基于金属有机框架材料的比率荧光印迹探针测定磺胺嘧啶
黄勇强1，明秦1，黄卫红1，杨文明*2
（1. 江苏大学环境与安全工程学院，镇江 212013；2. 江苏大学材料科学与工程学院，镇江 212013）
摘要：基于荧光分析法与分子印迹技术，构建了一种可快速、灵敏检测自来水和牛奶中磺胺嘧啶的荧光探针。以磺胺嘧啶为模板分子，3-氨丙基三乙氧基硅烷为功能单体，金属有机框架材料（MOFs）为载体，将碲化镉量子点（CdTe QDs）包埋于MOFs中，镁氮共掺杂的石墨烯量子点（Mg，N/GQDs）为响应信号，通过溶胶凝胶法制备了荧光分子印迹探针。对合成探针的形貌、化学结构和性能进行表征。结果显示，磺胺嘧啶浓
度在0~100 μmol/L范围内，与荧光强度呈良好的线性关系，检出限为11.23 nmol/L，回收率在96.2%~101.2%之间，相对标准偏差（RSD）小于1.7%。该探针已成功应用于实际样品自来水和牛奶中磺胺嘧啶的检测。
关键词：磺胺嘧啶；比率荧光；金属有机框架；分子印迹聚合物
中图分类号：O657.3 文献标识码：A 文章编号：1000-0720（2024）06-0767-07
Detection for sulfadiazine by ratio fluorescent imprinting probe based on metal organic framework materials
HUANG Yongqiang1，MING Qin1，HUANG Weihong1，YANG Wenming*2
1. School of Environment and Safety Engineering，Jiangsu University，Zhenjiang 212013，China；2. School of Materials Science and Engineering，Jiangsu University，Zhenjiang 212013，China）
Abstract：Based on fluorescence analysis and molecular imprinting technology，a fluorescent probe for rapid and sensitive detection of sulfadiazine in tap water and milk was constructed. Using sulfadiazine as template molecule，3-aminopropyltriethoxysilane as functional monomer，and metal organic framework materials （MOFs） as carrier，CdTe quantum dots （CdTe QDs） were embedded in MOFs. Then，Mg and N co doped graphene quantum dots （Mg，N/GQDs） were used as response signals，and the fluorescent molecular imprinting probes were prepared by sol-gel method. The morphology，chemical structure and properties of the synthesized probe were characterized. The results showed that the concentration of sulfadiazine had a good linear relationship with fluorescence intensity in the range of 0-100 μmol/L. The detection limit was 11.23 nmol/L，the recoveries were 96.2%-101.2%，and the relative standard deviations were less than 1.7%. The probe has been successfully applied to the detection of sulfadiazine in actual samples of tap water and milk.
Keywords：sulfadiazine；ratio fluorescence；metal organic framework；molecularly imprinted polymer
反相高效液相色谱法同时拆分3种手性杀菌剂
周励*1，唐婧2，范荣华1，陈彤1，欧阳玉1
（1. 沈阳医学院公共卫生学院，沈阳 110034；2. 清华大学临床医学院，清华大学附属北京清华长庚医院，北京 102218）
摘要：应用Chiralpak IH手性色谱柱，建立了一种同时拆分多效唑、己唑醇、糠菌唑3种三唑类杀菌剂对映异构体的高效液相色谱分析方法。采用反相色谱条件，以乙腈-水为流动相，在230 nm下进行分析，在优化条件下，即乙腈-水（40∶60，V/V）为流动相，柱温35 ℃、流速1.0 mL/min时，3种三唑类杀菌剂对映异构体能同时实现手性分离。
关键词：高效液相色谱法；手性分离；反相；Chiralpak IH手性柱；三唑类杀菌剂
中图分类号：TQ450.7 文献标识码：A 文章编号：1000-0720（2024）06-0774-06
Simultaneous enantiomeric separation of three triazole fungicides by reversed-phase high performance liquid chromatography
ZHOU Li*1，TANG Jing2，FAN Ronghua1，CHEN Tong1，OUYANG Yu1
1. School of Public Health，Shenyang Medical College，Shenyang 110034，China；2. School of Clinical Medicine，Beijing Tsinghua Changgung Hospital，Tsinghua University，Beijing 102218，China）
Abstract：A high performance liquid chromatographic method was established for the simultaneous chiral separation of three triazole fungicides，including paclobutrazol，hexaconazole and bromuconazole with Chiralpak IH column. The analysis of three triazole fungicides was carried out by reversed-phase high performance liquid chromatography with the mobile phase of acetonitrile and water. The wavelength of UV detector was 230 nm. Under the optimized separation conditions as follows：acetonitrile-water （40∶60，V/V） as mobile phase，column temperature of 35 ℃ and flow rate of 1.0 mL/min，three triazole fungicides were chiral separated simultaneously.
Keywords：high performance liquid chromatography；chiral separation；reversed phase；Chiralpak IH column；triazole fungicide
碳点比率荧光探针测定果蔬中的甲胺磷
韩雍*
，汪慧，张晓燕
（陇东学院农林科技学院，庆阳 745000）
摘要：以邻苯二胺与浓硫酸为原料，通过一步水热法合成了荧光碳点（oPD-CDs），构建了一种检测果蔬中甲胺磷（MTP）的oPD-CDs比率荧光传感器。在优化条件下，oPD-CDs传感器的荧光比值（F430/F483）与甲胺磷浓度在0~160 ng/mL范围内呈良好的线性关系，相关系数R2为0.99，检出限（LOD）为14.3 ng/mL，加标回收率为92.0%~108.0%，相对标准偏差（RSDs）为0.7%~1.6%。该方法可用于果蔬中甲胺磷残留的检测。
关键词：农药残留；荧光碳点；甲胺磷；快速检测
中图分类号：O657.3；O661.1 文献标识码：A 文章编号：1000-0720（2024）06-0780-05
Carbon dots-based ratiometric fluorescent probe for the detection of methamidophos residues in fruits and vegetables
HAN Yong*，WANG Hui，ZHANG Xiaoyan
College of Agriculture and Forestry，Longdong University，Qingyang 745000，China）
Abstract：In this work，o-phenylenediamine and concentrated sulfuric acid were used as precursors to prepare multi-emissive fluorescent carbon dots （oPD-CDs） through a one-step hydrothermal method. Then，oPD-CDs were employed as a fluorescent probe for the detection of methamidophos （MTP） residues in fruits and vegetables. Under the optimal conditions，the fluorescence ratio values （F430/F483） of the oPD-CDs sensor showed a good linear relationship with the MTP concentration in the range of 0-160 ng/mL，with the correlation coefficient （R2） of 0.99. The limit of detection （LOD） was calculated as 14.3 ng/mL，the spiked recoveries were 92.0%-108.0%，and the relative standard deviations （RSDs） were 0.7%-1.6%. The method can be applied to the detection of MTP residues in fruits and vegetables.
Keywords：pesticide residues；fluorescence carbon dots；methamidophos；rapid detection
鲁米诺-还原金纳米粒子/碳纳米管三维复合材料基电化学发光传感器检测血清中的乳酸
赵慧1，娄方明1，2，石晓冉1，张涵1，李群芳*1，2
（1. 湖北民族大学化学与环境工程学院，恩施 445000；2. 风湿性疾病发生与干预湖北省重点实验室，恩施 445000）
摘要：采用一锅水热法制备了鲁米诺-还原金纳米粒子/碳纳米管三维复合材料（Lu-AuNPs/CNTs），用其制备固态电化学发光（ECL）传感器，并用于血清中乳酸的检测。采用场发射扫描电子显微镜（FSEM）、透射电子显微镜（TEM）、X射线粉末衍射仪（XPS）和X射线光电子能谱仪（EDS）对Lu-AuNPs/CNTs的形貌、结构、尺寸进行了表征。结果表明，碳纳米管（CNTs）为三维立体网状结构，鲁米诺-还原金纳米粒子（Lu-AuNPs）尺寸均一地分布在CNTs的表面。将Lu-AuNPs/CNTs固定在玻碳电极表面制成固态ECL传感器，其电化学发光信号约是Lu-AuNPs的2倍。该传感器的电化学发光强度与溶液中H2O2浓度成正比，线性范围为0.5~200 μmol/L，检测限为0.2 μmol/L。Lu-AuNPs/CNTs可用于固定乳酸氧化酶，所制备的传感器对乳酸的检测限为3.0 μmol/L。该生物传感器可用于人血清样品中乳酸的测定。
关键词：一步水热合成；鲁米诺-还原金纳米粒子/碳纳米管三维复合材料；过氧化氢；乳酸
中图分类号：O657.1 文献标识码：A 文章编号：1000-0720（2024）06-0785-08
Detection of lactate in serum by electrochemiluminescence biosensor based on luminol-reduced gold nanoparticles/carbon nanotubes three dimensional nanocomposites
ZHAO Hui1，LOU Fangming1，2，SHI Xiaoran1，ZHANG Han1，LI Qunfang*1，2
1. School of Chemistry and Environmental Engineering，Hubei University for Nationalities，Enshi 445000，China；2. Hubei Provincial Key Laboratory of Rheumatic Disease Occurrence and Intervention，Enshi 445000，China）
Abstract：An electrochemiluminescence （ECL） biosensor was constructed for the detection of lactate in serum based on a new synthesized luminol-reduced gold nanoparticles/carbon nanotubes three dimensional nanocomposites （Lu-AuNPs/CNTs） synthesized by one-pot hydrothermal method. The morphology，structure，and size of Lu-AuNPs/CNTs were characterized using field emission scanning electron microscopy （FSEM），transmission electron microscopy （TEM），X-ray powder diffractometer （XPS），and X-ray photoelectron spectroscopy （EDS）. The results showed that Lu-AuNPs/CNTs had a three-dimensional network structure，and the Lu-AuNPs uniformly distributed on the surface of CNTs. A solid-state ECL sensor was constructed by fixing Lu-AuNPs/CNTs on the surface of a glassy carbon electrode，and the signal of Lu-AuNPs/CNTs was approximately twice of that of Lu-AuNPs. The ECL intensity of Lu-AuNPs/CNTs increased linearly with the increase of H2O2 concentration in the range from 0.5 to 200 μmol/L，and the limit of detection （LOD） was 0.2 μmol/L. Lactate oxidase was immobilized on Lu-AuNPs/CNTs to fabricate a lactate ECL biosensor，the LOD for lactate was 3 μmol/L. This biosensor can be used for the determination of lactate in human serum.
Keywords：one-pot hydrothermal synthesis；luminol-reduced gold nanoparticles/carbon nanotubes three dimensional nanocomposites；hydrogen peroxide；lactate
分子印迹固相萃取-高效液相色谱法检测奶粉中3种β-兴奋剂
魏盘，王建*，石雨，祁迎春，任景俞，黄华，牛志睿，孙召
（延安市环境检测与修复重点实验室，延安大学石油工程与环境工程学院，延安 716000）
摘要：以β-兴奋剂3-甲氧酪胺（3-MT）、多巴胺（DA）和去氧肾上腺素（PE）为模板，采用沉淀聚合法，分别制备了3种单模板分子印迹聚合物（SMIP）和3种混合模板分印迹聚合物（MMIP），并在水和乙醇中对其吸附和分离性能进行了评价。结果表明，以3-MT为模板的SMIP1在乙醇中对上述3种β-兴奋剂具有最佳选择性，25 min可达吸附平衡。在对3-MT的初始浓度为0.03 mmol/L时，印迹因子（IF）最大，为2.12。SMIP1对3-MT，DA和PE的吸附量随吸附初始浓度增加而增加，在3 mmol/L时分别达到41.26，39.83和40.47 μmol/g。以SMIP1为吸附剂从奶粉中同时高选择性固相萃取3-MT，DA和PE，在上样浓度为0.01，0.02和0.03 mmol/L时，高效液相色谱法（HPLC）检测的回收率分别为98%~100%，92.5%~96%和90.3%~94%，相对标准差（RSD）分别为1.9%~5.1%，2.0%~4.0%和2.1%~4.2%。该方法适用于奶粉中3-MT的定量分析以及DA和PE的定性检测。
关键词：β-兴奋剂；分子印迹聚合物；固相萃取；奶粉
中图分类号：O657 文献标识码：A 文章编号：1000-0720（2024）06-0793-06
Detection of three kinds of β-Agonists in milk powder by molecularly imprinted solid phase extraction-high performance liquid chromatography
WEI Pan，WANG Jian*，SHI Yu，QI Yingchun，REN Jingyu，HUANG Hua，NIU Zhirui，SUN Zhao
Key Laboratory of Environmental Testing and Restoration，School of Petroleum Engineering and Environmental Engineering，Yan'an University，Yan'an 716000，China）
Abstract：In this study，three single-template molecular imprinted polymers （SMIP） and three mixed template-molecular imprinted polymers （MMIP） were prepared by precipitation polymerization using 3-methoxytyine （3-MT），dopamine （DA） and phenylephrine （PE） as the templates，and their adsorption and separation performance were evaluated in water and ethanol. The performance tests showed that the adsorption capacity of SMIP1 with 3-MT as template had the best selectivity for the above three β-Agonists in ethanol，and the adsorption equilibrium can be reached at 25 min. When the initial concentration of 0.03 mmol/L，the imprinting factor （IF） reached the highest value of 2.12. The adsorption capacity of SMIP1 for 3-MT，DA and PE increased with the initial concentration，reaching 41.26，39.83 and 40.47 μmol/g at 3 mmol/L，respectively. The selective simultaneous extraction of 3-MT，DA and PE from milk powder were achieved by employing this SMIP1 as a solid phase extraction adsorbent. At the spiked concentrations of 0.01，0.02 and 0.03 mmol/L，the mean recoveries of 3-MT，DA and PE，as detected by high performance liquid chromatography （HPLC） method，ranged from 98% to 100%，92.5% to 96%，and 90.3% to 94%，respectively. The relative standard deviations （RSDs） ranged from 1.9% to 5.1%，2.0% to 4.0% and 2.1% to 4.2%，respectively. This method is suitable for quantitative analysis of 3-MT and qualitative detection of DA and PE in milk powder.
Keywords：β-Agonists；molecularly imprinted polymers；solid-phase extraction；milk powder
电感耦合等离子体串联质谱法检测食用农产品中的总溴
李爱阳1，吴路辉1，殷子懿1，陈宇1，蔡玲1，黄建华*2
（1. 湖南工学院化学与环境工程学院，衡阳 421002；2. 湖南省中医药研究院中药研究所，长沙 410013）
摘要：建立了电感耦合等离子体串联质谱（ICP-MS/MS）测定食用农产品中总溴的方法，以N2O作为反应气消除质谱干扰。在MS/MS模式下，研究了在八极杆反应池系统（ORS）中N2O与Br+的相互作用。基于氧原子转移反应，将Br+转移为氧化物离子BrO+，利用Br+→BrO+为离子对，消除质谱干扰。将N2O反应结果与采用O2的反应结果比较，N2O能更有效地形成氧化物离子，灵敏度更高，背景等效浓度（BEC）和检出限（LOD）更低，消除干扰更彻底。通过分析标准参考物质，评价方法的准确性和精密度，发现测定结果与标准参考物质的认证值基本一致。溴的LOD为38.4~52.6 ng/L，相对标准偏差（RSD）为1.8%~4.3%，加标回收率在96.8%~103.0%之间。所建立的方法适用于食用农产品中总溴的测定。
关键词：电感耦合等离子体串联质谱；食用农产品；总溴；N2O；氧原子转移反应
中图分类号：O657.31 文献标识码：A 文章编号：1000-0720（2024）06-0799-06
Determination of total bromine in edible agricultural products by inductively coupled plasma tandem mass spectrometry
LI Aiyang1，WU Luhui1，YIN Ziyi1，CHEN Yu1，CAI Ling1，HUANG Jianhua*2
1. Department of Chemical and Environmental Engineering，Hunan Institute of Technology，Hengyang 421002，China；2. Institute of Chinese Materia，Hunan Academy of Traditional Chinese Medicine，Changsha 410013，China）
Abstract：A new method for the determination of total bromine （Br） in edible agricultural products by inductively coupled plasma-tandem mass spectrometry （ICP-MS/MS） was established. A new strategy of using N2O as reaction gas to eliminate the spectral interference was proposed. In the MS/MS mode，the interaction between N2O and Br+ in the octopole reaction system （ORS） was studied. Based on the oxygen atom transfer reaction，Br+ was transferred to the oxide ion BrO+，and the spectral interferences were eliminated by using Br+→BrO+ as the ion pair. Comparison of the results using N2O and O2 as reaction gas revealed that N2O was more effective at forming oxides，obtaining higher sensitivity，lower background equivalent concentration （BEC） and limit of detection （LOD），and eliminating interference more thoroughly. The accuracy and precision of the method were assessed by analyzing the standard reference materials. It was found that the determination results were in good agreement with the certified values of the reference materials. The LODs of Br were 38.4-52.6 ng/L，the relative standard deviations （RSDs） were 1.8%-4.3%，and the spiked recoveries were 96.8%-103.0%. The developed analytical method is suitable for the determination of total Br in edible agricultural products.
Keywords：inductively coupled plasma tandem mass spectrometry；edible agricultural products；total bromine；N2O；oxygen atom transfer reaction
AgNPs/SiO2纳米碗表面增强拉曼光谱基底的制备及多环芳烃检测
王世强，金艳，姜慧芸，安飞，朱亮*，肖安山
（化学品安全控制国家重点实验室，中石化安全工程研究院有限公司，青岛 266100）
摘要：以胶体自组装方法为基础，制备二氧化硅（SiO2）纳米碗阵列；利用多巴胺在其表面原位还原一层银纳米颗粒（AgNPs）；然后修饰一层硫醇分子，得到硫醇修饰的AgNPs/SiO2纳米碗复合表面增强拉曼光谱（SERS）基底。通过调节AgNPs的密度和硫醇分子的种类，得到最优化的SERS基底。该SERS基底对芘和菲的检出限均为1×10-7 mol/L，在1×10-2~1×10-7 mol/L浓度范围内，拉曼信号强度与芘和菲浓度呈线性关系，相关系数（R2）均大于0.99。该基底具有良好的均一性和重复性，芘分子（1×10-5 mol/L）在592和1402 cm-1处拉曼信号强度的相对标准偏差（RSD）分别为4.0%和4.9%。该方法制备的复合SERS基底在水中痕量多环芳烃以及其他污染物的高灵敏度检测等方面有广阔的应用前景。
关键词：表面增强拉曼光谱；银纳米颗粒/二氧化硅纳米碗；硫醇；疏水作用；多环芳烃
中图分类号：O657.37 文献标识码：A 文章编号：1000-0720（2024）06-0805-09
Fabrication of surface enhanced Raman spectroscopy substrates composed of silver nanoparticles/SiO2 nanobowls for the detection of polycyclic aromatic hydrocarbons
WANG Shiqiang，JIN Yan，JIANG Huiyun，AN Fei，ZHU Liang*，XIAO Anshan
State Key Laboratory of Safety and Control for Chemicals，SINOPEC Research Institute of Safety Engineering Co.，Ltd.，Qingdao 266100，China）
Abstract：Based on the colloidal self-assembly method，the silica （SiO2） nanobowl arrays were easily fabricated. A layer of silver nanoparticles （AgNPs） was in-situ reduced by dopamine on the surface of the nanobowls，and then the mercaptan molecules were added to fabricate mercaptan modified AgNPs/SiO2 nanobowls hierarchical surface enhanced Raman spectroscopy （SERS） substrates. The optimized SERS substrates could be obtained by adjusting the density of AgNPs and the type of mercaptan molecule. The experimental results indicated that the limits of detection of pyrene and phenanthrene by the SERS substrates were both 1×10-7 mol/L，and the linear correlation coefficients （R2） of Raman signal intensity and concentration were also above 0.99 in the concentration range of 1×10-2-1×10-7 mol/L. The SERS substrates showed excellent uniformity and repeatability. The relative standard deviations （RSDs） of the Raman signal intensity of pyrene molecules （1×10-5 mol/L） at 592 cm-1 and 1402 cm-1 were 4.0% and 4.9%，respectively. The SERS substrate prepared by this method will be applied in various application areas，such as high sensitivity detection of trace amounts of polycyclic aromatic hydrocarbons （PAHs） and other contaminants in water.
Keywords：surface enhanced Raman spectroscopy；silver nanoparticles/SiO2 nanobowls；mercaptan；hydrophobic interaction；polycyclic aromatic hydrocarbons
香豆素衍生物-纸芯片体系对3种生物硫醇的选择性检测
张剑，王祖黎，唐新萍，李一冰，郑志鸿，王月萍，张博，刘春叶*
（西安医学院药学院，西安 710021）
摘要：合成了一种7-（二乙氨基）香豆素衍生物荧光探针，并通过红外吸收光谱、质谱和核磁共振波谱对其进行结构表征。该探针可与同型半胱氨酸（Hcy）、半胱氨酸（Cys）、谷胱甘肽（GSH）发生不同的显色反应，以微流控纸芯片为平台，实现了对3种生物硫醇的特异性检测。手机拍照记录显色结果，Photpshop软件分析RGB通道颜色强度（RGB值）。当探针浓度为10 μmol/L，3种生物硫醇浓度在10~50 μmol/L范围内时，RGB值与生物硫醇浓度呈良好线性关系。该方法在6 min内即可完成实际样品分析，结果相对误差均小于3%，可用于疾病危险因子的快速实时检测。
关键词：荧光探针；微流控纸芯片；同型半胱氨酸；半胱氨酸；谷胱甘肽
中图分类号：O652 文献标识码：A 文章编号：1000-0720（2024）06-0814-05
Selective detection of three biomercaptan by a coumarin derivative based paper chip
ZHANG Jian，WANG Zuli，TANG Xinping，LI Yibing，ZHENG Zhihong，WANG Yueping，ZHANG Bo，LIU Chunye*
School of Pharmacy，Xi'an Medical University，Xi'an 710021，China）
Abstract：A fluorescent probe of 7-（diethylamino） coumarin derivative was synthesized，and characterized by fourier transform infrared （FT-IR） spectroscopy，mass spectrometry （MS） and nuclear magnetic resonance （NMR） spectroscopy，respectively. This probe is capable of interacting with homocysteine （Hcy），cysteine （Cys），and glutathione （GSH） and present different colors，which supports a distinguishing detection of three biomercaptan using microfluidic paper chips as a platform. The result photos were recorded using a mobile phone，and the color intensity of RGB channel （RGB value） were assessed by Photoshop software. Favourable linear relationships were obtained between color intensity and concentrations of the three biomercaptan in the range of 10-50 μmol/L with the probe concentration of 10 μmol/L. The real sample was analyzed within 6 min，and the relative errors of the results were all less than 3%. The work demonstrates that the method is enable to be employed for rapid and real-time detection of risk factors of diseases.
Keywords：fluorescent probe；micro?uidic paper-based analytical devices；homocysteine；cysteine；glutathione
小型质子转移反应质谱仪离子源的设计与优化
陈蹇平1，王俊1，闻路红1，2，3，陈腊*1，2
（1. 宁波大学宁波高等技术研究院，宁波 315211；2. 宁波华仪宁创智能科技有限公司，宁波 315191；3. 广州市华粤行仪器有限公司，广州 511400）
摘要：作为一种快速、高灵敏的挥发性有机物（VOCs）检测技术，质子转移反应质谱（PTR-MS）被越来越多地应用于环境、医学、公共安全等领域。作为PTR-MS的关键部件之一，空心阴极辉光放电离子源对仪器性能具有重要影响。本文通过有限元仿真优化了空心阴极结构，在阴极内径为20 mm、阳极与阴极间隙为4 mm时，离子源放电效果较好。将优化后的空心阴极辉光放电离子源与便携式质谱仪联用，并测试了离子信号与放电气压和放电电流的关系。结果表明，最佳放电气压约为200 Pa，最佳放电电流为9~13 mA。采用乙腈样品测试了仪器性能，系统响应时间在10 s以内，乙腈检出限约为10-9（V/V），线性范围为50×10-9~350×10-9 （V/V），线性相关系数R2=0.991。利用该装置检测了苹果发酵过程中产生的VOCs随时间的变化，证明了该仪器可用于实际样品检测。
关键词：质子转移反应质谱；空心阴极辉光放电离子源；挥发性有机物；线性离子阱；有限元仿真
中图分类号：O657.31；X832 文献标识码：A 文章编号：1000-0720（2024）06-0819-09
Design and optimization of the ion source for miniature proton transfer reaction mass spectrometer
CHEN Jianping1，WANG Jun1，WEN Luhong1，2，3，CHEN La*1，2
1. Ningbo Institute of Advanced Technologies，Ningbo University，Ningbo 315211，China；2. China Innovation Instrument Co. Ltd.，Ningbo 315191，China；3. Hua Yue Enterprise Holdings Ltd.，Guangzhou 511400，China）
Abstract：As a rapid and highly sensitive technique for volatile organic compounds （VOCs） detection，proton transfer reaction mass spectrometry （PTR-MS） is increasingly used in environment，medical，and public safety fields. As a key component of PTR-MS，the hollow cathode glow discharge ion source is very important for the performance of the instrument. In this work，the hollow cathode structure was optimized by finite element simulation，and the best discharge effect had been achieved with a cathode at inner diameter of 20 mm and a gap of 4 mm between anode and cathode. The hollow cathode glow discharge ion source was coupled to a portable mass spectrometer. The effects of pressure and discharge current on ion signals were verified experimentally. The results showed that the optimum discharge pressure was about 200 Pa and the optimum discharge current was between 9 and 13 mA. The instrument performance was tested with acetonitrile samples. The results showed that the response time of the system to acetonitrile was within 10 s，the limit of detection was about 10-9（V/V），and the linearity range was 50×10-9-350×10-9 （V/V） with a correlation coefficient of R2=0.991. Finally，the device was used to detect the variation of VOCs released during apple fermentation over time，demonstrating that the instrument can be used for actual samples analysis.
Keywords：proton transfer reaction mass spectrometry；hollow cathode glow discharge ion source；volatile organic compounds；linear ion trap；finite element simulation
化学样品前处理设备的研制及应用
王晓香*1，时雪钊2，陈鹏飞1
（1. 冰冻圈科学国家重点实验室，中国科学院西北生态环境资源研究院，兰州 730000；2. 兰州大学化学化工学院，兰州 730000）
摘要：设计开发了一套多功能样品前处理设备，可在线或离线完成样品处理。该设备以电渗析原理为基础，将膜交换与阀切换技术组合使用，实现了酸碱中和、除盐、过滤、稀释、浓缩、基体消除等功能。通过实验验证了仪器的可靠性和可行性。采用75 μm的树脂和1.5 mm管径，得到最佳中和容量；中和能力可通过调节电流大小进行调控。饱和溶液的中和/除盐效率达100%，2~100倍稀释，连续8次测试的相对标准偏差（RSD）<5%；浓缩连续5次进样的RSD<4.5%。基体消除能力强，甲醇处理后可直接进入分析仪器进行测试。各功能可自由组合，也可连接离子色谱、等离子体质谱等仪器，进行在线样品前处理；特别是设备中和单元，可在线自动再生，弥补了现有技术的不足。该设备可广泛应用于食品、化工、生物、医药、水处理、核电、环境和材料等领域的样品前处理。
关键词：前处理；设备研制；电渗析；中和；应用
中图分类号：TH122 文献标识码：A 文章编号：1000-0720（2024）06-0828-06
Development and application of pretreatment equipment for chemical samples
WANG Xiaoxiang*1，SHI Xuezhao2，CHEN Pengfei1
1. State Key Laboratory of Cryospheric Science，Northwest Institute of Eco-Environment and Resources，Chinese Academy of Sciences，Lanzhou 730000，China；2. College of Chemistry and Chemical Engineering，Lanzhou University，Lanzhou 730000，China）
Abstract：Based on the principle of electrodialysis，a multi-functional sample pretreatment equipment，which can complete sample processing online or offline，was designed and developed. The equipment combines membrane exchange and valve switching technology to achieve acid-base neutralization，desalination，filtration，dilution，concentration，matrix elimination and other functions. The reliability and feasibility of the instrument were verified through experiments. When using 75 μm resin and 1.5 mm pipe，the optimal neutralization capacity can be obtained for the equipment，and it can be controlled by tuning the current. The neutralization/desalination efficiency of the saturated solution reached 100%，with the relative standard deviation （RSD） less than 5% for 8 times consecutive dilutions at 2 to 100 times，and the RSD was less than 4.5% for 5 consecutive injection tests for concentration. The matrix elimination ability of this equipment is excellent，the samples can be directly fed into analysis instruments after methanol treatment. Each function can be freely combined or be connected to analytical instruments such as ion chromatography and plasma mass spectrometry for sample pre-treatment. Especially，the neutralization unit of the equipment can automatically regenerate online，which compensates for the shortcomings of existing technology. This equipment can be widely applied in sample pretreatment in food，chemical，biology，medicine，water treatment，nuclear power，environment and materials fields.
Keywords：pretreatment；equipment development；electrodialysis；neutralization；application
基质分散固相萃取-气质联用法测定皮革中12种挥发性全氟和多氟化合物
高永刚1，王岩2，李晓瞳3，牛增元*1，罗忻1，叶曦雯1，张艳艳4，郑丽莎1，王铭1
（1. 青岛海关技术中心，青岛 266114；2. 山东鲁检科技有限公司，青岛 266002；3. 中国海洋大学海洋环境与生态教育部重点实验室，青岛 266100；4. 青岛市产品质量检验研究院，青岛 266022）
摘要：建立了分散固相萃取（d-SPE）-气相色谱-质谱法（GC-MS）同时测定皮革中12种挥发性全氟和多氟化合物（PFAS）的方法，包括4种氟化调聚物醇（FTOHs）、3种氟调聚丙烯酸酯（FTAs）、5种全氟辛烷磺酰胺（FOSAs）。考察了提取条件、净化方法和定容溶剂对提取效率的影响。最终确定采用10 mL乙腈为提取溶剂，50 ℃下超声提取20 min，取1 mL提取液经100 mg GCB分散固相萃取净化后，GC-MS选择离子模式（SIM）检测，外标法定量。结果表明：12种挥发性PFAS在0.02~5.0 mg/L范围内线性关系良好，相关系数（R2）均不低于0.9990；方法回收率为77.6%~110.5%，相对标准偏差（RSD）为1.5%~11%，方法定量限（LOQ）为0.2 mg/kg。该方法适用于皮革中PFAS的确证和定量分析。
关键词：皮革；挥发性全氟和多氟化合物；分散固相萃取；气相色谱-质谱法
中图分类号：O657.63 文献标识码：A 文章编号：1000-0720（2024）06-0834-07
Determination of 12 volatile perfluoroalkyl and polyfluoroalkyl substances in leathers by dispersive solid-phase extraction-gas chromatography-mass spectrometry
GAO Yonggang1，WANG Yan2，LI Xiaotong3，NIU Zengyuan*1，LUO Xin1，YE Xiwen1，ZHANG Yanyan4，ZHENG Lisha1，WANG Ming1
1. Technology Center of Qingdao Customs，Qingdao 266114，China；2. Shandong Lujian Technology Co.，LTD，Qingdao 266002，China；3. Key Laboratory of Marine Environment and Ecology，Ministry of Education，Ocean University of China，Qingdao 266100，China；4. Qingdao Product Quality Testing Research Institute，Qingdao 266022，China）
Abstract：A method for the simultaneous determination of 12 perfluoroalkyl and polyfluoroalkyl substances （PFAS） in leathers by dispersive solid-phase extraction （d-SPE）-gas chromatography-mass spectrometry （GC-MS） was developed. The target compounds including 4 kinds of fluorotelomer alcohols （FTOHs），3 kinds of fluorotelomer acrylates （FTAs），and 5 kinds of fluorooctane sulfonamides（FOSAs）. The effects of the extraction conditions，purification method，solvent for constant volume on the extraction efficiency were investigated. The target compounds were extracted at 50 ℃ for 20 min with acetonitril，then 1 mL extracting solution was purified by 100 mg graphitized carbon black （GCB），subsequently detected by GC/MS in the scan ion monitoring （SIM） mode and quantified using the external standard method. The results showed that the 12 kinds of PFAS had good linear relationships in the concentration ranges of 0.02-5.0 mg/L with the correlation coefficients （R2）>0.9990. The average recoveries were in the range of 77.6%-110.5%，with relative standard deviations （RSDs） in the range of 1.5%-11%. The limits of quantification were 0.2 mg/kg. This method could meet the needs for detection of PFAS in leathers.
Keywords：leathers；perfluoroalkyl and polyfluoroalkyl substances （PFAS）；dispersive solid-phase extraction （d-SPE）；gas chromatography-mass spectrometry （GC-MS）
基于滤过型净化的液相色谱-串联质谱法测定畜禽肉中89种兽药残留
冯月超1，王建凤1，乔祎娜2，刘佳1，刘艳*1
（1. 北京市科学技术研究院分析测试研究所（北京市理化分析测试中心），北京市食品安全分析测试工程技术研究中心，北京 100089；2. 北京市城市学院生物医药学部，北京100094）
摘要：建立了一种采用滤过型净化柱对畜禽肉样品进行前处理、同时测定89种兽药残留的液相色谱-串联质谱（UPLC-MS/MS）检测方法。畜禽肉用10 mL含1% （V/V）乙酸的乙腈提取，FaVEx-NM柱净化，ACQUITY BEH C18（2.1 mm×100 mm，1.7 μm）柱分离，电喷雾正、负离子模式下多反应监测方式（MRM）采集数据，外标法定量。89种被测物，包括磺胺类、喹诺酮类、硝基咪唑类及其代谢物、苯并咪唑类及其代谢物、β2-兴奋剂类、β-阻滞剂类、利尿剂类共7类化合物，在一定浓度范围内线性关系良好（R2>0.99），在鸡肉、牛肉和猪肉中的加标回收率范围为52.3%~119.8%，相对标准偏差（RSD）均小于20%。利尿剂类的5个化合物，检出限（LODs）范围为0.86~4.51 μg/kg，定量限（LOQs）范围为2.87~15.0 μg/kg，其余84个化合物的LODs范围为0.02~0.44 μg/kg，LOQs范围为0.07~1.48 μg/kg；LODs均满足GB 31650-2019的要求。该方法适用于畜禽肉类中兽药残留的高通量快速筛查。
关键词：超高效液相色谱-串联质谱；兽药；畜禽肉；滤过型净化柱
中图分类号：TS207.5；O657.63 文献标识码：A 文章编号：1000-0720（2024）06-0841-09
Determination of 89 kinds of veterinary drugs in livestock and poultry meat by ultra-high performance liquid chromatography-tandem mass spectrometry based on pass-through solid phase extraction purification
FENG Yuechao1，WANG Jianfeng1，QIAO Yina2，LIU Jia1，LIU Yan*1
1. Institute of Analysis and Testing，Beijing Academy of Science and Technology （Beijing Center for Physical & Chemical Analysis），Beijing Engineering Research Center of Food Safety Analysis，Beijing 100089，China；2. School of Biomedicine，Beijing City University，Beijing 100094，China）
Abstract：An ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method with a pass-through solid phase extraction （SPE） purification was developed for the determination of 89 veterinary drug residues in livestock and poultry meat simultaneously. The meat was extracted with 10 mL acetonitrile containing 1% （V/V） acetic acid，and purified by FaVEx-NM solid phase extraction column.The target analytes were separated on ACQUITY BEH C18 （2.1 mm×100 mm，1.7 μm） column，detected with electrospray ionization in the positive or negative ion mode using multiple reaction monitoring （MRM），and quantified by external standard method. The results showed that 89 kinds of veterinary drugs，including sulfonamides，quinolones，nitroimidazoles and their metabolites，benzimidazoles and their metabolites β2-stimulants，β-blockers and diuretics，had good linear relationships with the correlation coefficients （R2） higher than 0.99. The recoveries of the compounds were in the range of 52.3%-119.8% in the three matrices of chicken，pork and beef. The relative standard deviations （RSDs） were less than 20%. The limits of detections （LODs） of 5 compounds belonging to the class diuretics were 0.86-4.51 μg/kg，and the limits of quantitation （LOQs） were 2.87-15.0 μg/kg. While the LODs of the other 84 compounds were 0.02-0.44 μg/kg，and the LOQs were 0.07-1.48 μg/kg. All the LODs of the target analytes were lower than the requirements of GB 31650-2019. This method is suitable for high-throughput screening of the veterinary drug residues in livestock and poultry meat.
Keywords：ultra-high performance liquid chromatography-tandem mass spectrometry；veterinary drugs；livestock and poultry meat；pass-through solid phase extraction （pass-through SPE）
计算机辅助制备烟碱分子印迹聚合物及其在烟碱纯化中的应用
李增良，顾丽莉*，景联鹏，唐徐禹，李国栋，杨发容
（昆明理工大学化学工程学院，昆明 650500）
摘要：基于密度泛函理论（DFT）对烟碱分子印迹聚合体系进行辅助设计，并优化了烟碱分子印迹聚合物（NMIPs）的制备工艺。以三氟甲基丙烯酸（TFMAA）为功能单体、乙二醇二甲基丙烯酸酯（EGDMA）为交联剂、偶氮二异丁腈（AIBN）为引发剂，烟碱与TFMAA摩尔比为1∶3、乙腈用量为60 mL时，所得NMIPs吸附效果较优，印迹因子为1.8。考察了NMIPs的吸附性能，并借助Scatchard模型分析发现：NMIPs存在高亲和和低亲和两类吸附结合位点，最大表观结合量为28.56 mg/g。利用所制备的NMIPs纯化烟草复烤尾气，使烟碱相对含量由63.58%上升至89.78%；经NMIPs纯化，新鲜烟叶挥发油中的烟碱相对含量由89.39%上升至95.71%。
关键词：烟碱；计算机模拟；分子印迹；纯化
中图分类号：TQ314.2 文献标识码：A 文章编号：1000-0720（2024）06-0850-08
Computer assisted preparation of nicotine molecularly imprinted polymer and its application in the purification of nicotine
LI Zengliang，GU Lili*，JING Lianpeng，TANG Xuyu，LI Guodong，YANG Farong
Faculty of Chemical Engineering，Kunming University of Science and Technology，Kunming 650500，China）
Abstract：The nicotine molecular imprinting polymerization system was designed based on the density functional theory （DFT），and the preparation process of nicotine molecular imprinting polymers （NMIPs） was optimized. Under the conditions of 2-（trifluoromethyl） acrylic acid （TFMAA） as functional monomer，ethylene glycol dimethacrylate （EGDMA） as cross-linking agent，azobisisobutyronitrile （AIBN） as initiator，the molar ratio of nicotine to TFMAA of 1∶3，and the dosage of acetonitrile of 60 mL，the prepared NMIPs had better adsorption capacity，with the imprinting factor of 1.8. The adsorption performance of NMIPs was investigated by Scatchard analysis，it indicated that there were two types of binding sites with high and low affinity of adsorption in the NMIPs，and the maximum apparent binding amount was 28.56 mg/g. When the NMIPs were used to purify nicotine from tobacco regrilling tail gas and the volatile oil of fresh tobacco leaves，the relative contents of nicotine increased from 63.58% to 89.78% and 89.39% to 95.71%，respectively.
Keywords：nicotine；computer simulation；molecular imprinting；purification
电位滴定法测定铁中间合金中铁含量
刘含笑1，刘凯1，王祥德1，薛婷婷1，郭飞1，吕东芹1，王巍*1，2
（1. 国合通用（青岛）测试评价有限公司，青岛 266000；2. 国合通用测试评价认证股份公司，北京 101400）
摘要：建立了铁中间合金中铁含量测定的自动电位滴定法，考察了溶样体系、还原剂类型及用量、滴定环境和共存离子干扰等因素的影响。结果表明，硝酸、过氧化氢和氢氟酸对测定结果有较大的影响，在滴定前应去除；磷酸会导致三氯化钛水解，影响测定结果，应避免引入；共存的Cr，Co和Cu等金属离子对测定结果没有影响。在1%~99%含量范围内，方法的相对标准偏差（RSD）为0.08%~0.26%。使用硅铁、锰铁和钕铁硼等有证标准样品验证了方法的准确度。该方法解决了可视滴定方法存在的滴定终点颜色干扰问题，减少了磷酸等试剂的用量，规避了分离干扰离子的复杂操作，简化了实验步骤，同时提高了铁含量测定的精密度。
关键词：电位滴定；中间铁合金；铁含量测定
中图分类号：O655.23；TF03.1 文献标识码：A 文章编号：1000-0720（2024）06-0858-06
Determination of iron content in intermediate ferroalloy by automatic potentiometric titration method
LIU Hanxiao1，LIU Kai1，WANG Xiangde1，XUE Tingting1，GUO Fei1，LV Dongqin1，WANG Wei*1，2
1. China United Test & Evaluation （Qingdao） Co.，Ltd.，Qingdao 266000，China；2. China United Test & Certification Co.，Ltd.，Beijing 101400，China）
Abstract：The automatic potentiometric titration method was established for the determination of iron content in intermediate ferroalloys. The factors affecting the determination results of iron content，including sample dissolving system，the type and amount of reducing agent，the titration environment and the interference of coexisting ions，were studied. The results showed that nitric acid，hydrofluoric acid，and hydrogen peroxide had great influence on the determination results，which should be removed before titration. Phosphoric acid promoted the hydrolysis of titanium trichloride affecting the determination results and should be avoided. Coexisting metal ions such as Cr，Co and Cu did not affect the determination results. Within the content range of 1%-99%，the relative standard deviations （RSDs） of the method were 0.08%-0.26%，and the accuracy of the method was verified with certified reference materials such as ferrosilicon，ferromanganese and neodymium iron boron. This method solves the problem of color interference of titration end point in visual titration method，reduces the amount of hazardous chemicals such as phosphoric acid，avoids complex operations that interfering ion separation and improves the precision of iron content determination.
Keywords：potentiometric titration；intermediate ferroalloy；iron content determination
SWCSS-DS算法在纸浆材综纤维素近红外分析模型传递中的应用
王红鸿1，汪莹1，黄浩冉1，熊智新*1，胡云超1，刘智健1，梁龙2
（1. 南京林业大学轻工与食品学院，南京 210037；2. 中国林业科学研究院林产化学工业研究所，南京 210042）
摘要：以纸浆材为研究对象，对其综纤维素含量模型进行传递分析，以解决不同近红外光谱仪间多元校正模型无法共享的问题。利用筛选出仪器间具有稳定一致光谱信号的波长（SWCSS）算法，选出稳定性较好的波长，并采用直接校正法（DS）对SWCSS方法校正后仍然存在的系统误差进一步校正。该联合算法能够提高主机模型的普适性，降低光谱矩阵维数，使模型转移更稳定和简单。将本文结果与单独的SWCSS，DS和分段直接标准化（PDS）算法校正后的传递结果进行比较。结果表明，与模型传递前分析能力相比，SWCSS-DS联用算法对2台从机样品的预测标准偏差（RMSEP）分别从2.48和2.31下降到了1.05和1.07，优于单独的SWCSS，DS和PDS算法结果。
关键词：综纤维素含量；近红外光谱；稳定一致波长；DS；模型传递
中图分类号：O657.63 文献标识码：A 文章编号：1000-0720（2024）06-0864-07
Application of SWCSS-DS algorithm in the transfer of near infrared analysis model for holocellulose in pulpwood
WANG Honghong1，WANG Ying1，HUANG Haoran1，XIONG Zhixin*1，HU Yunchao1，LIU Zhijian1，LIANG Long2
1. College of Light Industry and Food Engineering，Nanjing Forestry University，Nanjing 210037，China；2. Institute of Chemical Industry of Forest Products，Chinese Academy of Forestry，Nanjing 210042，China）
Abstract：In this paper，the holocellulose content model in pulpwood was transferred and analyzed to solve the problem that the multivariate calibration models between different near-infrared spectrometers could not be shared. The wavelength with stable and consistent spectral signals （SWCSS） between the instruments algorithm was used to select the wavelength with better stability，and the direct standardization （DS） method was used to further correct the systematic errors that still exist after being corrected by the SWCSS method. The combined algorithm can improve the universality of the master model，reduce the dimension of the spectral matrix，and make the model transfer more stable and simpler. The results of this work were compared with the transfer results corrected by SWCSS，DS and piecewise direct standardization （PDS） algorithm. The results showed that the root mean squared error for prediction （RMSEP） of the SWCSS-DS combined algorithm for two slave samples decreased from 2.48 and 2.31 to 1.05 and 1.07，respectively，compared with the pre-transfer analysis ability of the model，which was better than the results of the single SWCSS，DS and PDS algorithms.
Keywords：holocellulose content；near infrared spectroscopy；stable consistent wavelength；DS algorithm；model transfer
基于分子内电荷转移的比率型荧光探针用于次氯酸检测和细胞成像
张晓文*，张飞
（山西大学分子科学研究所，化学生物学与分子工程教育部重点实验室，太原 030006）
摘要：利用碳碳双键（C=C）可被次氯酸（HClO）选择性氧化的特性，研究了一种具有分子内电荷转移（ICT）效应的HClO检测荧光探针TPS。该探针由于内部具有推拉电子结构，探针本身在激发态下会发生ICT，发出橙红色荧光。加入HClO后，探针分子内不饱和C=C被氧化成醛基，ICT效应减弱，荧光蓝移。反应前后的光谱变化表明探针TPS可用于HClO的比率荧光检测。选择性实验表明探针TPS对HClO具有显著的特异性识别能力。在磷酸盐（PBS）缓冲溶液中，探针TPS对HClO的线性检测范围为0~80 μmol/L，检出限为56 nmol/L。探针TPS也被证实可用于活细胞内HClO荧光成像。
关键词：荧光探针；次氯酸；分子内电荷转移；细胞成像
中图分类号：O657.3 文献标识码：A 文章编号：1000-0720（2024）06-0871-05
A ratiometric fluorescent probe based on intramolecular charge transfer for hypochloric acid detection and cell imaging
ZHANG Xiaowen*，ZHANG Fei
Key Laboratory of Chemical Biology and Molecular Engineering，Ministry of Education，Institute of Molecular Science，Shanxi University，Taiyuan 030006，China）
Abstract：A fluorescence probe TPS based on intramolecular charge transfer （ICT） effect was prepared for hypochloric acid （HClO） detection according to a mechanism that HClO is capable of selectively oxidizing the carbon-carbon double bond （C=C）. Because of the internal push-pull electronic structure，the probe TPS underwent ICT in the excited state and emitting orange-red fluorescence. After the addition of HClO，the unsaturated carbon-carbon double bond of the probe was oxidized to be aldehyde group，which weakened the ICT effect and lead to a fluorescence blue-shift. The spectral changes before and after the reaction proved that the probe TPS can be employed for the ratio detection of HClO. Moreover，the selectivity experiments demonstrated that the probe TPS possesses significant specific recognition of HClO. In PBS buffer solution，the probe TPS is capable of detecting HClO in the range of 0-80 μmol/L，with a detection limit of 56 nmol/L. Importantly，TPS can be utilized for HClO fluorescence imaging in live cells due to its low cytotoxicity.
Keywords：fluorescent probe；hypochlorous acid；intramolecular charge transfer；cell imaging
离子液体萃取-高效液相色谱法同时测定破壁灵芝孢子粉中10种三萜化合物
梁涵，张诚贤，孙梦莹，成霄，吴巧攀，王新财*
（湖州市食品药品检验研究院，湖州 313000）
摘要：建立了离子液体萃取-高效液相色谱法测定破壁灵芝孢子粉中10种灵芝三萜化合物的分析方法。样品采用液液萃取的方法，以1-丁基-3-甲基咪唑四氟硼酸盐为分散剂，以1-己基-3-甲基咪唑六氟磷酸盐为萃取剂提取灵芝三萜类目标化合物，经Shim Nex Phenyl色谱柱分离，外标法定量。结果表明：10个三萜化合物色谱峰分离良好，在测定的质量浓度范围内线性关系良好，相关系数均大于0.999，相对标准偏差（RSD）为2.3%~9.0%，实际样品加标回收率为77.6%~91.2%。本方法适用于灵芝三萜的定量检测。
关键词：离子液体；破壁灵芝孢子粉；萃取；灵芝三萜
中图分类号：O657.31；X832 文献标识码：A 文章编号：1000-0720（2024）06-0876-05
Simultaneous determination of ten triterpenoids contained in the powders of broken Ganoderma lucidum spore by high-performance liquid chromatography combined with ionic liquids extraction
LIANG Han，ZHANG Chengxian，SUN Mengying，CHENG Xiao，WU Qiaopan，WANG Xincai*
Huzhou Institute for Food and Drug Control，Huzhou 313000，China）
Abstract：A method was proposed for the simultaneous determination of ten triterpenoids in broken Ganoderma lucidum spore powders （GLSP） by combining ionic liquid extraction with high-performance liquid chromatography （HPLC）. The target Lingzhi triterpenoids were extracted through liquid-liquid extraction by taking 1-butyl-3-methylimidazolium tetrafluoroborate as dispersant and 1-hexyl-3-methylimidazolium hexafluorophosphate as extractant. Then，the extracts were separated using Shim Nex Phenyl chromatographic column and quantified by external standard method. The chromatographic peaks of ten triterpenoids were effectively separated，and the linear relationships of the ten components were satisfactory in the measured ranges of concentration. The correlation coefficients（r） exceeded 0.999，the relative standard deviations were 2.3%- 9.0%，and the average recoveries were 77.6%-91.2%. This method is suitable for the determination of triterpenoids in GLSP.
Keywords：ionic liquid；broken Ganoderma lucidum spore powders；extraction；triterpenoids
超高效液相色谱-四极杆/静电场轨道阱高分辨质谱检验血和尿中的舒泰成分
张婧文1，孙鑫2，刘俊宁2，王勇2，杨瑞琴*1
（1. 中国人民公安大学侦查学院，北京 100038；2. 南京市公安局刑事科学技术研究所，南京 210001）
摘要：建立了液液萃取-超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法检验血和尿中的舒泰成分替来他明和唑拉西泮。以乙酸乙酯为萃取溶剂，ACQUITY UPLC BEH C18柱为分析柱，乙腈及含有0.1%甲酸和5 mmol/L甲酸铵的水为流动相等度洗脱，在正离子模式下以全扫描-平行反应监测扫描模式采集分析，外标法定量。结果表明，替来他明和唑拉西泮在0.1~50 μg/L范围内线性关系良好，血液和尿液中替来他明和唑拉西泮的检出限分别为0.005，0.001 μg/L，定量限分别为0.017，0.003 μg/L。在低、中、高加标浓度下，血液中替来他明和唑拉西泮的回收率为97.5%~105.0%，日内相对标准偏差（RSD）为2.5%~5.7%，日间RSD为2.7%~10.4%，尿液中2种物质的回收率为90.6%~101.2%，日内RSD为1.2%~4.3%，日间RSD为4.2%~9.7%。该方法可用于法庭科学领域吸食舒泰案件中生物检材的快速检测。
关键词：舒泰；替来他明和唑拉西泮；血液；尿液；液液萃取；超高效液相色谱-四极杆/静电场轨道阱高分辨质谱
中图分类号：O657.7；O657.6 文献标识码：A 文章编号：1000-0720（2024）06-0881-06
Determination of Zoletil in human blood and urine by ultra performance liquid chromatography-Q Exactive orbitrap high-resolution mass spectrometry
ZHANG Jingwen1，SUN Xin2，LIU Junning2，WANG Yong2，YANG Ruiqin*1
1. School of Criminal Investigation，People’s Public Security University of China，Beijing 100038，China；2. Institute of Forensic Science and Technology of Nanjing Public Security Bureau，Nanjing 210001，China）
Abstract：A liquid-liquid extraction-ultra performance liquid chromatography-Q Exactive orbitrap high-resolution mass spectrometry method was developed for the determination of tiletamine and zolazepam in Zoletil in blood and urine. Ethyl acetate was used as the extraction solvent，and an ACQUITY UPLC BEH C18 column was used as the analytical column. The mobile phase was consisted of acetonitrile and water containing 0.1% formic acid and 5 mmol/L ammonium formate with isocratic elution. The mass spectrometry was performed in positive ion mode under Full MS-PRM scan mode，and the quantification was calculated by the external standard method. The linearities of tiletamine and zolazepam were good in the range of 0.1-50 μg/L. The limits of detection were 0.005 and 0.001 μg/L，and the limits of quantification were 0.017 and 0.003 μg/L for tiletamine and zolazepam in blood and urine，respectively. The recoveries of tiletamine and zolazepam in blood at low，medium，and high spiked concentrations were 97.5%-105.0%，with intra-day relative standard deviations （RSDs） of 2.5%-5.7% and inter-day RSDs of 2.7%-10.4%，and the recoveries of the two substances in urine were 90.6%-101.2%，with intra-day RSD of 1.2%-4.3% and inter-day RSD of 4.2%-9.7%. The method can be used for the rapid determination of biological materials in Zoletil abuse cases in forensic science.
Keywords：Zoletil；tiletamine and zolazepam；blood；urine；liquid-liquid extraction；ultra performance liquid chromatography-Q Exactive orbitrap high-resolution mass spectrometry
在线固相萃取-超高效液相色谱-质谱法检测水中8种微囊藻毒素
袁东1，张恒2，张旭方1，韩聪1，徐秀丽3，柏杨巍*2，段平洲2，侯嵩*2
（1. 滨州市生态环境服务中心，滨州 256603；2. 中国环境科学研究院，国家环境保护化学品生态效应与风险评估重点实验室，北京 100012；3. 滨州市环境保护科学技术研究所，滨州 256614）
摘要：建立了一种在线固相萃取-超高效液相色谱-质谱同时检测水中8种微囊藻毒素的方法。水样经在线富集、色谱柱分离后，梯度洗脱，采用电喷雾离子源正离子多反应监测模式，外标法定量。该方法分析时长为11.0 min，标准曲线的线性相关系数R2＞0.98，地表水样品的回收率为83.8%~97.2%，相对标准偏差（RSD）为1.8%~4.9%，检出限为0.28~0.91 ng/L。该方法适用于水体中微囊藻毒素的快速检测。
关键词：地表水；微囊藻毒素；在线固相萃取；超高效液相色谱-质谱
中图分类号：X832 文献标识码：A 文章编号：1000-0720（2024）06-0887-05
Determination of 8 microcystins in water by on-line solid phase extraction coupled with ultra performance liquid chromatography-mass spectrometry
YUAN Dong1，ZHANG Heng2，ZHANG Xufang1，HAN Cong1，XU Xiuli3，BAI Yangwei*2，DUAN Pingzhou2，HOU Song*2
1. Binzhou Ecological Environment Service Center，Binzhou 256603，China；2. Chinese Research Academy of Environmental Sciences，State Environmental Protection Key Laboratory of Ecological Effect and Risk Assessment of Chemicals，Beijing 100012，China；3. Institute of Environmental Protection Science and Technology，Binzhou 256614，China）
Abstract：An online solid-phase extraction-ultra performance liquid chromatography-mass spectrometry （UPLC-MS） method was developed for the simultaneous detection of eight microcystins in water. The water samples were enriched online，separated on a chromatographic column with gradient elution，and quantified by external standard method using electrospray ionization source in positive ions multiple reaction monitoring mode. The analytical time of the method was 11.0 min，the linear correlation coefficients （R2） were higher than 0.98，the recoveries of surface water samples were 83.8%-97.2%，the relative standard deviations （RSDs） were 1.8%-4.9%，and the detection limits were 0.28-0.91 ng/L. The method is suitable for the rapid determination of microcystins in water.
Keywords：surface water；microcystin；online solid-phase extraction；ultra performance liquid chromatography-mass spectrometry
合成大麻素4CN-BINACA-ADB斑马鱼体内代谢研究
谢宜陈，茹俊辉，周善慧，王旻昊，吴剑丙*，范一雷*
（浙江警察学院，浙江省毒品防控技术研究重点实验室，杭州 310053）
摘要：采用斑马鱼模型结合超高效液相色谱串联四极杆-静电场轨迹离子阱Q Exactive质谱（UHPLC-Q-Obitrap-HRMS）技术，研究合成大麻素4CN-BINACA-ADB的体内代谢途径。结果表明，4CN-BINACA-ADB共产生酯水解、羧酸化、羟基化、氰基被羟基还原取代、N-烷基化等Ⅰ相代谢物11种，葡萄糖醛酸化、硫酸化等Ⅱ相代谢物3种。结合代谢物的独特性和含量，推荐羧酸化产物C20H24N4O5 （M2.1）以及羧酸化和氰基还原产物C20H26N4O5 （M2.2）作为主要代谢标志物。研究结果可为生物样品中4CN-BINACA-ADB代谢物的检验鉴定提供理论支撑。
关键词：4CN-BINACA-ADB；合成大麻素；斑马鱼；代谢产物；代谢途径
中图分类号：O657.31；X832 文献标识码：A 文章编号：1000-0720（2024）06-0892-08
Study on metabolites of synthetic cannabinoid 4CN-BINACA-ADB in zebrafish
XIE Yichen，RU Junhui，ZHOU Shanhui，WANG Minhao，WU Jianbing*，FAN Yilei*
Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province，Zhejiang Police College，Hangzhou 310053，China）
Abstract：The metabolic pathway of synthetic cannabinoid 4CN-BINACA-ADB was investigated using zebrafish model combined with ultra-high performance liquid chromatography tandem quadrupole-Orbitrap high-resolution mass spectrometry （UHPLC-Q-Obitrap-HRMS）. The results showed that 4CN-BINACA-ADB produced a total of eleven metabolites of phase I include ester hydrolysis，carboxylation，N-alkylation，hydroxylation，and reduction of cyanide by hydroxyl，and three metabolites of phase II such as glucuronidation and sulfation. Relying on the uniqueness and content of metabolites，carboxylation products C20H24N4O5 （M2.1） and C20H26N4O5 （M2.2） were chosen as the main metabolic biomarkers of 4CN-BINACA-ADB in vivo. This study provides a theoretical support for inspection appraisal of 4CN-BINACA-ADB metabolites in biological samples.
Keywords：4CN-BINACA-ADB；synthetic cannabinoids；zebrafish；metabolites；metabolic pathways
Ag掺杂CuO微米管制备及气敏性能测试
郭峰旗，孙凤云*，张恩诚，陆佳梁，梁衍宇
（黑龙江省微纳敏感器件与系统重点实验室，黑龙江大学电子工程学院，哈尔滨 150080）
摘要：以脱脂棉为模板，硝酸铜为铜源，采用浸渍与烧结方法制备CuO；引入不同量的Ag修饰CuO形成Ag/CuO微米管复合结构，用于挥发性有机物检测。利用热分析仪（TG）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）和X射线光电子能谱（XPS）等手段分析样品的烧结情况、表面形貌、微结构、晶体结构和化学成分。结果表明，所制备的CuO样品均为单斜相，且成功复刻了脱脂棉结构，整体呈微米管状；引入的Ag与CuO成功复合，形成Ag/CuO微米管复合结构。引入适当含量Ag可有效提升CuO微米管对乙醇的检测能力，Cu/Ag摩尔比10∶1的传感器对100 μL/L乙醇的检测灵敏度达14.87，响应/恢复时间为349 s/147 s，具有良好的重复性与长期稳定性。
关键词：CuO微米管；Ag；乙醇；气敏性能
中图分类号：TP212 文献标识码：A 文章编号：1000-0720（2024）06-0900-06
Fabrication and gas sensing performance of Ag doped CuO microtubes
GUO Fengqi，SUN Fengyun*，ZHANG Encheng，LU Jialiang，LIANG Yanyu
Heilongjiang Provincial Key Laboratory of Micro-nano Sensitive Devices and Systems，School of Electronic Engineering，Heilongjiang University，Haerbin 150080，China）
Abstract：Taking absorbent cotton （AC） as template，Cu（NO3）2 as copper source，CuO was prepared by impregnation and sintering method，and then different amounts of Ag was added to modify CuO to achieve Ag/CuO microtubes composite structure，which can be used for the detection of volatile organic compounds. The sintering situation，morphology，microstructure，crystal structure and chemical composition were analyzed by thermogravimetric analyzer （TG），scanning electron microscope （SEM），transmission electron microscope （TEM），X-ray diffractometer （XRD） and X-ray energy spectrum （XPS）. The results showed that the prepared monoclinic CuO successfully replicated the structure of AC with a tubular structure in whole；the added Ag was successfully complexed with CuO，forming Ag/CuO microtube composite structure. Appropriate amount of Ag was introduced to effectively improve the detection ability of CuO microtubes for ethanol. At 160 ℃，the sensor with copper-silver molar ratio of 10∶1 had a sensitivity of 14.87 to 100 μL/L ethanol，with the response/recovery time of 349 s/147 s，and good repeatability and long-term stability.
Keywords：CuO microtube；Ag；ethanol；gas sensing performance
基于氮硫掺杂碳点黄色荧光增强效应选择性检测环境水体中的Cu2+
张晓淳1，江晓君2，霍志铭*2
（1. 广东省中山生态环境监测站，中山 528400；2. 广东药科大学公共卫生学院，广州 510006）
摘要：以邻苯二胺为氮源，硫脲为硫源，通过一步溶剂热法合成氮硫掺杂碳点（NS-CDs），其荧光量子产率为6.9%；加入Cu2+后荧光量子产率跃升至45.6%，同时荧光从淡灰黄色变成强烈的亮黄色。基于该Off-On型荧光增强效应，建立了水中Cu2+的荧光快速检测方法，线性范围为0.05~10.0 μmol/L，检出限低至0.01 μmol/L。应用于环境水体中Cu2+检测，实际样品加标回收率在83.3%~115.7%之间，相对标准偏差（RSD）<7.0%。样品测定结果与ICP-MS法结果基本一致。结合便携LED光源，可实现环境水体中Cu2+的现场快速监测。
关键词：氮硫掺杂碳点；荧光增强；Cu2+；快速检测
中图分类号：O661.1；X832 文献标识码：A 文章编号：1000-0720（2024）06-0906-08
Selective detection of copper ion in environmental water based on yellow fluorescence-enhanced effect of nitrogen and sulfur-doped carbon dots
ZHANG Xiaochun1，JIANG Xiaojun2，HUO Zhiming*2
1. Zhongshan Ecology and Environment Monitoring Station of Guangdong Province，Zhongshan 528400，China；2. School of Public Health，Guangdong Pharmaceutical University，Guangzhou 510006，China）
Abstract：Nitrogen and sulfur co-doped carbon dots （NS-CDs） were prepared by the one-step solvothermal synthesis method with o-phenylenediamine as nitrogen source and thiourea as sulfur source. The fluorescence quantum yield of NS-CDs was 6.9%. After adding Cu2+，the fluorescence quantum yield jumped to 45.6%，and the fluorescence changed from pale yellow to strong bright yellow. Based on the Off-On fluorescence-enhanced effect of NS-CDs，a new fluorescent method had been established for the rapid detection of Cu2+ in water in the linear range from 0.05 to 10.0 μmol/L，with the detection limit as low as 0.01 μmol/L. Furthermore，the results of NS-CDs applied for the detection of Cu2+ in environmental water were satisfied，the spiked recoveries were from 83.3% to 115.7% and the relative standard deviations （RSDs） were less than 7.0%，which were basically consistent with those of ICP-MS method. The method can be applied for rapid on-site monitoring of Cu2+ in environmental water with the help of portable LED light source.
Keywords：nitrogen and sulfur doped carbon dots；fluorescent enhancement；copper ion；rapid detection
基于成像和质谱的流式细胞术在医学诊断中的应用进展
杨瑞1，张纪媛1，于玉洁1，张顺心1，王合宇1，刘大喜1，2，田亮*1，2，崔建升*1，2
（1. 河北科技大学环境科学与工程学院，石家庄 050018；2. 河北省污染防治生物技术实验室，石家庄 050018）
摘要：人体内部分细胞的种类变化和生理状态是人体健康的重要指标，对细胞进行生化分析是医学诊断的重要手段。基于成像和质谱的流式细胞术，在细胞分析上具有高通量、特异性强的优点，能够表征人体血液或组织样本中特定的细胞类型和形态特征，从而实现疾病的诊断。本文综述了成像流式细胞术（IFC）、质谱流式细胞术（CyTOF）和成像质谱细胞术（IMC）在肿瘤学、免疫学、血液学等医学领域中最新的应用进展。
关键词：流式细胞术；细胞分析；生物标志物检测；医学诊断
中图分类号：O657；R446 文献标识码：A 文章编号：1000-0720（2024）06-0914-11
Application progress of imaging and mass spectrometry based flow cytometry in medical diagnosis
YANG Rui*1，ZHANG Jiyuan1，YU Yujie1，ZHANG Shunxin1，WANG Heyu1，LIU Daxi1，2，TIAN Liang*1，2，CUI Jiansheng*1，2
1. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050018，China；2.Hebei Key Laboratory of Pollution Prevention Biotechnology，Shijiazhuang 050018，China）
Abstract：The variety and physiological state of some cells in human body are important indicators for human health. Hence，biochemical analysis of cells is an important method of medical diagnosis. Imaging and mass spectrometry based flow cytometry has the advantages of high throughput and specificity in cellular assays，which can characterize the types and morphological of specific cells in human blood or tissue samples to realize the disease diagnostic. Thus，this review summarizes the latest advances of imaging flow cytometry （IFC），cytometry by time-of-flight （CyTOF） and imaging mass cytometry （IMC） in oncology，immunology，and hematology.
Keywords：flow cytometry；cell analysis；biomarker detection；medical diagnosis
