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基于碳點的“開-關-開”型熒光探針測定蔬菜中的谷胱甘肽

韓雍^*，汪慧，杜雪蓉

（隴東學院農林科技學院，慶陽 745000）

摘要：以鄰苯二胺、檸檬酸、乙醇為前體物質，采用自下而上的一步水熱法，制備了一種藍色熒光碳點（BCDs），以此構建熒光探針，用于檢測蔬菜中的谷胱甘肽（GSH）。結果表明，在碳點（CDs）中加入Cu²⁺后可使BCDs熒光猝滅；在該猝滅體系中加入GSH后會使BCDs-Cu²⁺體系的熒光恢復。由此建立了一種“開-關-開”型檢測GSH的新方法。在激發波長390 nm下，BCDs發射峰位于445 nm處，可以實現對GSH的檢測，方法線性范圍是0~80 μmol/L，檢出限（LOD）為0.0368 μmol/L。該方法用于實際樣品蔬菜中GSH的測定，回收率為89.6%~104.3%，相對標準偏差（RSDs）為1.2%~5.2%。

關鍵詞：碳點；快速熒光檢測；谷胱甘肽

中圖分類號：O657.3；O661.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0609-06

“On-off-on” fluorescent probe based on carbon dots for the detection of glutathione in vegetables

HAN Yong^*，WANG Hui，DU Xuerong

College of Agriculture and Forestry，Longdong University，Qingyang 745000，China）

Abstract：In this work，o-phenylenediamine，citric acid and ethanol were used as precursors to prepare blue-emissive fluorescent carbon dots（BCDs） through a bottom-up hydrothermal one-step method. Then，BCDs were employed as a fluorescent probe for rapid detection of Cu²⁺ and glutathione （GSH） in vegetables. The results showed that the fluorescence of BCDs could be quenched by copper ion，and the quenched fluorescence of BCDs-Cu²⁺ can be recovered by GSH. Based on this principle，an 'on-off-on' method for detection of GSH was established. The emission peak of BCDs-Cu²⁺ located at 445 nm under excitation wavelength of 390 nm. The linear range of the method was 0-80 μmol/L and limit of detection （LOD） was 0.0368 μmol/L. The recoveries of GSH in the actual vegetable samples were 89.6%-104.3%，with the relative standard deviations （RSDs） of 1.2%-5.2%.

Keywords：carbon dots；rapid fluorescence detection；glutathione

基于酶輔助的比率型電化學適配體傳感器用于前列腺特異性抗原檢測

關志敏，謝瑤瑤，馬會凱，王萍^*

（河南科技大學基礎醫學與法醫學院，洛陽 471000）

摘要：基于核酸外切酶III（Exo Ⅲ）輔助靶標循環策略，構建了比率型電化學適配體傳感器，并用于前列腺特異性抗原（PSA）的檢測。利用亞甲基藍（MB）作為內置參考信號，當PSA存在時，發夾探針1（HP1）的適配體序列與PSA特異性結合，引起Exo Ⅲ的2次切割過程，從而實現2次循環擴增反應，導致電極上更多的MB標記的發夾探針3（MB-HP3）被切割；再加入二茂鐵（Fc）標記的DNA鏈（Fc-DNA）與MB-HP3酶切后的片段進行雜交；最終，Fc的信號（I_Fc）增加，而MB的信號（I_MB）基本保持不變。在最佳條件下，I_Fc/I_MB與PSA濃度的對數值在0.001~100 ng/mL范圍內呈良好的線性關系，檢出限為0.24 pg/mL。該傳感器在臨床實際樣品檢測中具有較好的應用前景。

關鍵詞：前列腺特異性抗原；核酸外切酶III；比率型電化學適配體傳感器

中圖分類號：O657.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0615-06

An enzyme-assisted ratiometric electrochemical aptasensor for the detection of prostate specific antigen

GUAN Zhimin，XIE Yaoyao，MA Huikai，WANG Ping^*

College of Basic Medicine and Forensic Medicine，Henan University of Science and Technology，Luoyang 471000，China）

Abstract：A ratiometric electrochemical aptasensor based on exonuclease III（Exo III）-assisted target recycling strategy was developed for the detection of prostate specific antigen（PSA）. Methylene blue（MB）was used as a built-in reference signal.In the presence of PSA，the specific binding between the aptamer region of hairpin probe1（HP1） and PSA could trigger two cleavage processes of Exo Ⅲ，thus achieving two cyclic amplification reactions，accompanying by more MB-labeled hairpin probe 3 （MB-HP3） on the electrode to be digested. The addition of ferrocene （Fc）-labeled DNA （Fc-DNA） was hybridized with the digested fragment of MB-HP3，resulting in an enhancement of Fc signal （I_Fc），while the signal of MB （I_MB） remained basically unchanged. Under the optimal conditions，a linear relationship was obtained between the I_Fc/I_MB value and the logarithm value of PSA concentration in the range from 0.001 to 100 ng/mL，and the detection limit was 0.24 pg/mL. The sensor has a good application prospect in determination of PSA in clinical samples.

Keywords：prostate specific antigen；exonuclease III；ratiometric electrochemical aptasensor

基于脈沖加熱-紅外吸收/熱導法測定燒結氮化硅陶瓷材料中晶格氧含量

王群¹，段于森²，錢榮^*1，卓尚軍^*1，朱月琴¹

（1. 中國科學院上海硅酸鹽研究所無機材料分析測試中心，上海 200050；2. 中國科學院上海硅酸鹽研究所高性能陶瓷和超微結構國家重點實驗室，上海 200050）

摘要：基于脈沖加熱-紅外吸收/熱導法，比較分析了恒定式、斜線式及階梯式3種功率控制升溫模式在燒結氮化硅陶瓷材料氧氮含量測定中的特點。優化后選擇階梯式功率控制升溫模式并設置合理的分析參數，獲得了分離良好的氧氮分量峰。結合在脈沖加熱熔融樣品過程中特定點位取樣的X射線衍射物相分析，確定了燒結氮化硅材料的晶格氧分量峰位置及含量。測試得出Yb₂O₃做助劑的燒結氮化硅陶瓷晶格氧含量為0.094%，相對標準偏差為1.6%，與此材料的熱導率水平（88.61 W/m·K）相符合。本方法適用于多種非氧化物陶瓷材料中晶格氧含量的測定。

關鍵詞：脈沖加熱-紅外吸收/熱導法；燒結氮化硅陶瓷；晶格氧；熱導率

中圖分類號：O657.33    文獻標識碼：A    文章編號：1000-0720（2024）05-0621-06

Determination of lattice oxygen content in sintered silicon nitride ceramics by pulse heating-infrared absorption and thermal conductivity method

WANG Qun¹，DUAN Yusen²，QIAN Rong^*1，ZHUO Shangjun^*1，ZHU Yueqin¹

1. Analysis and Testing Center for Inorganic Material，Shanghai Institute of Ceramics，Chinese Academy of Sciences，Shanghai 200050，China；2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure，Shanghai Institute of Ceramics，Chinese Academy of Sciences，Shanghai 200050，China）

Abstract：Based on the pulse heating-infrared absorption and thermal conductivity method，the characteristics of three power-controlled heating modes （constant，oblique and stepped） in the determination of oxygen and nitrogen contents in sintered silicon nitride ceramic materials were compared and analyzed. After optimization，the stepwise power control heating mode was selected and reasonable analysis parameters were set，and the oxygen and nitrogen component peaks with good separation were obtained. Furthermore，the position and content of lattice oxygen component peak of sintered silicon nitride material were determined by combining with X-ray diffraction phase analysis of some specific point samples during pulse heating and melting process. The results showed that the lattice oxygen content of sintered silicon nitride ceramics with Yb₂O₃ as additive was 0.094%，with the relative standard deviation of 1.6%，which was consistent with the thermal conductivity level of this material （88.61 W/m·K）. This method is applicable to the determination of lattice oxygen content in various non-oxide ceramic materials.

Keywords：pulse heating-infrared absorption and thermal conductivity method；sintered silicon nitride ceramics；lattice oxygen；thermal conductivity

SiO₂/MnFe₂O₄磁性固相萃取-HPLC測定水中喹諾酮類抗生素

魏霄¹，陳雨瑩¹，鐘佳祺¹，朱霞萍^*1，任維²，趙平²

（1. 成都理工大學材料與化學化工學院，成都 610059；2. 貴州省地質礦產勘查開發局一〇五地質大隊，貴陽 550018）

摘要：通過溶膠-凝膠法制備了SiO₂/MnFe₂O₄復合材料，使用X-射線衍射儀、全自動物理吸附儀、振動樣品磁強計、場發射掃描電鏡和X射線光電子能譜儀對其進行了表征。將其作為磁性固相萃取材料，建立了SiO₂/MnFe₂O₄磁性固相萃取-高效液相色譜法（MSPE-HPLC）測定水中氟羅沙星（FLE）、氧氟沙星（OFX）、諾氟沙星（NOR）、環丙沙星（CIP）和恩諾沙星（ENR）的新方法。磁性固相萃取的最佳條件為：SiO₂/MnFe₂O₄用量50 mg，萃取20 min后，用4 mL氨水/甲醇（12/88，V/V）混合液洗脫4 min。最佳條件下，SiO₂/MnFe₂O₄對FLE，OFX，NOR，CIP，ENR的富集倍數分別為57.3，62.5，53.2，49.8和51.5倍。MSPE-HPLC測定5種抗生素的線性范圍為0.004~1 mg/L，相對標準偏差（RSDs）為2.5%~5.3%，檢出限為0.0012~0.0023 mg/L。將建立的方法應用于稻田水和魚塘水中5種抗生素的測定，加標回收率介于78.8%~102.8%之間，RSDs為2.5%~5.3%。

關鍵詞：鐵酸錳；磁性固相萃取；喹諾酮類抗生素；地表水

中圖分類號：O661.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0627-06

Determination of quinolone antibiotics in water by SiO₂/MnFe₂O₄ magnetic solid phase extraction-high performance liquid chromatography

WEI Xiao¹，CHEN Yuying¹，ZHONG Jiaqi¹，ZHU Xiaping^*1，REN Wei²，ZHAO Ping²

1. College of Materials and Chemistry and Chemical Engineering，Chengdu University of Technology，Chengdu 610059，China；2. 105 Geological Brigade，Guizhou Bureau of Geology and Mineral Resources Exploration and Development，Guiyang 550018，China）

Abstract：SiO₂/MnFe₂O₄ composites were prepared by sol-gel method and characterized by X-ray diffraction，automatic physical adsorption，vibrating sample magnetometer，field emission scanning electron microscope and X-ray photoelectron spectroscopy. A method for the determination of fleroxacin （FLE），ofloxacin （OFX），norfloxacin （NOR），ciprofloxacin （CIP） and enrofloxacin （ENR） in water samples was established by SiO₂/MnFe₂O₄ magnetic solid phase extraction-high performance liquid chromatography （MSPE-HPLC）. The optimum conditions for magnetic solid phase extraction were as follows：the SiO₂/MnFe₂O₄ amount of 50 mg，the extraction time of 20 min，and the eluent time of 4 min with 4 mL of ammonia/methanol （12/88，V/V） mixture. Under the optimum conditions，the enrichment ratios of SiO₂/MnFe₂O₄ to FLE，OFX，NOR，CIP and ENR were 57.3，62.5，53.2，49.8 and 51.5 times，respectively. The linear ranges of MSPE-HPLC determination for five antibiotics were 0.004-1 mg/L，the relative standard deviations （RSDs） were 2.5%-5.3%，and the detection limits were 0.0012-0.0023 mg/L. The method was applied to the determination of five antibiotics in paddy field water and fish-pond water，showing the recoveries of spiked antibiotics ranged from 78.8% to 102.8%，and the RSDs were 2.5% to 5.3%.

Keywords：manganese ferrate；magnetic solid phase extraction；quinolone antibiotics；surface water

D-異抗壞血酸鈉熱解碳構建電化學傳感器檢測黃芩素和木犀草素

高儀¹，陳泇冰^1，2，劉耀鵬^1，2，儲婷婷^1，2，黃文勝¹，鄭寅^*1，2

（1. 湖北民族大學化學與環境工程學院，恩施 445000；2. 生物資源保護與湖北省重點實驗室，湖北民族大學，恩施 445000）

摘要：以廉價易得的D-異抗壞血酸鈉為前驅體，通過一步熱解法制備了具有三維互連多孔結構的熱解碳材料（SDAIPC），利用掃描電子顯微鏡（SEM）、透射電子顯微鏡（TEM）和X射線衍射（XRD）對材料的形貌和結構進行了表征。結果表明，制備的SDAIPC是一類具有高比表面積的碳材料。以SDAIPC為電極修飾材料，構建了用于同時檢測黃芩素（BA）和木犀草素（LU）的電化學傳感器。通過電化學交流阻抗譜（EIS）和循環伏安法（CV）研究了傳感器的電化學性能；采用微分脈沖伏安法（DPV）研究了BA和LU在不同電極上的電化學行為。在優化條件下，SDAIPC修飾電極對BA和LU進行單獨檢測時的線性范圍為0~8.0 μmol/L，檢出限（LOD）分別為1.39×10^-9 mol/L和3.02×10^-10 mol/L；對BA和LU進行同時檢測時的線性范圍為0.05~2.0 μmol/L，LOD分別為3.76×10^-9 mol/L和3.78×10^-10 mol/L。該電化學傳感器已成功用于BA和LU的實際樣品檢測。

關鍵詞：多孔碳材料；電化學傳感器；黃芩素；木犀草素

中圖分類號：O657.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0633-09

Electrochemical sensor constructed of sodium ascorbate pyrolysis carbon for the determination of baicalein and lignocaine

GAO Yi¹，CHEN Jiabing^1，2，LIU Yaopeng^1，2，CHU Tingting^1，2，HUANG Wensheng¹，ZHENG Yin^*1，2

1. College of Chemical and Environmental Engineering Hubei Minzu University，Enshi 445000，China；2. Hubei Provincial Key Labortory of Occurrence and Interervention of Rheumatic Diseases，Hubei Minzu University，Enshi 445000，China）

Abstract：Pyrolytic carbon materials with three-dimensional interconnected porous structures （SDAIPC） were prepared by one-step pyrolysis using inexpensive and readily available sodium D-isoascorbate as a precursor. The morphology and structure of the material were characterized using scanning electron microscopy （SEM），transmission electron microscopy （TEM） and X-ray diffraction （XRD）. The results showed that the prepared SDAIPC was a class of carbon materials with high specific surface area. An electrochemical sensor for the simultaneous detection of baicalein （BA） and lignocaine （LU） was constructed using SDAIPC as the electrode modification material.The electrochemical performance of the sensor was investigated by electrochemical impedance spectroscopy （EIS） and cyclic voltammetry （CV），and the electrochemical behavior of BA and LU at different electrodes was studied by differential pulse voltammetry （DPV）. Under the optimized conditions，the linear detection ranges of SDAIPC-modified electrode for BA and LU were 0-8.0 μmol/L，and the limits of detection （LODs） were 1.39×10^-9 mol/L and 3.02×10^-10 mol/L，respectively. The linear detection range for the simultaneous detection of BA and LU was 0.05-2.0 μmol/L，and the LODs were 3.76×10^-9 mol/L and 3.78×10^-10 mol/L，respectively. The electrochemical sensor could be used for the detection of BA and LU in real samples.

Keywords：porous carbon material；electrochemical sensor；baicalein；luteolin

N-羥基琥珀酰亞胺作為（pq）₂Ir（acac）共反應劑電致化學發光法檢測Hg²⁺

付云峰¹，任美娟¹，吳芳輝^*1，2，葉明富^1，3，殷國霞²，王晨¹

（1. 安徽工業大學化學與化工學院，馬鞍山 243000；2. 生物膜法水質凈化及利用技術教育部工程研究中心，安徽工業大學建筑工程學院，馬鞍山 243000；3. 信息材料及器件化應用四川省高校重點實驗室，成都信息工程大學，成都 610225）

摘要：制備了（pq）₂Ir（acac）（pq=2-苯基喹啉，acac=乙酰丙酮）并對其進行表征。采用N-羥基琥珀酰亞胺（NHS）作為中性混合溶劑中（pq）₂Ir（acac）的共反應劑，獲得強的電致化學發光（ECL）信號。向該體系中加入Hg²⁺后，因NHS與Hg²⁺的特異性螯合作用，阻斷了NHS與（pq）₂Ir（acac）之間的共反應，使得其ECL響應顯著降低，據此構建了靈敏檢測Hg²⁺的方法。優化條件下，（pq）₂Ir（acac）/NHS體系ECL強度變化的對數值與Hg²⁺濃度的自然對數值在0.1~90 μmol/L范圍內呈良好的線性關系，檢出限達33 nmol/L。（pq）₂Ir（acac）/NHS體系對Hg²⁺具有良好的選擇性和穩定性。該方法可用于測定實際水樣中Hg²⁺濃度。

關鍵詞：環金屬銥配合物；N-羥基琥珀酰亞胺；電致化學發光；汞離子；檢測

中圖分類號：O657.3；R123.3    文獻標識碼：A    文章編號：1000-0720（2024）05-0642-07

N-hydroxysuccinimide as coreactant of （pq）₂Ir（acac） for the detection of Hg²⁺ by electrochemiluminescence

FU Yunfeng¹，REN Meijuan¹，WU Fanghui^*1，2，YE Mingfu^1，3，YIN Guoxia²，WANG Chen¹

1. School of Chemistry and Chemical Engineering，Anhui University of Technology，Ma’anshan 243000，China；2. Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education，Civil Engineering & Architecture，Anhui University of Technology，Ma’anshan 243000，China；3. Information Materials and Devices Applications Key Laboratory of Sichuan Provincial Universities，Chengdu University of Information Technology，Chengdu 610225，China）

Abstract：（pq）₂Ir（acac） （pq=2-phenylquinoline，acac=acetylacetone） was synthesized and characterized. A strong electrochemiluminescence （ECL） signal was obtained while N-hydroxysuccinimide （NHS） exploited as an efficient coreactant for（pq）₂Ir（acac） ECL in mixed neutral medium. Then a highly sensitive ECL assay in a “turn-off” mode for the detection of Hg²⁺ was developed based on the specific chelation of NHS and Hg²⁺，which inhibited the reaction between NHS and （pq）₂Ir（acac）. Under the optimized conditions，the logarithm of the ECL intensity change of the （pq）₂Ir（acac）/NHS system and the natural logarithm of the Hg²⁺ concentration showed a good linear relationship in the range of 0.1-90 μmol/L，and the detection limit of Hg²⁺ was 33 nmol/L.This method was applied to determine Hg²⁺ in real water samples with good recovery.

Keywords：cyclometallic iridium complex；N-hydroxysuccinimide；electrochemiluminescence；mercury ion；measurement

USB電源供電表面增強拉曼基底快速制備裝置的開發及其在農藥殘留檢測中的應用

朱津毅¹，黃天雄²，王甜¹，杜一平²，龔雪¹，彭潔¹，李煒^*3

（1. 江蘇中煙工業有限責任公司，南京卷煙廠品質管理處，南京 210019；2. 上海功能性材料化學重點實驗室，華東理工大學化學與分子工程學院，上海 200237；3. 江蘇中煙工業有限責任公司技術中心，南京 210019）

摘要：利用現用現制的方法快速制備SERS基底，以解決基底因儲藏而導致穩定性變差和使用壽命不長的問題。研制了快速制備銀溶膠基底的裝置，該裝置以USB電源供電，帶有加熱控溫以及攪拌功能，可在10 min內制備銀溶膠基底。透射電鏡（TEM）結果顯示，利用該裝置制備的銀溶膠納米顆粒（AgNPs）分布均勻，粒徑約80 nm；用于對羅丹明6G進行檢測，多批次制備基底的SERS信號較強且穩定，相對標準偏差（RSD）在5%左右。將該裝置用于檢測蘋果汁中農藥殘留敵草快，檢出限達5.3 μg/L，與氣相色譜-質譜聯用（GC-MS）和超高效液相色譜-質譜聯用（UHPLC-MS）法的檢出限結果相當；且1581 cm^-1處的SERS信號強度與敵草快濃度間具有良好的線性關系，相關系數（R²）為0.992，加標回收率在107%~112%之間，RSD在1.4%~3.6%之間。使用現制的銀溶膠基底檢測蘋果汁中的敵草快殘留靈敏度和準確度較高，為農殘快速檢測提供了一個新途徑。

關鍵詞：表面增強拉曼光譜；基底；制備裝置；農藥；快檢

中圖分類號：O657.3    文獻標識碼：A    文章編號：1000-0720（2024）05-0649-05

Development of fast fabrication device for surface enhanced Raman spectroscopy substrate synthesis based on USB-power supply and its application for pesticide detection

ZHU Jinyi¹，HUANG Tianxiong²，WANG Tian¹，DU Yiping²，GONG Xue¹，PENG Jie¹，LI Wei^*3

1. China Tobacco Jiangsu Industrial Co.，Ltd.，Quality Management Department of Nanjing Cigarette Factory，Nanjing 210019，China；2. Shanghai Key Laboratory of Functional Materials Chemistry，School of Chemistry & Molecular Engineering，East China University of Science and Technology，Shanghai 200237，China；3. Technology Center，China Tobacco Jiangsu Industrial Co.，Ltd.，Nanjing 210019，China）

Abstract：A method for freshly synthesized surface enhanced Raman spectroscopy （SERS） substrate was proposed to solve the problem of low stability and short life of the substrate due to aggregation of nanoparticles. Based on USB power supply，a device with functions of heating，temperature control and stirring was designed and fabricated to synthesize silver colloid. Preparation of a substrate of Ag colloid for SERS detection could be completed in about 10 min by this device. The transmission electron microscope （TEM） image revealed that Ag nanoparticles （AgNPs） in the synthesized colloid show uniform distribution，with the particle size of about 80 nm. SERS signal of R6G was strong and stable，and the relative standard deviation （RSD） for five-batch substrates was around 5%. The limit of detection （LOD） of pesticide diquat in apple juice by SERS using the  synthesized substrate was 5.3 μg/L，closing to those obtained by gas chromatography-mass spectrometry （GC-MS） and ultra-high performance liquid chromatography-mass spectrometry （UHPLC-MS） methods. There was a linear relationship between SERS signal intensity at 1581 cm^-1 and concentration of diquat，and the correlation coefficient （R²） was 0.992. The recoveries were in the range of 107%-112%，and the relative standard deviations （RSDs） were 1.4%-3.6%. The sensitivity and accuracy of detecting diquat in apple juice by using the synthesized substrate were high，supplying a new way for the rapid detection of pesticide residuals.

Keywords：surface enhanced Raman spectroscopy；substrate；fabrication device；pesticide；rapid detection

羥基磷灰石修飾碳納米電極制備及其對抗壞血酸的測定

豐明佳¹，錢功明^*1，2，熊苓雅¹，韓荻¹

（1. 武漢科技大學資源與環境工程學院，武漢 430081；2. 冶金礦產資源高效利用與造塊湖北省重點實驗室，武漢 430081）

摘要：通過恒電位沉積法，將納米羥基磷灰石（HAP）成功修飾到碳納米電極（CNE）上，制備出一種能快速檢測抗壞血酸（AA）的修飾電極（HAP-CNE）。采用循環伏安法（CV）和計時安培法（CA）研究了HAP-CNE電極對AA的檢測，考察了多巴胺（DA）和模擬體液pH對電極檢測AA的影響。掃描電鏡（SEM）結果表明，HAP已經成功修飾于CNE尖端與外壁上。電化學實驗表明，與CNE相比，HAP-CNE電極信噪比顯著提高，同時AA在HAP-CNE上能發生氧化還原反應，電荷轉移速率提高。AA濃度在1×10^-5~2×10^-3 mol/L范圍內與響應電流呈近似線性關系，檢出限為1.3×10^-7 mol/L。利用HAP-CNE檢測AA具有廣泛的pH適應性且對DA的抗干擾能力強。該電極是一種潛在原位探針，有望為生物醫學研究提供新的檢測方法，并成為一種能應用于活體實時檢測生物小分子代謝過程的新型傳感器。

關鍵詞：碳納米電極；羥基磷灰石；電化學檢測；抗壞血酸

中圖分類號：O657.15    文獻標識碼：A    文章編號：1000-0720（2024）05-0654-06

Preparation of hydroxyapatite modified carbon nanoelectrode and its application in determination of antiascorbic acid

FENG Mingjia¹，QIAN Gongming^*1，2，XIONG Lingya¹，HAN Di¹

1. School of Resources and Environmental Engineering，Wuhan University of Science and Technology，Wuhan 430081，China；2. Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources，Wuhan 430081，China）

Abstract：Nano-hydroxyapatite （HAP） was successfully modified onto carbon nanoelectrode （CNE） by potentiostatic deposition method，and a novel modified electrode （HAP-CNE） was prepared for rapid determination of ascorbic acid （AA）. Cyclic voltammetry （CV） and chronoamperometry （CA） were used to detect AA on HAP-CNE，and the effects of dopamine （DA） and pH were investigated. The results of scanning electron microscopy （SEM） showed that HAP had been modified successfully on the tip and outer wall of CNE. Electrochemical experiments showed that the signal-to-noise ratio of HAP-CNE electrode was significantly higher than that of CNE electrode. Meanwhile，the REDOX reaction of AA happened on HAP-CNE electrode，and the transfer rate increased. In addition，the AA concentration was approximately linear with the response current in the range of 1×10^-5-2×10^-3 mol/L，and the detection limit was1.3×10^-7 mol/L. The detection of AA by HAP-CNE had a wide range of pH adaptability and strong anti-interference ability to DA. The electrode is a potential in situ probe that is expected to provide new detection methods for biomedical research and to become a novel sensor that can be applied to the real-time detection of metabolic processes of small molecules in vivo.

Keywords：carbonnanoelectrode；hydroxyapatite；electrochemistry detection；ascorbic acid

一種含1，2，3-三氮唑席夫堿的Al³⁺熒光探針及其應用

廖元淏，王帥，馮華杰，陳光英，宋媛，吳祿勇^*，何文英^*

（熱帶藥用資源化學教育部重點實驗室，海南師范大學化學與化工學院，海口 571158）

摘要：本文設計合成了5-苯基-2-苯基-1，2，3-三唑-1-4-酰肼（PP），將其與水楊醛反應，構建了一種席夫堿熒光探針（PPS）。熒光光譜及紫外光譜測定表明，PPS能夠高選擇性和強抗干擾性地檢測乙醇溶液中的Al³⁺，檢出限為8.28 nmol/L；在紫外光下可發生明顯的溶劑變色效應，在含水量大于60%的有機溶劑中存在聚集誘導發光（AIE）效應，質譜、工作曲線、核磁滴定及理論計算結果均證明，PPS和Al³⁺可以絡合比1∶1進行反應，生成平面結構的化合物。該探針具有低的細胞毒性且成功用于HeLa細胞的顯色成像，有望被開發利用為具有AIE聚集效應的發光材料及生物體內測定Al³⁺的熒光探針。

關鍵詞：5-苯基-2-苯基-1，2，3-三唑-1-4-酰肼席夫堿；Al³⁺；識別機理；細胞成像

中圖分類號：O657.31；X832    文獻標識碼：A    文章編號：1000-0720（2024）05-0660-09

A fluorescent probe of 1，2，3-triazole modified by Schiff base for detecting Al³⁺ and its application

LIAO Yuanhao，WANG Shuai，FENG Huajie，CHEN Guangying，SONG Yuan，WU Luyong^*，HE Wenying^*

Key Laboratory of Tropical Medicinal Resource Chemistry of Ministry of Education，Hainan Normal University，Haikou 571158，China）

Abstract：5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid （PP） was designed and synthesized based on “click chemistry”. The fluorescence probe PPS（5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid-O-hydroxymethylbenzene） containing Schiff base was further constructed by a chemical reaction between PP and salicylaldehyde. PPS could be used to determine Al³⁺ in ethanol solution with high sensitivity and strong anti-interference performance by fluorescence and UV-vis spectroscopic methods. The limit of detection for Al³⁺ was 8.28 nmol/L，and the probe PPS showed an obvious solvatochromic effect under ultraviolet light. The aggregation-induced emission （AIE） effect of PPS was found in organic solvent when water content was more than 60%. Furthermore，the results of mass spectrometry （MS），Job’s plot，NMR titration，and density functional theory （DFT） calculation confirmed that the probe PPS and Al³⁺ could react to form a compound with a planar structure at 1∶1 complexation ratio. The probe PPS showed less low cytotoxicity to HeLa cells，so it was successfully used for chromatic bioimaging Al³⁺ in HeLa cells. It is expected to be developed and utilized as a kind of luminous material with AIE effect and a fluorescence probe for detecting Al³⁺ in vivo.

Keywords：5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid Schiff base （PPS）；Al³⁺；recognition mechanism；living cell imaging

基于紅色碳點/二氧化錳納米探針熒光法檢測果汁總抗氧化性

王幸幸^1，3，4，李景敏²，楊順¹，周揚¹，羅林^*2，鄧浩³，何鎮熹²，徐振林²，賈寶珠^*1

（1. 廣東第二師范學院生物與食品工程學院，廣州 510303；2. 廣東省食品質量安全重點實驗室，華南農業大學食品學院，廣州 510642；3. 海南省農業科學院農產品加工設計研究所，海南省熱帶果蔬冷鏈研究重點實驗室，海口 570100；4. 深圳市通量檢測科技有限公司，深圳 518038）

摘要：以紅色熒光碳點（R-CDs）與二氧化錳（MnO₂）納米片為熒光探針，構建了一種靈敏、快速、簡便的熒光分析方法，并用于測定食物總抗氧化性。以抗壞血酸（AA）為模型檢測靶標，采用AA當量評價食品總抗氧化性，通過單因素實驗優化MnO₂納米片濃度、R-CDs稀釋倍數、MnO₂與R-CDs的作用時間及其與AA的作用時間。在最佳條件下，熒光強度與AA濃度的對數值在4.0~12 μmol/L范圍內呈良好的線性關系，檢出限達到0.06 μmol/L。該方法測定標準添加果汁樣品的回收率在85.8%~113.0%之間，具有較好的靈敏度與準確性。

關鍵詞：MnO₂納米片；紅色熒光碳點；熒光；抗氧化劑

中圖分類號：O657.31；X832    文獻標識碼：A    文章編號：1000-0720（2024）05-0669-07

Fluorescent assay for the determination of total antioxidant capacity of fruit juices based on red-emitting carbon dot/MnO₂ nanoprobe

WANG Xingxing^1，3，4，LI Jingmin²，YANG Shun¹，ZHOU Yang¹，LUO Lin^*2，DENG Hao³，HE Zhenxi²，XU Zhenlin²，JIA Baozhu^*1

1. College of Biological and Food Engineering，Guangdong University of Education，Guangzhou 510303，China；2. Guangdong Key Laboratory of Food Quality and Safety，College of Food Science，South China Agricultural University，Guangzhou 510642，China；3. Key Laboratory of Tropical Fruit and Vegetable Cold-chain of Hainan Province，Institute of Agro-products Processing and Design，Hainan Academy of Agricultural Sciences，Haikou 570100，China；4. Shenzhen Total-Test Technology Co.，Ltd.，Shenzhen 518038，China）

Abstract：A fluorescent assay for the determination of total antioxidant capacity （TAC） of foods was developed by using red-emitting carbon dots （R-CDs）/manganese dioxide nanosheets （MnO₂ NSs） as nanoprobe. Ascorbic acid （AA），as a typical antioxidant，was employed as model analyte，and AA equivalents was used as the index for TAC assessment. Single-factor experiments were conducted to optimize the concentration of MnO₂ nanosheets，dilution factor of R-CDs，interaction time for MnO₂ with R-CDs and AA with the nanoprobe. Under the optimal conditions，the fluorescence intensity showed a good linear relationship with AA concentration in the range of 4.0-12 μmol/L，with the detection limit of 0.06 μmol/L. The recoveries of the standard added juice samples ranged from 85.8% to 113.0%，demonstrating the high potential detection of TAC in food.

Keywords：MnO₂ nanosheet；red-emitting carbon dots；fluorescence；antioxidant

基于雙發射碳量子點的比率型熒光探針檢測阿司匹林

劉荔貞^*，陳夢，袁琳，米智，李彩琴，王利剛，馮鋒

（山西大同大學化學與化工學院，大同 037009）

摘要：以間苯二胺和酒石酸為原料，通過一步水熱法合成了在單一激發波長下具有雙發射特性的碳量子點（CQDs）。利用透射電鏡（TEM）、傅里葉變換紅外光譜（FTIR）、X射線光電子能譜（XPS）、紫外-可見吸收光譜（UV-vis）和熒光光譜對其結構和光學性質進行了表征。當激發波長為390 nm時，該CQDs在440和502 nm處有2個發射峰。阿司匹林能夠使502 nm處的發射峰熒光強度增加，而440 nm處的發射峰強度基本不變，基于此，構建了一種CQDs比率型熒光探針檢測阿司匹林的新方法。阿司匹林濃度在0.5~160 μmol/L范圍內與CQDs的2個發射峰的熒光強度比（F₅₀₂/F₄₄₀）呈良好的線性關系，檢出限低至0.062 μmol/L。該方法成功用于藥品中阿司匹林的檢測。

關鍵詞：碳量子點；阿司匹林；比率型熒光探針

中圖分類號：O657.3    文獻標識碼：A    文章編號：1000-0720（2024）05-0676-06

Ratiometric fluorescent sensor based on double emission carbon quantum dots for the detection of Aspirin

LIU Lizhen^*，CHEN Meng，YUAN Lin，MI Zhi，LI Caiqing，WANG Ligang，FENG Feng

College of Chemistry and Chemical Engineering，Shanxi Datong University，Datong 037009，China）

Abstract：Carbon quantum dots （CQDs） with dual emission property at a single excitation wavelength were synthesized by a one-step hydrothermal method using m-phenylenediamine and tartaric acid as raw materials. The structure and optical properties of CQDs were characterized by transmission electron microscope，Fourier transform infrared spectrometer，X-ray photoelectron spectroscopy，ultraviolet-visible absorption spectroscopy and fluorescence spectroscopy. When the excitation wavelength was 390 nm，the CQDs had two emission peaks at 440 and 502 nm. The presence of aspirin can increase the fluorescence intensity of the emission peak at 502 nm，while the intensity of the emission peak at 440 nm was basically unchanged. Based on this，a novel CQDs based ratiometric fluorescent sensor was constructed for the determination of aspirin. The concentration of aspirin in the range of 0.5-160 μmol/L had a good linear relationship with the fluorescence intensity ratio （F₅₀₂/F₄₄₀） of the two emission peaks of CQDs，and the detection limit was as low as 0.062 μmol/L. The developed method has been successfully applied to the determination of aspirin in actual drugs.

Keywords：carbon quantum dots（CQDs）；aspirin；ratio metricfluorescent sensor

液相色譜串聯質譜法同時測定豬肉中氟雷拉納和五氯酚殘留量

伍華雯¹，劉正才²，馬欣欣¹，韓穎¹，占春瑞¹，柯秋璇²，陳練洪²，朱立怡¹，萬建春^*1

（1. 南昌海關技術中心，南昌 330038；2. 福州海關技術中心，福州 350003）

摘要：采用基質分散固相萃取凈化結合液相色譜-串聯三重四極桿質譜分析技術，基于待測物的油水分配系數和樣品前處理正交試驗設計，建立了豬肉中氟雷拉納和五氯酚殘留量的檢測方法。試樣采用酸化乙腈均質提取，提取液加入QuEChERS萃取凈化包快速凈化，過膜直接上機測定。以5 mmol/L乙酸銨溶液和乙腈為流動相，氟雷拉納和五氯酚經C18色譜柱梯度洗脫分離后，質譜負離子模式掃描檢測。豬肉樣品中分別添加1.0，2.0，10.0 μg/kg 3個濃度水平待測物，氟雷拉納和五氯酚的加標回收率分別在82.3%~104.0%和71.6%~79.8%之間，相對標準偏差（RSD）分別在3.7%~5.3%和1.2%~3.4%之間。本方法檢測氟雷拉納和五氯酚的定量限均為1.0 μg/kg，適用于豬肉中氟雷拉納和五氯酚殘留量的測定。

關鍵詞：液相色譜串聯質譜；豬肉；氟雷拉納；五氯酚；殘留檢測

中圖分類號：O657.63    文獻標識碼：A    文章編號：1000-0720（2024）05-0682-05

Simultaneous determination of fluralaner and pentachlorophenol residues in pork by liquid chromatography tandem mass spectrometry

WU Huawen¹，LIU Zhengcai²，MA Xinxin¹，HAN Ying¹，ZHAN Chunrui¹，KE Qiuxuan²，CHEN Lianhong²，ZHU Liyi¹，WAN Jianchun^*1

1. Technology Center of Nanchang Customs District，Nanchang 330038，China；2. Technology Center of Fuzhou Customs District，Fuzhou 350003，China）

Abstract：The simultaneous determination of fluralaner and pentachlorophenol residues in pork was developed by using matrix dispersion solid phase extraction to purify the sample solution and liquid chromatography-tandem triple quadrupole tandem mass spectrometry，based on the oil-water distribution coefficient of the tested substance and the orthogonal experimental design of sample pretreatment. After extracting by acidified acetonitrile，the extract was added into the QuEChERS extraction purification package for rapid purification and filtered with the membrane，then the purified liquid was analyzed by LC-MS/MS. With 5 mmol/L ammonium acetate solution and acetonitrile as the mobile phase，fluralaner and pentachlorophenol were separated by gradient elution on the C18 column，and then the negative mode scanning of mass spectrometry was performed. At three spiked concentration levels of 1.0，2.0，10.0 μg/kg in the pork，the recoveries of fluralaner and pentachlorophenol were 82.3%-104.0% and 71.6%-79.8%，respectively，and the relative standard deviations （RSDs） were 3.7%-5.3% and 1.2%-3.4%，respectively. The quantitative limits of fluralaner and pentachlorophenol were 1.0 μg/kg，which is suitable for the determination of fluralaner and pentachlorophenol residues in pork.

Keywords：LC-MS/MS；pork；fluralaner；pentachlorophenol；residue detection

直接進樣-高效液相色譜-串聯質譜法快速檢測飲用水中草銨膦、草甘膦及其代謝物氨甲基膦酸

方力^*1，邱鳳梅²

（1. 浙江省海產品健康危害因素關鍵技術研究重點實驗室，舟山市疾病預防控制中心，舟山 316021；2. 浙江省舟山市普陀區疾病預防控制中心，舟山 316100）

摘要：建立了高效液相色譜串聯三重四極桿質譜（HPLC-MS/MS）定量檢測飲用水中草銨膦、草甘膦及其代謝產物氨甲基膦酸的方法。水樣直接經親水PTFE膜過濾，以50 mmol/L甲酸銨（pH 3.0）為流動相，Acclaim Trinity Q1色譜柱分離，電噴霧離子化（ESI-）、選擇反應監測（SRM）模式檢測，外標法定量，總運行時間僅為5 min。草甘膦、氨甲基膦酸和草銨膦在10.0~1000 μg/L濃度范圍內存在較好的線性關系，相關系數大于0.999，其定量限分別為5.0，5.0和10.0 μg/L；目標化合物日內和日間加標回收率分別為92.7%~102.1%和89.3%~99.9%，日內與日間相對標準偏差（RSD）均小于7.7%。該方法能滿足水源水和飲用水中草銨膦、草甘膦及其代謝物氨甲基膦酸的應急檢測或日常檢測要求。

關鍵詞：草甘膦；氨甲基膦酸；草銨膦；飲用水；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）05-0687-06

Rapid determination of glufosinate ammonium，glyphosate and aminomethyl phosphonic acid in drinking water by direct injection - liquid chromatography - tandem mass spectrometry

FANG Li^*1，QIU Fengmei²

1. Key Laboratory of Health Risk Factors for Seafood of Zhejiang Province，Zhoushan Municipal District Center for Disease Control and Prevention，Zhoushan 316021，China；2. Putuo Center for Disease Control and Prevention，Zhoushan 316100，China）

Abstract：A method for quantitative analysis of glufosinate ammonium，glyphosate，and its metabolite of aminomethyl phosphonic acid in drinking water was established by utilizing liquid chromatography coupled with triple quadrupole mass spectrometry （LC-MS/MS）. The water sample was directly filtered through a 0.22 μm PTFE membrane. The analytes were separated on an Acclaim Trinity Q1 column with the mobile phase of 50 mmol/L ammonium formate （pH 3），and detected in selected reaction monitoring （SRM） mode via negative electrospray ionization （ESI-）. The external standard method was used for quantitation. There were good linearities for glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid in the concentration ranges of 10.0-1000 μg/L，respectively，and the correlation coefficients were higher than 0.999. The quantification limits of glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid in drinking water were 5.0，5.0 and 10.0 μg/L，respectively. The inter-day and intra-day recoveries of glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid were 92.7%-102.1% and 89.3%-99.9%，respectively，with the inter-day and intra-day relative standard deviations （RSDs） lower than 7.7%. The method can satisfy the requirements of emergency testing or routine testing.

Keywords：glyphosate；aminomethyl phosphonic acid；glufosinate ammonium；drinking water；liquid chromatography-tandem mass spectrometry

基于非標記適配體結構變化熒光法檢測黃曲霉毒素B1

于潔，朱科曉，王  超^*，時鵬飛^*

（臨沂大學化學化工學院，臨沂 276000）

摘要：構建了一種基于非標記適配體結構變化熒光檢測黃曲霉毒素B1（AFB1）的方法。無AFB1時，一條非標記的AFB1適配體同時與2條短互補DNA鏈雜交，形成DNA雙鏈結構，導致標記于其中一條互補DNA的3’端的熒光素（FAM）與標記于另一條互補DNA的5’端的淬滅劑（BHQ1）相鄰近，發生熒光共振能量轉移，FAM熒光被BHQ1淬滅。AFB1存在時，適配體與AFB1結合，而不與互補DNA發生雜交。此時，FAM與BHQ1距離較遠，FAM熒光不能被淬滅。通過測量體系熒光強度變化可定量檢測AFB1。方法檢出限0.2 nmol/L，定量檢測范圍1.0 nmol/L~4.0 μmol/L。該方法無需共價標記適配體，操作簡便，特異性好，能夠用于檢測復雜基質樣品中的AFB1。

關鍵詞：黃曲霉毒素B1；適配體；熒光淬滅；快速檢測

中圖分類號：O657.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0693-06

A fluorescence method for detection of aflatoxin B1 based on structural change of unlabeled aptamer

YU Jie，ZHU Kexiao，WANG Chao^*，SHI Pengfei^*

College of Chemistry and Chemical Engineering，Linyi University，Linyi 276000，China）

Abstract：A simple method was constructed for fluorescence detection of aflatoxin B1 （AFB1） based on the structural change of an unlabeled aptamer. In the absence of AFB1，an unlabeled AFB1 aptamer simultaneously hybridized with two complementary short DNA strands，forming a DNA duplex structure. As results，the fluorescein FAM labeled at 3’ end of a complementary DNA was adjacent to the quencher BHQ1 labeled at 5’ end of the other complementary DNA. In this case，fluorescence resonance energy transfer occurred，and FAM fluorescence was quenched by BHQ1. In the presence of AFB1，the aptamer bound to AFB1 instead of hybridizing with complementary DNAs. As results，FAM and BHQ1 were far away from each other，and FAM fluorescence could not be quenched. AFB1 was quantitatively detected by measuring fluorescence intensity of the system. Detection limit of this method was 0.2 nmol/L，and quantitative detection range was 1.0 nmol/L-4.0 μmol/L. This method could be used for rapid detection of AFB1 in complex matrix samples for not requiring labeling of aptamer，easy to operate，and good specificity.

Keywords：aflatoxin B1；aptamer；fluorescence quenching；rapid detection

一鍋法制備生物炭-金屬有機骨架復合材料用于吸附全氟辛酸

周瑤璐^1，2，祝紹玉^1，2，劉樹仁¹，錢一帆^1，2，柏珊珊^*1

（1. 浙江省污染暴露與健康干預重點實驗室，浙江樹人學院交叉科學研究院，杭州 310015；2. 浙江樹人學院生物與環境工程學院，杭州 310015）

摘要：通過一鍋法制備了一種新型生物炭-鐵基金屬有機骨架復合材料（MIL-101（Fe）@BC）。利用傅里葉紅外光譜、掃描電鏡和氮氣吸附-脫附分析對材料進行表征，探究了MIL-101（Fe）@BC對全氟辛酸（PFOA）的吸附效能和作用機制，并將其與5種常用工程碳材料進行對比。結果表明，MIL-101（Fe）@BC在吸附環境pH為4，吸附時間為1 h時達到最佳吸附效果，最佳投加量為0.05 g/L。MIL-101（Fe）@BC對PFOA的吸附等溫線既符合Langmuir模型又符合Freundlich模型，最大飽和吸附量為925.93 μmol/g，吸附過程符合準二級動力學方程，孔隙填充和氫鍵作用是吸附的主要機制。MIL-101（Fe）@BC吸附和再生效能均優于已廣泛使用的工程碳材料，在新污染物治理領域具有較大的應用潛力。

關鍵詞：生物炭；復合材料；吸附；全氟辛酸

中圖分類號：X52    文獻標識碼：A    文章編號：1000-0720（2024）05-0699-06

Preparation of biochar-metal organic framework composite by one-pot method for the adsorption of perfluorooctanoic acid

ZHOU Yaolu^1，2，ZHU Shaoyu^1，2，LIU Shuren¹，QIAN Yifan^1，2，BAI Shanshan^*1

1. Zhejiang Provincial Key Laboratory of Pollution Exposure and Health Intervention，Interdisciplinary Research Academy，Zhejiang Shuren University，Hangzhou 310015，China；2. College of Biology and Environmental Engineering，Zhejiang Shuren University，Hangzhou 310015，China）

Abstract：A novel biochar-metal organic framework composite material （MIL-101（Fe）@BC） was prepared using the one-pot method. The material was characterized using Fourier-transform infrared spectroscopy，scanning electron microscopy，and nitrogen adsorption-desorption analysis. The adsorption efficiency and mechanism of MIL-101（Fe）@BC to perfluorooctanoic acid （PFOA） were investigated and compared with five commonly used engineering carbon materials. The results showed that MIL-101（Fe）@BC achieved optimal adsorption at pH 4，with an optimum dosage of 0.05 g/L within 1 h. The adsorption isotherm of PFOA on MIL-101（Fe）@BC followed both Langmuir and Freundlich models，with a maximum saturation adsorption capacity of 925.93 μmol/g. The adsorption process followed pseudo-second-order kinetics，and pore filling and hydrogen bonding were identified as the main adsorption mechanisms of MIL-101（Fe）@BC to PFOA. MIL-101（Fe）@BC exhibited superior adsorption and regeneration efficiency compared to widely used engineering carbon materials，indicating significant practical application potential.

Keywords：biochar；composite materials；adsorption；perfluorooctanoic acid

流動注射-串聯質譜法分析污水中11種毒品

鄭吳淇¹，寧弘宇²，陳昊¹，黃忠平²，范一雷^*1，柯星^*1

（1. 浙江警察學院浙江省毒品防控技術研究重點實驗，杭州 310053；2. 浙江工業大學化工學院，杭州 310014）

摘要：建立了一種流動注射-串聯質譜法（FIA-MS/MS）快速檢測污水中11種常見毒品。樣品經Oasis MCX固相萃取小柱凈化和濃縮后，注入FIA-MS/MS系統進行分析。質譜采用正離子模式掃描，在多反應監測模式（MRM）下，同位素內標法定量。結果表明，11種毒品在0.16~200 ng/L范圍內線性關系良好，相關系數r²≥0.9902，檢出限（LOD）為0.05~0.53 ng/L，定量限（LOQ）為0.16~1.60 ng/L。11種毒品在低、中、高3種加標濃度下，方法回收率為74.5%~113.7%，日內相對標準偏差（RSD）在1.0%~6.9%之間，日間RSD在2.2%~11%之間。該方法適用于污水樣品中毒品的高通量篩查和定量分析。

關鍵詞：流動注射-串聯質譜法；污水；毒品檢測；高通量檢測

中圖分類號：O657.31；X832    文獻標識碼：A    文章編號：1000-0720（2024）05-0705-06

Analysis of 11 drugs in wastewater by flow injection-tandem mass spectrometry

ZHENG Wuqi¹，NING Hongyu²，CHEN Hao¹，HUANG Zhongping²，FAN Yilei^*1，KE Xing^*1

1. Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province，Zhejiang Police College，Hangzhou 310053，China；2. College of Chemical Engineering，Zhejiang University of Technology，Hangzhou 310014，China）

Abstract：A flow injection tandem mass spectrometry （FIA-MS/MS） method has been developed for the rapid detection of 11 common drugs in wastewater. Samples were purified and concentrated by the Oasis MCX solid-phase extraction cartridge，followed by injection into the FIA-MS/MS system. Positive ion scanning mode was used for mass spectrometry，and isotope internal standard method in multiple reaction detection mode （MRM） was employed for quantification. The results showed that all the 11 drugs had good linear relationships in the range of 0.16-200 ng/L，with correlation coefficients of r²≥0.9902. The limits of detection （LODs） and limits of quantification （LOQs） were 0.05-0.53 ng/L and 0.16-1.60 ng/L，respectively. At low，medium，and high spiked concentrations，the recoveries of 11 drugs were 74.5%-113.7%，and the relative standard deviations （RSDs） of intra-day and inter-day were 1.0%-6.9% and 2.2%-11%，respectively. The present work provides a method suitable for high-throughput screening and quantitative analysis of toxic substances in wastewater samples.

Keywords：flow injection-tandem mass spectrometry；wastewater；drug detection；high-throughput detection

基于UHPLC-Q-Orbitrap高分辨質譜聯用快速鑒定半夏中的化學成分

王靜，崔潔，劉子怡，楊楊，李展，劉慧靈^*

（中國醫學科學院藥用植物研究所，北京 100193）

摘要：利用UHPLC-Q-Orbitrap四極桿-靜電場軌道阱高分辨質譜聯用技術對半夏的化學成分進行快速識別和鑒定。以80%（V/V）甲醇提取，Acquity UPLC BEH C18色譜柱（2.1 mm×100 mm，1.7 μm）分離，0.1%甲酸水（A）-0.1%甲酸的乙腈（B）溶液作為流動相進行梯度洗脫。質譜采用正、負離子監測模式，利用全掃描及自動觸發二級質譜掃描，快速識別和鑒定半夏中的化學成分。根據高分辨質譜數據，從半夏中共分析鑒定出111個化合物，包括生物堿類37個、氨基酸及其衍生物20個、黃酮類17個、萜類12個、有機酸及其衍生物6個、苯丙素類5個、其它類14個。該方法可為半夏質量控制和藥效物質研究提供參考。

關鍵詞：半夏；UHPLC-Q-Orbitrap四極桿-靜電場軌道阱高分辨質譜；化學成分；生物堿；氨基酸

中圖分類號：R284.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0711-08

Rapid identification of chemical components in Pinelliae Rhizoma by UHPLC-Q-Orbitrap high resolution mass spectrometry

WANG Jing，CUI Jie，LIU Ziyi，YANG Yang，LI Zhan，LIU Huiling^*

Institute of Medicinal Plant Development，Chinese Academy of Medical Sciences，Beijing 100193，China）

Abstract：An UHPLC-Quadrupole-Orbitrap high resolution mass spectrometry method was developed to rapidly identify the chemical components from Pinelliae Rhizoma by using 80% （V/V） methanol as the extraction solution. For UHPLC separation，Acquity UPLC BEH C18 column （2.1 mm×100 mm，1.7 μm） was used，and gradient elution was performed with 0.1% formic acid water （A）-0.1% formic acid acetonitrile （B） solution as mobile phase. The chemical components in Pinelliae Rhizoma were quickly identified by the mass spectrometry adopting positive and negative ion monitoring modes，full scanning and automatic triggering of secondary mass spectrometry. As a result，a total of 111 compounds have been identified from Pinelliae Rhizoma，including 37 kinds of alkaloids，20 kinds of amino acids and derivants，17 kinds of flavonoids，12 kinds of terpenoids，6 kinds of organic acids and derivants，5 kinds of phenylpropanoids，and 14 other kinds of compounds. The method provides a reference for quality control and pharmacodynamic material basics.

Keywords：Pinelliae Rhizoma；UHPLC-Q-Orbitrap high resolution mass spectrometry；chemical components；alkaloid；amino acid

基于小區域地表感知橫縱波時差的頁巖壓裂定位方法研究

田新琦¹，魏冰^*2，郝曉敏^*2，胡照乾²

（1. 中石化石油工程地球物理有限公司，北京 100024；2. 中石化石油工程地球物理有限公司科技研發中心，南京 211100）

摘要：針對頁巖油勘探中傳統的壓裂定位方法存在定位模型復雜、精度低以及技術成本高等不足，提出了基于小區域地表感知橫縱波時差的頁巖壓裂定位模型及其算法。首先，采用變分模態分解的信號處理技術分解微地震波低頻響應，可提高原始壓裂響應的信噪比。其次，將長短時窗算法（STA/LTA）與赤池信息準則（AIC）算法相結合，有效地識別分解信號的起跳點，從而完成橫縱波之間的時差拾取。最后，建立了橫縱波時差與壓裂源坐標、小區域地表檢波器坐標之間定位數學模型，通過最小二乘法，實現基于多個定位數學模型的壓裂源坐標計算，其坐標值均值可有效提高定位計算精度。

關鍵詞：頁巖壓裂；定位；信號分解；時差拾取；小區域地表

中圖分類號：TE377    文獻標識碼：A    文章編號：1000-0720（2024）05-0719-07

Research on shale fracturing localization method based on transverse and longitudinal wave time difference of small-region surface perception

TIAN Xinqi¹，WEI Bing^*2，HAO Xiaomin^*2，HU Zhaoqian²

1. Sinopec Geophysical Corp.，Beijing 100024，China；2. Research and Development Center，Sinopec Geophysical Corp.，Nanjing 211100，China）

Abstract：Aiming at the shortcomings of the traditional shale fracturing localization methods for shale oil exploration，such as the complexity of localization model，low accuracy and high technical cost，both a shale fracturing localization model and its algorithm are proposed based on the time difference of transverse and longitudinal waves of small-area surface sensing. Firstly，the signal processing technology of variational mode decomposition is used to decompose the low frequency response of microseism wave，which can improve the signal-to-noise ratio of the original fracturing response. Secondly，the long and short time window algorithm （STA/LTA） is combined with the Akaike information criterion （AIC） algorithm to effectively identify the take-off point of the decomposed signal，so as to complete the time difference picking between the transverse and longitudinal waves. At last，the localization mathematical model is established among the time difference of transverse and longitudinal waves and the coordinates of fracturing source and the coordinates of small area surface geophones，the calculation of fracturing source coordinates based on various localization mathematical models can be realized by means of the least square method，and the average value of coordinate value can effectively improve the accuracy of localization calculation.

Keywords：shale fracturing；localization；signal decomposition；time difference picking；small-region surface

基于不同背景選取方式四極質譜儀數據庫匹配分析

于佳佳^*1，2，沈輝^1，2，王玉涵¹，羅勇¹，唐朝陽¹

（1. 上海裕達實業有限公司，上海 200240；2. 上海衛星裝備研究所，上海 200240）

摘要：電解液測試屬于鋰電池研究的重點方向之一。質譜法在線測試電解液時，背景信號對搜庫結果匹配度有明顯的影響。研究了在不同背景選取方式下四極質譜儀識別電解液譜峰的匹配度，結果表明，基于進樣階段選取背景的扣除方法，可更有效地去除環境空氣對搜庫的干擾，獲得更高的搜庫匹配度。實驗結果為鋰電池電解液溶劑原位測試與譜庫匹配數據處理提供了科學依據，為復雜環境現場測試的數據處理方法提供了思路。

關鍵詞：鋰電池；背景扣除；譜圖檢索；質譜儀

中圖分類號：O657.63    文獻標識碼：A    文章編號：1000-0720（2024）05-0726-05

Quadrupole mass spectrometer database identification analysis based on different background selection methods

YU Jiajia^*1，2，SHEN Hui^1，2，WANG Yuhan¹，LUO Yong¹，TANG Chaoyang¹

1. Shanghai Yuda Industrial Co.，Ltd.，Shanghai 200240，China；2. Shanghai Institute of Spacecraft Equipment，Shanghai 200240，China）

Abstract：Electrolyte analysis is one of the key directions of lithium ion battery research. When testing the electrolyte online by mass spectrometry，the background signal has a significant effect on the matching degree of the sprectrum identification. The matching degree of electrolyte sprectrum identified by quadrupole mass spectrometer upon different background selection methods was studied. The results showed that the deduction method based on the background selection in the injection stage can more effectively remove the interference of ambient air on the spectrum identification and obtain a higher matching degree. The experimental results provide a scientific basis for the in-situ test and spectrum identification of electrolyte，and ideas for the data processing method of complex environments testing.

Keywords：lithium-ion batteries；background deduction；spectrum identification；mass spectrometry

復雜基質中有機磷酸酯化合物的2D NMR快速分析

張盈盈¹，呂家樂²，劉石磊³，黃桂蘭³，夏俊美³，夏明珠^*1，袁鈴^*3

（1. 南京理工大學化學與化工學院，南京 210094；2. 四川輕化工大學化學工程學院，自貢 643002；3. 國民核生化災害防護國家重點實驗室，北京 102205）

摘要：以有機磷酸酯為目標物，編譯包含¹H-³¹P異核多鍵相關譜（HMBC）和¹H-¹H DQF-同核位移相關譜（COSY）的NOAH2_BD脈沖序列，并與非均勻采樣技術相結合，通過優化遠程耦合演化延遲時間和非均勻采樣比例等采集參數，得到¹H-³¹P HMBC和¹H-¹H DQF-COSY譜圖，實現了復雜有機廢液中有機磷酸酯的快速鑒定。方法檢出限可達到10 μg/mL；與傳統的二維核磁方法相比，在保持相近的譜圖質量下，NOAH2_BD能將檢測時間縮短44%，NOAH2_BD結合NUS=30%可將檢測時間縮短82%。

關鍵詞：有機磷酸酯；二維核磁；氫核檢測有序采樣核磁共振；非均勻采樣

中圖分類號：O657    文獻標識碼：A    文章編號：1000-0720（2024）05-0731-06

Rapid 2D NMR analysis for organophosphate compounds in complex matrixes

ZHANG Yingying¹，LYU Jiale²，LIU Shilei³，HUANG Guilan³，XIA Junmei³，XIA Mingzhu^*1，YUAN Ling^*3

1.School of Chemistry and Chemical Engineering，Nanjing University of Science and Technology，Nanjing 210094，China；2.School of Chemical Engineering，Sichuan University of Science & Engineering，Zigong 643002，China；3. State Key Laboratory of NBC Protection for Civilian，AMS，Beijing 102205，China）

Abstract：A new NMR by ordered acquisition using ¹H-detection （NOAH）2_BD pulse program with non-uniform sampling containing ¹H-³¹P heteronuclear multiple-bond correlation （HMBC） and ¹H-¹H DQF-correlation spectroscopy （COSY） was compiled. The ¹H-³¹P HMBC and ¹H-¹H DQF-COSY spectra were obtained by optimizing the acquisition parameters such as the delay for evolution of long range couplings time and non-uniform sampling ratio to achieve rapid identification of organophosphates in complex matrixes. The results showed that the detection limit of the method for organophosphates can reach 10 μg/mL. Compared with the traditional 2D NMR methods，the detection time of NOAH2_BD can be reduced by 44% and the detection time of NOAH2_BD with NUS ratio of 30% can be reduced by 82% while maintaining the similar spectral quality.

Keywords：organophosphates；2D NMR；NMR by ordered acquisition using ¹H-detection （NOAH）；non-uniform sampling

納米材料在漆酶電化學傳感器中的應用和研究進展

張鈺涓^1，2，陶文強¹，張志衡^1，2，宋志華^1，2，錢立生^*1，張越^*1

（1. 安徽科技學院生命與健康科學學院，滁州 233100；2. 安徽科技學院食品工程學院，滁州 233100）

摘要：高性能納米材料通過負載漆酶制備生物傳感電極，可以實現漆酶電化學傳感器的高靈敏度、寬線性檢測范圍、較好的穩定性和較強的固定化強度，能夠應用于食品、環境、醫藥等領域目標物濃度的精準檢測。近年來，隨著許多新型納米材料不斷開發以及與漆酶分子之間固定化方式研究的不斷深入，證明了納米材料在漆酶電化學傳感電極構建中的巨大潛力。開發新型納米材料和建立與酶分子之間搭配和固定化策略，能夠實現高性能傳感電極的制備，進而指導組建面向性能需求的高應用性傳感器，最終推動生物傳感、酶工程與蛋白質工程和材料學之間的交叉應用。本文對固定漆酶制備傳感電極的高性能納米材料種類進行了分析與討論，主要從金屬納米材料、碳納米材料和高分子納米材料固定化漆酶在生物電化學傳感方面的研究進展進行綜述，并對納米材料在漆酶電化學中的應用前景與未來進行了討論，為今后在漆酶電化學傳感器中開發新型納米材料和選擇固定化方式提供參考。

關鍵詞：漆酶；納米材料；電化學

中圖分類號：O657.1    文獻標識碼：A    文章編號：1000-0720（2024）05-0737-12

Application and research progress of nanomaterials in laccase biosensors

ZHANG Yujuan^1，2，TAO Wenqiang¹，ZHANG Zhiheng^1，2，SONG Zhihua^1，2，QIAN Lisheng^*1，ZHANG Yue^*1

1. College of Life and Health Sciences，Anhui Science and Technology University，Chuzhou 233100，China；2. College of Food Science and Engineering，Anhui Science and Technology University，Chuzhou 233100，China）

Abstract：Nanomaterials with high performance are used to produce biosensing electrodes through loading laccase，which contributes to the high sensitivity，wide linear range，better stability and strong immobilization strength for laccase electrochemical sensors，and can also be applied to the precise determination of target components in food，environmental and medical fields. In recent years，with the continuous development of advanced nanomaterials and the deeper studies on the immobilization modes between laccase molecules，the great potential of nanomaterials in the construction of laccase electrochemical sensing electrodes has been demonstrated. Attempts to develop novel nanomaterials and establish collocation and immobilization strategies with enzyme molecules can enable the preparation of high-performance sensing electrodes，thereby guide the formation of highly applicable sensors meeting the high performance needs，which ultimately promote cross-applications between biosensing，enzyme engineering and protein engineering and materials science. In this paper，the types of high performance nanomaterials for sensing electrodes prepared by immobilized laccase were discussed，mainly including the research progress of metal nanomaterials，carbon nanomaterials and polymer nanomaterials used in immobilized laccase in bioelectrochemical sensing fields. The prospect and future application of nanomaterials in laccase electrochemistry were also discussed to provide references for the development of advanced nanomaterials and methods selection for laccase in electrochemical fields.

Keywords：laccase；nanomaterials；electrochemistry

樹枝狀介孔納米粒子檢測有害物質研究進展

王艷妮¹，何花²，王亞斌^*1，2，丁秀萍³

（1. 延安大學化學與化工學院，延安 716000；2. 三嗪化合物與多級孔材料研究所，延安 716000；3. 中國科學院青海鹽湖研究所，西寧 810008）

摘要：有機和無機有害物質嚴重危害著環境安全和人類健康，因此，加強對這些有害物質的檢測具有實際意義。本文總結了樹枝狀介孔納米粒子（DMNs）在有害物質檢測領域的最新研究進展。涉及的有害物質主要包括酚類化合物、醫藥及農藥、食品添加劑、揮發性有機化合物（VOCs）、苯甲酮類紫外線吸收劑、重金屬離子及有毒非金屬元素。重點分析了以樹枝狀介孔納米粒子為基礎，構建有害物質檢測傳感器的設計思路和制備過程，為發展其它新型檢測系統提供參考。對樹枝狀介孔納米粒子型傳感器的未來研究方向進行了討論與展望。

關鍵詞：有害物質；樹枝狀介孔納米粒子；檢測傳感器

中圖分類號：O611.4    文獻標識碼：A    文章編號：1000-0720（2024）05-0749-08

Recent progress on the detection of hazardous substances by dendritic mesoporous nanoparticles

WANG Yanni¹，HE Hua²，WANG Yabin^*1，2，DING Xiuping³

1. College of Chemistry and Chemical Engineering，Yan’an University，Yan’an 716000，China；2. Institute for Triazine Compounds & Hierarchical Porous Materials，Yan’an 716000，China；3. Qinghai Institute of Salt Lakes，Chinese Academy of Sciences，Xining 810008，China）

Abstract：Organic and inorganic hazardous substances can badly destroy environmental safety and human health，which makes the detection of these compounds practically significant. This article summarizes the latest progress on the detection of hazardous substances by dendritic mesoporous nanoparticles （DMNs）. The hazardous substances mainly cover phenolic compounds，pharmaceutical and agricultural chemicals，food additives，volatile organic compounds （VOCs），benzophenone-type UV filters，heavy metal ions，and nonmetallic toxic elements. The design strategies and preparation processes of detection sensors based on DMNs have been emphatically reviewed to provide references for the development of other new detection systems. In addition，the future research direction and prospect have been discussed.

Keywords：hazardous substances；dendritic mesoporous nanoparticles；detection sensors

人體呼氣中揮發性有機化合物檢測方法在肺癌無創診斷中的應用

陳京¹，宗成華²，徐永紅¹，李榮鵬^*1，3

（1. 江蘇師范大學生命科學學院，徐州 221000；2. 江蘇師范大學化學與材料科學學院，徐州 221000；3. 江蘇氙能生命科學研究院，徐州 221000）

摘要：肺癌是最常見最難治療的惡性腫瘤之一。由于在早期階段幾乎是無癥狀的，絕大多數肺癌被發現時即為晚期。而早發現可以提高肺癌患者的生存率，因此，肺癌的早期診斷至關重要。呼氣分析具有快速、無創、采樣方便以及對人體友好等優點，具有應用于肺癌早篩的巨大潛力。本文綜述了人體呼氣中揮發性有機化合物的采樣與富集方法以及不同檢測技術在肺癌中的應用，并對其存在的局限性及未來發展趨勢進行了討論。

關鍵詞：肺癌；揮發性有機化合物；呼氣檢測

中圖分類號：R734.2    文獻標識碼：A    文章編號：1000-0720（2024）05-0757-10

Application of volatile organic compound detection method for human breath in non-invasive diagnosis of lung cancer

CHEN Jing¹，ZONG Chenghua²，XU Yonghong¹，LI Rongpeng^*1，3

1. College of Life Science，Jiangsu Normal University，Xuzhou 221000，China；2. College of Chemistry and Materials Science，Jiangsu Normal University，Xuzhou 221000，China；3. Jiangsu Xenon Life Science Research Institute，Xuzhou 221000，China）

Abstract：Lung cancer is one of the most common and the most lethal malignant tumors. Since lung cancer is almost asymptomatic in its early stage，most of them are advanced when diagnosed. Early detection can improve the survival rate of lung cancer，therefore，early diagnosis of lung cancer is essential. Breath analysis method has the advantages of rapid，non-invasive，convenient sampling and human friendly，leading to its great potential for early screening of lung cancer. In this paper，the methods of sampling and enrichment of volatile organic compounds （VOCs） in human breath and the applications of different detection techniques in lung cancer were reviewed，and their limitations and future development trends were discussed.

Keywords：lung cancer；volatile organic compounds；breath testing