【综述与专论】
基于天然产物的PROTAC及其在靶标验证中的应用进展
徐琳1，王京2，张磊*1,2
（1.遵义医科大学 药学院，贵州 遵义 563000；2.凯里学院 大健康学院，贵州 凯里 556011）
摘要：天然产物是创新药物先导化合物的重要来源，具有结构多样性以及功能独特性。目前，天然产物在癌症、心脑血管疾病、神经系统疾病、自身免疫性疾病等的治疗中发挥重要作用。同时，PROTAC技术的兴起为临床分子靶向药物耐药提供了新的解决方案，天然产物及其衍生物作为PROTAC的重要组成部分，在靶向蛋白降解药物的开发中发挥着重要作用。本文综述了基于天然产物的PROTAC以及PROTAC技术在天然产物靶标鉴定中的应用进展。
关键词：PROTAC；靶点鉴定；靶向药物；天然产物；研究进展
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2024）06-0001-08
DOI：10.13822/j.cnki.hxsj.2024.0005
Natural Products PROTAC Based on and Its Application in Target Validation XU Lin1, Wang Jing2, ZHANG Lei*1,2（1.School of Pharmacy, Zunyi Medical University, Zunyi 563000, China；2.School of Life and Health Sciences, Kaili University, Kaili 556011, China）
Abstract：Natural products are the important sources of lead compounds for innovative drugs, exhibiting structural diversity and functional specificity. At present, natural products play an important role in the targeted therapy of cancer, cardiovascular and cerebrovascular diseases, nervous system diseases, and autoimmune diseases. The development of protein degradation targeted chimeras（PROTAC）provides a new strategy for clinical molecular targeted drug resistance. Natural products and their derivatives, as important parts of PROTAC, play an important role in the development of protein targeted drugs. This article reviews the progress in the application of natural product-based PROTAC, as well as PROTAC technology for the identification of natural products targets.
Key words: PROTAC; target identification; targeted drug; natural product; research progress
引用本文：徐琳，王京，张磊. 基于天然产物的PROTAC及其在靶标验证中的应用进展[J]. 化学试剂，2024，46（6）：1-8.
【生化与药用试剂】
多维度综合评价瞬时高温灭菌对丹参质量的影响
庄新慧1,2，焦连庆*1，于敏1，田齐聪2，张凤清*2
（1. 吉林省中医药科学院，吉林 长春 130012；2. 长春工业大学 化学与生命科学学院，吉林 长春 130012）
摘要：为考察瞬时高温灭菌对丹参质量的影响，采用HPLC法测定10批灭菌前后丹参中8种化学成分含量，DPPH•法测定丹参灭菌前后抗氧化活性，MTT法测定灭菌前后丹参大鼠肝星状细胞（HSC-T6）存活率。建立HPLC指纹图谱，液质联用（LC-MS）法确定共有峰结构，采用聚类分析和正交偏最小二乘法判别分析（OPLS-DA）预测不同丹参差异性质量标志物；通过丹参与过量DPPH反应后的HPLC峰面积变化，筛选丹参抗氧化成分；采用偏最小二乘法回归（PLS-DA）分析法，得出共有峰与DPPH•抗氧化活性间的谱效关系，结合单体化合物抗氧化活性大小，最终确定丹参抗氧化活性质量标志物。灭菌前后8种化学成分含量、DPPH•清除率及细胞存活率经t检验均无显著性差异（P＞0.05）；灭菌前后指纹图谱相似度均大于0.9，同一批次样品灭菌前后聚为一类，瞬时高温灭菌对丹参质量未产生影响；紫草酸甲酯、丹酚酸B、丹参酸甲酯、丹参酮I、隐丹参酮、丹酚酸F、丹参酮IIA、二氢丹参酮I可作为丹参质量差异标志物；迷迭香酸、丹酚酸B、紫草酸、丹酚酸F可作为抗氧化活性的质量标志物。
关键词：丹参；瞬时高温灭菌；DPPH•抗氧化活性；质量标志物；质量评价
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2024）06-0009-08
DOI：10.13822/j.cnki.hxsj.2023.0803
Multi-Dimensional Comprehensive Evaluation of the Impact of Instantaneous High-Temperature Sterilization on the Quality of Salvia Miltiorrhiza ZHUANG Xin-hui1,2, JIAO Lian-qing*1, YU Min1, TIAN Qi-cong2, ZHANG Feng-qing*2（1. Jinlin Provincial Academy of Traditional Chinese Medicine, Changchun 130012, China, China; 2. School of Chemistry and Life Sciences, Changchun University of Technology, Changchun 130012）
Abstract: To investigate the impact of instantaneous high-temperature sterilization on the quality of Salvia miltiorrhiza, the content of eight chemical components in Salvia miltiorrhiza before and after sterilization was determined using HPLC, the antioxidant activity of Salvia miltiorrhiza before and after sterilization was measured using the DPPH• method, and the cell viability of rat hepatic stellate cells （HSC-T6） before and after sterilization was measured using the MTT method. Set up HPLC fingerprints,the shared peak structures were determined using liquid chromatography-mass spectrometry （LC-MS）, differential quality markers for different batches of Salvia miltiorrhiza were obtained through cluster analysis and orthogonal partial least squares discriminant analysis （OPLS-DA）. The antioxidant components of salvia miltiorrhiza were screened by HPLC peak area changes after reaction with excess DPPH. Partial least square regression （PLS-DA） analysis method was used to obtain the spectral effect relationship between the common peak and DPPH• antioxidant activity, combined with the antioxidant activity of monomer compounds, and finally determine the antioxidant activity quality markers of salvia miltiorrhiza. The contents of 8 chemical components, DPPH•clearance rate and cell survival rate were not significantly different by t test before and after sterilization （P>0.05）. The similarity of fingerprints before and after sterilization was greater than 0.9, the same batch of samples clustered into one class before and after sterilization, instantaneous high temperature sterilization had no effect on the quality of Salvia miltiorrhiza. Methyl vioxalate, salvianolic acid B, methyl salvianolic acid, tanshinone I, cryptotanshinone, salvianolic acid F, tanshinone IIA and dihydrotanshinone I could be used as markers of quality difference of salvianone. Rosmarinic acid, salvianolic acid B, purple oxalic acid, salvianolic acid F can be used as quality markers of antioxidant activity.
Key words: salvia miltiorrhiza; instantaneous high-temperature sterilization; DPPH• antioxidant activity; quality markers; quality evaluation
引用本文：庄新慧，焦连庆，于敏，等. 多维度综合评价瞬时高温灭菌对丹参质量的影响[J] .化学试剂, 2024, 46（6）：9-16.
基于气相色谱质谱研究肺癌呼气特征性挥发有机化合物
吕伟1，石雯闽1，尹怡2，王祥麒2，冯卫生1，张志娟*1,3
（1. 河南中医药大学 药学院，郑州 450056；2. 河南中医药大学第三附属医院 肿瘤科，河南 郑州 450056；3. 暨南大学 质谱仪器与大气环境研究所，广东 广州 510632）
摘要：对肺癌患者呼出气体中挥发性有机化合物（VOCs）进行定性定量检测，研究肺癌患者呼气VOCs浓度变化，筛查肺癌特异性呼气VOCs。应用气相色谱质谱联用仪（GC-MS）检测360例受试者的呼气VOCs样品，包括134名健康志愿者、176名肺癌患者和50名乳腺癌患者。每个受试者采集3个平行样，以及1个室内环境样。对检测到的挥发性有机物（VOCs）进行定量分析，联合使用Mann-Whitney U检验和正交偏最小二乘判别分析（OPLS-DA）模型筛选出8种肺癌患者呼气特征性VOCs，包括顺式-2-丁烯、苯、1,2-二氯丙烷、三氯乙烯、4-甲基-2-戊酮、3-甲基庚烷、正辛烷和萘。模型诊断的准确度、精准率、灵敏度和特异性分别为95.41%、95.15%、93.99%和96.67%，F1分数为94.51%，诊断性能好。综上，以上8种VOCs可作为肺癌患者的呼气特征性VOCs，为肺癌的早期呼气诊断提供新的数据支撑和方法。
关键词：气相色谱质谱联用仪；VOCs；特征性；肺癌；呼气
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2024）06-0017-09
DOI：10.13822/j.cnki.hxsj.2023.0812
Application of Gas Chromatography-Mass Spectrometry （GC-MS） on Characteristic Breath Volatile Organic Compounds of Lung Cancer LV Wei1, SHI Wen-min1, YIN Yi2, WANG Xiang-qi2, FENG Wei-sheng1, ZHANG Zhi-juan *1,3 （1. College of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450056, China; 2. Department of Oncology, The Third Affiliated Hospital of Henan University of Chinese Medicine, Zhengzhou 450056, China; 3. Institute of Mass Spectrometer and Atmospheric Environment, Jinan University, Guangzhou 510632, China）
Abstract: The volatile organic compounds （VOCs） in the exhaled breath of lung cancer patients were analyzed, and the concentration changes of sampled VOCs were evaluated. Finally, the characteristic VOCs of lung cancer were screened out. In this paper, a total of 360 subjects were analyzed using gas chromatography-mass spectrometry （GC-MS）, including 134 healthy individuals, 176 lung cancer patients and 50 breast cancer patients. Three parallel samples and one indoor air sample were collected for each subject. Volatile organic compounds （VOCs） were quantitatively analyzed. Furthermore, 8 potential characteristic VOCs for lung cancer patients were screen out by using orthogonal partial least-squares discrimination analysis （OPLS-DA） model combined with Mann-Whitney test, including cis-2-butene, benzene, 1,2-dichloropropane, trichloroethylene, 4-methyl-2-pentanone, 3-methylheptane, n-octane and naphthalene. In addition, the diagnostic accuracy, precision, sensitivity and specificity were 95.41%, 95.15%, 93.99%, and 96.67%, respectively, while the F1 ratio was 94.51%. Conclusion In conclusion, these 8 VOCs can be taken as characteristic breath VOCs of lung cancer patients, providing new ideas and methods for early respiratory diagnosis of lung cancer.
Key words: gas chromatography-mass spectrometry; VOCs; characteristic; lung cancer; breath
引用本文：吕伟，石雯闽，尹怡，等. 基于气相色谱质谱研究肺癌呼气特征性挥发有机化合物[J]. 化学试剂, 2024, 46（6）：17-25.
【功能材料】
基于羧酸基-酚羟基配体Pr配合物的结构、荧光性质以及辅助配体的影响
罗仕超，彭庆鹏，张洪涛，刘楚湖，江尚坤，王莹，关磊*
（辽宁石油化工大学 石油化工学院 辽宁 抚顺113001）
摘要：采用3,3′-偶氮双（6-羟基苯甲酸）二钠（Na2H2L）为配体，通过水热法与Pr3+反应得到两个配合物[Pr（H2L）0.5（L）0.5（H2O）2]n（1）和Pr（HL）（phen）（H2O）5·2H2O（2）（phen = 1,10-邻菲罗啉）。配合物1中，H2L2-阴离子作为四齿配体，2个羧酸基分别以μ2-η1:η1的方式与Pr3+配位，形成二维层状结构，并且，L4-阴离子作为桥连配体，利用羧酸基和酚羟基分别以μ2-η2:η1和桥连模式将二维层中三个相邻的Pr3+连接，将结构拓展成三维网络结构，其Schläfli符号为{42·84}{46·66·83}{47·63}2。引入phen分子，配合物2变为单核结构，phen与Pr3+螯合配位，HL3-作为单齿配体与Pr3+配位。配合物1和2分别在638 和778 nm，652 和781 nm有Pr3+的特征荧光发射峰，颜色落在色度图的橙色区域内，是1S0→1I6和1D2→3H4能级跃迁所致。配合物2的荧光强度高于配合物1，且主峰红移14 nm，归因于phen的共轭体系以及与Pr3+配位作用。
关键词：镨离子；配位聚合物；三维结构；荧光；辅助配体
中图分类号：O614.33，TQ133.3 文献标识码：A 文章编号：0258-3283（2024）06-0026-07
DOI：10.13822/j.cnki.hxsj.2024.0041
Structures, Fluorescence Properties and Influence of Auxiliary Ligand on Pr Complexes Based on Carboxylate-Phenol Ligand LUO Shi-chao, PENG Qing-peng, ZHANG Hong-tao, LIU Chu-hu, JIANG Shang-kun, WANG Ying, GUAN Lei* （School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China）
Abstract: Two complexes [Pr（H2L）0.5（L）0.5（H2O）2]n （1） and Pr（HL）（phen）（H2O）5·2H2O （2） （Na2H2L = 3,3'-azobis（6-hydroxybenzoic acid） disodium, phen = 1,10-phenanthroline） were synthesized by hydrothermal reaction with Pr3+ using Na2H2L as ligand. In complex 1, the H2L2- anions act as tetradentate ligands, which bind to Pr3+ ions through two carboxylate groups in μ2-η1:η1 coordination mode, forming a two-dimensional layered structure. Moreover, the L4- anions serve as bridging ligands, which connect the three adjacent Pr3+ ions in two-dimensional layers via the carboxylate and phenol groups in μ2-η2:η1 and bridging fashions, respectively, expanding into a three-dimensional network structure with the Schläfli symbol of {42·84}{46·66·83}{47·63}2. The structure of complex 2 transforms into a mononuclear one by the introduction of phen molecules, where phen molecules chelate with Pr3+, while HL3- anions act as monodentate ligands, coordinating with Pr3+. Complexes 1 and 2 exhibit the characteristic emissions of Pr3+ at 638 and 778 nm, 652 and 781 nm, which fall within the orange region of the CIE chromaticity diagram, corresponding to 1S0→1I6 and 1D2→3H4 energy transitions, respectively. The fluorescence intensity of complex 2 is higher than complex 1, and the main peak has red-shift of 14 nm, which is attributed to the conjugated system of phen and its coordination with Pr3+.
Keywords: praseodymium ion; coordination polymer; three-dimensional structure; fluorescence; auxiliary ligand
引用本文：罗仕超，彭庆鹏，张洪涛，等. 基于羧酸基-酚羟基配体Pr配合物的结构、荧光性质以及辅助配体的影响[J]. 化学试剂, 2024, 46（6）：26-32.
用于H2PO4－检测的比率型荧光探针合成及性能研究
郭昌晟，陈君霞，刘忆茹，卢钰盛，董智云，席福贵*
（忻州师范学院 化学学院，山西 忻州 034000）
摘要：设计合成了一种基于吖啶-苯并咪唑鎓的大环受体ABIM，可作为H2PO4－的荧光比率传感器。借助荧光光谱研究了受体ABIM对H2PO4－的选择性识别，在大环受体ABIM的乙腈溶液中加入H2PO4－后，在426 nm处荧光发射明显“关闭”，506 nm处荧光发射明显“打开”，溶液荧光颜色由蓝色变为蓝绿色，新的荧光发射峰可能是由于H2PO4－诱导两个受体中的吖啶环之间形成Excimer产生的。ABIM与H2PO4－以1 : 1的化学计量比结合，结合常数为（7.13 ± 0.48）×106 L/mol，检出限为2.38×10-7 mol/L，最佳响应时间为2 min。回收实验表明，ABIM可应用于样品中H2PO4－的检测。
关键词：吖啶；苯并咪唑鎓；H2PO4－；大环；比率型荧光探针
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）06-0033-06
DOI：10.13822/j.cnki.hxsj.2024.0062
Synthesis and properties of ratiometric fluorescent sensor for H2PO4－ GUO Change-sheng, Chen Jun-xia, LIU Yi-ru, LU Yu-sheng, DONG Zhi-yun, Xi Fu-gui* （Department of Chemistry, Xinzhou Teachers University，Xinzhou 034000, China）
Abstract：An ariding-benzimidazolium based macrocyclic fluorescent sensor ABIM were designed and synthesized, which can be used as ratiometric fluorescent sensor for H2PO4－. The selectivity of sensor ABIM with H2PO4－ was investigated by fluorescence spectroscopy. A clear “turn-off” of fluorescence emission at 426 nm and an apparent “turn-on” of fluorescence emission at 506 nm were observed upon addition of H2PO4－, giving rise to change in the fluorescence color from blue to blue-green. The new fluorescence emission may be attributed to the H2PO4－ induced assembly of sensor ABIM forming the excimer conformation between two acridine rings. The results showed that the binding ratio for sensor ABIM to H2PO4－ was 1 : 1. The binding constant was calculated to be （7.13 ± 0.48）×106 L/mol and the detection limit was 2.38×10-7 mol/L. The results also showed that sensor ABIM could be used to detection of H2PO4－ in the samples.
Key words：acridine; benzimidazolium; H2PO4－; macrocyclic; ratiometric fluorescent sensor
引用本文：郭昌晟，陈君霞，刘忆茹，等. 用于H2PO4－检测的比率型荧光探针合成及性能研究[J]. 化学试剂，2024，46（6）：33-38.
【电化学和新能源】
碳酸钙还原低热耦合与二氧化碳绿色原位转化
王正义1，唐美2，张冰姿3，蔡正宇4，何国强*1
（1.中国计量大学 材料与化学学院，浙江 杭州 310018；2.广西大学 物理科学与工程技术学院，广西 南宁 530004；3.杭州职业技术学院 生态健康学院 浙江 杭州 310018；4. 三亚学院 盛宝金融科技商学院 海南 三亚 572022）
摘要：碳酸钙（CaCO3）是水泥和钢铁生产等行业常见的矿产资源。然而，其高温分解产生的能源损失和二氧化碳（CO2）排放亟需关注。因此，文章提出了利用甲烷（CH4）、氢气（H2）、碳（C）和乙醇（C2H5OH）与亚微米级CaCO3的耦合反应以降低分解温度并实现CO2原位转化，在此基础上进行了热力学和耦合产物的分析，同时在经济层面上展开了对比。研究表明，CH4对CaCO3分解温度的降低最显著，H2次之；C被用作还原剂时可获得纯净产物系统；C2H5OH与CaCO3的耦合反应中H2和一氧化碳（CO）的产率最高。通过还原剂耦合不仅可以在较低温度下再生氧化钙（CaO），还可将CO2原位转化为高值产物，如H2和CO，从而减少CO2排放。
关键词：CaCO3分解；耦合反应；低热还原；CO2原位转化；CO2排放
中图分类号：TQ115 文献标识码：A 文章编号：0258-3283（2024）06-0039-07
DOI：10.13822/j.cnki.hxsj.2023.0851
Low-thermal Coupling of CaCO3 Reduction and Green In-situ Conversion of CO2 WANG Zheng-yi, He Guo-qiang* （1. College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China；2.School of Physical Science and Technology, Guangxi University, Nanning 330100, China；3.Ecology and Health Institute, Hangzhou Vocational & Technical College, Hangzhou 310018, China；4.Saxo Fintech Business School, University of Sanya, Sanyan 572022, China）
Abstract：Calcium carbonate （CaCO3） is a common mineral resource in industries such as cement and steel production. However, the energy loss and CO2 emissions associated with its high-temperature decomposition are of urgent concern. In this study, a coupling reaction between submicron CaCO3 and CH4, H2, C, and C2H5OH was proposed to reduce the decomposition temperature and facilitate in-situ CO2 conversion. Thermodynamic analysis and characterization of the coupling products were conducted, along with an economic evaluation. The results demonstrate that CH4 has the most significant effect on reducing the decomposition temperature of CaCO3, followed by H2. When C is utilized as the reducing agent, a pure product system can be obtained. In the coupling reaction of C2H5OH with CaCO3, higher productivity of H2 and CO is observed. The utilization of these reducing agents not only enables the regeneration of CaO at lower temperatures but also facilitates the conversion of CO2 into valuable products such as H2 and CO, leading to a reduction in CO2 emissions.
Key words：CaCO3 decomposition; coupling reaction; low-thermal reduction; in-situ conversion of CO2; CO2 emissions
引用本文：王正义，唐美，张冰姿，等. 碳酸钙还原低热耦合与二氧化碳绿色原位转化[J]. 化学试剂, 2024, 46（6）:39-45.
氮掺杂的绿色碳点开关型荧光传感器灵敏检测组氨酸
蔡留莹a，康鹏a，董微*b
（沈阳医学院 a. 公共卫生学院；b. 化学教研室，辽宁 沈阳 110034）
摘要：以柠檬酸为碳源，尿素提供氮源，N,N-二甲基甲酰胺（DMF）为溶剂，采用水热法一步合成水溶性好的氮掺杂绿色荧光碳点（N-CDs）。为增强N-CDs的荧光强度，选用1，6-己二胺作为表面修饰剂，制备的N-CDs荧光量子产率达20.8%。该N-CDs形貌近似球形，平均粒径约为30 nm。同时本实验基于荧光猝灭法构建N-CDs/Bio“开-关”型荧光传感器，利用传感器荧光强度的变化灵敏检测组氨酸（His）。传感器荧光强度变化（ΔF）与His浓度在1.73 ～25.85 mmol/L范围内呈现良好线性关系，线性方程为ΔF=6.133×[His]+4.531，相关系数R2=0.9984，检测下限为0.3669 mmol/L。进一步检测实际人血清样本中的His，回收率为96.3%～100.1%。该传感器检测方法简便、灵敏度高，是优异的His荧光检测传感器。
关键词：绿色荧光碳点；组氨酸；水热法；开关；荧光传感器
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2024）06-0046-07
DOI：10.13822/j.cnki.hxsj.2023.0820
Detection of Histidine by Switch Sensitive Sensor Based on N-Doped Green Fluorescent CDs CAI Liu-yinga, KANG Penga, DONG Wei*b （a. School of Public Health, b. Department of Chemistry, Shenyang Medical College, Shenyang 110034, China）
Abstract：We used citric acid as the carbon source, urea as the nitrogen source, and N,N-Dimethylformamide （DMF） as the solvent to successfully prepare a Green fluorescent CDs by the hydrothermal method. Simultaneously, 1,6-Hexanediamine was used as a modifier to significantly enhance the photoluminescence intensity of N-CDs and the fluorescence quantum yield can reach 20.8%. The N-CDs is approximate spherical morphology, and the average particles size of about 30 nm. At the same time, a N-CDs/Bio fluorescence sensor like "Switch” was constructed based on the fluorescence quenching method. The change in fluorescence intensity of sensor was used to detect histidine （His）. The sensor has a good linear relationship in the range of 1.73 mmol/L to 25.85 mmol/L. The linear equation ΔF=6.133×[His]+4.531, the correlation coefficient R2=0.9984, and the detection limit is 0.3669 mmol/L. Further detection of His in serum, the recovery rate was 96.3%~100.1%, the detection of sensor is simple and sensitive. This is an excellent His detection fluorescent probe.
Key words：green fluorescent CDs; histidine; hydrothermal method; switch; fluorescence sensor
引用本文: 蔡留莹, 康鹏, 董微, 等.氮掺杂的绿色碳点开关型荧光传感器灵敏检测组氨酸[J]. 化学试剂, 2024, 46（6）: 46-52.
【化学品与环境】
磁性固相萃取技术在土壤污染物检测中的应用研究进展
王泽岚1，李瑞雪*1，李谦1，吴明1，朱捷1，孟哲2
（1. 宁夏回族自治区食品检测研究院（国家市场监管重点实验室（枸杞和葡萄酒质量安全）），宁夏 银川 750001；
2. 宁夏大学 化学化工学院，省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏 银川 750021）
摘要：近年来，各种污染物通过多种途径进入土壤环境中并积累，对土壤环境质量、食品安全和人体健康产生极大的危害。土壤基质较为复杂，采用高效、选择性好、灵敏度高、便捷简单的前处理技术对土壤中的污染物进行分析检测尤为重要。磁性固相萃取技术作为一种新型的前处理方法，与传统前处理技术相比具有多种优势。随着磁性纳米材料的兴起，根据土壤中污染物的不同，通过对磁性纳米粒子进行功能化修饰可以得到不同吸附性能的吸附材料，从而对土壤中的各种污染物进行选择性吸附。文章梳理了土壤中存在的主要污染物、传统的前处理技术、磁性固相萃取技术简介及优势，详细阐述了磁性固相萃取技术在土壤污染物分析检测中的应用研究进展，为磁性固相萃取技术在土壤污染物实际检测应用中提供参考。
关键词：土壤；磁性固相萃取技术；污染物残留；分析检测
中图分类号：S132 文献标识码：A 文章编号：0258-3283（2024）06-0053-10
DOI：10.13822/j.cnki.hxsj.2023.0789
Research Progress on the Application of Magnetic Solid-phase Extraction Technology in Soil Pollutant Detection Wang Ze-lan1, Li Rui-xue*1, Li Qian1, Wu Ming1, Zhu Jie1, Meng Zhe2 （1. Ningxia Food Testing and Research Institute （Key Laboratory of Quality Safety of Chinese Wolfberry and Wine for State Market Regulation ）,Yinchuan 750001, China; 2. State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry, Chemical Engineering, Ningxia University, Yinchuan 750021, China）
Abstract：In recent years, various pollutants have entered the soil environment through various ways and accumulated, posing a great threat to food safety, soil environmental quality, and human health. The soil matrix is relatively complex, and it is particularly important to use efficient, selective, and convenient pre-treatment techniques to analyze and detect pollutants in the soil. Magnetic solid-phase extraction technology, as a new pre-treatment method, has multiple advantages compared to traditional pre-treatment techniques. With the rise of magnetic nanomaterials, according to the different pollutants in the soil, functional modification of magnetic nanoparticles can obtain adsorption materials with different adsorption properties, thereby selectively adsorbing various pollutants in the soil. The article summarizes the main present pollutants in the soil, traditional pre-treatment technologies, brief introduction and advantages of magnetic solid-phase extraction technology, and elaborates on the application research progress of magnetic solid-phase extraction technology in soil pollutant analysis and detection, providing reference for the practical application of magnetic solid-phase extraction technology in soil pollutant detection.
Key words：soil; magnetic solid-phase extraction technology; pollutant residues; analysis and detection
引用本文：王泽岚，李瑞雪，李谦，等. 磁性固相萃取技术在土壤污染物检测中的应用研究进展[J]. 化学试剂，2024，46（6）： 53-62.
重金属吸附剂巯基化核桃壳制备条件优化
孙淏1，张翠玲*1,2，潘樟梓1，尚志栋1，贺懿琛1，滕泽璟1
(1. 兰州交通大学 环境与市政工程学院，甘肃 兰州 730070；
2. 甘肃省黄河水环境重点实验室，甘肃 兰州 730070)
摘要：为提高核桃壳（WS）对重金属离子的吸附性能，利用L-半胱氨酸（L-Cys）对 WS进行改性，得到巯基化核桃壳（CWS）。以CWS对Pb(Ⅱ)吸附量为评价指标，利用单因素试验、响应面试验逐步优化CWS制备条件，并借助场发射扫描电镜（SEM）、能谱仪（EDS）和傅里叶红外光谱（FT-IR）等表征方法探讨CWS的制备机理。结果表明：L-Cys和WS质量比是影响CWS吸附Pb(Ⅱ)性能的主要因素，温度影响次之， pH与温度之间存在显著的交互作用；CWS最优制备条件为m(L-Cys):m(WS)=1.58:1、温度为63.2 ℃、pH为9.89、反应时间为4 h，最优条件下制备的CWS对Pb(Ⅱ)吸附量可达24.06 mg/g；CWS表面呈现许多凹陷、孔状结构丰富，CWS制备机理主要以发生酰胺化反应为主。研究显示，经巯基化核桃壳可用于Pb(Ⅱ)等重金属离子废水的处理。
关键词：核桃壳；L-半胱氨酸；吸附；响应面；铅废水
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）06-0063-08
DOI：10.13822/j.cnki.hxsj.2024.0049
Optimization the Preparation Conditions of Sulfhydrated Walnut Shell as a Heavy Metal Adsorbent Sun Hao1, Zhang Cui-ling*1,2, Pan Zhang-zi1, Shang Zhi-dong1, He Yi-che1, Teng Ze-jing1 (1.School of Environmental and Municipal Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China; 2. Gansu Provincial Key Laboratory of Yellow River Water Environment, Lanzhou 730070, China)
Abstract: In order to improve the adsorption performance of walnut shell (WS) for heavy metal ions, WS was modified with L-cysteine (L-Cys) to obtain thiolated walnut shell (CWS).Taking the adsorption amount of Pb(Ⅱ) as the evaluation index, single factor experiments and response surface experiments were used to gradually optimize the preparation conditions of CWS, and the preparation mechanism of CWS was explored with the help of SEM, EDS, FT-IR and other characterization methods.The results show that the mass ratio of L-Cys to WS is the main factor affecting the adsorption performance of CWS for Pb(Ⅱ), followed by temperature. There is a significant interaction between pH and temperature; the optimal condition of CWS is m(L-Cys ): m(WS)=1.58:1, the temperature is 63.2 ℃, the pH is 9.89, and the reaction time is 4 h. The adsorption capacity of CWS prepared under the optimal conditions for Pb(Ⅱ) can reach 24.06 mg/g; CWS surface presentation There are many depressions and rich pore structures, and the preparation mechanism of CWS is mainly based on amidation reaction.Research shows that thiolated walnut shells can be used to treat heavy metal ion wastewater such as Pb(Ⅱ).
Keywords: walnut shell; L-cysteine; adsorption; response surface methodology; lead wastewater
引用本文：孙淏，张翠玲，潘樟梓，等. 重金属吸附剂巯基化核桃壳制备条件优化[J]. 化学试剂，2024，46（6）：63-70.
吡啶-氧杂二氮唑在钯离子萃取分离中的应用
张丽芬1，李书启*1，叶泽聪*2，梁宁3，许奕超3，刘志豪4
（1. 天津天狮学院 食品工程学院，天津 301700；2. 广东工业大学 轻工化工学院，广东 广州 510006；3. 泰灵佳科技（天津）有限公司，北京 100020；4. 甘肃味美食品有限公司，甘肃 兰州 730070）
摘要：高放废液中钯的萃取分离对贵金属钯资源的回收利用和核燃料循环中的玻璃固化过程都有重要意义，其关键在于高效高选择性萃取体系的开发和设计。基于氮杂环配体高效配合钯离子的特性，设计合成了一种具有吡啶-氧杂二氮唑结构的萃取剂6,6'-（（4-异丁氧基吡啶-2,6-二基）双（1,2,4-氧杂二氮唑-5,3-二基））双（4-异丁氧基吡啶甲腈）（T2），用于酸性条件下钯离子的选择性萃取。以间硝基三氟甲苯为稀释剂且在1 mol/L 2-溴己酸存在下，配体T2对钯离子体现出较好的萃取能力。萃取动力学表明2h即可萃取68%的钯进入有机相。该体系适用酸度广泛，在0.2～4 mol/L硝酸条件下均对钯几乎展现出定量萃取，表明其优异的酸稳定性。此外，在多种阳离子共存的条件下，该体系能高选择性地分离萃取出钯离子，表明其良好的实际应用潜力。研究不仅提供了一类高效的钯萃取剂，更为其它新型钯萃取剂和萃取体系的开发提供了重要参考。
关键词：钯分离；氮杂环；高放废液；溶剂萃取；配体
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2024）06-0071-06
DOI：10.13822/j.cnki.hxsj.2024.0056
Synthesis of Pyridine-oxadiazole Ligand and Its Application in Palladium Ion Extraction and Separation ZHANG Li-fen1, LI Shu-qi*1, YE Ze-cong*2, LIANG Ning3, XU Yi-chao3, LIU Zhi-hao4 （1. School of Food Engineering, Tianjin Tianshi College, Tianjin 301700, China; 2. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; 3. Telinga Technology （Tianjin） Limited Company, Beijing 100020, China; 4. Gansu Weimei Food Limited Company, Lanzhou 730070, China）
Abstract：The extraction and separation of palladium from high-level liquid waste is of great significance to the recovery and utilization of precious metal palladium resources and the glass solidification process in the nuclear fuel cycle. The key lies in the development and design of efficient and highly selective extraction system. Based on the characteristics of efficient complexation of palladium ions with nitrogen heterocyclic ligands, an extractant 6,6'-（（4-isobutoxypyridine-2,6-diyl）bis（1,2,4-oxadiazole-5,3-diyl））bis（4-isobutoxypicolinonitrile） （T2） with pyridine-oxadiazole structure was designed and synthesized for the selective extraction of palladium ions under acidic conditions. With 3-nitrobenzotrifluoride as the diluent and in the presence of 1 mol/L 2-bromhexanoic acid, ligand T2 has a good extraction ability for palladium ion. The extraction kinetics showed that 68% of palladium could be extracted into the organic phase within 2 hours. The system is applicable to a wide range of acidity, and almost shows quantitative extraction of palladium under the condition of 0.2～4 mol/L nitric acid, indicating its excellent acid stability. In addition, under the condition of coexistence of multiple cations, the system can selectively separate and extract palladium ions, indicating its good practical application potential. This work not only provides a kind of efficient palladium extractants, but also provides an important reference for the development of other new palladium extractants and extraction systems.
Key words：palladium separation; nitrogen heterocycle; high level liquid waste; solvent extraction;lignad
引用本文：张丽芬，李书启，叶泽聪, 等. 吡啶-氧杂二氮唑在钯离子萃取分离中的应用[J]. 化学试剂，2024，46（6）：71-76.
【分析与测试】
高效液相色谱串联质谱法分析沉积物中壬基酚和双酚A
王安冬，赵明，周刚，祝永卫*
（北京工业大学 分析测试中心，北京 100124）
摘要：建立并优化了基于超高相液相色谱-三重四级杆串联质谱技术测定沉积物中壬基酚和双酚A含量的方法。沉积物样品经HLB-SPE萃取柱处理后，以甲醇-5 mmol甲酸铵为流动相，通过Agilent Eclipse Plus C18 RRHD超高效液相色谱柱进行分离和分析，选择电喷雾离子源，多反映监测负离子模式下进行测定。结果表明，壬基酚和双酚A在质量浓度5~100 μg/L范围内均呈良好的线性关系，R2 ≥ 0.99，检出限范围为 0.066 ~ 0.14 μg/L，平均回收率为88.9% ~ 105%，精密度为 2.97% ~ 8.20 %。方法的选择性、灵敏度及准确性均良好，可实现沉积物中壬基酚和双酚A含量的同时准确测定。
关键词：壬基酚；双酚A；沉积物；高效液相色谱质谱联用；新污染物
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2024）06-0077-06
DOI：10.13822/j.cnki.hxsj.2023.0779
Analysis of Trace Nonylphenol and Bisphenol A in Soil Sediments by HPLC/MS/MS WANG An-dong, ZHAO Ming, ZHOU Gang, ZHU Yong-wei* （Analysis and Testing Center, Beijing University of Technology, Beijing 100124, China）
Abstract：A method for determining the content of nonylphenol and bisphenol A in soil sediment using high-performance liquid chromatography mass spectrometry was established via optimizing various parameters, such as mobile phase, chromatographic column, mass spectrometry parameters. After extracting, the soil sediments were concentrated and purified by solid phase extraction. While, methanol-5 mmol/L ammonium formate was used as mobile phase for separating and analyzing by Agilent Eclipse Plus C18 RRHD ultra high performance liquid chromatography column, in which, the negative electrospray （ESI−） under multiple reaction monitoring （MRM） mode was detected. The results demonstrated that its detection limit range was 0.066 ~ 0.14 μg/L and its linear range was 5-100 μg/L with R2 ≥ 0.99. especially, its average recovery range was 88.9 ~ 105% and relative standard deviation range was 2.97 ~ 8.20 % This method presented a good selectivity, sensitivity, accuracy, and repeatability, which could meet the needs of accurate trace determination of nonylphenol and bisphenol A content in soil sediments.
Key words：nonylphenol；bisphenol A；seposit sediment；liquid chromatography-mass spectrometry；emerging contaminant
引用本文：王安冬，赵明，周刚，等. 高效液相色谱串联质谱法分析沉积物中壬基酚和双酚A[J]. 化学试剂, 2024, 46（6）:77-82.
基于高分辨液质联用的双标记氨基酸同位素丰度测定方法研究
赵雅梦1,2,3 , 徐增益1,2, 范若宁1,2, 解龙1,2, 侯静华1, 李良君1, 刘建军3, 雷雯*1,2
（1. 上海化工研究院有限公司，上海 200062；2. 上海市稳定同位素检测及应用研发专业技术服务平台， 上海 200062；3. 上海交通大学医学院附属仁济医院，核医学科，上海 200127）
摘要：近年来，稳定同位素标记化合物，尤其是同位素标记氨基酸在合成生物学、蛋白质组学、代谢组学等前沿科学研究中发挥着越来越重要的作用。建立了一种基于高分辨液质联用的双标记氨基酸同位素丰度检测方法，以13C2,15N-甘氨酸为例，考察了样品浓度、质谱扫描张数等影响因素对同位素丰度计算结果的影响，结果表明该方法具有良好的准确性和稳定性，所需样品用量少，操作简单，有望成为一种简便、通用的同位素试剂质控方法；也将为代谢组学、海洋学等同位素示踪技术应用研究提供数据支持。
关键词：双标记氨基酸；同位素丰度；高分辨液质联用仪；质量控制；13C2,15N-甘氨酸
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）06-0083-06
DOI：10.13822/j.cnki.hxsj.2023.0664
Analysis of Isotope Abundance for Double-labelled Amino Acid with Liquid Chromatography-High Resolution Mass Spectrometer ZHAO Ya-meng1,2,3, XU Zeng-yi1,2, FAN Ruo-ning1,2, XIE Long1,2, HOU Jing-hua1, LI Liang-jun1, LIU Jian-jun3, LEI Wen*1,2 （1. Shanghai Research Institution of Chemical Industry Co. Ltd., Shanghai 200062, China; 2. Shanghai Professional Technology Service Platform on Detection and Application Development for Stable Isotope, Shanghai 200062 China; 3. Department of Nuclear Medicine, Renji Hospital, School of Medicine, Shanghai Jiao Tong University, Shanghai 200127, China）
Abstract: In recent years, stable isotope-labeled compounds, especially isotope-labeled amino acids are widely used in frontier scientific research such as synthetic biology, proteomics and metabolomics. In this paper, an analytical method for the isotopic abundance calculation of 13C, 15N double-labeled amino acids was established based on liquid chromatography-high resolution mass spectrometer （LC-HRMS）. Application conditions, sample concentration and the number of scanned mass spectra were investigated. Results showed that the method has good accuracy and stability, requires less sample and is easy to operate. It is expected to be a simple and generalized method for quality control of isotope reagents, and also to support frontier scientific research such as fermentation engineering and metabolomics.
Key Words: double-labelled amino acid; isotope abundance; liquid chromatography-high resolution mass spectrometer; quality control; 13C2,15N-glycine
引用本文：赵雅梦，徐增益，范若宁，等. 基于高分辨液质联用的双标记氨基酸同位素丰度测定方法研究[J]. 化学试剂, 2024, 46（6）:83-88.
基于高光谱技术的穿心莲药材中穿心莲内酯类成分
检测研究
肖丹1，王思曼1，张悦1，刘地发2，郝庆秀1,3，白瑞斌*1,3，杨健*1,3
（1. 中国中医科学院 中药资源中心，道地药材品质保障与资源持续利用全国重点实验室，北京 100700；2. 江西青峰药业有限公司，江西 赣州 341000；3. 江西省道地药材质量评价研究中心，江西 赣江新区 330000）
摘要：基于高光谱技术结合化学计量学，建立不同种质穿心莲药材中穿心莲内酯类成分含量的检测方法。采集穿心莲样品的高光谱信息，获得原始光谱数据（Raw Data）。采用一阶导数（D1）、二阶导数（D2）、SG平滑（SG）、乘性散射校正（MSC）对Raw Data预处理，结合偏最小二乘判别分析（PLS-DA）建立分类模型，结合偏最小二乘回归（PLSR）、反向传播神经网络（BPNN）、随机森林回归（RFR）建立回归模型。应用连续投影算法（SPA）简化模型。不同种质的穿心莲最佳分类模型为D1-PLS-DA。穿心莲内酯、新穿心莲内酯、去氧穿心莲内酯、脱水穿心莲内酯和上述4种穿心莲内酯类化合物总含量的最佳回归模型分别为SG-PLSR、MSC-PLSR、Raw Data-SPA-BPNN、MSC-SPA-BPNN和Raw Data-PLSR。应用高光谱技术可实现穿心莲品质的快速准确检测。
关键词：高光谱成像技术；化学计量学；穿心莲；预测模型；BP神经网络；偏最小二乘法；随机森林回归
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2024）06-0089-10
DOI：10.13822/j.cnki.hxsj.2024.0018
Research on the detection of andrographolide components in Andrographis paniculata Based on Hyperspectral Technology XIAO Dan1, WANG Si-man1, ZHANG Yue1, LIU Di-fa2, HAO Xiu-qin1,3, BAO Rui-bing*1,3, YANG Jian*1,3 （1. State Key Laboratory for Quality Ensurance and Sustaainable Use of Dao-di Herbs, National Resource Center for Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China; 2. Jiangxi Qingfeng Pharmaceutical Co. Ltd., Ganzhou 341000, China;3. Evaluation and Research Center of Daodi Herbs of Jiangxi Province, Ganjiang New Area 330000, China）
Abstract: Based on hyperspectral technology combined with chemometrics, to establish a method for detecting the content of andrographolide components in different germplasm of Andrographis paniculata. The hyperspectral information of Andrographis paniculata samples was collected to obtain the raw spectral data （Raw Data）. The Raw Data was preprocessed using first derivative （D1）, second derivative （D2）, smoothing with Gaussian （SG）, multiplicative scatter correction （MSC）, and a classification model was established using partial least squares discriminant analysis （PLS-DA）. Regression models were established using partial least squares regression （PLSR）, back propagation neural network （BPNN）, and random forest regression （RFR）. The application of successive projection algorithm （SPA） simplified the model. The optimal classification model for different germplasm of Andrographis paniculata is D1-PLS-DA. The optimal regression models for andrographolide, neoandrographolide, deoxyandrographolide, dehydroandrographolide, and total content of the four andrographolide components mentioned above are SG-PLSR, MSC-PLSR, Raw Data-SPA-BPNN, MSC-SPA-BPNN, and Raw Data-PLSR, respectively. The application of hyperspectral technology can achieve rapid and accurate detection of the quality of Andrographis paniculata.
Key words: hyperspectral imaging technology; chemometric; Andrographis paniculata; prediction model; backpropagation neural network; partial least squares method; random forest regression
引用本文：肖丹，王思曼，张悦，等. 基于高光谱技术的穿心莲药材中穿心莲内酯类成分检测研究[J].化学试剂，2024, 46（6）：89-98.
QuEChERS-超高效液相色谱-串联质谱法测定牦牛肉中多种抗生素残留
李增明a,b，解玉龙*a,c，马春光b
（青海民族大学a. 化学化工学院，b. 西宁市疾病预防控制中心，c. 青海省纳米材料与技术重点实验室，青海 西宁 810007）
摘要：建立了用氨基化多壁碳纳米管和C18作为净化剂，用超高效液相色谱-串联质谱法同时快速测定牦牛肉中四环素类、喹诺酮类和磺胺类31种抗生素残留的方法，牦牛肉经过均质，然后用2 mL（0.1 mol/L）Na2EDTA-McLlvaine试剂和8 mL乙腈超声提取，离心提取上清液后用QuEChERS（氨基化多壁碳纳米管和C18作为净化剂）法净化，浓缩定容后用Waters ACQUITY UPLCTM BEH C18柱分离，电喷雾正离子模式（ESI+）电离，多反应离子监测（MRM）采集信号，外标法定量。研究结果表明：31种抗生素残留在1~200 μg/kg的线性范围内有良好线性关系（r>0.9950）。该方法的检出限和定量限分别为0.06~0.77 和0.18~2.31 μg/kg。空白加标样品在20、100 和200 μg/ kg 3个浓度水平时，31种兽药残留平均回收率为63%~126%，相对标准偏差为0.69%~11.5%（n=6），方法快捷简单，方法重现性好、准确度高，适合对牦牛肉中残留的31种抗生素进行分析检测。
关键词：抗生素残留；QuEChERS；超高效液相色谱-串联质谱；牦牛肉；净化剂
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）06-0099-08
DOI：10.13822/j.cnki.hxsj.2023.0832
Determination of Veterinary Drμg Residues in Yak Meat by QuEChERS-Ultra High Performance Liquid Chromatography-tandem Mass Spectrometry LI Zeng-minga,b, XIE Yu-long*a,c, MA Chun-guangb （a. School of Chemistry and Chemical Engineering, b. Xining Center for Disease Control and Prevention, c. Key Laboratory of Nanomaterials and Technology in Qinghai Province, Qinghai Minzu University, Xining 810007, China ）
Abstract: In this study, an ultra-high performance liquid chromatography-tandem mass spectrometry （UHPLC-MS） method was established for the simultaneous and rapid determination of 31 kinds of antibiotics residues of tetracycline, quinolone and sulfonamides in yak meat by using amination multi-wall carbon nanotubes and C18 as purification agent. Then, 2 mL（0.1mol /L） Na2EDTA-McLlvaine reagent and 8 mL acetonitrile were ultrasonically extracted, the supernatant was centrifuged and purified by QuEChERS （amination multi-wall carbon nanotubes and C18 as purification agent） method. After concentration and volume determination, the Water ACQUITY UPLCTM BEH C18 column was used for separation, electrospray positive ion mode （ESI+） ionization, multiple reactive ion monitoring （MRM） signals were collected and quantified by external standard method. The results showed that the residues of 31 antibiotics had a good linear relationship in the linear range of 1-200 μg/kg （r>0.9950）. The limits of detection and quantification were 0.06～0.77 μg/kg and 0.18～2.31 μg/kg, respectively. The average recovery of 31 veterinary drugs was 63%～126% and the relative standard deviation was 0.69%～11.5% （n=6） at the concentration of 20, 100 and 200 μg/ kg blank labeled samples. The method was fast and simple, with good reproducibility and high accuracy, which was suitable for the analysis and detection of 31 kinds of antibiotics in yak meat.
Key words: antibiotic residue; QuEChERS; ultra performance liquid chromatography-tandem mass（UPLC-MS）; yak meat; purification agent
引用本文：李增明，解玉龙，马春光. QuEChERS-超高效液相色谱-串联质谱法测定牦牛肉中多种抗生素残留[J].化学试剂，2024，46（6）：99-106.
离子色谱法测定9V、11A、19A型肺炎球菌多糖中碘化钠残留量
朱向国，王立勇，张晓康，马庆华*，郑佳
（北京智飞绿竹生物制药有限公司，北京 100176）
摘要：建立检测9V、11A、19A型肺炎球菌多糖中碘化钠残留量的离子色谱方法，并进行验证。以Dionex IonPac AS11-HC 阴离子交换层析柱为分析柱，Dionex IonPac AG11-HC阴离子交换柱为保护柱；采用低浓度氢氧化钠溶液为淋洗液等度洗脱，以电化学检测器进行检测。碘化钠的质量浓度在0.01~1.00 μg/mL的范围具有良好的线性关系，决定系数R2可达到0.9999，检出限为0.002 μg/mL，定量限为0.010 μg/mL。3个型别肺炎球菌多糖在低、中、高3个加标水平下的平均回收率为94.40%~103.91%，相对标准偏差（RSD）为0.17%~1.71%，均满足检测要求。方法无需复杂的样品前处理过程，测定快速，灵敏度高，结果准确，重复性好，可用于9V、11A、19A型肺炎球菌多糖中痕量碘化钠残留的检测。
关键词：肺炎球菌多糖；离子色谱；电化学检测器；碘化钠；残留检测
中图分类号：O65 文献识别码：A 文章编号：0258-3283（2024）06-0107-05
DOI：10.13822/j.cnki.hxsj.2024.0012
Determination of Sodium Iodide Residue in the Type 9V, 11A or 19A Pneumococcal Polysaccharides by Ion Chromatography ZHU Xiang-guo, WANG Li-yong, ZHANG Xiao-kang, MA Qing-hua*, ZHENG Jia （Beijing ZhifeiLvzhu Biopharmaceutical Co.,Ltd. Beijing 100176, China）
Abstract: To develop and validate an ion chromatography method for the determination of residual sodium iodide in the serotype 9V, 11A or 19A pneumococcal polysaccharides. Successful quantification of residual sodium iodide in the serotype 9V, 11A or 19A pneumococcal polysaccharides was achieved by electrochemical detector, using Dionex IonPac AS11-HC anion exchange chromatography column as the analytical column, Dionex IonPac AG11-HC anion exchange column as the protective column, low-concentration sodium hydroxide solution as eluent for isocratic elution. The method is found to be linear in the range of 0.01~1.00 μg/mL with a coefficient of determination（R2） of 0.9999. The detection limit is 0.002 μg/mL and the quantitation limit is 0.010 μg/mL. The average spiked recoveries at low, medium and high three levels range from 94.40%~103.91%, with the relative standard deviations（RSD） of 0.17%~1.71%, of which all meet the detection requirements. The method is suitable for the determination of trace sodium iodide residues in the serotype 9V, 11A or 19A pneumococcal polysaccharides for its simplicity, rapidness, sensitivity, accuracy and repeatability.
Key words: pneumococcal polysaccharides; ion chromatography; electrochemical detector; sodium iodide; residue detection
引用本文：朱向国，王立勇，张晓康，等. 离子色谱法测定9V、11A、19A型肺炎球菌多糖中碘化钠残留量[J]. 化学试剂, 2024, 46（6）:107-111.
【标准物质与标准品】
氮中一氧化氮、二氧化硫、一氧化碳气体标准物质的研制
夏春，汪圣甲，王海燕，杨倩，李剑*
（青岛市计量技术研究院，山东 青岛 266101）
摘要：介绍了氮中一氧化氮、二氧化硫、一氧化碳气体标准物质的研制过程。以高纯一氧化氮气体、高纯二氧化硫气体、高纯一氧化碳气体、高纯氮气为原料，采用称量法制备了氮中一氧化氮、二氧化硫、一氧化碳气体标准物质，采用与同基体国家一级标准物质比较的方法定值。对原料气中的杂质进行了分析，基于傅里叶变换红外光谱分析仪建立了分析方法，对制备的气体标准物质进行了均匀性和稳定性考察。结果表明：研制的氮中一氧化氮、二氧化硫、一氧化碳气体标准物质均匀性和稳定性良好，浓度特征量值范围为：一氧化氮：200~1000 μmol/mol、二氧化硫：200~1000 μmol/mol、一氧化碳：1000~5000 μmol/mol，相对扩展不确定度为1.5%（k=2）。
关键词：一氧化氮；二氧化硫；一氧化碳；标准物质；不确定度；比较法
中图分类号：O657.71 文献标识码：A 文章编号：0258-3283（2024）06-0112-07
DOI：10.13822/j.cnki.hxsj.2023.0819
Preparation of Gas Reference Material For Nitric Oxide、Sulfur Dioxide and Carbon Monoxide in Nitrogen XIA Chun, WANG Sheng-jia, WANG Hai-yan, YANG Qian, Li Jian* （Qingdao Institute of Measurement Technology，Qingdao 266101，China）
Preparation of gas reference material of nitric oxide, sulfur dioxide and carbon monoxide mixed in nitrogen was reported. Using high-purity nitric oxide gas, high-purity sulfur dioxide gas, high-purity carbon monoxide gas and high-purity nitrogen as parents gases, the gas reference materials were prepared by gravimetric method, and the values were determined by comparison method. The impurities in the parent gases were analyzed. The comparision method was established based on the Fourier Transform Infrared Spectrometer. The homogeneity and stability of the prepared gas reference materials were investigated. The results showed the homogeneity and stability of the gas reference materials were well. The ranges of property values of nitric oxide, sulfur dioxide and carbon monoxide were （200~1000） μmol/mol, （200~1000） μmol/mol, （1000~5000） μmol/mol respectively, with the relative expanded uncertainty 1.5% （k=2） for all.
Key words：nitric oxide；sulfur dioxide；carbon monoxide；reference material；uncertainty；comparison method
引用文本：夏春，汪圣甲，王海燕，等. 氮中一氧化氮、二氧化硫、一氧化碳气体标准物质的研制[J].化学试剂, 2024, 46（6）:112-118.
