《分析試驗室》2024年4月第43卷第4期中英文摘要
基于Co3O4@CNTs信號放大的有機磷與葡萄糖酶基傳感器
李杰，張捷，王康康，董社英*
（西安建筑科技大學化學與化工學院，西安 710055）
摘要：利用六水合硝酸鈷（Co（NO3）2·6H2O）與對苯二甲酸（HOOC-C6H4-COOH）合成MOF-71前驅體，將其與雙氰胺（C2H4N4）混合熱解，得到在Co3O4上生長碳納米管（CNTs）的Co3O4@CNTs電極修飾材料。采用掃描電子顯微鏡（SEM）、N2吸附-脫附曲線（BET）、X射線衍射（XRD）、X射線能譜分析（EDS）對材料進行表征。結果表明，該納米復合材料具有豐富的孔隙結構和較大的比表面積，可增大乙酰膽堿酯酶（AChE）和葡萄糖氧化酶（GOD）的負載量，起到信號放大的作用。電化學研究表明：MOF-71的熱解及其與CNTs的復合使Co3O4@CNTs具有優良的導電性，也有利于信號的提升。將其分別固定AChE和GOD，構建酶基傳感器用于檢測有機磷農藥和葡萄糖（Glu）。檢測甲基對硫磷時，其線性范圍為1.0×10-3~1.0 ng/mL，檢出限低至0.31 pg/mL；檢測對氧磷時，其線性范圍為1.0×10-3~1.0 ng/mL，檢出限低至0.34 pg/mL；檢測Glu時，其線性范圍為0.1~5 μmol/L和10~200 μmol/L，檢出限為0.04 μmol/L。
關鍵詞：Co3O4@CNTs；甲基對硫磷；對氧磷；葡萄糖；電化學生物酶傳感器
中圖分類號：O646 文獻標識碼：A 文章編號：1000-0720（2024）04-0455-08
Organophosphorus and glucose enzyme-based sensors based on Co3O4@CNTs signal amplification
LI Jie，ZHANG Jie，WANG Kangkang，DONG Sheying*
School of Chemistry and Chemical Engineering，Xi'an University of Architecture and Technology，Xi'an 710055，China）
Abstract：Co3O4@CNTs electrode modification materials were obtained by mixed pyrolysis of dicyandiamide （C2H4N4） and MOF-71 precursors synthesized by cobalt nitrate hexahydrate （Co（NO3）2·6H2O） and pure terephthalic acid（HOOC-C6H4-COOH）. The materials were characterized by scanning electron microscope （SEM），Brunner-Emmet-Teller measurement （BET），X-ray diffraction （XRD），and energy dispersive spectroscopy （EDS）. The results showed that the nanocomposites had rich pore structures and large surface area，which could increase the loading of acetylcholinesterase （AChE） and glucose oxidase （GOD） for signal amplification. Meanwhile，the electrochemical performance study showed that Co3O4@CNTs had excellent conductivity and elevated signal due to the pyrolysis of MOF-71 and its combination with CNTs. AChE and GOD were further immobilized onto the Co3O4@CNTs to construct enzyme-based sensors for the detection of organophosphorus pesticides and glucose （Glu）. The linear concentration ranges were 1.0×10-3-1.0 ng/mL，1.0×10-3-1.0 ng/mL and 0.1-5 μmol/L as well as10-200 μmol/L for methyl parathion detection，paraoxon detection and Glu detection，respectively，accompanied by low detection limit of 0.31 pg/mL，0.34 pg/mL and 0.04 μmol/L.
Keywords：Co3O4@CNTs；methyl parathion；paraoxon；glucose；electrochemical biological enzyme sensor
氣相色譜-質譜法測定食品接觸材料及制品中4種檸檬酸酯類化合物的遷移量
劉仕途，曾銘，陳湘穎，李丹*，董犇，阿文偉，鐘懷寧
（廣州海關技術中心，廣州 510070）
摘要：建立了測定食品接觸材料及制品中檸檬酸三乙酯（TEC）、乙酰檸檬酸三乙酯（ATEC）、檸檬酸三丁酯（TBC）和乙酰檸檬酸三丁酯（ATBC）遷移量的氣相色譜-質譜（GC-MS）法。食品接觸材料樣品經遷移試驗后，所得水基浸泡液和橄欖油浸泡液分別經正己烷和乙腈萃取后測定，95%乙醇浸泡液和異辛烷浸泡液直接測定。結果表明，4種目標化合物的標準工作曲線在0.2~2.0 mg/L濃度范圍內線性關系良好，相關系數（r2）大于0.995；4種檸檬酸酯類化合物在4%乙酸、10%乙醇、20%乙醇、50%乙醇、95%乙醇、異辛烷、橄欖油等模擬物中的檢出限為0.05~0.11 mg/L，定量限為0.15~0.30 mg/L。對基質空白浸泡液進行低、中、高3個濃度水平添加實驗，加標回收率在90.6%~110%之間，相對標準偏差（RSD）為0.9%~8.6%。該方法能夠滿足食品接觸材料及制品中4種檸檬酸酯類化合物遷移量檢測的需求。
關鍵詞：檸檬酸三乙酯（TEC）；乙酰檸檬酸三乙酯（ATEC）；檸檬酸三丁酯（TBC）；乙酰檸檬酸三丁酯（ATBC）；食品接觸材料；氣相色譜-質譜法（GC-MS）
中圖分類號：O657.71；O622.3 文獻標識碼：A 文章編號：1000-0720（2024）04-0463-06
Determination of migration of four citrate compounds in food contact materials and products by gas chromatography-mass spectrometry method
LIU Shitu，ZENG Ming，CHEN Xiangying，LI Dan*，DONG Ben，A Wenwei，ZHONG Huaining
Guangzhou Customs Technical Center，Guangzhou 510070，China）
Abstract：A gas chromatography-mass spectrometry （GC-MS） method was established to determine the migration of triethyl citrate （TEC），acetyl triethyl citrate （ATEC），tributyl citrate （TBC），and acetyl tributyl citrate （ATBC） in food contact materials and products. After the migration test of food contact material samples，the obtained water-based soaking solution and the olive oil soaking solution were extracted with n-hexane and acetonitrile respectively，and then determined by GC-MS，while the 95% ethanol soaking solution and isooctane soaking solution were directly determined by GC-MS. The results showed that the method had correlation coefficients （r2） greater than 0.995. The detection limits of four citrate compounds in 4% acetic acid，10% ethanol，20% ethanol，50% ethanol，95% ethanol，isooctane，and olive oil simulants were 0.05-0.11 mg/L，the limits of quantification were 0.15-0.30 mg/L，and the linear ranges were 0.2-2.0 mg/L. The average spiked recoveries of this method at low，medium，and high levels were 90.6%-110%，and the relative standard deviations （RSDs） were 0.9%-8.6%. This method can meet the requirements for determination of the migration amounts of four citrate compounds in food contact materials and their products.
Keywords：triethyl citrate （TEC）；acetylcitrate triethyl ester （ATEC）；tributyl citrate （TBC）；acetyl tributyl citrate （ATBC）；food contact materials；gas chromatography-mass spectrometry（GC-MS）
基于紫外光譜研究溶解性黑炭質子化
張竑1，2，3，穆玉寧1，2，楊晨宇1，蘇友波1，2，蔣明1，張繼來*1，2，傅開道3，張乃明1，2，陳文華4
（1. 云南農業大學資源與環境學院，昆明 650500；2. 云南省土壤培肥與污染修復工程實驗室，昆明 650201；3. 云南大學國際河流與生態安全研究院，昆明 650091；4. 保山學院資源與環境學院，保山 678000）
摘要：運用紫外光譜滴定技術結合差分光譜與二維相關光譜分析，對溶解性黑炭（DBC）的質子化過程進行定性和定量研究。結果發現：熱解溫度為280，360，440 ℃的DBC在消光光譜200~250 nm間有特征吸收峰，但DBC特征峰并未隨pH變化出現發色團去質子化和結構改變；運用差分光譜分析發現，3個熱解溫度下DBC均于波長280，355，385 nm處形成特征差分吸收峰，且吸收峰強度與H+濃度成正相關（p＜0.05）；二維紫外相關光譜分析表明，DBC的質子化主要發生于羧基及含酚官能團上。以上結果表明，紫外差分光譜滴定法可以定量分析DBC的質子化，DBC發生質子化的主要位點與腐殖酸類似，均為羧基及酚羥基。
關鍵詞：生物碳；溶解性黑炭；質子化；紫外吸收光譜
中圖分類號：O657.3 文獻標識碼：A 文章編號：1000-0720（2024）04-0469-07
Study of dissolved black carbon protonation based on ultraviolet spectroscopy
ZHANG Hong1，2，3，MU Yuning1，2，YANG Chenyu1，SU Youbo1，2，JIANG Ming1，ZHANG Jilai*1，2，FU Kaidao3，ZHANG Naiming1，2，CHEN Wenhua4
1. College of Resources and Environment，Yunnan Agricultural University，Kunming 650500，China；2. Lab of Soil Fertilization and Pollution Remediation Engineering，Yunnan Province，Kunming 650201，China；3. Institute of International Rivers and Ecological Security，Yunnan University，Kunming 650091，China；4. School of Resources and Environment，Baoshan University，Baoshan 678000，China）
Abstract：The quantitative and qualitative study of the protonation process of dissolved black carbon （DBC） were carried out by combining ultraviolet （UV） spectral titration technique combining with differential spectroscopy and two-dimensional correlation spectroscopy analysis. It was found that DBC with pyrolysis temperatures of 280，360 and 440 ℃ had characteristic absorption peaks in the extinction spectral range of 200-250 nm，but the characteristic peaks of DBC did not show deprotonation of chromophores and structural changes with pH changes. Differential spectroscopy analysis revealed that the DBC at the three pyrolysis temperatures formed characteristic differential absorption peaks at 280，355 and 385 nm，and the intensity of the absorption peaks was positively correlated with the H+ concentration （p<0.05）. Two-dimensional UV correlation spectroscopy showed that the protonation of DBC mainly occurred at the carboxyl group and phenol-containing functional groups. The above results indicated that the UV differential spectroscopy titration method could quantitatively analyze the protonation of DBC，and the main sites of protonation of DBC were carboxyl and phenolic hydroxyl groups，where were similar to those of humic acid.
Keywords：biochar；dissolved black carbon；protonation；ultraviolet absorption spectrum
基于磁性金屬有機骨架材料的固相萃取電感耦合等離子體質譜法測定環境水中的重金屬元素
王意*1，鄒昊彤2，薛濤1，劉洋1，林奎1，李方2，鄧小娟1
（1. 天津大學分析測試中心，天津 300072；2. 天津大學材料學院，天津 300072）
摘要：利用水熱反應，成功合成了一種功能化的金屬有機骨架材料，磁性MIL-101（Fe），并將其用作磁性固相萃取（MSPE）吸附劑，與電感耦合等離子體質譜（ICP-MS）聯用，實現高效、靈敏的痕量重金屬離子測定。利用掃描電子顯微鏡、透射電子顯微鏡、X射線衍射和X射線光電子能譜對磁性MIL-101（Fe）進行了表征，并通過間歇吸附實驗優化了溶液pH、吸附時間和解吸時間等萃取參數。結果表明，所合成的MIL-101（Fe）磁性固相萃取劑具有良好的晶體結構和表面功能化納米顆粒。在優化實驗條件下，所建立的MSPE-ICP-MS方法線性范圍為0.5~500 μg/L，As（III），Pb（II）和Cu（II）的檢出限為0.177~0.301 μg/L，相對標準偏差為1.7%~3.2%，在連續7次循環使用后回收率仍可達82%。該方法用于環境水樣中痕量重金屬離子的測定，加標回收率為90.0%~113.2%，可用于環境水樣中痕量重金屬檢測。
關鍵詞：磁性固相萃取；電感耦合等離子體質譜；金屬有機骨架材料；重金屬離子
中圖分類號：O657.63 文獻標識碼：A 文章編號：1000-0720（2024）04-0476-06
Determination of heavy metals in environmental water by magnetic solid phase extraction-inductively coupled plasma mass spectrometry based on magneticmetal-organic framework materials
WANG Yi*1，ZOU Haotong2，XUE Tao1，LIU Yang1，LIN Kui1，LI Fang2，DENG Xiaojuan1
1. Analysis and Testing Center，Tianjin University，Tianjin 300072，China；2. College of Materials Science and Engineering，Tianjin University，Tianjin 300072，China）
Abstract：A functionalized metal-organic framework material，magnetic MIL-101（Fe） composite，was successfully synthesized through hydrothermal reaction. MIL-101 （Fe） composite was used as a magnetic solid phase extraction （MSPE） agent，which was coupled with inductively coupled plasma mass spectrometry （ICP-MS） to realize the efficient and sensitive analysis of trace heavy metal ions. The synthesized magnetic MIL-101（Fe） composite was characterized by scanning electron microscopy，transmission electron microscopy，X-ray diffraction and X-ray photoelectron spectroscopy. The extraction parameters including solution pH，adsorption time and desorption time，were optimized by batch adsorption experiments. The experimental results showed that the MSPE agent was nanoparticles with good crystal structure and surface functionality. Under the optimized experimental conditions，the established MSPE-ICP-MS method had a linear range of 0.5-500 μg/L，the detection limits of As（III），Pb（II） and Cu（II） ions were 0.177-0.301 μg/L，and the relative standard deviations were 1.7%-3.2%. The recycled magnetic MIL-101 （Fe） composite exhibited good reusability，and the recovery was higher than 82% after seven adsorption-desorption cycles. The method was successfully applied to the determination of trace heavy metal ions in environmental water samples. The recoveries of arsenic，lead and copper ions in seawater and lake water samples ranged from 90.0% to 113.2%. This method can be used for the determination of trace heavy metals in environmental water samples.
Keywords：magnetic solid phase extraction；inductively coupled plasma mass spectrometry；metal-organic framework；heavy metal ions
鈉離子促進消解-電感耦合等離子體質譜法測定植物中的硅
孫文軍1，2，劉向磊*1，2，蔡煥花1，張宏麗3，4，文田耀1，2，王騰飛1
（1. 河南省地質礦產勘查開發局第一地質礦產調查院，洛陽 471023；2. 河南省金銀多金屬成礦系列與深部預測重點實驗室，洛陽 471023；3. 中國地質科學院鄭州礦產利用研究所，鄭州 450006；4. 國家非金屬資源綜合利用工程技術中心，鄭州 450006）
摘要：植物中的硅因具有含量低、難消解、用含氟酸處理易損失等特點，一直是濕法處理的難點。本研究選擇硝酸+氫氟酸+氯化鈉混合消解液和高通量微波密閉消解植物樣品，通過優化消解液配比、消解溫度和消解時間、碰撞氣體流量，建立了鈉離子促進消解-電感耦合等離子體質譜法測定植物中硅的方法。結果表明，使用硝酸+氫氟酸混合消解溶液，可有效消解植物樣品基體及基體中的硅元素；向消解液中加入一定量的鈉離子和使用微波密閉消解法，能夠促進試樣中二氧化硅消解完全，提高消解效率及避免氟硅化合物的揮發損失。使用聚四氟乙烯同心圓霧化器、聚四氟乙烯旋流霧化室和藍寶石中心管，可有效降低由溶液中氫氟酸介質腐蝕石英進樣系統引入的儀器本底值；選擇氦氣作為碰撞氣并控制氦氣流量，可以有效消除氮、碳、鋁、硼、氫、氧等元素的多原子離子對28Si的質譜干擾，提高方法的靈敏度。硅的方法檢出限為0.001%，相對標準偏差（RSD）和誤差（RE）分別在1.8%~7.7%和-1.8%~4.5%之間。方法適合于植物樣品中硅的準確、快速測定，也可為農業考古和植物碳匯潛力研究中硅的總量分析提供技術支撐。
關鍵詞：硅；鈉離子；植物樣品；微波消解；電感耦合等離子體質譜
中圖分類號：O652.4；O657.63 文獻標識碼：A 文章編號：1000-0720（2024）04-0482-06
Determination of silicon in plants by sodium ion promoted digestion-inductively coupled plasma mass spectrometry
SUN Wenjun1，2，LIU Xianglei*1，2，CAI Huanhua1，ZHANG Hongli3，4，WEN Tianyao1，2，WANG Tengfei1
1. No.1 Institute of Geological and Mineral Resources Survey，Henan Bureau of Geoexploration and Mineral Development，Luoyang 471023，China；2. Key Laboratory of Au-Ag-Polymetallic Deposit Series and Deep-seated Metallogenic Prognosis of Henan Province，Luoyang 471023，China；3. Zhengzhou Institute of Multipurpose Utilization of Mineral Resources，Chinese Academy of Geological Sciences，Zhengzhou 450006，China；4. China National Engineering Research Center for Utilization of Industrial Minerals，Zhengzhou 450006，China）
Abstract：Silicon in plants has always been one of the difficulties in wet treatment because of its low content，difficult digestion，and easy loss of fluorine-containing acid treatment. In this study，HNO3+HF+NaCl mixed digestion solution and high-throughput microwave closed digestion for plant samples were selected. By optimizing the ratio of digestion solution，digestion temperature and digestion time，collision gas flow，a method for the determination of silicon in plants by inductively coupled plasma mass spectrometry with sodium ion promoted digestion was established. The results showed that the use of HNO3-HF mixed digestion solution could effectively digest the plant sample matrix and the silicon element in the matrix. The addition of a certain amount of sodium ions to the digestion solution and the use of microwave closed digestion method could promote the complete digestion of silica in the sample，improve the digestion efficiency and avoid the volatilization loss of fluorosilicone compounds. The use of polytetrafluoroethylene concentric atomizer，polytetrafluoroethylene swirl atomizing chamber and sapphire central tube can effectively reduce the instrument background value introduced by the hydrofluoric acid medium corrosion quartz injection system in the solution. Choosing helium （He） as collision gas and controlling the flow rate of helium can effectively eliminate the mass spectral interference of polyatomic ions of nitrogen，carbon，aluminum，boron，hydrogen，oxygen and other elements on 28Si，and improve the sensitivity of the method. The detection limit of silicon was 0.001%，and the relative standard deviations （RSDs） and error （RE） of the method were 1.8%-7.7% and -1.8%-4.5%，respectively. The method is suitable for the accurate and rapid determination of silicon in plant samples，and can also provide technical support for the total amount analysis of silicon in agricultural archaeology and plant carbon sink potential research.
Keywords：silicon；sodium ion；plant samples；microwave digestion；inductively coupled plasma-mass spectrometry
基于Hg/Au基納米酶過氧化物酶活性比色/SERS雙模式檢測煙堿
張海1，何彬1，高憲輝1，周渭皓1，劉磊1，李秋蘭2，吳偉2，楊德志*2，楊亞玲*2
（1. 云南省煙草煙葉公司，昆明 650218；2. 昆明理工大學生命科學與技術學院，昆明 650500）
摘要：利用Hg2+與Au基納米材料形成金汞齊制備Hg/Au基納米酶（AuNPs@Hg）。基于納米酶表面增強拉曼光譜（SERS）活性和模擬酶催化活性，建立了比色/SERS雙模式檢測煙堿的方法。結果表明，AuNPs@Hg可以模擬過氧化物酶，催化過氧化氫氧化無色的3，3'，5，5'-四甲基聯苯胺（TMB），同時也可以作為SERS底物，檢測TMB氧化產物（oxTMB）的SERS信號，而煙堿則可以顯著增加AuNPs@Hg的過氧化物酶活性。基于比色法，在煙堿濃度1.25~375 μg/mL范圍內呈良好的線性關系，檢出限（LOD）為0.34 μg/mL。基于SERS法，煙堿濃度在6.25×10-3~1.25 mg/mL范圍內有較好的線性校準曲線，LOD為1.80 μg/mL。實際樣品中煙堿的回收率在96.1%~105.3%范圍內，相對標準偏差（RSD）為2.4%~4.7%，且實際樣品中存在的共存物質對所建立的方法幾乎無干擾作用，檢測結果與行業標準方法測定結果一致。本研究可為多功能傳感器的設計及SERS在煙草行業中的應用提供新的策略和途徑。
關鍵詞：煙堿；納米酶；表面增強拉曼光譜；過氧化物酶；金汞齊
中圖分類號：O657.37 文獻標識碼：A 文章編號：1000-0720（2024）04-0488-09
Colorimetric/SERS dual-mode detection of nicotine based on the peroxidase-like activity of Hg/Au-nanozyme
ZHANG Hai1，HE Bin1，GAO Xianhui1，ZHOU Weihao1，LIU Lei1，LI Qiulan2，WU Wei2，YANG Dezhi*2，YANG Yaling*2
1. Yunnan Tobacco Leaf Company，Kunming 650218，China；2. Faculty of Life Science and Technology，Kunming University of Science and Technology，Kunming 650500，China）
Abstract：The preparation of Hg/Au-based nanozyme （AuNPs@Hg） by the formation of gold amalgam between Hg2+ and Au-based nanomaterials was proposed. Based on the enhanced SERS activity and simulated catalytic activity of the nanozyme，a colorimetric/SERS dual-mode method was established for the detection of nicotine. The results showed that AuNPs@Hg could simulate peroxidase to catalyze the oxidation of colorless 3，3'，5，5'- tetramethylbenzidine （TMB） by hydrogen peroxide （H2O2）. Meanwhile，it could also be used as SERS substrate to detect the SERS signal of TMB oxidation products （oxTMB）. Nicotine can significantly increase the peroxidase activity of AuNPs@Hg. Based on TMB colorimetric assay，nicotine showed good linearity in the range of 1.25-375 μg/mL with the limit of detection （LOD） of 0.34 μg/mL. Based on the SERS method，the nicotine concentration in the range of 6.25×10-3-1.25 mg/mL had a good linear calibration curve，and the LOD was 1.80 μg/mL. The recoveries of nicotine in the real e-cigarette liquid samples were in the range of 96.1%-105.3% with the relative standard deviations （RSDs） of 2.4%-4.7%. The coexisting substances in the actual samples had almost no interference，and the detection results were consistent with that of the industry standard method. This research can provide a new strategy and approach for the design of multi-functional sensor and SERS application in the tobacco industry.
Keywords：nicotine；nanozyme；surface-enhanced Raman spectroscopy；peroxidase；Au-Hg amalgam
聚多巴胺涂覆的磺丁基醚-β-環糊精開管毛細管電色譜柱的制備及應用
黃子為，霍虹懿，龍科，石爽，關瑾*
（沈陽化工大學理學院，沈陽 110142）
摘要：制備了以聚多巴胺/磺丁基醚-β-環糊精（PDA/SBE-β-CD）為手性固定相的開管毛細管電色譜柱。最佳制備條件為：SBE-β-CD濃度10.0 mg/mL，多巴胺濃度5.0 mg/mL，涂覆時間2 h。通過紅外光譜和掃描電鏡對制備的色譜柱進行了表征，并將其應用于奧美拉唑對映體的毛細管電色譜（CEC）分離分析。在110 mmol/L Tris-H3PO4（pH 6.0）緩沖溶液和外加電壓15 kV條件下，奧美拉唑對映體在13 min內成功分離，分離度為5.82。對映異構體質量濃度在50~600 μg/mL 范圍內線性關系良好（r2=0.9958），遷移時間和峰面積的相對標準偏差（RSD）分別小于2.8%和4.8%。PDA/SBE-β-CD固定相在毛細管電色譜（CEC）手性分離中具有良好的應用潛力。
關鍵詞：毛細管電色譜；手性分離；開管柱；磺丁基醚-β-環糊精；聚多巴胺
中圖分類號：O657.8 文獻標識碼：A 文章編號：1000-0720（2024）04-0497-05
Preparation and application of polydopamine/sulfobutyl ether-β-cyclodextrin coated open tube capillary electrochromatographic column
HUANG Ziwei，HUO Hongyi，LONG Ke，SHI Shuang，GUAN Jin*
College of Science，Shenyang University of Chemical Technology，Shenyang 110142，China）
Abstract：An open tube capillary electrochromatographic column was prepared using polydopamine/sulfobutyl ether-β-Cyclodextrin （PDA/SBE-β-CD） as chiral stationary phase. The optimal conditions of fabricated capillary column were as follows：SBE-β-CD concentration of 10.0 mg/mL，dopamine concentration of 5.0 mg/mL，and coating time of 2 h. The fabricated capillary column was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Furthermore，the chiral separation effectiveness of the fabricated capillary column was evaluated by capillary electrochromatography （CEC） using enantiomers of omeprazole as model analyte. The enantiomers of omeprazole were resolved within 13 min with high resolution of 5.82 using 110 mmol/L Tris-H3PO4 buffer （pH 6.0） at an applied voltage of 15 kV. Good linearities were obtained in the concentration range of 50-600 μg/mL with the correlation coefficients of r2=0.9958 for the enantiomers of omeprazole. And for the migrated time and peak areas，the relative standard deviations （RSDs） were below 2.8% and 4.8%，respectively. The results reveal that PDA/SBE-β-CD has great potential as chiral stationary phases for enantio separation in CEC.
Keywords：capillary electrochromatography；chiral separation；open tubular column；sulfobutyl ether-β-cyclodextrin；polydopamine
基于直接標準化與分段直接標準化聯用的木質素近紅外模型傳遞方法研究
劉智健1，熊智新*1，胡云超1，汪瑩1，黃浩冉1，王紅鴻1，梁龍2
（1. 南京林業大學輕工與食品學院，南京 210037；2. 中國林業科學研究院林產化學工業研究所，南京 210042）
摘要：為了提高木質素近紅外分析模型轉移的質量，提出了將直接標準化（DS）與分段直接標準化（PDS）聯用的DS-PDS方法，即利用PDS算法校正使用DS方法全局校正后儀器之間仍然存在的局部差異，并以3臺光譜儀（棱光為主機、Si-ware和Insion為從機）測得的81個樣品木質素光譜數據為研究對象，驗證該方法的可行性。結果表明，該聯用算法能充分發揮DS算法與PDS算法各自的優點，與單獨使用DS的最優結果相比，標樣集并未增加，PDS算法的窗口寬度、偏最小二乘回歸（PLSR）模型的主因子數均減小，對從機樣品的預測精度進一步提高。對Si-Ware而言，相對標準偏差（RPD）值由DS方法的3.3853提高到4.0335，Insion的RPD值則從2.8600提高到3.4462。DS-PDS聯用算法除了使用更少的參數，還能減弱模型轉移中光譜不連續現象，彌補了單獨使用DS和PDS算法的缺點，為近紅外光譜的模型轉移提供了一種新的解決方案。
關鍵詞：木質素；近紅外光譜；模型傳遞；DS-PDS
中圖分類號：O657.63 文獻標識碼：A 文章編號：1000-0720（2024）04-0502-09
Research on near-infrared model transfer for lignin based on the combined direct standardization-piecewise direct standardization method
LIU Zhijian1，XIONG Zhixin*1，HU Yunchao1，WANG Ying1，HUANG Haoran1，WANG Honghong1，Liang long2
1. College of Light Industry and Food，Nanjing Forestry University，Nanjing 210037，China；2. Institute of Chemical Industry of Forest Products，Chinese Academy of Forestry，Nanjing 210042，China）
Abstract：In order to improve the transfer performance of the lignin near-infrared analysis model，a method combining direct standardization （DS） and piecewise direct standardization （PDS），named DS-PDS，was proposed. The PDS algorithm was used to correct the local differences between instruments still existed after the global correction using the DS method. The lignin spectral data of 81 samples measured by three spectrometers （Lengguang as master instrument，and Si-Ware and Insion as target instruments，respectively） were used to verify the feasibility of the new method. The experimental results showed that the combined algorithm can exploit the advantages of DS algorithm and PDS algorithm respectively. Compared with the optimal results of using DS algorithm alone，the standard sample set did not increase. For PDS algorithm，the window width，and the number of principal factors of the partial least square regression （PLSR） model were reduced，while the prediction accuracy of the target instruments was further improved. The ratio of prediction to deviation （RPD） value for Si-Ware increased from 3.3853 to 4.0335 comparing to the previous DS method，and the RPD value for Insion increased from 2.8600 to 3.4462. In addition to using fewer parameters，the combined DS-PDS algorithm can also reduce the phenomenon of spectral discontinuity in model transfer，which makes up for the shortcomings of using DS and PDS algorithms alone，and provides a new solution to the model transfer strategy of near-infrared spectroscopy.
Keywords：lignin；near-infrared spectroscopy；model transfer；DS-PDS
基于四氧化三鐵/聚（苯乙烯-4-乙烯吡啶）的食品中四環素殘留的快速篩選
沈唐文1，折歡歡1，張毅1，嚴恒2，謝衛紅*1
（1. 湖北工業大學生物工程與食品學院，武漢 430068；2. 湖北省食品質量安全監督檢驗研究院，武漢 430075）
摘要：基于四環素對四氧化三鐵（Fe3O4）/聚（苯乙烯-4-乙烯吡啶）（Fe3O4/P（st-4vp））的過氧化物酶活性的抑制作用，建立了一種快速篩選牛奶和蜂蜜中四環素殘留的方法。酸性條件下，所制備的Fe3O4/P（st-4vp）能夠催化H2O2氧化3，3，5，5’-四甲基聯苯胺（TMB）生成藍色的氧化TMB（oxTMB），在652 nm處出現可見吸收特征峰。四環素對該反應產生抑制作用，在pH 5.0、50 ℃水浴、反應時間20 min、H2O2濃度10 mmol/L、Fe3O4/P（st-4vp）濃度1.0 mg/mL、TMB濃度0.36 mmol/L條件下，四環素對Fe3O4/P（st-4vp）酶活性的抑制作用最強。根據四環素濃度與酶抑制率的關系曲線，對牛奶和蜂蜜中的加標四環素進行了篩查。結果表明，Fe3O4/P（st-4vp）對四環素加標量范圍5~197.5 μg/kg的牛奶和蜂蜜的篩查準確度分別為94.4%和96.3%。
關鍵詞：四氧化三鐵；聚（苯乙烯-4-乙烯吡啶）；納米酶；四環素殘留；快檢
中圖分類號：TS207.3 文獻標識碼：A 文章編號：1000-0720（2024）04-0511-06
Rapid screening of tetracycline residues in food based on Fe3O4/poly（styrene-4-vinyl pyridine） nanocomposites
SHEN Tangwen1，SHE Huanhuan1，ZHANG Yi1，YAN Heng1，XIE Weihong*2
1. College of Biotechnology and Food，Hubei University of Technology，Wuhan 430068，China；2. Hubei Provincial Institute for Food Supervision and Test，Wuhan 430075，China）
Abstract：A rapid screening method for tetracycline residues in milk and honey samples was developed based on the inhibitory effect of tetracycline on the peroxidase activity of Fe3O4/poly（styrene-4-vinylpyridine） （Fe3O4/P（st-4vp））. Under acidic conditions，the prepared Fe3O4/P（st-4vp） was able to catalyze the oxidation of 3，3，5，5'- tetramethylbenzidine （TMB） by H2O2 to produce blue oxidized TMB （oxTMB），with a characteristic absorption peak at 652 nm. The reaction was inhibited by tetracycline，which showed the strongest inhibition of Fe3O4/P （st-4vp） enzyme activity under conditions of pH 5.0，50 ℃ of water bath，20 min of reaction time，10 mmol/L of H2O2，1.0 mg/mL of Fe3O4/P（st-4vp），and 0.36 mmol/L of TMB. Based on the relationship curve between tetracycline concentration and enzyme inhibition rate，the spiked tetracycline in milk and honey samples was screened，and the results showed that the screening range of Fe3O4/P（st-4vp） for tetracycline spiked in milk and honey was 5-197.5 μg/kg，and the relative accuracy were 94.4% and 96.3%，respectively.
Keywords：Fe3O4；poly（styrene-4-vinylpyridine）；nanozyme；tetracycline residue；quick test
十六烷基三甲基溴化銨增敏化學發光法測定東莨菪內酯
趙悅1，張羅一覽3，程軻1，向警1，吳文婕2，王琴2，張雨潤2，黃文靜2，孫建敏4，楊憲*1，鄭紅*2
（1. 重慶師范大學生命科學學院，活性物質生物技術教育部工程研究中心，重慶 401331；2. 重慶師范大學化學學院，活性物質生物技術教育部工程研究中心，重慶 401331；3. 重慶市水利投資（集團）有限公司中心實驗室，重慶 401100；4. 重慶師范大學科研處，重慶 401331）
摘要：本文提供了一種新的測定東莨菪內酯的化學發光方法。酸性條件下，十六烷基三甲基溴化銨（CTAB）可增強東莨菪內酯在高錳酸鉀（K2MnO4）-甲醛體系中的發光強度，因此以CTAB作為增敏劑和助溶劑，聯合流動注射法對東莨菪內酯進行測定。在優化條件下，相對發光強度與東莨菪內酯濃度在0.1~26.0 μmol/L范圍內有良好的線性關系，檢出限（3σ）達1.40 nmol/L。對2.0 μmol/L東莨菪內酯連續測定11次，相對標準偏差（RSD）為1.1%。本方法可用于測定樣品中東莨菪內酯的含量。
關鍵詞：東莨菪內酯；增敏；十六烷基三甲基溴化銨；流動注射；化學發光
中圖分類號：O657.3；R284.1 文獻標識碼：A 文章編號：1000-0720（2024）04-0517-05
Determination of scopoletin by chemiluminescence with cetyltrimethylammonium bromide as sensitizer
ZHAO Yue1，ZHANG Luoyilan3，CHENG Ke1，XIANG Jing1，WU Wenjie2，WANG Qin2，ZHANG Yurun2，HUANG Wenjing2，SUN Jianmin4，YANG Xian*1，ZHENG Hong*2
1. College of Life Sciences，Chongqing Normal University，Engineering Research Center of Active Matter Biotechnology，Ministry of Education，Chongqing 401331，China；2. College of Chemistry，Chongqing Normal University，Engineering Research Center of Active Matter Biotechnology，Ministry of Education，Chongqing 401331，China；3. Central Laboratory of Chongqing Water Conservancy Investment （Group） Company Limited，Chongqing 401100，China；4. Scientific Research Department of Chongqing Normal University，Chongqing 401100，China）
Abstract：A new chemiluminescence method for the determination of scopoletin was developed. Under acidic conditions，cetyltrimethylammonium bromide （CTAB） can enhance the luminescence intensity of scopoletin in the potassium permanganate-formaldehyde system. Therefore，using CTAB as sensitizer and co-solvent，scopoletin could be measured by combining chemiluminescence with flow injection method. Under the optimized conditions，the relative luminescence intensities showed good linearity with scopoletin concentrations in the range of 0.1-26.0 μmol/L，and the detection limit （3σ） was 1.40 nmol/L. In addition，the relative standard deviation （RSD） was 1.1% for 11 consecutive determinations of 2.0 μmol/L of scopoletin. The developed method can be applied to the determination of scopoletin in samples with satisfactory results.
Keywords：scopoletin；sensitization；cetyltrimethylammoniumbromide （CTAB）；flow injection；chemiluminescence
液相色譜-串聯質譜法測定植物源驅蚊防蚊產品中11種致敏芳香劑和3種化學驅避劑
胡玉霞1，2，李紅艷1，陳德文*3
（1. 浙江省產品質量安全科學研究院，杭州310018；2. 浙江經貿職業技術學院，杭州310018；3. 杭州職業技術學院生態健康學院，杭州 310018）
摘要：建立了植物源驅蚊防蚊產品中11種致敏性芳香劑和3種化學驅避劑同時測定的液相色譜-串聯質譜方法。樣品用二氯甲烷超聲提取，在電噴霧離子源（ESI）正負離子多反應監測模式下同時采集，以乙腈-水為流動相梯度洗脫，采用Fastcore C18色譜柱進行分離，外標法定量。結果表明，該方法可以有效分離同分異構體6-甲基香豆素和7-甲基香豆素，14種目標化合物在0.4 ~20000 μg/L范圍內線性關系良好，相關系數R2>0.99，方法定量限為0.001~1.0 mg/kg。以定量限、4倍定量限和10倍定量限3個水平進行加標實驗，回收率為80.6%~118%，相對標準偏差（RSD）為1.1%~7.4%。采用本方法對30批驅蚊產品進行檢測，檢出香蘭素、香豆素、避蚊胺和丁香酚4種目標物。該方法適用于同時檢測植物源驅蚊產品中致敏性芳香劑和化學驅避劑。
關鍵詞：液相色譜-串聯質譜法（LC-MS/MS）；致敏性芳香劑；化學驅避劑；驅蚊
中圖分類號：O657.63 文獻標識碼：A 文章編號：1000-0720（2024）04-0522-06
Determination of 11 allergic fragrances and 3 chemical repellents in plant derived mosquito repellent and anti-mosquito products by liquid chromatography-tandem mass spectrometry
HU Yuxia1，2，LI Hongyan1，CHEN Dewen*3
1. Zhejiang Institute of Product Quality and Safety Science，Hangzhou 310018，China；2. Zhejiang Institute of Economics and Trade，Hangzhou 310018，China；3. Hangzhou Vocational & Technical College，Ecology and Health Institute，Hangzhou 310018，China）
Abstract：A liquid chromatography-tandem mass spectrometry （LC-MS/MS） method was developed for the simultanous determination of 11 allergic fragrances and 3 chemical repellents in plant derived mosquito repellent and anti mosquito products. After ultrasonic extraction with dichloromethane，the samples were analyzed simultaneously under electric spray ion source （ESI） positive and negative ion multi reaction monitoring mode （MRM）. Chromatographic separation of the migration solution was performed on a Fastcore C18 chromatographic column by a gradient elution of acetonitrile and water. The external standard method was used for the quantitative analysis. The results showed that the isomers 6-methylcoumarin and 7-methylcoumarinthe could be separated efficiently. There were good linear relationships for the14 targets in the concentration range of 0.4-20000 μg/L，with the correlation coefficients higher than 0.99，and the method limits of quantification （LOQs） were 0.001-4.0 mg/kg. The recoveries of the targets were 80.6%-118% at three spiked levels of LOQ，4×LOQ and 10×LOQ. The relative standard deviations （RSDs） were 1.1%-7.4%. This method was used to detect 30 mosquito repellent products，and 4 targets including vanillin，coumarin，N，N-diethyl-meta-toluamide （DEET） and eugenol were detected. This method could be applied for the determination of allergenic fragrances and chemical repellents in plant derived mosquito repellent and anti-mosquito products.
Keywords：liquid chromatography-tandem mass spectrometry （LC-MS/MS）；allergic fragrance；chemical repellent；mosquito repellent
高效液相色譜-串聯質譜法測定化妝品中12種N-亞硝胺類物質
李靜，周智明*，陳張好，陸土柳
（國家藥品監督管理局化妝品風險評估重點實驗室（廣東省藥品檢驗所），廣州 510525）
摘要：建立了化妝品中12種N-亞硝胺類物質的高效液相色譜-串聯三重四極桿質譜（HPLC-MS/MS）檢測方法。0.5 g樣品用25 mL 50%（V/V）甲醇水溶液溶解后，冰浴超聲提取5 min，10000 r/min離心5 min凈化，以PFP 色譜柱為分析柱，5 mmol/L甲酸胺（含0.1%甲酸）水溶液-甲醇為流動相梯度洗脫，大氣壓化學電離源電離后正離子、多反應監測模式測定，外標法定量。12種亞硝胺類物質在5~200 μg/L范圍內線性良好（r2＞0.99），檢出限為5~50 μg/kg。膏霜、乳液和水劑3種基質的平均回收率為78.9%~119.7% ，相對標準偏差為0.71%~8.8%。本方法能夠為化妝品中12種亞硝胺類物質的監測評估提供技術手段。
關鍵詞：N-亞硝胺類物質；高效液相色譜-串聯質譜法；化妝品
中圖分類號：O657.7；TQ651.2 文獻標識碼：A 文章編號：1000-0720（2024）04-0528-07
Determination of 12 N-nitrosamines in cosmetics by high performance liquid chromatography-triple quadrupole mass spectrometry
LI Jing，ZHOU Zhiming*，CHEN Zhanghao，LU Tuliu
National Medical Products Administration Key Laboratory for Safety Risk Assesment of Cosmetics （Guangdong Institute for Drug Control），Guangzhou 510525，China）
Abstract：The method for the simultaneous determination of twelve N-nitrosamines from cosmetics by high performance liquid chromatography-triple quadrupole mass spectrometry （HPLC-MS/MS） was developed. 0.5 g of sample was dissolved in 25 mL of 50% （V/V） methanol solution，then the 12 kinds of N-nitrosamines were extracted from cosmetics by ice bath supersonic extraction for 5 min，and the extracts were purified by centrifugation with 10000 r/min for 5 min. The chromatographic separation was performed on PFP column by gradient elution，with 5 mmol/L formic acid amine （containing 0.1% formic acid） aqueous solution-methanol as mobile phase at a flow rate of 0.3 mL/min．The 12 kinds of N-nitrosamines were analyzed in positive ions mode under multiple reaction monitoring （MRM） mode，after ionization by atmospheric pressure chemical ionization source，and quantified by external standard method. Results showed that there were good linear relationships for the 12 kinds of N-nitrosamines in the range of 5-200 μg/L，with their correlation coefficients （r2） more than 0.99. The limits of detection were 5-50 μg/kg. The average recoveries of the 12 kinds of N-nitrosamines in cream，emulsion and water ranged from 78.9% to 119.7%，with the relative standard deviations （RSDs） of 0.71%-8.8%. The method can be used for monitoring and evaluation of 12 kinds of N-nitrosamines in cosmetics.
Keywords：N-nitrosamine；high performance liquid chromatography-triple quadrupole mass spectrometry；cosmetics
棉簽固相微萃取結合高效液相色譜-串聯質譜法檢測蜂蜜中9種大環內酯類抗生素
宮小明，李凱*，許文娟，王洪濤，劉孟孝，孔彩霞
（濰坊海關綜合技術服務中心，濰坊 261041）
摘要：通過“dip-coating”法制備了一種表面覆蓋聚丙烯腈（PAN）/親水-疏水平衡顆粒（HLB）涂層的棉簽固相微萃取（SPME）。該棉簽SPME制作方法簡便、成本低廉（1元/支）、可重復使用，并可實現樣品前處理的半自動化。通過優化PAN和HLB的組成比例，使棉簽SPME對9種大環內酯類抗生素標準品的吸附率達到80%以上，解吸率達到99%以上。使用棉簽SPME結合高效液相色譜-串聯質譜法（HPLC-MS/MS），同時檢測蜂蜜中9種大環內酯類抗生素（MACs）。9種MACs在1~20 μg/L濃度范圍內呈良好線性關系，線性相關系數（R2）均大于0.9978。9種MACs在1，5，10 μg/kg 3個標準添加濃度下的平均回收率為71.8%~86.4%，相對標準偏差（RSD）為2.2%~5.3%，檢出限（LOD）為0.24~1.35 μg/kg，定量限（LOQ）為1.02~4.62 μg/kg。
關鍵詞：大環內酯類抗生素；固相微萃取；蜂蜜；高效液相色譜-串聯質譜
中圖分類號：O657.31；X832 文獻標識碼：A 文章編號：1000-0720（2024）04-0535-06
Quantification of macrolide antibiotics in honey by using cotton swab based solid-phase microextraction combined with high performance liquid chromatography-tandem mass spectrometry
GONG Xiaoming，LI Kai*，XU Wenjuan，WANG Hongtao，LIU Mengxiao，KONG Caixia
Comprehensive Technical Service Center of Weifang Customs，Weifang 261041，China）
Abstract：A cotton swab based solid-phase microextraction （SPME） covered with polyacrylonitrile （PAN）/hydrophilic-hydrophobic balance （HLB） particles，which is simple，inexpensive，reusable，and semi-automated for sample pretreatment，was prepared by the dip-coating method. By optimizing the composition ratio of PAN to HLB，the adsorption rate of swab SPME for nine macrolide antibiotic standards reached more than 80% and the desorption rates were more than 99%. Detection of 9 macrolide antibiotics （MACs） in honey was performed using this SPME in combination with HPLC-MS/MS. The nine MACs showed good linearity in the concentration range of 1-20 μg/L，with linear correlation coefficients （R2） greater than 0.9978. The average recoveries of the nine MACs at three spiked standard concentrations of 1，5 and 10 μg/kg ranged from 71.8% to 86.4%，with the relative standard deviations （RSDs） of 2.2%-5.3%. The limits of detection （LODs） were 0.24-1.35 μg/kg and the limits of quantification （LOQs） were 1.02-4.62 μg/kg.
Keywords：macrolide antibiotics；solid-phase microextraction；honey；high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）
基于熒光共軛聚合物和氧化石墨烯的核酸外切酶I檢測
程昆淇1，高夢瑩1，邢佳貝1，趙一帆1，盧宏飛1，劉學國*2，邢小靜*1
（1. 南陽師范學院化學與制藥工程學院，南陽 473061；2. 南陽理工學院生物與化學工程學院，南陽 473004）
摘要：核酸外切酶I（Exo I）作為一種重要的核酶參與了許多生物學過程，具有維持遺傳信息穩定性的功能，因此建立有效檢測Exo I活性的方法具有重要的研究價值。基于聚芴類熒光共軛聚合物-poly［（9，9-bis（6′-N，N，N-trimethyl-ammonium）hexyl）-fluorenylene phenylene dibromide］（PFP）不能與吸附在氧化石墨烯（GO）表面的單鏈DNA結合的實驗發現，借助GO對單鏈DNA和雙鏈DNA作用力強度大小的差異，構建了一個背景信號低、靈敏度高的Exo I檢測新方法。GO和PFP的最適濃度分別為2.5和7.2 mg/L。在最佳條件下，Exo I 濃度在0.5~4.0 U/mL范圍內與體系的熒光強度呈良好的線性關系，線性方程為F=-0.11c+0.861，檢出限為0.16 U/mL。該方法可用于血清模擬樣品中Exo I活性的檢測，加標回收率為103.6%~106.0%。
關鍵詞：熒光共軛聚合物；氧化石墨烯；DNA；低背景；核酸外切酶I
中圖分類號：O657.3 文獻標識碼：A 文章編號：1000-0720（2024）04-0541-06
Detecting exonuclease I based on fluorescent conjugated polymers and graphene oxide
CHENG Kunqi1，GAO Mengying1，XING Jiabei1，ZHAO Yifan1，LU Hongfei1，LIU Xueguo*2，XING Xiaojing*1
1. College of Chemistry and Pharmaceutical Engineering，Nanyang Normal University，Nanyang 473061，China；2. Department of Biology and Chemical Engineering，Nanyang Institute of Technology，Nanyang 473004，China）
Abstract：As an important ribozyme，exonuclease I （Exo I） engages in a series of biological processes and has the capability to keep stability of genetic information. Therefore，it has great research value to establish an effective method to detect the Exo I activity. According to the finding that the polyfluorene-based fluorescent conjugated polymers-poly［（9，9-bis（6′-N，N，N-trimethyl-ammonium）hexyl）-fluorenylene phenylene dibromide］（PFP） couldn't interact with single-stranded DNA adsorbed on graphene oxide （GO） surface，a novel method with low background and high sensitivity for sensing Exo I was constructed by utilizing the difference in the interaction force of GO on single stranded DNA and double stranded DNA. The results showed the optimal concentrations of GO and PFP were 2.5 and 7.2 mg/L，respectively. Under the optimum conditions，the fluorescence intensity at 525 nm exhibited a good linearity with Exo I concentration in the range of 0.5-4.0 U/mL，where the linear equation was F=-0.11c+0.861，and the detection limit was 0.16 U/mL. The method was successfully used for the detection of Exo I in serum with recoveries of 103.6%-106.0%.
Keywords：fluorescent conjugated polymers；graphene oxide；DNA；low background；exonuclease I
QuEChERS-超高效液相色譜-串聯質譜法測定牧草中氟喹諾酮類藥物殘留
謝敏1，徐俊*1，2，費丹1，侯玉潔3，劉昌林3，俞莉3，周瑤敏1，于翔4，王夢芝*4
（1. 江西省農業科學院農產品質量安全與標準研究所，江西省農產品質量安全重點實驗室，南昌 330200；2. 江西省農業科學院畜牧獸醫研究所，南昌 330200；3. 南昌市農業科學院，南昌 330200；4. 揚州大學動物科學與技術學院，揚州 225009）
摘要：建立了QuEchERS-超高效液相色譜-串聯質譜（UPLC-MS/MS）檢測牧草中7種氟喹諾酮類藥物殘留的方法。樣品采用0.1 mol/L Na2EDTA-Mcllvaine 緩沖液和1%乙酸-乙腈提取，經QuEchERS凈化后Agilent ZORBAX Eclipse Plus C18色譜柱分離，正離子模式掃描，多反應監測模式，內標法定量。7種氟喹諾酮類藥物在0.5~50 μg/L范圍內線性相關系數（R2）均大于0.9955，方法檢出限為0.05~0.2 μg/kg，定量限為0.1~0.5 μg/kg。平均添加回收率為79.0%~115.4%，相對標準偏差為0.20%~8.5%。該方法適用于牧草中氟喹諾酮類藥物檢測分析，可為牧草中氟喹諾酮類藥物殘留風險評估、質量安全監管、牧草品質評價等提供技術支撐。
關鍵詞：牧草；QuEchERS；超高效液相色譜串聯質譜；氟喹諾酮；殘留
中圖分類號：S859.84；O657.6 文獻標識碼：A 文章編號：1000-0720（2024）04-0547-06
Simultaneous determination of quinolones in forage grass by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry
XIE Min1，XU Jun*1，2，FEI Dan1，HOU Yujie3，LIU Changlin3，YU Li3，ZHOU Yaomin1，YU Xiang4，WANG Mengzhi*4（1. Institute of Quality Safety and Standards of Agricultural Products，Jiangxi Academy of Agricultural Sciences，Key Laboratory of Agro-product Quality and Safety of Jiangxi Province，Nanchang 330200，China；2. Animal Husbandry and Veterinary Science of Jiangxi Academy of Agricultural Sciences，Nanchang 330200，China；3. Institute of Nanchang Agricultural Sciences Academy of Agricultural Sciences，Nanchang 330200，China；4. College of Animal Science and Technology，Yangzhou University，Yangzhou 225009，China）
Abstract：A QuEChERS-ultra-high performance liquid chromatography tandem mass spectrometry （UPLC-MS/MS） method for the simultaneous determination of 7 kinds of fluorchinolones in forage grass was developed. Forage grass sample was extracted with 0.1 mol/L Na2EDTA-Mcllvaine buffer and 1% acid-acetonitrile solution，and purified by QuEChERS. Then the target compounds were separated by Agilent ZORBAX Eclipse Plus C18 column，analyzed by electrospray ionization in positive ion scanning under multiple reaction monitoring mode，and quantified with internal standard method. The 7 kinds of fluorchinolones displayed good linearity in the range of 0.5-50 μg/L，and the correlation coefficients （R2） were above 0.9955. The limits of detection were 0.05-0.2 μg/kg，and the limits of quantification were 0.1-0.5 μg/kg. In addition，the recoveries were 79.0%-115.4%，and the relative standard deviations （RSDs） were between 0.2% and 8.5%. The method is suitable for the simultaneous analysis of 7 kinds of fluorchinolones in forage grass，which can provide a scientific basis for fluorchinolones residues risk assessment，quality and safety supervision，and forage grass quality evaluation.
Keywords：forage grass；ultra-high performance liquid chromatography tandem mass spectrometry；QuEchERS；fluorchinolone；residuals
基于酞菁敏化CuCo2O4的光電化學傳感器選擇性檢測L-半胱氨酸
岑亞來，諸葛文鳳*，彭金云，黃青，何詩詩
（廣西民族師范學院化學與生物工程學院，崇左 532200）
摘要：通過水熱法制備了具有3D形貌的CuCo2O4微米花，基于酞菁（Pc）敏化CuCo2O4修飾氧化銦錫（ITO）玻璃電極（Pc/CuCo2O4/ITO），建立了一種L-半胱氨酸（L-Cys）光電化學傳感器。研究表明，Pc/CuCo2O4復合材料具有良好的光電化學活性，其光電流是純CuCo2O4的15倍、Pc的18倍。以紅光作為激發源，在偏置電壓-0.05 V，電解液pH 4.0條件下，在0.25~15.0 μmol/L范圍內，光電流與L-Cys濃度呈線性相關，檢出限為0.0296 μmol/L。在其他氨基酸、制劑輔料和常見無機離子存在下，Pc/CuCo2O4/ITO檢測L-Cys具有良好的專屬性。該傳感器已成功用于L-半胱氨酸膠囊的含量測定。
關鍵詞：光電化學傳感；Pc/CuCo2O4；L-半胱氨酸
中圖分類號：O657.1 文獻標識碼：A 文章編號：1000-0720（2024）04-0553-06
A photoelectrochemical sensor based on phthalocyanine sensitized CuCo2O4 for selective detection of L-Cysteine
CEN Yalai，ZHUGE Wenfeng*，PENG Jinyun，HUANG Qing，HE Shishi
College of Chemical and Biological Engineering，Guangxi Minzu Normal University，Chongzuo 532200，China）
Abstract：CuCo2O4 micron flowers were synthesized via hydrothermal method. An effective photoelectrochemical （PEC） sensor was established for detection of L-Cysteine （L-Cys） based on indium tin oxide （ITO） glass electrode （Pc/CuCo2O4/ITO） modified by phthalocyanine （Pc）-sensitized CuCo2O4. The result has shown that Pc/CuCo2O4 composite material exhibited admirable photoelectrochemical activity，its photocurrent was 15-fold and 18-fold those of pure CuCo2O4 micron flowers or Pc，respectively. Using red light as the excitation source，under the conditions of external bias potential of -0.05 V，the pH value of electrolyte solution at pH 4.0，the photocurrent was linearly correlated with L-Cys concentration in the range of 0.25-15.0 μmol/L，and the detection limit was 0.0296 μmol/L. The proposed sensor exhibited good selectivity for L-Cys in the presence of other amino acids，medical excipient and common inorganic ions. This PEC sensor has been successfully used for the content determination of L-Cys capsules.
Keywords：photoelectrochemmical sensor；Pc/CuCo2O4；L-cysteine
CRISPR/Cas12a聯合催化發夾自組裝的miRNA21檢測
李甜*，鄒紅敏，陳菲，游蕓，張莉萍
（河南科技大學基礎醫學與法醫學院，洛陽 471023）
摘要：構建了一種基于CRISPR/Cas12a和催化發夾自組裝（CHA）的miRNA21檢測方法。目標物miRNA21可引發CHA，產生大量的雙鏈DNA復合物。作為Cas12a的底物，雙鏈DNA復合物包含原型間隔序列毗鄰基序（5′-TTTN-3′），可激發Cas12a的附屬切割活性，剪切一端帶有熒光基團、另一端帶有猝滅基團的單鏈DNA熒光報告探針，產生可檢測的熒光信號。考察了CHA反應溫度、發夾探針濃度、熒光報告探針濃度和Cas12a切割時間的影響。在優化條件下，熒光信號與miRNA21濃度的對數呈良好的線性關系，線性相關系數R2=0.9924，檢出限為1.1 pmol/L。利用本方法對miRNA21加標的胎牛血清樣品進行分析，20 pmol/L和100 pmol/L miRNA21的回收率分別為（92.0±4.2）%和（94.1±4.7）%。CRISPR/Cas12a聯合催化發夾自組裝的miRNA檢測方法，使miRNA檢測擺脫了熱循環儀器，操作簡單，通用性強，具有實際應用潛力。
關鍵詞：催化發夾自組裝；CRISPR/Cas12a；miRNA21；熒光
中圖分類號：O661.1 文獻標識碼：A 文章編號：1000-0720（2024）04-0559-05
Detection for MiRNA21 by combining CRISPR/Cas12a with catalytic hairpin assembly
LI Tian*，ZOU Hongmin ，CHEN Fei，YOU Yun，ZHANG Liping
College of Basic Medicine and Forensic Medicine，Henan University of Science and Technology，Luoyang 471023，China）
Abstract：A detection strategy for miRNA21 based on CRISPR/Cas12a and catalytic hairpin self-assembly （CHA） was constructed. The target miRNA21 could trigger CHA and produce a large number of double-stranded DNA complexes. As the substrate of Cas12a，the double-stranded DNA complex contained a prototype spacer sequence adjacent to the motif （5'-TTTN-3'），which could stimulate the accessory cleavage activity of Cas12a. It cleaved a single-stranded DNA fluorescence reporter with a fluorescent group at one end and a quenching group at the other end，thereby leading to the generation of appreciable fluorescence signals. The effects of reaction temperature for CHA，hairpin concentration，fluorescent reporter concentration and Cas12a cleavage time were investigated. Under the optimized conditions，the fluorescence signal and the logarithm of miRNA21 concentration showed a good linear relationship，along with the correlation coefficient （R2） of 0.9924 and the detection limit of 1.1 pmol/L. The spiked recoveries of miRNA21 in fetal bovine serum were （92.0±4.2）% and （94.1±4.7）% for 20 pmol/L and 100 pmol/L of miRNA21，respectively. This strategy constructed by combining CRISPR/Cas12a and CHA，made miRNA detection simple，universal and nonuse of thermal cycling instruments，showing great potential for practical application.
Keywords：catalytic hairpin assembly；CRISPR/Cas12a；miRNA21；fluorescence
氮自摻雜碳量子點的合成及其在細胞成像中的應用
瞿金為1，楊淑瓊1，陳盛余2，胡月芳*1
（1. 賀州學院，廣西碳酸鈣資源綜合利用重點實驗室，材料與化學工程學院，賀州 542899；2. 百色學院，桂西區域生態環境分析與污染控制重點實驗室，化學與環境工程學院，百色 533000）
摘要：以特色農產品廢棄物馬蹄皮為原料，通過水熱法合成了氮摻雜碳量子點（N-CQDs），對溫度及反應時間等合成條件進行了優化。在最佳合成條件下，得到量子產率為22%的N-CQDs，對其結構、形貌、組成、熒光及電化學性能進行分析。實驗結果表明，N-CQDs穩定性良好，表現出更優異的熒光性能和電化學性能，且具有良好的生物相容性和細胞膜穿透性，可用于細胞內多色細胞成像。本研究為促進N-CQDs的綠色合成及其在生物醫學領域的應用提供了新的思路。
關鍵詞：氮自摻雜碳量子點；水熱法；光學性能；電化學性能；細胞成像
中圖分類號：O657.1 文獻標識碼：A 文章編號：1000-0720（2024）04-0564-08
Synthesis of nitrogen self-doped carbon quantum dots and their application in cell imaging
QU Jinwei1，YANG Shuqiong1，CHEN Shengyu2，HU Yuefang*1
1. Guangxi Key Laboratory of Calcium Carbonate Resources Comprehensive Utilization，College of Materials and Chemical Engineering，Hezhou University，Hezhou 542899，China；2. Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi，College Chemistry and Environment Engineering，Baise University，Baise 533000，China）
Abstract：Nitrogen-doped carbon quantum dots （N-CQDs） were synthesized by hydrothermal method using horseshoe skin as raw material. The synthesis conditions of temperature and reaction time were optimized. N-CQDs with a quantum yield of 22% were obtained under the optimal synthesis conditions. The structure，morphology，composition，fluorescence and electrochemical properties of the synthesized N-CQDs were analyzed. The experimental results showed that N-CQDs were stable and exhibited better fluorescence and electrochemical properties，and had good biocompatibility and cell membrane penetration，which could be used for intracellular multicolor cell imaging. This study provides a new way to promote the green synthesis and application of N-CQDs in the biomedical field.
Keywords：nitrogen-doped carbon quantum dots；hydrothermal synthesis method；optical performance；electrochemical properties；cell imaging
一種咪唑-香豆素類熒光探針的合成及其對Cu2+的選擇性識別
胡浩1，尹紀臣2，姚葉林1，鄧林龍1，薛蕾1，王海濱*1
（1. 寧夏師范學院化學化工學院，固原 756000；2. 康龍化成（北京）新藥技術股份有限公司，北京 102600）
摘要：以7-（二乙氨基）香豆素-3-甲醛和苯偶酰為原料，合成了一種咪唑-香豆素類熒光探針7-（二乙基氨基）-3-（4，5-二苯基-1H-咪唑-2-基）苯并吡喃-2酮（L），并表征了其結構。該探針在乙腈溶液中對Cu2+表現出高選擇性識別，并具有較強的抗干擾能力。在Cu2+濃度7.5~29.5 μmol/L范圍內，探針L在508 nm處的熒光強度與Cu2+濃度呈良好的線性關系，線性相關系數R2=0.9955。探針L與Cu2+的結合比是2∶1，結合常數為1.02×102 （L/mol）1/2。探針L對Cu2+的檢出限為0.082 μmol/L。該探針可被制成試紙用于檢測Cu2+。
關鍵詞：熒光探針；識別；Cu2+；香豆素；咪唑
中圖分類號：O657.31 文獻標識碼：A 文章編號：1000-0720（2024）04-0572-06
Synthesis of an imidazole coumarin based fluorescent probe and its selective recognition for Cu2+
HU Hao1，YIN Jichen2，YAO Yelin1，DENG Linlong1，XUE Lei1，WANG Haibin*1
1. College of Chemistry and Chemical Engineering，Ningxia Normal University，Guyuan 756000，China；2. Pharmaron Beijing Co.，Ltd.，Beijing 102600，China）
Abstract：An imidazole coumarin based fluorescent probe named 7-（diethylamino）-3-（4，5-diphenyl-1H-imidazol-2-yl）chromen-2-one （L） was synthesized using dibenzoyl and 7-diethylaminocoumarine-3-aldehyde as raw materials，and the structure of L was characterized. The probe L demonstrated high selectivity and strong anti-interference ability towards Cu2+ recognition in acetonitrile solution. The fluorescence intensity of probe L at 508 nm showed a linear relationship with Cu2+ concentration in the range of 7.5-29.5 μmol/L，with the correlation coefficient （R2） of 0.9955. The binding ratio of probe L toward Cu2+ was 2∶1，and the binding constant was 1.02×102 （L/mol）1/2. The limit of detection of probe L toward Cu2+was 0.082 μmol/L. The probe can be made to test papers for detecting Cu2+.
Keywords：fluorescent probe；recognizition；Cu2+；coumarin；imidazole
高效液相色譜法同時檢測化妝品中視黃醇及其衍生物
楊淡梅1，2，付寒1，王鵬1，劉兆賓2，鄔曉鷗2，邱穎姮*2
（1. 深圳市慢性病防治中心深圳市皮膚病防治研究所，深圳 518020；2. 深圳市藥品檢驗研究院，國家藥品監督管理局化妝品監測評價重點實驗室，深圳 518057）
摘要：建立了檢測化妝品中視黃醇及其衍生物等16種組分含量的高效液相色譜分析方法。分離檢測16種同類物質及同分異構體的優化條件為：采用Kromasil 100-5-C18色譜柱（250 mm×4.6 mm，5 μm）分離，以甲醇為流動相A，四氫呋喃為流動相B，10 mmol/L磷酸二氫鈉溶液為流動相C，梯度洗脫，流速為1.0 mL/min，柱溫為25 ℃。使用二極管陣列檢測器，標準曲線法定量。16種組分的線性相關系數均大于0.999，在3個添加水平下，16種組分的平均回收率為91.2%~107.8%，相對標準偏差為0.5%~4.0%。該方法可以為化妝品質量監督提供有效的技術支持。
關鍵詞：視黃醇及其衍生物；化妝品；高效液相色譜法
中圖分類號：O657.72；TQ047.2 文獻標識碼：A 文章編號：1000-0720（2024）04-0578-05
Simultaneous determination of retinol and its derivatives by high performance liquid chromatography
YANG Danmei1，2，FU Han1，WANG Peng1，LIU Zhaobin2，WU Xiaoou2，QIU Yingheng*2
1. Shenzhen Center for Chronic Disease Control，Shenzhen Institute of Dermatology，Shenzhen 518020，China；2. Shenzhen Institute for Drug Control，NMPA Key Laboratory for Monitoring and Evaluationof Cosmetics，Shenzhen 518057，China）
Abstract：A high performance liquid chromatography （HPLC） method for the determination of 16 components including retinol and its derivatives in cosmetics was established. The optimized conditions for the separation and detection of the 16 components were as follows：separated by a Kromasil 100-5-C18 column （250 mm×4.6 mm，5 μm），and gradient elution with methanol as mobile phase A，tetrahydrofuran as mobile phase B and 10 mmol/L sodium dihydrogen phosphate solution as mobile phase C，with a flow rate of 1.0 mL/min and the column temperature of 25 ℃. The analysis was completed using photo-diode array detector and quantified by standard curve method. The results showed that the linear correlation coefficients of the 16 components were greater than 0.999，the average recoveries were 91.2%-107.8%，and the relative standard deviations were 0.5%-4.0% at three spiked levels. This method can provide effective technical support for cosmetics quality supervision.
Keywords：retinol and its derivatives；cosmetics；high performance liquid chromatography
新型碳材料用于固相萃取環境和食品中鄰苯二甲酸酯的研究進展
陳昊翔1，2，周遠浩1，2，李順瀅1，2，王丹青1，2，石勝鵬3，葉宏*1，2
（1. 北京食品質量與安全實驗室，北京工商大學輕工科學技術學院，北京 100048；2. 中國輕工業釀酒分子工程重點實驗室，北京工商大學輕工科學技術學院，北京 100048；3. 中國石油化工股份有限公司北京化工研究院，北京100013）
摘要：鄰苯二甲酸酯類物質（PAEs）是一類對人體健康危害嚴重的內分泌干擾物，當前在食品和環境中的污染問題十分突出。固相萃取技術廣泛應用于針對PAEs的樣品前處理過程，其分離富集的關鍵在于固相萃取材料。隨著各種吸附材料制備技術快速發展，基于新型碳材料的固相萃取技術應用日益廣泛。本文對近年來新型碳材料用于固相萃取環境和食品中PAEs的應用進行了總結分析，綜述了碳納米管、石墨烯等新型碳材料作為固相萃取材料在PAEs分析檢測應用中的最新進展，為該領域固相萃取材料的開發、改性和應用提供了新的研究思路和方向。
關鍵詞：鄰苯二甲酸酯；碳材料；固相萃取
中圖分類號：O652.6；TQ414.1 文獻標識碼：A 文章編號：1000-0720（2024）04-0583-12
Research progress of novel carbon materials for solid phase extraction of phthalate esters in environment and food
CHEN Haoxiang1，2，ZHOU Yuanhao1，2，LI Shunying1，2，WANG Danqing1，2，SHI Shengpeng3，YE Hong*1，2
1. Beijing Laboratory of Food Quality and Safety，College of Light Industry Science and Technology，Beijing Technology and Business University，Beijing 100048，China；2. Key Laboratory of Brewing Molecular Engineering of China Light Industry，College of Light Industry Science and Technology，Beijing Technology and Business University，Beijing 100048，China；3. SINOPEC Beijing Research Institute of Chemical Industry，Beijing 100013，China）
Abstract：Phthalate esters （PAEs） are a kind of endocrine disruptors that are seriously harmful to human health，and the pollution problem in food and environment is very prominent. Solid phase extraction （SPE） technology is widely used in the sample pre-treatment process of PAEs，and the key to its separation and enrichment lies in the SPE materials. With the rapid development of various adsorption material preparation technologies，SPE technologies based on new carbon materials are increasingly widely used. In this paper，the applications of new carbon materials in SPE of PAEs in environment and food in recent years were summarized，and the latest progress of carbon nanotubes，graphene and other new carbon materials as SPE materials in PAEs detection were reviewed，providing the new research idea and direction for the development，modification and application of SPE materials in this field.
Keywords：phthalate esters；carbon materials；solid phase extraction
基于文獻計量的抗生素適配體傳感技術研究進展與熱點分析
梁剛1，2，高羽菲3，甄建輝4，鞏文雯*1，2，陳瑞春4，李再興3，潘立剛1，2
（1. 北京市農林科學院質量標準與檢測技術研究所，北京 100097；2. 農業部農產品質量安全風險評估實驗室（北京），北京 100097；3. 河北科技大學環境科學與工程學院，石家莊 050024；4. 石家莊海關技術中心，石家莊 050001）
摘要：適配體是經體外篩選得到的短鏈寡核苷酸序列，能與靶標進行高親和力和強特異性結合，以適配體為識別元件的生物傳感器被廣泛用于小分子傳感檢測研究。近年來，抗生素作為一類新興污染物，其在環境和食品中的出現引起了人們的廣泛關注。本文采用文獻計量分析可視化工具VOSviewer，以Web of Science（WoS）核心數據庫的文獻資料為數據源，對抗生素適配體領域研究的發展過程、主要研究力量、研究熱點及前沿等進行了分析。結果表明，抗生素適配體的研究發文數量不斷增長，尤其是近10年呈快速增長態勢；中國的累計論文發表數量最多，為378篇，占全球總發文量的57.62%，在國際合作網絡中占據重要地位，而韓國、美國等國家的發文質量更高。關鍵詞共現分析表明，抗生素適配體研究熱點主要體現在“抗生素適配體篩選及性能表征”、“適配體傳感器的構建及抗生素檢測研究”以及“納米材料在適配體傳感檢測抗生素中的應用”等3個方面。本研究提出了抗生素適配體領域未來發展方向和研究重點，有助于推進適配體生物傳感技術的產業化發展。
關鍵詞：抗生素；適配體；文獻計量；研究進展；研究熱點
中圖分類號：O6-04；O652.7 文獻標識碼：A 文章編號：1000-0720（2024）04-0595-14
Progress and hotspots analysis of antibioticaptamer-based sensing technology：A bibliometric analysis
LIANG Gang1，2，GAO Yufei3，ZHEN Jianhui4，GONG Wenwen*1，2，CHEN Ruichun4，LI Zaixing3，PAN Ligang1，2
1. Institute of Quality Standard and Testing Technology，Beijing Academy of Agriculture and Forestry Sciences，Beijing 100097，China；2. Risk Assessment Lab for Agro-products （Beijing），Beijing 100097，China；3. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050024，China；4. Shijiazhuang Customs Technology Center，China，Shijiazhuang 050001，China）
Abstract：Aptamers are short-chain oligonucleotide sequences screened in vitro，which can bind to the target with high affinity and strong specificity. They have been widely used as molecular recognition elements within biosensors for the detection of small molecules. In recent years，the emergence of antibiotics as a kind of new pollutants in environment and food has attracted extensive attentions. Accordingly，the development process，main researchers，research hotspots and frontiers in the field of antibiotic aptamers were analyzed by using the bibliometric analysis visualization tool VOSviewer with the Web of Science （WoS） Core Collection data as the data source. The results showed that the number of publications on antibiotic aptamers is increasing，especially in recent ten years. China has the largest cumulative number of publications （378 papers，accounting for 57.62% of the total number of published papers in the world），occupying an important position in the international cooperation network，while the United States and South Korea published higher quality papers. Keyword co-occurrence analysis showed that the research hotspots of antibiotic aptamers were mainly in three aspects："screening and characterization of antibiotic aptamers"，"construction of aptamer sensors and detection of antibiotic"，and "application of nanomaterials in antibiotics aptamer sensors". This study puts forward the future development direction and research focus in the field of antibiotic aptamers，which is helpful to promote the industrial development of aptamer biosensing technology.
Keywords：antibiotics；aptamer；bibliometric；research progress；research hotspots
