jìn)一步探究模型對(duì)混合組分最低濃度的檢測(cè)能力，采用香蘭素和乙醇兩組分溶液進(jìn)行檢出限的研究。結(jié)果表明混合物中香蘭素的質(zhì)量濃度為0.03 g/mL時(shí)準(zhǔn)確率為100.00%，誤判率為14.29%；香蘭素質(zhì)量濃度低于0.03 g/mL時(shí)，準(zhǔn)確率下降20.00%，誤判率上升19.04%。故可認(rèn)為該研究能識(shí)別出的香蘭素乙醇溶液中香蘭素的最低質(zhì)量濃度為0.03 g/mL。
關(guān)鍵詞：紅外光譜；混合物；多參數(shù)；BP神經(jīng)網(wǎng)絡(luò)；組分識(shí)別
中圖分類號(hào)：O657.3；O642.5 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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
超高效液相色譜－高分辨質(zhì)譜法同時(shí)測(cè)定白酒中19種氨基酸
尹艷艷，楊軍林，田棟偉，蔣力力，尤小龍，張健，程平言*
（貴州茅臺(tái)酒廠（集團(tuán)）習(xí)酒有限責(zé)任公司，貴州省白酒制造業(yè)創(chuàng)新中心，貴州 遵義 564622）
摘要：建立了白酒樣品中19種氨基酸的超高效液相色譜－高分辨質(zhì)譜（UPLC－HRMS）檢測(cè)方法。樣品經(jīng)烘箱干燥法除乙醇，水定容，使用水相濾膜過濾后上機(jī)檢測(cè)。以甲醇-0.1%甲酸作為流動(dòng)相，經(jīng)Hypersil GOLD色譜柱（150 mm × 2.1 mm，1.9 μm）分離，在正離子掃描模式下，一級(jí)母離子全掃描采集化合物信息，外標(biāo)法定量分析。結(jié)果表明，19種氨基酸在其線性范圍內(nèi)線性關(guān)系良好，相關(guān)系數(shù)（r2）不小于0.986 2，方法的檢出限為0.003 ~ 0.015 μmol/L，定量下限為0.008 ~ 0.050 μmol/L，白酒樣品中19種氨基酸的加標(biāo)回收率為 88.2% ~ 119%，相對(duì)標(biāo)準(zhǔn)偏差為0.23% ~ 5.6%，適用于白酒樣品中氨基酸分析。利用該方法分析了不同輪次醬香酒中氨基酸含量，檢出L-丙氨酸、L-精氨酸、L-天冬氨酸、L-谷氨酸、甘氨酸、L-組氨酸、L-異亮氨酸、L-亮氨酸、L-賴氨酸、L-苯丙氨酸、L-脯氨酸、L-絲氨酸、L-蘇氨酸、L-酪氨酸、L-纈氨酸和L-瓜氨酸共16種氨基酸。不同輪次酒中氨基酸含量的顯著水平P值均小于0.05，表明不同輪次酒中氨基酸含量具有顯著性差異。
關(guān)鍵詞：氨基酸；白酒；超高效液相色譜－高分辨質(zhì)譜（UPLC－HRMS）
中圖分類號(hào)：O657.63；O629.7 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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－h(huán)igh 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－h(huán)igh resolution mass spectrometry（UPLC－HRMS）
固相萃取凈化/超高效液相色譜－串聯(lián)質(zhì)譜法測(cè)定養(yǎng)殖環(huán)境中地西泮及其代謝物
王旭峰，王強(qiáng)，張英俠，黃珂*
（農(nóng)業(yè)農(nóng)村部漁業(yè)環(huán)境及水產(chǎn)品質(zhì)量監(jiān)督檢驗(yàn)測(cè)試中心（廣州），中國(guó)水產(chǎn)科學(xué)研究院南海水產(chǎn)研究所，廣東 廣州 510300）
摘要：建立了固相萃取凈化/超高效液相色譜－串聯(lián)質(zhì)譜（SPE/UPLC－MS/MS）同時(shí)測(cè)定養(yǎng)殖水和沉積物樣品中地西泮及其3種代謝物的分析方法。水樣經(jīng)0.45 μm玻璃纖維膜過濾，沉積物采用1%氨水－乙酸乙酯提取后，均通過混合型陽(yáng)離子交換固相萃取（MCX SPE）柱富集凈化。目標(biāo)物用5%氨水－乙腈溶液洗脫后吹干，1 mL 40%乙腈水溶液溶解殘?jiān)?/span>，UPLC－MS/MS測(cè)定。經(jīng)Phenomenex Kinetex C18（100 mm × 2.1 mm，1.7 μm）色譜柱分離，乙腈和0.1%甲酸水溶液為流動(dòng)相進(jìn)行梯度洗脫。采用電噴霧正離子電離，多反應(yīng)監(jiān)測(cè)（MRM）模式下測(cè)定，內(nèi)標(biāo)法定量。4種目標(biāo)物在0.1 ~ 100 μg/L范圍內(nèi)的線性關(guān)系良好，相關(guān)系數(shù)（r2）大于0.999。水體和沉積物中的方法檢出限分別為1.0 ~ 2.0 ng/L和0.02 ~ 0.05 μg/kg，定量下限分別為2.0 ~ 5.0 ng/L和0.05 ~ 0.1 μg/kg；平均加標(biāo)回收率為90.2% ~ 115%，相對(duì)標(biāo)準(zhǔn)偏差（RSD，n = 6）為2.1% ~ 9.6%。該方法靈敏度高，實(shí)用性強(qiáng)，可滿足養(yǎng)殖環(huán)境中地西泮及其代謝物的測(cè)定要求。
關(guān)鍵詞：地西泮；代謝物；固相萃取（SPE）；超高效液相色譜－串聯(lián)質(zhì)譜（UPLC－MS/MS）；養(yǎng)殖環(huán)境
中圖分類號(hào)：O657.7；X132 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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，F(xiàn)ishery 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
高效液相色譜－串聯(lián)質(zhì)譜法測(cè)定水產(chǎn)品中的乙氧基喹啉和乙氧基喹啉二聚體
王夢(mèng)茹1，2，殷耀1*，寧曉盼1，張萍1，彭軍1，樓蕓1，丁濤1，吳麗娜2，柳菡1，張曉燕1
（1．南京海關(guān) 動(dòng)植物與食品檢測(cè)中心，江蘇 南京 210019；2．南京師范大學(xué) 食品與制藥工程學(xué)院，江蘇 南京 210023）
摘要：建立了檢測(cè)魚、蝦、泥鰍和螃蟹等水產(chǎn)品中乙氧基喹啉和乙氧基喹啉二聚體殘留的高效液相色譜－串聯(lián)質(zhì)譜（HPLC－MS/MS）方法。在樣品制備時(shí)加入適量維生素C，以乙腈作為提取溶劑，正己烷進(jìn)行液液萃取。上清液經(jīng)Oasis PRiME HLB固相萃取柱凈化后旋蒸至近干，乙腈定容后采用Agela Phenomenex Kinetex C18色譜柱（100 mm × 4.6 mm × 2.6 μm）分離，在電噴霧電離源正離子模式下采用選擇反應(yīng)監(jiān)測(cè)（SRM）模式進(jìn)行檢測(cè)，外標(biāo)法定量。乙氧基喹啉和乙氧基喹啉二聚體在1 ~ 100 μg/L質(zhì)量濃度范圍內(nèi)線性關(guān)系良好，相關(guān)系數(shù)（r2）均大于0.994，檢出限（LOD）均為0.5 μg/kg，定量下限（LOQ）均為1.5 μg/kg。兩種目標(biāo)物質(zhì)在1.5、5、10、100 μg/kg 4個(gè)加標(biāo)濃度下的平均回收率為75.8% ~ 103%，相對(duì)標(biāo)準(zhǔn)偏差（RSD）為0.58% ~ 9.6%。該方法靈敏度高，準(zhǔn)確度和精密度好，適用于魚、蝦、泥鰍和螃蟹等水產(chǎn)品中乙氧基喹啉及乙氧基喹啉二聚體的檢測(cè)。
關(guān)鍵詞：高效液相色譜－串聯(lián)質(zhì)譜；水產(chǎn)品；乙氧基喹啉；乙氧基喹啉二聚體；固相萃取
中圖分類號(hào)：O657.7；TS207.3 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-ru1，2，YIN Yao1*，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
基于近紅外光譜的塑料分選技術(shù)預(yù)處理方法的優(yōu)化
李家?guī)?sup>1，薛蓮蓮2，王凱1，劉俊成1，吳翰1，李華清1，尹鳳福1*
（1．青島科技大學(xué) 機(jī)電工程學(xué)院，山東 青島 266042；2．青島工程職業(yè)學(xué)院 信息工程學(xué)院，山東 青島 266112）
摘要：為進(jìn)行不同塑料種類的識(shí)別，采集了尼龍（PA）、聚丙烯（PP）、聚苯乙烯（PS）、聚氯乙烯（PVC）4類塑料的近紅外光譜數(shù)據(jù)，并針對(duì)光譜數(shù)據(jù)采集時(shí)存在的噪聲、基線和光程問題，基于3點(diǎn)Savitzky－Golay卷積平滑（S－G）、一階導(dǎo)數(shù)（FD）、二階導(dǎo)數(shù)（SD）、標(biāo)準(zhǔn)正態(tài)變量變換（SNV）、多元散射校正（MSC）進(jìn)行了預(yù)處理組合優(yōu)化研究，以競(jìng)爭(zhēng)性自適應(yīng)重加權(quán)算法（CARS）進(jìn)行特征波長(zhǎng)提取，并運(yùn)用支持向量機(jī)算法（SVM）建立模型。結(jié)果顯示：所有預(yù)處理方法中，預(yù)處理組合S－G + FD + SNV獲得的結(jié)果最優(yōu)，S－G + FD + SNV + SVM模型的平均準(zhǔn)確率高達(dá)96.67%，其訓(xùn)練集和驗(yàn)證集的平均準(zhǔn)確率均為100%。上述預(yù)處理組合優(yōu)化方法可為4類常見塑料的鑒別研究提供參考。
關(guān)鍵詞：塑料分選；近紅外光譜（NIR）；預(yù)處理；組合；預(yù)測(cè)分析
中圖分類號(hào)：O657.3；TH145.42 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-fu1*
（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/氣相色譜－質(zhì)譜法測(cè)定氟［18F］脫氧葡糖注射液塑料生產(chǎn)組件浸提液中16種鄰苯二甲酸酯類增塑劑
昝艷楠1，2，張曉蕓2，商少華2，陳寧2，丁逸梅1，2*
（1．南京工業(yè)大學(xué) 藥學(xué)院，江蘇 南京 211816；2．江蘇藥物研究所有限公司 藥品檢測(cè)與包材研究中心，江蘇 南京 210009）
摘要：建立了基于液液萃取（LLE）/氣相色譜－質(zhì)譜（GC－MS）檢測(cè)氟［18F］脫氧葡糖注射液塑料生產(chǎn)組件浸提液中16種鄰苯二甲酸酯類（PAEs）增塑劑的方法。根據(jù)生產(chǎn)工藝，采用含5%乙醇、5%乙腈的混合溶液作為模擬溶劑，在40 ℃條件下進(jìn)行模擬浸提。采用Thermo TG－5 SIL MS色譜柱分離，選擇離子掃描模式（SIM）進(jìn)行分析。通過對(duì)儀器條件與萃取條件進(jìn)行優(yōu)化，確定最佳前處理方法和儀器條件。在優(yōu)化實(shí)驗(yàn)條件下，16種PAEs在50～500 ng/mL范圍內(nèi)與峰面積呈良好的線性關(guān)系，相關(guān)系數(shù)（r）均不小于0.990 6，檢出限（LOD）和定量下限（LOQ）分別為10、30 ng/mL。以二氯甲烷為萃取溶劑時(shí)，平均回收率為83.0%～114%，相對(duì)標(biāo)準(zhǔn)偏差（RSD，n = 6）為1.9%～4.2%。采用該方法對(duì)浸提液進(jìn)行測(cè)定，16種PAEs均未超過分析評(píng)價(jià)閾值（AET）。該法操作簡(jiǎn)便，專屬性強(qiáng)，可用于氟［18F］脫氧葡糖注射液塑料生產(chǎn)組件的相容性研究。
關(guān)鍵詞：氣相色譜－質(zhì)譜法；液液萃取；增塑劑；氟［18F］脫氧葡糖注射液；塑料組件
中圖分類號(hào)：O657.7；TS206.4 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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-nan1，2，ZHANG Xiao-yun2，SHANG Shao-hua2，CHEN Ning2，DING Yi-mei1，2*
（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
定量核磁共振氫譜法測(cè)定枸櫞酸托法替布片的有效含量
劉慢，趙闐，劉會(huì)利，陳林*
（黃河科技學(xué)院 河南省小分子新藥研發(fā)國(guó)際聯(lián)合實(shí)驗(yàn)室，河南省食藥兩用植物資源綜合利用工程技術(shù)研究中心，
鄭州市天然產(chǎn)物合成生物學(xué)重點(diǎn)實(shí)驗(yàn)室，河南 鄭州 450063）
摘要：建立了枸櫞酸托法替布片中有效含量的定量核磁共振氫譜測(cè)定方法。以托法替布化學(xué)位移δ 7.13為定量峰，3，5-二甲基吡唑化學(xué)位移δ 5.73為內(nèi)標(biāo)峰，氘代二甲亞砜（DMSO－D6）為溶劑，使用核磁共振譜儀采集混合物的氫譜，對(duì)枸櫞酸托法替布片中的有效成分進(jìn)行定量測(cè)定。該方法專一性強(qiáng)，在0.793 ~ 7.925 mg/mL范圍內(nèi)呈現(xiàn)良好的線性關(guān)系（r2= 0.998 4）。精密度、重復(fù)性和穩(wěn)定性的相對(duì)標(biāo)準(zhǔn)偏差（RSD）分別為0.82%、1.7%和0.67%。該方法測(cè)得的枸櫞酸托法替布片中托法替布的質(zhì)量分?jǐn)?shù)為2.25%，其結(jié)果與高效液相色譜法基本一致。定量核磁共振氫譜法具有操作方便簡(jiǎn)單，可同時(shí)進(jìn)行定性與定量，檢測(cè)時(shí)間短，無需對(duì)照品等優(yōu)勢(shì)，可用于枸櫞酸托法替布片有效含量的測(cè)定。
關(guān)鍵詞：定量核磁共振氫譜法；枸櫞酸托法替布片；3，5-二甲基吡唑；含量測(cè)定
中圖分類號(hào)：O657.7；R917 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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
適配體生物傳感器在黃曲霉毒素B1檢測(cè)中的應(yīng)用
韓文浩1，2，李延生1，2*，高國(guó)偉1，2，張學(xué)記3
（1．北京信息科技大學(xué) 傳感器重點(diǎn)實(shí)驗(yàn)室，北京 100101；2．北京信息科技大學(xué) 現(xiàn)代測(cè)控技術(shù)教育部重點(diǎn)實(shí)驗(yàn)室，北京 100192；
3．深圳大學(xué) 生物醫(yī)學(xué)工程學(xué)院，廣東 深圳 518060）
摘要：該文首先對(duì)黃曲霉毒素B1（AFB1）的相關(guān)性質(zhì)及其傳統(tǒng)檢測(cè)方法進(jìn)行了介紹，隨后概述了近年來基于光學(xué)、電化學(xué)以及微流控芯片的適配體生物傳感器的構(gòu)建及其在AFB1檢測(cè)領(lǐng)域中的應(yīng)用，旨為適配體生物傳感器的實(shí)際應(yīng)用提供參考；并通過探討目前開發(fā)的檢測(cè)方法存在的問題，對(duì)適配體生物傳感器前景和未來趨勢(shì)進(jìn)行了展望。
關(guān)鍵詞：黃曲霉毒素B1；適配體；生物傳感器；應(yīng)用
中圖分類號(hào)：O657；S951.4 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：1004-4957（2023）03-0368-07
Application of Aptamer Biosensor in Detection of Aflatoxin B1
HAN Wen-hao1，2，LI Yan-sheng1，2*，GAO Guo-wei1，2，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
