敞开式离子化质谱技术在中药材及中药饮片质量评价中的应用进展
黄文静1,2，叶楚璇1,3，徐浩然1,4，黄志伟1,3，王登辉1，王乐琪1,3，李莎莎*1,2,3，严诗楷1,2,3,4，肖雪*1,2
（1. 广东药科大学 中医药研究院 中药学院 广东省代谢病中西医结合研究中心，广东 广州 510006；
2. 国家药品监督管理局药品快速检验技术重点实验室（广东省药品检验所），广东 广州 510663；
3. 广州中医药大学第二附属医院，广东 广州 510120；4. 上海交通大学 药学院，上海 200240）
摘要：中药材及中药饮片是中药产业链的重要组成部分，其质量是保障中成药质量和稳定发挥临床疗效的基础。为了实现中药材及中药饮片质量更高效的控制与监管，新技术、新设备、新方法不断产生。敞开式离子化质谱技术是近些年迅速发展起来的一种新型检测技术，具有实时、直接、准确、快速的特有优点，在中药分析、质量分析与质量控制领域的应用越来越多，取得了良好的应用效果。归纳梳理了敞开式离子化质谱技术的基本原理、特点，及其在中药材及中药饮片质量分析与评价中的应用现状，总结该技术在中药材及中药饮片质量评价中所面临的问题，并对其未来发展方向进行展望。
关键词：敞开式离子化；质谱；中药材；中药饮片；质量控制
中图分类号：R917 文献标识码：A 文献编号：0258-3283（2022）
Application Progress in Quality Evaluation of Chinese Medicinal Materials and Chinese Medicine Decoction Pieces based on Ambient Ionization Mass Spectrometry HUANG Wen-jing1,2, YE Chu-xuan1,3, XU Hao-ran1,4, HUANG Zhi-wei1,3, WANG Deng-hui1, Wang Le-qi1,3, LI Sha-sha*1,2,3, YAN Shi-kai1,2,3,4, XIAO Xue*1,2 (1. Institute of Traditional Chinese Medicine, School of Traditional Chinese Medicine, Guangdong Metabolic Disease Research Center of Integrated Chinese and Western Medicine, Guangdong Pharmaceutical University, Guangzhou 510006; 2. NMPA Key Laboratory for Rapid Testing Technology of Drugs, Guangdong Institute for Drug Control, Guangzhou 510663; 3. The Second Affiliated Hospital of Guangzhou University of Chinese Medicine, Guangzhou 510120; 4. School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China), Huaxue Shiji, 2022, 44(8), ～
Abstract: Chinese medicinal materials and Chinese medicinal decoction pieces are the important parts of the Chinese medicine industry chain, and the quality is the basis of guaranteeing the quality of Chinese patent medicine and developing its clinical efficacy stably. To effectively supervise the quality of Chinese medicinal materials and decoction pieces, new techniques, advanced instruments and new methods for quality control have been developed. Ambient ionization mass spectrometry (AIMS) is a new detection technology developed rapidly in recent years. AIMS has the unique advantages of being real-time, direct, accurate, and fast. In recent years, AIMS has been applied in this field. In this paper, the basic principle, characteristics, and application progress of AIMS in quality evaluation of Chinese herbal decoction pieces were summarized, the problems faced by this technology in quality evaluation of Chinese herbal decoction pieces were summarized and the future development direction of this technology has prospected.
Key words：ambient ionization; mass spectrometry; Chinese medicinal materials; Chinese herbal medicine; quality control
引用本文：黄文静, 叶楚璇, 徐浩然, 等.敞开式离子化质谱技术在中药材及中药饮片质量评价中的应用进展[J]. 化学试剂, 2022, 44（8）：1079-1087.
植物乳杆菌发酵黑果枸杞的代谢组学研究
李丽1，冯华峰*2，周淳3，胡坪1，章弘扬*1
（1. 华东理工大学 化学与分子工程学院，上海市功能性材料化学重点实验室，上海 200237；2. 上海商学院 食品系，上海 200235；3. 上海甘泓生物医学科技有限公司，上海 200131)
摘要：以植物乳杆菌GH-6发酵黑果枸杞浆为研究对象，分析发酵前后黑果枸杞浆中差异性代谢物的含量变化。采用超高效液相色谱-静电场轨道肼质谱联用（UPLC-Orbitrap MS）技术，首先对发酵前后黑果枸杞浆的成分进行分析，共鉴定出61个代谢物。随后，在原浆、发酵液以及添加蔗糖及乳清蛋白后的发酵液中筛选出22个差异性代谢物，其中4种花青素类、3种有机酸类、2种糖类、3种氨基酸类、7种小肽类和3种嘌呤类。结果表明，由于植物乳杆菌GH-6糖苷酶的水解作用，促使花青素类及糖类物质的含量上升；经发酵引起的乳酸生成增加，可有效调节黑果枸杞发酵液的风味；益生乳酸菌具有的肽转运系统使得二肽、三肽类物质水解，天冬氨酸-异亮氨酸、缬氨酰-谷氨酸及缬氨酰-缬氨酰-缬氨酸在发酵后未被检出，说明这三种肽类可能优先被植物乳杆菌GH-6所利用。此外，植物乳杆菌GH-6还具有降解嘌呤的能力，致使发酵液中嘌呤类物质的含量降低。总之，通过植物乳杆菌GH-6发酵能显著影响黑果枸杞浆中的代谢变化，本研究将为黑果枸杞有效营养成分的开发利用以及发酵制品等相关产品的研发提供参考和新的应用方向。
关键词：黑果枸杞；植物乳杆菌GH-6；发酵；代谢组学；多元变量统计分析
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2022）--
Metabolomics study of Lactobacillus Plantarum Fermented Lycium Ruthenicum Murr. Li Li1, Huafeng Feng*2, Chun Zhou3, Ping Hu1, Hongyang Zhang*1 (1. Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. The Department of Food, Shanghai Business School, Shanghai 200235, China; 3. Shanghai Ganhong Biomedical Technology Co., Ltd., Shanghai 200131, China), Huaxue Shiji, 44(8), ～
Abstract：Taking lactobacillus plantarum GH-6 fermented Lycium Ruthenicum Murr. as the research object, the content changes of differential metabolites in Lycium Ruthenicum Murr. before and after fermentation was analyzed. By using ultra-high-performance liquid chromatography-orbitrap mass spectrometry (UPLC-Orbitrap MS), the composition of Lycium Ruthenicum Murr. before and after fermentation was analyzed, and a total of 61 metabolites were identified. After then, 22 differential metabolites were screened in the puree, fermentation broth, and fermentation broth after adding sucrose and whey protein, including 4 anthocyanins, 3 organic acids, 2 carbohydrates, and 3 amino acids, 7 small peptides, and 3 purines. The results demonstrated that due to the hydrolysis of lactobacillus plantarum GH-6 glycosidase, the content of anthocyanins and sugars increased. The increment of lactic acid induced by fermentation could effectively adjust the flavor of the fermentation broth of Lycium Ruthenicum Murr. The peptide transport system of probiotic lactic acid bacteria could hydrolyze dipeptide and tripeptide compounds, and Asp-Ile, Val-Glu, and Val-Val-Val were not detected after fermentation, indicating that these peptides might be preferentially utilized by lactobacillus Plantarum GH-6. In addition, lactobacillus plantarum GH-6 can degrade purines, which reduces the content of purines in the fermentation broth. In conclusion, the fermentation of Lactobacillus plantarum GH-6 can significantly affect the metabolic alterations in Lycium Ruthenicum Murr., and this study can provide a reference and novel application directions for the development and utilization of effective nutritional components of Lycium Ruthenicum Murr., as well as the research and development of its fermented products and other related products.
Key words：Lycium Ruthenicum Murr.; lactobacillus plantarum GH-6; fermentation; metabolomics; multivariate statistical analysis
引用本文：李丽，冯华峰，周淳，等. 植物乳杆菌发酵黑果枸杞的代谢组学研究[J]. 化学试剂，2022, 44（8）：1088-1096.
基于中药Q-marker理论的经典名方枳实薤白桂枝汤关键成分发现与量质传递研究
李明潺1，杨红素2，徐家山2，曲珍妮3，段宏泉3，董林毅*3，孙露*4
(1. 天津医科大学总医院，天津 300052；2. 通化玉圣药业有限公司，吉林 通化 134000；3. 天津医科大学 药学院，天津 300070；4. 天津医科大学 朱宪彝纪念医院 天津市内分泌研究所 国家卫健委激素与发育重点实验室 天津市代谢性疾病重点实验室，天津 300134)
摘要：枳实薤白桂枝汤收录于国家经典名方目录，中药质量标志物（Q-marker）理论有助于方剂中关键成分的发现与量质传递研究。采用液质联用技术指认枳实薤白桂枝汤中的Q-marker，进行指纹图谱方法学考察和相似度分析，计算方剂出膏率和关键成分的含量转移率。最终指认大麦芽碱、麦角甾苷、新北美圣草苷、芸香柚皮苷、柚皮苷、橙皮苷、新橙皮苷、异米拉素、苜蓿素、和厚朴酚和厚朴酚为枳实薤白桂枝汤Q-marker，18批样品指纹图谱相似度分析结果均大于0.92，平均出膏率为17.06%，关键成分的转移率以腺苷、辛弗林、桂皮醛、厚朴酚、和厚朴酚计算分别为87.49%、79.95%、25.04%、6.18%、8.80%。本实验确定了枳实薤白桂枝汤质量标志物，结合指纹图谱及关键成分的量质传递研究，为枳实薤白桂枝汤质量评价提供了依据。
关键词：枳实薤白桂枝汤；液质联用；中药指纹图谱；中药质量标志物；经典名方
中图分类号：R286.02 文献标识码：A 文章编号：0258-3283（2022）--
Study on the discovery of the index components and quantitative-qualitative transfer of Classical prescription Zhishi Xiebai Guizhi Decoction based on Q-marker LI Ming-chan1, YANG Hong-su2, XU Jia-shan2, QU Zhen-ni3, DUAN Hon-quan3，DONG Lin-yi*3，SUN Lu*4(1.General Hospital, Tianjin Medical University, Tianjin 300052, China; 2. Tonghua Yu Sheng Pharmaceutical Co., Ltd., Tonghua 134000, China; 3. College of Pharmacy, Tianjin Medical University, Tianjin 300070, China; 4. NHC Key Laboratory of Hormones and Development/Tianjin Key Laboratory of Metabolic Diseases, Chu Hsien-IMemorial Hospital/Tianjin Institute of Endocrinology, Tianjin Medical University, TIANJIN 300134, China), Huaxue Shiji, 44(8), ～
Abstract：Zhishi Xiebai Guizhi Decoction was included in the catalog of national classic prescriptions. Q-marker theory was helpful in the discovery of the index components and quantitative-qualitative transfer study in Chinese herbal prescriptions. Q-marker in Zhishi Xiebai Guizhi Decoction was identified by LC-MS and the fingerprint methodology was investigated, and the similarity analysis was evaluated. The paste-forming rate and the transfer rate of index components were also calculated. Q-marker were identified as follows: Hordenine, Verbascoside, Neoeriocitrin, Narirutin, Naringin, Hesperidin, Neohesperidin, Isoramil, Tricin, Honokiol, Magnolol. The similarity of 18 batches of Zhishi Xiebai Guizhi Decoction samples was more than 0.92. The average paste-forming rate was 17.06%. The transfer rates of adenosine, synephrine, cinnamaldehyde, honokiol, and honokiol were 87.49%, 79.95%, 25.04%, 6.18%, and 8.80%, respectively. In this study, the Q-markers of Zhishi Xiebai Guizhi Decoction were determined. Combined with the fingerprint and the quantitative-qualitative transfer of index components, it provided a basis for the quality evaluation of classical prescription Zhishi Xiebai Guizhi Decoction.
Key words：Zhishi Xiebai Guizhi decoction; LC-MS; fingerprints; Q-marker；classical prescription
引用本文：李明潺，杨红素，徐家山，等. 基于中药Q-marker理论的经典名方枳实薤白桂枝汤关键成分发现与量质传递研究[J]. 化学试剂，2022，44（8）:1097-1102.
2D-LC在中药分析与质量控制中的应用进展
叶楚璇1,3，黄文静1,2，覃思意1，麦子盈1,4，王乐琪1,3，李莎莎*1,2,3，徐浩然1，王登辉1，严诗楷1,3,4，肖雪*1,2
（1. 广东药科大学 中医药研究院 广东省代谢病中西医结合研究中心，广东 广州 510006；2. 国家药品监督管理局 药品快速检验技术重点实验室（广东省药品检验所），广东 广州 510663；3. 广州中医药大学 第二附属医院，广东 广州 510120；4. 上海交通大学 药学院，上海 200240）
摘要：中药质量控制是保证其药效及安全的关键因素，也是中医药产业良性发展的重要保障。高效液相色谱技术作为一种经典、高效的检测技术，具有强大的分离效能，能够对中药中复杂成分进行有效分离及含量测定，已广泛应用于中药的质量控制中。随着液相技术的发展，二维液相色谱技术的出现弥补了一维液相色谱技术中样品前处理复杂，基体干扰较大等缺点，其灵敏度更高，分离度更好，能够快速，准确对中药做出分析、评价及质量控制。二维液相色谱技术因其普适性与简便性，使得中药分析更加全面、更加完善。本文从二维液相色谱技术在中药化学成分的系统分离、全面定性、精准定量、风险物质检测等多个方面，阐述二维液相色谱技术在中药分析及质量控制中发挥的作用。
关键词：二维液相；中药分析；质量控制；应用进展
中图分类号： 文献标识码：A 文章编号：0258-3283（2022）--
Application Progress of 2D-LC in Analysis and Quality Control of Traditional Chinese Medicine YE Chu-xuan1,3, HUANG Wen-jing1,2, QIN Si-yi1, Mai Zi-ying1,4, Wang Le-qi1,3, LI Sha-sha*1,2,3, XU Hao-ran1, WANG Deng-hui1, YAN Shi-kai1,3,4, XIAO Xue*1,2 (1. Institute of Traditional Chinese Medicine, Guangdong Metabolic Disease Research Center of Integrated Chinese and Western Medicine, Guangdong Pharmaceutical University, Guangzhou 510006, China; 2. NMPA Key Laboratory for Rapid Testing Technology of Drugs, Guangdong Institute for Drug Control, Guangzhou 510663, China; 3. The Second Affiliated Hospital of Guangzhou University of Chinese Medicine, Guangzhou 510120, China; 4. School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China), Huaxue Shiji, 44(8), ～
Abstract：Quality control of Traditional Chinese medicine is the key factor to ensuring its efficacy and safety, and also an important guarantee for the continuous development of the Traditional Chinese medicine industry. As a classic and efficient detection technology, high-performance liquid chromatography (HPLC) has been widely used in the quality control of Traditional Chinese medicine because of its powerful separation skills and effective separation and content determination of complex components in Traditional Chinese medicine. With the development of liquid phase technology, the appearance of two-dimensional liquid chromatography technology (2D-LC) has made up for the shortcomings of one-dimensional liquid chromatography technology, such as complex sample pretreatment, large matrix interference, and so on. Its sensitivity is higher, the separation degree is better, and it can quickly and accurately evaluate and control the quality of Traditional Chinese medicine. Due to its universality and simplicity, 2D-LC makes qualitative and quantitative analysis of TCM more comprehensive. This paper aims to expound on the role of 2D-LC in the analysis and quality control of Traditional Chinese medicine from the following aspects, such as the overall characterization, the study of chemical composition, the quantitative analysis of complex components, and the control and control of risk substances, etc.
Key words：two-dimensional liquid chromatography; analysis of traditional Chinese medicine; quality control; Application progress
引用本文：叶楚璇，黄文静，覃思意，等. 2D-LC在中药分析与质量控制中的应用进展[J]. 化学试剂，2022, 44（8）：1103-1110.
小叶黄杨的化学成分及心肌细胞保护作用研究
王瑞1，张岩1，MUHAMMAD Ishaq1，田艳2，付登林2，郁华军*2，肖雪3，严诗楷1,2,3，金慧子*1
(1.上海交通大学 药学院，上海 200240; 2.贵州景诚制药有限公司，贵州 贵阳 550200;
3.广东药科大学 中医药研究院，广东 广州 510006)
摘要：研究小叶黄杨(Buxus sinica var. parvifolia M. Cheng)叶子的化学成分及心肌细胞保护作用。综合运用硅胶、Sephadex LH-20、MCI、半制备液相等多种色谱分离方法，对小叶黄杨中等极性部位进行分离纯化，采用波谱学技术对分离的单体化合物进行结构鉴定。另外，对提取各部位和分离得到的16个化合物进行体外心肌细胞保护作用测试。从小叶黄杨干燥叶中共分离得到14个化合物，分别为香草酸乙酯（1）、香草醛（2）、花椒毒素（3）、反式对羟基肉桂酸乙酯（4）、3,4,5-trimethoxycinnamyl alcohol（5）、丁香酸乙酯（6）、(S)-5-hydroxy-3,4-dimethyl-5-pentylfuran-2(5H)-one （7）、桦木酸（8）、4-羟基-3,5-二甲氧基苯甲醛（9）、7,3′,4′-三甲基槲皮素（10）、白桦脂醇（11）、penduletin（12）、23-O-(E)-p-coumaroyl-23-hydroxybetulin（13）、松脂素（14）。其中化合物2、5和6为首次从该植物中分离得到，体外实验表明EA部位和化合物14（松脂素）可显著改善H2O2诱导的心肌细胞损伤。
关键词：小叶黄杨；化学成分；心肌保护作用；H9c2细胞
中图分类号：O629.9 文献标识码：A 文章编号：0258-3283（2022）--
Chemical constituents and cardioprotective effects of Buxus Sinica var. parvifolia M. Cheng
WANG Rui1, ZHANG Yan1, MUHAMMAD Ishaq1, TIAN Yan2, FU Deng-lin2, YU Hua-jun*2, XIAO Xue3, YAN Shi-kai1,2,3, JIN Hui-zi*1 (1. School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China; 2. Guizhou Jingcheng Pharmaceutical Co., Ltd, Guiyang 550200, China; 3. Institute of Chinese Medicinal Sciences, Guangdong Pharmaceutical University, Guangzhou 510006, China), Huaxue Shiji, 2022, 44(8), ～
Abstract: The chemical constituents from the leaves of Buxus Sinica var. parvifolia M. Cheng and their cardioprotective bioactivities were studied. The chemical constituents from the ethyl acetate (EA) part of this plant were isolated and purified by column chromatography such as silica gel, Sephadex LH-20, MCI, and preparative HPLC. The structures of isolates were elucidated by spectroscopic analyses. A hydrogen peroxide (H2O2)-induced cardiomyocyte line H9c2 was used as an in vitro model of damaged cardiomyocytes to evaluate the effects of the extracts and the isolates. Fourteen compounds were isolated and elucidated as ethyl 4-hydroxy-3-methoxybenzoate (1), vanillin (2), xanthotoxin (3), trans-p-hydroxycinnamic acid ethyl ester (4), 3,4,5-trimethoxycinnamyl alcohol (5), syringic acid ethyl ester (6), (S)-5-hydroxy-3,4-dimethyl-5-pentylfuran-2(5H)-one (7), betulinic (8), 4-hydroxy-3,5-dimethoxybenzaldehyde (9), 7,3′,4′-trimethylquercetin (10), betulin (11), Pendleton (12), 23-O-(E)-p-coumaroyl-23-hydroxybetulin (13) and pinoresinol (14). Compounds 2, 5, and 6 were firstly isolated from this plant. The EA part and compound 14 (pinoresinol) showed significant protective effects against H2O2-induced cardiomyocyte injury in H9c2 cells.
Key words: Buxus sinica; chemical constituents; cardioprotective effects; H9c2 cells
引用本文：王瑞，张岩，MUHAMMAD Ishaq，等. 小叶黄杨的化学成分及心肌细胞保护作用研究[J]. 化学试剂,2022,44(8): 1111-1117。
突变异柠檬酸脱氢酶抑制剂治疗胶质瘤的研究进展
王健博1,2a，孟晓燕2a，张雍鑫2a，孔晓华2a，徐中琦2a，李兴伟2a，靳京2a，杨天明*2a,2b，黄长江*2a,2b
（1. 内蒙古医科大学 药学院，内蒙古 呼和浩特 010110；2. 天津药物研究院a. 天津市新药设计与发现重点实验室，b. 释药技术与药代动力学国家重点实验室，天津 300301）
摘要：胶质瘤常伴随异柠檬酸脱氢酶的突变，催化α-酮戊二酸转变为2-羟基戊二酸并大量蓄积，导致DNA/RNA甲基化，影响细胞分化。突变异柠檬酸脱氢酶抑制剂通过与肿瘤细胞中突变体特异性结合，使其失去催化α-酮戊二酸为2-羟基戊二酸的功能，引起下游信号通路的改变，达到抑制肿瘤生长的效果。总结突变异柠檬酸脱氢酶抑制剂治疗胶质瘤的研究进展，重点介绍作用机制、共晶结构、临床试验等，并且讨论了发展方向。
关键词：胶质瘤；突变异柠檬酸脱氢酶；抑制剂；2-羟基戊二酸；共晶结构
中图分类号：R979.1 文献标识码：A 文章编号：0258-3283（2022）--
Progress of Inhibitors of MutantIsocitrate Dehydrogenase for the Treatment of Gliomas WANG Jian-bo1,2a, MENG Xiao-yan2a, ZHANG Yong-xin2a, KONG Xiao-hua2a, XU Zhong-qi 2a, LI Xing-wei2a, JIN Jing 2a, YANG Tian-ming *2a,2b, HUANG Chang-jiang*2a,2b(1. School of Pharmacy, Inner Mongolia Medical University, Hohhot 010110, China; 2a. Tianjin Key Laboratory of Molecular Design and Drug Discovery, 2b. State Key Laboratory of Drug Delivery Technology and Pharmacokinetics, Tianjin Institute of Pharmaceutical Research, Tianjin 300301, China), Huaxue Shiji，2022，44 (8)， ~
Abstract：Glioma is often accompanied by mutations in isocitrate dehydrogenase, which convert α-ketoglutarate (α-KG) into 2-hydroxyglutarate (2-HG), resulting in the accumulation of 2-HG, subsequently leading to DNA/RNA methylation that affects cell differentiation. The mutant isocitrate dehydrogenase inhibitors specifically bind to the mutant enzyme in tumor cells, causing the loss of the activity of catalyzing α-KG to 2-HG, and resulting in the changes of downstream signaling pathways to achieve the inhibition of tumor growth. This article summarizes the research progress of mutant isocitrate dehydrogenase inhibitors for the treatment of gliomas, emphasizing mechanism, cocrystal structures, and clinical trials, and discusses the development direction of this field.
Keywords: gliomas; mutant isocitratedehydrogenase; inhibitors; 2- hydroxyglutarate; cocrystal structures
引用本文：王健博，孟晓燕，张雍鑫，等. 突变异柠檬酸脱氢酶抑制剂治疗胶质瘤的研究进展 [J]. 化学试剂, 2022, 44(8): 1118-1127。
雷公藤甲素丁二酸单酯对A549/DDP细胞的抑制作用研究
杨俊1，王丹丹2，梁玉清1，丁丽娜1，卓俊睿1，梁光平*1
（1. 遵义医药高等专科学校，贵州 遵义 563006；2. 铜仁职业技术学院，贵州 铜仁 554300）
摘要：研究雷公藤甲素丁二酸单酯（YJ-4）对A549/DDP抑制作用及其机制。以雷公藤甲素为原料，与丁二酸酐在DMAP/Pyridine催化下反应后得到化合物YJ-4，其结构经1HNMR，13CNMR和HR-ESI-MS表征，采用MTT法评价其对人非小细胞肺癌细胞（A549）、人肺腺癌耐顺铂株（A549/DDP）、人乳腺癌细胞（MCF-7）的体外抗肿瘤活性；不同浓度的化合物YJ-4作用于A549/DDP细胞后，DAPI染色法检测细胞核状态，PI染色法检测细胞周期，Annexin V-FITC/PI双染法检测细胞凋亡；分子对接软件Autodock来评价化合物YJ-4与MDM2蛋白结合的能力。化合物YJ-4对A549/DDP（33.32 ± 3.55 μmol/L）、A549（4.31 ± 1.01 μmol/L）、MCF-7（16.08 ± 2.63 μmol/L）细胞株均具有良好的细胞毒性，是阳性对照药顺铂的数倍，且通过阻滞A549/DDP细胞周期G2/M期，从而诱导细胞凋亡，与MDM2的GLY-16氨基酸残基与形成氢键（d=1.9 Å），结合能（affinity）为 -8.4 kcal/mol，能够较好的结合。化合物YJ-4对耐药细胞株A549/DDP细胞具有良好的细胞毒活性，其作用机制为促进A549/DDP细胞凋亡、阻滞细胞周期G2/M期，可能与抑制MDM2蛋白和p53相互作用有关。
关键词 雷公藤甲素丁二酸单酯；衍生物；人肺癌耐顺铂株A549/DDP；体外抗肿瘤活性
中图分类号：R914.4 文献标识码：A 文章编号：0258-3283（2022）--
Antitumor Activities of Triptolide Succinate on A549/DDP Lung Cancer YANG Jun1, WANG Dan-dan2, LIANG Yu-qing1, DING Li-na1, ZHUO Jun-rui1, LIANG Guang-ping*1（1. Zunyi Medical And Pharmaceutical College, Zunyi 563006, China; 2. Tongren Polytechnic College, Tongren 554300, China), Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract: To investigate the effects and mechanisms of triptolide succinate monoester (YJ-4) on cisplatin-resistant human lung adenocarcinoma cells (A549/DDP). Compound YJ-4 was synthesized by catalyzing triptolide and succinic anhydride under DMAP/pyridine. Its structure was characterized by 1HNMR, 13CNMR, and HR-ESI-MS. Its anti-tumor activity in vitro against human non-small cell lung cancer cells (A549), human breast cancer cells (MCF-7), and A549/DDP cells were evaluated using the MTT method. After A549/DDP cells were treated with YJ-4 at different concentrations, the nuclear state was detected by DAPI staining, the cell cycle was detected by PI staining, and the apoptosis was detected by Annexin V-FITC/PI double staining. The binding ability of YJ-4 to MDM2 protein was evaluated using molecular docking software Autodock. Compound YJ-4 presented high cytotoxicity to A549/DDP（33.32 ± 3.55 μmol/L）, A549（4.31 ± 1.01 μmol/L）, and MCF-7（16.08 ± 2.63 μmol/L）cells, which was significantly superior to the positive control drug cisplatin. Additionally, YJ-4 blocked the G2/M phase of the A549/DDP cell cycle and induced apoptosis. It could form a hydrogen bond with amino acid residue GLY-16 of MDM2 (d=1.9 Å), with an affinity of -8.4 kcal/mol, suggesting a high binding ability. Compound YJ-4 has a high cytotoxic activity to drug-resistant cell line A549/DDP. Its mechanism is to promote A549/DDP cell apoptosis and block the G2/M phase of the cell cycle, which may be related to the inhibition of the interaction between MDM2 protein and p53.Key words: C14-triptolide succinate monoester; derivatives; Cisplatin-resistant human lung cancer cells; antitumor activity in vitro
引用本文：杨俊， 王丹丹， 梁玉清， 等. 雷公藤甲素丁二酸单酯对A549/DDP细胞的抑制作用研究[J]. 化学试剂, 2022, 44(8): 1128-1135。
喹啉类mTOR/HDAC双靶抑制剂的设计、合成与体外活性评价
李志，张明明，陶强强，何格，赵灿，钟国琛*，马晓东*
（安徽中医药大学 药学院 安徽省中医药科学院药物化学研究所，安徽 合肥 230012）
摘要：为发现新型mTOR/HDAC双靶抑制剂，基于药效团融合策略构建目标分子，并经亲核取代或缩合反应、羟胺解反应制得目标分子。体外抑酶活性测试结果显示，4'-((4-(4-(N-羟基戊酰胺)-哌嗪-1-基)-3-(三氟甲基)苯基)氨基)-[3,6'-二喹啉]-3'-甲酰胺呈现出中等强度的双靶抑酶活性（Mtor、HDAC1、HDAC6的 IC50 值分别为1444、832、230 nmol/L）；4'-((4-(4-(N-羟基乙酰胺)-哌嗪-1-基)-3-(三氟甲基)苯基)氨基)-[3,6'-二喹啉]-3'-甲酰胺对mTOR具有良好的抑制活性（IC50 = 64 nmol/L）。抗增殖活性测试结果显示，所有目标分子对A549细胞株的增殖抑制活性与阳性对照SAHA、MLN-0128相当或略优；4'-((4-(4-(N-羟基-1-羰基辛酰胺)哌嗪-1-基)-3-(三氟甲基)苯基)氨基)-[3,6'-二喹啉]-3'-甲酰胺对HCT116的抗增殖活性与MLN-0128相当。
关键词：mTOR；HDAC；双靶抑制剂；抑酶活性；抗增殖活性
Quinoline Derivatives of mTOR/HDAC Dual-Target Inhibitors : The Design, Synthesis and In vitro Biological Evaluation LI Zhi, ZHANG Ming-ming, TAO Qiang-qiang, HE Ge, ZHAO Can, ZHONG Guo-chen*, Ma Xia-odong* (School of Pharmacy, Anhui University of Chinese Medicine, Department of Medicinal Chemistry, Anhui Academy of Chinese Medicine, Hefei, Anhui 230031, China), Huaxue Shiji, 2022, 44(8), ～
Abstract：To discover novel mTOR/HDAC bi-functional inhibitors, target compounds were designed via a pharmacophore-merging strategy and prepared by nucleophilic substitution or condensation and the following hydroxylaminolysis. As demonstrated by the in vitro enzymatic assay, compound 14 exhibited moderate inhibitory activity against both mTOR and HDAC (mTOR IC50 = 1444 nmol/L; HDAC1 IC50 = 832 nmol/L; HDAC6 IC50 = 230 nmol/L). Besides, compound 13 displayed acceptable inhibitory activity against mTOR (IC50 = 64 nmol/L). In the anti-proliferative assay, all the synthesized compounds exhibited comparable or superior activity to the positive control SAHA and MLN-0128 against the A549 cell line. Additionally, compound 16 exerted comparable anti-proliferative activity to MLN-0128 against the HCT116 cell line.
Key words：mTOR; HDAC; bi-functional inhibitors; inhibitory activity against both mTOR and HDAC; anti-proliferative activity
引用本文：李志, 张明明, 陶强强, 等. 喹啉类mTOR/HDAC双靶抑制剂的设计、合成与体外活性评价[J]. 化学试剂, 2022, 44（8）：1136-1141.
基于甘草酸的荧光纳米碳点的合成及性能研究
黄湘，周莉佳，粟小燕，裴叔宸，柴水琴，管天冰*
(重庆科技学院 化学化工学院，重庆 401331)
摘要：随着抗生素在临床上滥用，开发新型的抗菌纳米材料显得尤为重要。本研究以甘草酸为原料，经一步水热法合成了的新型荧光纳米碳点材料并进行结构表征。碳点粒径分布范围为3.0～5.3 nm，厚度为3.0～4.0 nm，表面富含羧基、羟基、碳碳双键等官能团。荧光光谱中，碳点的最大激发波长为360 nm，最大发射波长为430 nm。碳点对微生物具有抑制作用，其中对金黄色葡萄球菌的MIC值为0.60 mg/mL，对大肠杆菌的MIC值为0.60 mg/mL。实验结果表明，该碳点具有稳定的荧光特性和良好的抗菌活性，有望在多功能生物医学纳米材料领域得到更广泛的应用。
关键词：甘草酸; 碳点; 纳米材料; 荧光性质; 抗菌活性
中图分类号：O613.71 文献标识码：A 文章编号：,0258-3283（2022）--
Synthesis, Fluorescence Properties and Antibacterial Activity of Fluorescent Carbon Dots Based on Glycyrrhizic Acid HUANG Xiang, ZHOU Li-jia, SU Xiao-yan, PEI Shu-chen, CHAI Shui-qin, GUAN Tian-bing (College of Chemistry and Chemical Engineering, Chongqing University of Science and Technology, Chongqing 401331, China), Huaxue Shiji, 2022, 44(8), ～
Abstract：With the abuse of antibiotics clinically, the development of new antibacterial nanomaterials is particularly important. In this study, a new type of fluorescent carbon dot was synthesized by a one-step hydrothermal method with glycyrrhizic acid and citric acid as raw materials, and the structure was characterized. The results show that the carbon dots have a particle size distribution range of 3.0 ～ 5.3 nm and a thickness of 3.0-4.0 nm. The surface is rich in functional groups such as carboxyl groups, hydroxyl groups, and carbon-carbon double bonds. In the fluorescence spectrum, the maximum excitation wavelength of carbon dots is 360 nm, and the maximum emission wavelength is 430 nm. Through the Minimum Inhibitory Concentration (MIC) experiment, it is determined that the carbon dot has an inhibitory effect on various microorganisms. Among them, the MIC value for Staphylococcus aureus is 0.60 mg/mL, and for Escherichia coli is 0.60 mg/mL. Experimental results show that the carbon dots have stable fluorescence characteristics and good antibacterial activity, and are expected to be more widely used in the field of multifunctional biomedical nanomaterials.
Key words：glycyrrhizic acid; carbon dots; nano materials; fluorescent property; antibacterial activity
引用本文：黄湘，周莉佳，粟小燕，等. 基于甘草酸的荧光纳米碳点的合成及性能研究[J]. 化学试剂, 2022, 44(8): 1142-1147.
β-FeOOH改性凹凸棒土的制备及其对单宁酸吸附性能研究
袁大英1，张红军1，潘绪华1，徐轶群2，胡庆松*2
（1. 中交上海航道局有限公司 江苏交通建设工程分公司，江苏 南京 210000；2. 扬州大学 环境科学与工程学院，江苏 扬州 225000）
摘要：为了提高凹凸棒土对单宁酸的吸附性能，采用水浴法制备β-FeOOH改性凹凸棒土（ATP/β-FeOOH）吸附剂。通过X射线衍射仪、X射线光电子能谱仪和红外光谱仪分析吸附剂的组成和化学基团，通过透射电子显微镜和比表面积分析技术观察吸附剂的形貌和孔径分布。以单宁酸为目标污染物，进行吸附动力学和吸附等温线实验，考察了吸附剂用量、污染物浓度、初始pH值和共存离子对吸附剂去除单宁酸效能的影响。吸附实验结果表明：ATP/β-FeOOH吸附单宁酸过程符合拟二级动力学模型，Langmuir模型比Freundlich模型更能反映吸附过程。其中，30 wt% ATP/β-FeOOH的吸附性能最佳，最高吸附容量可以达到38.63 mg/g，并确定最佳吸附条件为溶液初始pH值3.0，吸附剂投加量为1.0 g/L。本研究结果表明：β-FeOOH的引入显著增强了凹凸棒土对单宁酸的吸附性能，此外，ATP/β-FeOOH对单宁酸的吸附机理可以归结为螯合作用和静电作用。
关键词：丹宁酸；凹凸棒土；改性；羟基氧化铁；吸附
中图分类号：X5 文献标识码：A 文章编号：0258-3283（2022）--
Construction of β-FeOOH modified Attapulgite adsorbent and its Adsorption Property for the removal of Tannin YUAN Da-ying1, ZHANG Hong-jun1, PAN Xu-hua1, XU Yi-qun2, HU Qing-song*2 (1. Shanghai Dredging CO., LTD. Jiangsu Traffic Construction Engineering Branch, Nanjing 210000, China; 2. College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225000, China), Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract: As a kind of water-soluble polyphenol, tannin is widely employed in coating, food additives, and deodorants. It can pose a severe threat to human health after entering into aqueous environments. Among various technologies for eliminating tannin, adsorption is deemed a promising technology. Nevertheless, traditional adsorbents, like activated carbon, and attapulgite, are limited in their adsorption capacity. In order to improve the adsorption capacity of tannin over attapulgite, β-FeOOH modified attapulgite adsorbent is prepared via hydrothermal method. X-ray diffractometer, X-ray photoelectron spectrometer, and infrared spectrometer are employed to analyze the composition and chemical bond of the obtained samples. And the morphology and pore diameter distributes are acquired on account of transmission electron microscope and specific surface area analysis techniques. Tannin is selected as the target pollutant, and the adsorption kinetics and isotherm experiments are carried out. The effects of the amount of adsorbent, pollutant concentration, initial pH value, and coexisting ions on the removal efficiency of tannin are investigated. The experimental results demonstrate that the adsorption process abides by the pseudo-second-order model. And Langmuir model can simulate the adsorption process better than Freundlich model. Among these, 30 wt% ATP/β-FeOOH displays the best adsorption performance. And the highest adsorption capacity can reach 38.63 mg/g. The optimal adsorption conditions are initial pH value (3.0) and an adsorbent of dosage 1.0 g/L. This work indicates that the introduction of β-Obviously improves the adsorption performance of tannin. And the adsorption mechanism can be attributed to chelation and electrostatic interaction.
Key words: tannin; attapulgite; modification; FeOOH; adsorption
引用本文：袁大英，张红军，潘绪华，等. β-FeOOH改性凹凸棒土的制备及其对单宁酸吸附性能研究[J]. 化学试剂, 2022, 44(8): 1148-1156。
液晶型适配体生物传感器无标记快速检测黏蛋白1
潘兴隆1，于依楠1，李宁伟1，武雅静2，侯利杰1，申炳俊1，金丽虹*1
(1. 长春理工大学 生命科学技术学院，吉林 长春 130022；2. 长春理工大学 文学院，吉林 长春 130022)
摘要：构建了一种基于适配体分子识别的液晶型生物传感器，用于人体血液肿瘤标志物黏蛋白1（MUC1）无标记快速检测。传感器由下玻片、铜载网和上玻片组成，下玻片通过表面活性剂、硅烷化试剂修饰及固定适配体，诱导4-氰基-4'-戊基联苯（5CB）向列型液晶分子的垂直排列取向。传感器中适配体与MUC1特异性结合可破坏5CB原有垂直排列取向，导致其偏光显微图像由“暗”到“亮”，根据图像亮区覆盖率（Br）变化可实现MUC1定量检测。结果表明，文中编写的MATLAB程序可实现偏光显微图像Br自动计算；在1 fg/mL ～ 1 µg/mL范围内，MUC1浓度对数与Br间存在线性关系（Br = 7.979 9 LogCMUC1 +11.824 65，R2 = 0.984 39），MUC1检测限（LOD）达到0.47 fg/mL。液晶型适配体生物传感器具有较高的检测灵敏度及特异性，实现了人体血液样本MUC1有效检测，其有望应用于临床MUC1检测。
关键词：黏蛋白1；偏振光显微技术；适配体；液晶；生物传感器
中图分类号：TP212.3 文献标识码：A 文章编号：0258-3283（2022）--
A Liquid Crystal-based Aptasensor for Rapid Detection of MUC1 without Labeling PAN Xing-long1, YU Yi-nan1, LI Ning-wei1, Wu Ya-jing2, Hou Li-jie1, SHEN Bing-jun1, JIN Li-hong*1. (1. School of Life Science and Technology, Changchun University of Science and Technology, Changchun 130022, China; 2. School of Liberal Arts, Changchun University of Science and Technology, Changchun 130022, China) , Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract: A liquid crystal biosensor based on aptamer molecular recognition was constructed for rapid detection of human blood tumor marker mucin1(MUC1) without labeling. The sensor was composed of a lower slide, a copper substrate, and an upper slide. The lower slide was modified and immobilized by surfactant and silanization reagent to induce the homeotropic orientation of the nematic liquid crystal molecules of 4-cyano-4’-amyl biphenyl (5CB). The specific binding of MUC1 with the aptamer in the sensor can destroy the original vertical alignment of 5CB, resulting in the polarized optical microscopic image changing from dark to bright. Quantitative detection of MUC1 can be achieved according to the change of bright coverage (Br) in the image. The results show that the MATLAB program programmed in this paper can realize the automatic calculation of Br in the polarized optical microscopy image. The concentration of MUC1 is in the range of 1 fg/mL~1 µg/mL, and there is a linear relationship between its logarithmic concentration and Br (Br = 7.9799 LogCMUC1 + 11.82465, R2 = 0.98439). The detection limit (LOD) of MUC1 was 0.47 fg/mL. The liquid crystal biosensor based on aptamer has high detection sensitivity and specificity, realizing the effective detection of MUC1 in human blood samples, and it is expected to be applied in clinical MUC1 detection.
Keywords: MUC1; polarized optical microscopy; aptamer; liquid crystal; biosensor
引用本文：潘兴隆，于依楠，李宁伟，等. 液晶型适配体生物传感器无标记快速检测黏蛋白1[J]. 化学试剂, 2022, 44(8): 1157-1163。
两例基于对氯苯乙酸配体构筑的铜（II）配合物晶体结构及荧光性能测试
李波1，沈红*1，王霏宇1，毛逢银2，李勇辉1
（1. 宜宾职业技术学院，四川 宜宾 644000；2. 四川轻化工大学 ，四川 自贡 643000）
摘要：室温下，通过溶剂挥发法合成了对氯苯乙酸邻菲啰啉铜（II）配合物（C28H20Cl2CuN2O4）和对氯苯乙酸2,2'-联吡啶铜（II）配合物（C26H22Cl2CuN2O5）。用X射线单晶衍射测定了配合物的晶体结构；结果显示，配合物C28H20Cl2CuN2O4属于三斜晶系，P1空间群，每个不对称单元由一个铜（II）离子，两个对氯苯乙酸配体及一个邻菲啰啉配体组成。配合物C26H22Cl2CuN2O5属于单斜晶系，P21/n空间群；每个不对称单元由一个铜（II）离子，两个对氯苯乙酸配体及一个2，2'-联吡啶配体组成。在荧光光谱上，配合物C28H20Cl2CuN2O4的最强激发峰和发射峰在分别在380 nm和430 nm，配合物C26H22Cl2CuN2O5的最强激发峰和发射峰分别在380 nm和430 nm；两个配合物在室温下稳定。
关键词：铜（II）配合物；对氯苯乙酸；晶体结构；1，10-邻菲啰啉；2,2'-联吡啶
中图分类号：O614.121 文献标识码：A 文章编号：0258-3283（2022）--
Crystal Structure and Fluorescence Performance Testing of Two Copper (II) Complexes Based on 4-Chlorophenylacetic Acid Ligands Li Bo1, Shen Hong*1, Wang Fei-yu1, Mao Feng-yin2, Li Yong-hui1 (1. Yibin Vocational Technical College, Yibin Sichuan 644000; 2 Sichuan University of Science & Engineering, Zigong Sichuan 643000, China), Huaxue Shiji, 2022, 44（8），～
Abstract：The copper(II) complex [C28H20Cl2CuN2O4] (4-chlorophenylacetic acid, 1,10-phenanthroline) and complex [C26H22Cl2CuN2O5] (4-chlorophenylacetic acid, 2,2'-bipyridine) were synthesized via solvent evaporation method. Their crystal structures were determined by the crystal X-ray diffraction method. The results show that complex [C28H20Cl2CuN2O4] crystallizes in the triclinic space group P1 with each asymmetric unit consisting of one Cu(II) ions, two 4-chlorophenylacetic acid ligands, and one 1,10-phenanthroline ligand. Complex [C26H22Cl2CuN2O5] crystallizes in the monoclinic with space group P21/n with each asymmetric unit consisting of one Cu(II) ions, two 4-chlorophenylacetic acid ligand, s and one 2,2'-bipyridine ligands. The excitation peak of complex [C28H20Cl2CuN2O4] was 380 nm. The emission peak was 430 nm, the excitation peak of complex C26H22Cl2CuN2O5 was 380 nm, the and emission peak was 430 nm. Two complexes are stable at room temperature.
Key words：copper(II) complex; 4-chlorophenylacetic acid; crystal structure; 1,10-phenanthroline; 2,2'-bipyridine
引用本文：李波, 沈红, 王霏宇, 等. 两例基于对氯苯乙酸配体构筑的铜（II）配合物晶体结构及荧光性能测试[J]. 化学试剂, 2022, 44（8）：1164-1169.
超声酶法辅助提取水芹菜多糖工艺优化及生物学活性研究
张腊梅，黄红琴，李敏，苟鼎
（达州中医药职业学院，四川 达州 635000）
摘要：采用超声酶法辅助提取水芹菜多糖并研究其生物活性。采用单因素及响应面法优化研究超声酶法辅助提取水芹菜多糖提取工艺，并通过水芹菜多糖清除•OH自由基、DPPH自由基、ABTS+自由基及铁还原力来分析其抗氧化能力和测定DNA超螺旋结构含量评价对DNA氧化损伤保护。水芹菜多糖的最佳提取条件为：料液比1:30 (g:mL)、超声时间40 min、超声功率400 W、提取温度50 ℃、纤维素酶添加量3.6%，水芹菜多糖得率为18.92 %。水芹菜多糖有较强的清除•OH自由基、DPPH自由基、ABTS+自由基能力及铁还原力。水芹菜多糖对抑制DNA损伤具有显著作用。0.04 mg/mL时有最强的保护率，为63.23%。水芹菜多糖具有很强的生物学活性，可以作为一种天然食品添加剂。
关键词：水芹菜；多糖；超声酶法提取；抗氧化；DNA氧化损伤
中图分类号：R284 文献标识码: A 文章编号：0258-3283（2022）--
Optimization of Extraction Technology of Polysaccharide from Oenanthe Javanica by Ultrasonic and Enzyme-assisted Extraction and Its Biological Activities ZHANG La-mei1, HUANG Hong-qin, LI Min, GOU Ding ( Dazhou Vocational College of Chinese Medcine, Dazhou 635000, China ) , Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract： To extract polysaccharides from Oenanthe javanica by ultrasonic and enzyme-assisted, biological activity was studied. The ultrasonic and enzyme-assisted extraction process of polysaccharides from Oenanthe javanica was optimized by single factor and response surface methodology. The antioxidant activity was evaluated by the ability to scavenge •OH radical, DPPH, ABTS+, and iron reduction, and the protection against DNA oxidative damage was evaluated by measuring the content of DNA super helixix structure. The optimum extraction conditions were as follows: material-to-water ratio 1:30 (g: mL), ultrasonic time 50 min, ultrasonic power 400 W, extraction temperature 65 ℃, cellulose amount 3.6%, and the yield of polysaccharide from Oenanthe javanica was 18.92%. Polysaccharides from Oenanthe javanica had a strong ability to scavenge ·OH radical, DPPH radical, ABTS+ Radical and iron reduction. Polysaccharides from Oenanthe javanica had a significant effect on protecting activity against DNA damage, and the strongest protective rate was 0.04 mg/mL, which was 63.23Polysaccharideside from Oenanthe javanica had strong biological activity and could be used as a natural food additive.
Key words: Oenanthe javanica; polysaccharide; ultrasonic and enzyme-assisted extraction; antioxidation; oxidative DNA damage
引用本文：张腊梅，黄红琴，李敏，等. 超声酶法辅助提取水芹菜多糖工艺优化及生物学活性研究 [J]. 化学试剂, 2022, 44(8): 1170-1177。
超声-微波协同辅助提取蓝莓花色苷及其抗肿瘤活性研究
姚会敏1，孟宇竹2，李向果1，耿晓东*1,3
（1. 河南质量工程职业学院 食品与化工学院，河南 平顶山 467000；2. 平顶山技师学院 现代服务系，河南 平顶山 467000；3. 河南农业大学 林学院，河南 郑州 450002）
摘要：本文以蓝莓为原料，探究超声-微波协同辅助提取（Ultrasonic-microwave assisted extraction，UMAE）蓝莓花色苷工艺及其抗肿瘤活性。在单因素实验的基础上，通过正交实验优化UMAE蓝莓花色苷的工艺，同时利用扫描电镜观察蓝莓颗粒微观结构。通过MTT法研究在最优提取工艺下获得的蓝莓花色苷提取物（Blueberry anthocyanins extracts，BAEs）对A549细胞存活率的影响。采用全光谱流式细胞仪测定BAEs对A549细胞凋亡的影响。结果表明UMAE蓝莓花色苷最优工艺参数为超声功率500 W、微波功率100 W和乙醇体积分数60%，在此条件下，蓝莓花色苷得率为（7.15±0.13） mg/g。通过扫描电镜观察经超声-微波、超声和微波处理后蓝莓细胞微观结构，对比发现超声-微波处理后蓝莓细胞壁发生不同程度破裂，说明UMAE具有强化提取花色苷的作用。BAEs在质量浓度为10～80 mg/mL范围内，随BAEs浓度增加A549细胞存活率显著降低，而凋亡率显著增加。研究结果为蓝莓深加工提供重要依据。
关键词：超声-微波协同辅助提取；蓝莓；花色苷；工艺；抗肿瘤活性
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2022）--
Ultrasonic-microwave Assisted Extraction of Anthocyanins from Blueberry and Its Antitumor Activity YAO Hui-min1, MENG Yu-zhu2, LI Xiang-guo1, GENG Xiao-dong*1,3（1. Food and Chemical Engineering Department, Henan Quality Polytechnic, Pingdingshan 467000, China; 2. Modern Service Department, Pingdingshan Institute Technology, Pingdingshan 467000, China; 3. College of Forestry, Henan Agricultural University, Zhengzhou 450002,China）,Huaxue Shiji, 2022, 44(8), ～
Abstract: In this paper, blueberry was used as raw material to explore the ultrasonic-microwave-assisted extraction process of blueberry anthocyanins and its antitumor activity. The process of UMAE anthocyanins from blueberry anthocyanins was optimized by an orthogonal experiment based on a single factor experiment, and the microstructure of blueberry particles was observed by a scanning electron microscope. The effect of blueberry anthocyanins extracts (BAEs) obtained under the optimal extraction parameters on the survival rate of A549 cells was measured by the MTT method. The effect of BAEs on apoptosis of A549 cells was determined by full-spectrum flow cytometry. The results showed that the optimum extraction parameters to achieve the highest anthocyanins yield (7.15±0.13) mg/g from blueberry by UMAE were obtained under the ultrasonic power of 500 W and the microwave power of 1 W, and ethanol concentration of 60%. The microstructure of blueberry cells treated with ultrasound-microwave, ultrasound, and microwave was observed by scanning electron microscope. It was found that the cell wall of blueberry was broken in varying degrees after ultrasound-microwave treatment, indicating that UMAE can strengthen the extraction of anthocyanins. In the mass concentration range of 10～80 mg/mL, the survival rate of A549 cells decreased significantly and the apoptosis rate increased obviously with the increase in BAEs concentration. The findings provide an important basis for the further processing of blueberries.
Keywords: ultrasonic-microwave assisted extraction; blueberry; anthocyanins; process; antitumor activity
引用本文：姚会敏，孟宇竹，李向果，等. 超声-微波协同辅助提取蓝莓花色苷及其抗肿瘤活性研究[J]. 化学试剂，2022，44(8): 1178-1183。
基于二苯并噻吩砜多孔聚合物光解水制氢研究
王首明，黄晓锋，罗锦新，金耀城*，霍延平*
（广东工业大学 轻工化工学院，广东 广州 510006）
摘要：制备了两种基于二苯并噻吩砜单元的新型有机共轭多孔聚合物PBDFSO和PBDTSO，并将其应用于光解水制氢领域，通过主链含氧/硫杂原子修饰取代，系统研究了主链结构对材料光学吸收、化学能级以及光催化性能的影响。研究发现，两种共轭多孔聚合物都具有较宽的光学吸收范围，合适的光学带隙，并具有光解水制氢的能力。其中，含硫原子多孔聚合物PBDTSO在使用抗坏血酸作为牺牲剂时，模拟太阳光照射下展现出1973 μmol/(g·h)的析氢速率，高于含氧原子的多孔聚合物PBDFSO的析氢速率，并具有较好的光稳定性。这表明通过杂原子取代可以优化多孔聚合物结构，从而有效提高聚合物催化剂的光催化活性。
关键词：共轭多孔聚合物；二苯并噻吩砜；苯并双噻吩；苯并双呋喃；光催化水制氢
中图分类号：O631.1+1 文献标识码：A 文章编号：0258-3283（2022）--
Photocatalytic Performance of Organic Porous Polymers Based on Dibenzothiophene Sulfone Unit WANG Shou-ming, HUANG Xiao-feng, LUO Jin-xin, JIN Yao-cheng*, HUO Yan-ping* (School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China), Huaxue Shiji, 2022, 44(8)，～
Abstract：In recent years, significant progresses have achieved in the design and preparation of conjugated organic polymer photocatalysts. However, developing organic polymer photocatalysts with high conversion efficiency is still challenging. The rational structural design of organic polymer photocatalysts is the key to achieving high photocatalytic performance. Here, two novel organic conjugated porous polymers PBDFSO and PBDTSO based on a dibenzothiophene sulfone unit were prepared and applied to photocatalytic hydrogen production from water. The chemical structures and their influence on the absorption spectrum, energy level, and photocatalytic performance of the materials was systematically studied. The two prepared porous polymers had a wide optical absorption range and suitable optical band gap, and both two polymers could produce hydrogen by photocatalytic water. The results show that the sulfur atom-containing porous polymer PBDTSO exhibits a hydrogen evolution rate of 1973 μmol•g-1h-1 when ascorbic acid is used as a sacrificial agent under simulated sunlight irradiation, which is higher than that of the oxygen atom-containing porous polymer PBDFSO and has good photostability. It indicates that the porous polymer structure can be optimized by heteroatom substitution, which can effectively improve photocatalytic activity.
Key words：conjugated porous polymers; dibenzothiophene sulfone; benzodisthiophene; benzodisfuran; photocatalytic hydrogen production from water
引用本文：王首明, 黄晓锋, 罗锦新, 等. 基于二苯并噻吩砜多孔聚合物光解水制氢研究[J]. 化学试剂, 2022, 44（8）：1184-1190.
在线监测直接进样和罐采样方法一次性分析117组分VOCs的比较
王潇，王成然，李志昂，王凯，周鑫*
（中国测试技术研究院，四川 成都 610021）
摘要：使用新苏玛罐采样与模拟在线监测直接进样两种方法，通过预浓缩-气相色谱-火焰离子化检测器-质谱检测器（GC-FID-MS）系统对稀释至5 nmol/mol浓度的117组分VOCs标准气体进行分析。以直接进样的结果为标准，分析罐采样方法，结果发现苏玛罐对甲醛和丁烯醛有着较明显的吸附，甲醛降低32%，丁烯醛降低12%，其余组分的相对偏差均在10%以内，RSD在0.5% ~ 8%。之后在加湿（60%RH）与不加湿条件下比较了117种VOCs在苏玛罐中的响应，结果发现甲醛含量在加湿条件下继续降低18%。苏玛罐采样一次进样可以实现环境空气中117组分的检测，但是罐体本身的吸附会影响检测结果的准确性。
关键词：苏玛罐；直接进样；GC-FID-MS；117 VOCs
中图分类号：0657.71 文献标识码：A 文章编号：0258-3283（2022）--
Comparison of the Determination of 117 Component VOCs Simultaneously Using Online and Canister Sampling Method WANG Xiao, WANG Cheng-ran, LI Zhi-ang, WANG Kai, ZHOU Xin* (National Institute of Measurement and Testing Technology, Chengdu, Sichuan 610021, China), Huaxue Shiji, 2022, 44（8），～
Abstract: In this study, a 117 component VOCs standard gas mixture was diluted to 5 nmol/mol and then directly connected to GC-MS with a pre-concentration system (equal to the online sampling method), which was compared to that diluted into a new canister before analyzing by GC-MS (canister sampling method). The result showed that the differences of most components were less than 10% with the relative standard deviation (RSD) between 0.5% ~ and 8%, while a response of formaldehyde through a canister sampling method was significantly 30% lower than the direct sampling method and crotonaldehyde was also declined 12%. Besides, the concentration of formaldehyde decayed by 18% under 60% RH humidity conditions. It is possible to determine 117 component VOCs simultaneously using the canister sampling method but the adsorption should be seriously considered which will influence the accuracy.
Key words: SUMMA canister; online sampling method; GC-FID-MS; 117 VOCs
引用本文：王潇，王成然，李志昂，等.在线监测直接进样和罐采样方法一次性分析117组分VOCs的比较[J]. 化学试剂，2022，44（8）：1191-1196.
基于沸石咪唑酯骨架结构材料11的微固相萃取结合高效液相色谱用于水样中五种紫外吸收剂的测定
王颖臻，葛丹丹*，宋家漫，沈茂珍
(昆明学院 化学化工学院，云南 昆明 650214)
摘要：建立了一种基于ZIF-11的膜保护微固相萃取（µ-SPE）的样品前处理方法，并与高效液相色谱（HPLC）联用测定环境水样中五种紫外吸收剂。对洗脱剂种类、固相萃取剂用量、洗脱时间、萃取时间、盐浓度、pH值系列影响萃取效率因素的相关条件进行优化。结果表明，固相萃取剂用量10 mg、萃取时间8 min、洗脱剂V（甲醇）：V（乙腈）=3:7、洗脱时间9 min、溶液pH值7、10 mg/mL氯化钠条件下，5种紫外吸收剂在5 ～ 1000 ng/mL范围内线性关系良好，相关系数均大于0.992 5，检出限为0.8 ～ 1.5 ng/mL；定量限为2.5 ～5.0 ng/mL；相对标准偏差为0.9% ～ 6.5%。方法简单、快速、准确，用于测定湖水、河水、自来水中的紫外线吸收剂，回收率为88.7% ～ 112.3%，相对标准偏差为0.3% ～ 5.5%。
关键字：沸石咪唑酯骨架结构材料-11；漩涡辅助微固相萃取；紫外吸收剂；水样分析
中图分类号：X830 文献标识码：A 文章编号：0258-3283（2022）--
Zeolite Imidazolate Framework 11 Based Vortex-Assisted Micro-Solid-Phase Extraction of 5 Kinds of UV Filters in Water Samples Followed by High Performance Liquid Chromatography WANG Ying-zhen, GE Dan-dan, SONG Jia-man, SHEN Mao-zhen (School of Chemistry and Chemical Engineering, Kunming University, Kunming 650214) , Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract: Zeolite imidazolate framework 11 based micro-solid-phase extraction (µ-SPE), followed by high-performance liquid HPLC with diode array detection method was developed for the determination of 5 kinds of UV filters in water samples. Parameters affecting VA-µ-SPE efficiencies such as extraction sorbent amount, desorption solvent, vortex time, desorption time, solution pH, and salt concentration were investigated. The optimum extraction conditions were as follows: the amount of sorbent was 10 mg, extraction time was 8 min, desorption time was 9 min, desorption solvent was V (methanol) : V (acetonitrile) = 3:7, solution pH was 7 and salt concentration was 10 mg/mL of sodium chloride. Under the optimized conditions, the linearity range was in the range of 5～1000 ng/mL with correlation coefficients higher than 0.9925. Limits of detection and limits of quantification were in the range of 0.8～1.5 ng/mL and 2.5～5.0 ng/mL, respectively. Finally, the proposed method was successfully applied to determine UV filters in real water samples. The relative recoveries ranged from 88.7%～112.3%. The developed method proved to be simple, quick, exact, and can be used to determine UV filters in real water samples.
Keywords: Zeolite imidazolate framework 11; vortex-assisted micro-solid-phase extraction; UV filters; water sample
引用本文：王颖臻，葛丹丹，宋家漫，等. 基于沸石咪唑酯骨架结构材料11的微固相萃取结合高效液相色谱用于水样中五种紫外吸收剂的测定[J]. 化学试剂, 2022, 44(8): 1197-1202。
气相色谱-质谱联用法测定杜仲叶中活性成分肉桂酸
吕竹茵，陈燕秋，徐增益，肖斌，李猷，雷雯*
（上海化工研究院有限公司 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）
摘要：肉桂酸作为一种安全性高的活性物质，广泛用于香精、医药以及塑料、树脂等精细化工产品中。对杜仲叶进行预处理，通过优化净化条件，利用气相色谱-质谱联用法对中草药杜仲叶中的活性物质肉桂酸的含量进行了准确地定量。结果表明，色谱柱采用Agilent HP-5 MS毛细管柱（30 m×0.25 mm×0.25 μm）；载气为纯度为99.999%的高纯氦气；流速为1.0 mL/min；进样口温度280 ℃；分流比为1:50 (体积比)；利用多反应监测模式（MRM）采集样品的质谱信息，该方法检出限约为0.02 mg/g，定量限为0.07 mg/g，肉桂酸在3个加标浓度下的回收率为80.2%～104.6%。开发的检测方法重现性好、回收率高、精密度高，可为中药中活性成分的准确定量提供方法参考。
关键词：气相色谱-质谱联用法；肉桂酸；中草药；杜仲叶；准确定量
中图分类号：O658 文献标识码：A 文章编号：0258-3283（2022）--
Determination of the Active Ingredient Cinnamic Acid in Eucommia Ulmoides Leaves by Gas Chromatography-Mass Spectrometry LV Zhu-yin, CHEN Yan-qiu, XU Zeng-yi, XIAO Bin, LI You, LEI Wen* (Shanghai Research Institute of Chemical Industry Co, Ltd, Shanghai stable isotope detection and application R & D professional technical service platform, Shanghai 200062, China), Huaxue Shiji, 44(8), ～
Abstract: As a safe active substance, cinnamic acid is widely used in flavors, medicines, and fine chemical products such as plastics and resins. In this paper, Eucommia ulmoides leaves were pretreated, and the content of the active substance cinnamic acid in Chinese herbal medicine Eucommia ulmoides leaves was accurately quantified by gas chromatography-mass spectrometry by optimizing the purification conditions. The results show that the column adopts Agilent HP-5 MS capillary column (30 m×0.25 mm×0.25 μm); the carrier gas is high-purity helium with a purity of 99.999%; the flow rate is 1.0 mL/min; the inlet temperature is 280 ℃; the split ratio was 1:50 (volume ratio); the mass spectrometry information of the sample was collected by the multiple reaction monitoring modes (MRM), the detection limit of the method was about 0.02 mg/g, and the quantification limit was 0.07 mg/g. The recoveries at the three spiked concentrations were 80.2%~104.6%. The detection method developed in this paper has good reproducibility, high recovery rate, and high precision, which can provide a method reference for the accurate quantification of active components in traditional Chinese medicine.
Key words: gas chromatography-mass spectrometry; cinnamic acid; Chinese herbal medicine; Eucommia ulmoides leaves; accurate quantification
引用本文：吕竹茵，陈燕秋，徐增益，等. 气相色谱-质谱联用法测定杜仲叶中活性成分肉桂酸[J]. 化学试剂，2022，44(8)：1203-1207.
基于氧化石墨烯和三链DNA的三聚氰胺检测研究
张丽媛，范淼，卢宏飞，张廉奉*，邢小静*
（南阳师范学院 化学与制药工程学院，河南 南阳 473061）
摘要：发展成本低、准确高、特异性好的三聚氰胺检测方法具有重要的研究意义。基于氧化石墨烯（GO）自身较好的荧光猝灭性能，结合含脱碱基位点的三链DNA和核酸外切酶III的特殊性能，构建了一种高灵敏的特异性三聚氰胺检测新方法。首先制备了GO，并采用紫外-可见吸收光谱仪、傅里叶红外吸收光谱仪及透射电子显微镜对其进行了表征。在最佳的实验条件下，考察了设计方法对三聚氰胺的检测灵敏度和特异性。结果显示，体系荧光强度与三聚氰胺浓度呈现较好的线性关系，线性范围为0.5×10-9 mol/L～7.0×10-9 nmol/L，检测限为0.32×10-9 mol/L。此外，本方法对奶粉样品中三聚氰胺检测的回收率为92.8%～106.1%，表现出很好的实际应用潜力。
关键词：三聚氰胺；氧化石墨烯；三链DNA；脱碱基位点；核酸外切酶III
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2022）--
Study on Melamine Detection Based on Graphene oxide and DNA triplex structur ZHANG Li-yuan, FAN Miao, LU Hong-fei, Zhang Lian-feng*, XING Xiao-jing* (College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, China), Huaxue Shiji, 44(8), ～
Abstract：It is of great significance to develop a method for melamine detection with low-cost, high accuracy, and good specificity. Based on the fluorescence quenching property of graphene oxide (GO), combined with the special properties of DNA triplex structure with the abasic site and exonuclease III, a novel platform for melamine detection was developed. GO was first successfully prepared and characterized using UV-visible absorption spectroscopy, Fourier transforms infrared spectroscopy, and transmission electron microscopy. Under the optimum conditions, the detection sensitivity and specificity were investigated. The results showed that the fluorescence intensity displayed a good linear relationship with melamine concentration in the range from 0.5×10-9 mol/L to 7.0×10-9 nmol/L, and the detection limit was 0.32×10-9 mol/L. Moreover, the recovery of melamine spiked in milk powder was from 92.8 % to 106.1%, indicating the potential of the proposed method in practical application.
Key words：melamine; graphene oxide; triplex-stranded DNA; abasic site; exonuclease III
引用本文：张丽媛，范淼，卢宏飞，等. 基于氧化石墨烯和三链DNA的三聚氰胺检测研究[J]. 化学试剂, 2022, 44(8): 1208-1212。
高效液相色谱法测定工业双酚A中的微量杂质
黄煜*1 ，李杰2
（1. 中国石油化工股份有限公司 北京化工研究院 标准研究所 北京 100013；2. 上海市计量测试技术研究院 上海 201203）
摘要：建立了高效液相色谱法定量分析工业双酚A中微量杂质的方法。采用C18柱分离，（乙腈:甲醇）-水流动相梯度洗脱，紫外检测器在280 nm处检测、内标校正因子法定量。结果表明，在优化的色谱条件下，目标组分的分离度高，线性范围宽、重复性好，相对标准偏差0.5%～2.6%，最低检测限为0.05～0.1 mg/kg，5～400 ppm加标回收率为103%～108%。该方法简便、高效、准确、灵敏，应用于双酚A中微量杂质分析，可以满足工业双酚A产品质量检验需求和生产工艺优化、质量控制中对分析测试方法的需求。
关键词：高效液相色谱；内标法；工业双酚A；质量控制
中图分类号：O656 文献识别码：A 文章编号：0258-3283（2022）--
Determination of Trace Impurities in Industrial Bisphenol A by High Performance Liquid Chromatography HUANG Yu*1, LI Jie2 (1. Institute of standards, Beijing Research Institute of chemical industry, China Petrochemical Corporation, Beijng 100013, China; 2. Shanghai Institute of Metrology and testing technology, Shanghai 201203, China), Huaxue Shiji, 2022, 44(8), ～
Abstract: Established a high performance liquid chromatography method for quantitative analysis of trace impurities in industrial bisphenol A. Using C18 (4.6×250 mm×5 µm) column, UV detector, (acetonitrile: methanol)-water as mobile phase, and internal standard correction factor method for quantification. The results show that under the optimized chromatographic conditions, the target components have high resolution, wide linear range and good repeatability, the relative standard deviation is 0.5%～2.6%, the minimum detection limit is 0.05～0.1 mg/kg, the recovery rate of standard addition was 103%～108%. The method is simple, efficient, accurate and sensitive. It can be applied to the analysis of trace impurities in bisphenol A, and can meet the needs of quality inspection, production process optimization and quality control for industrial bisphenol A.
Keywords: high performance liquid chromatography；internal standard method；industrial bisphenol A；quality control
引用本文：黄煜，李杰. 高效液相色谱法测定工业双酚A中的微量杂质[J]. 化学试剂，2022，44（8）：1213-1217.
基于稳定同位素比质谱技术的进口牛肉产地溯源技术研究
陈庚超，杨雪娇*，王静，徐正华，吴思超，郭媛媛，郑思垳，黄智娟，房小晴，李星颖
（黄埔海关技术中心，广东 东莞 523000）
摘要：为有效打击冻肉走私、保障食品安全，采用元素分析仪-稳定同位素比质谱仪（EA-IRMS）技术建立了不同国家动物源性食品产地溯源方法。系统分析了来自欧洲、北美洲、南美洲、大洋洲等不同地区五大牛肉出口国的样品中四种稳定同位素的分布，采用方差分析（Analysis of variance，ANOVA）及主成分分析（Principal Component Analysis，PCA），探讨了五大地区牛肉样品中13C、15N、2H、18O等同位素组成的变化规律。结果显示，来自不同国家的牛肉的δ 13C、δ15N、δ 2H、δ 18O值存在显著差异，其中δ 13C含量主要与养殖饲料植物种类高度相关，δ 15N含量主要受养殖方式及饲料植物类型影响，δ 2H和δ 18O则主要受生长环境及饮用水的影响。δ 13C、δ15N、δ2H和δ 18O 4项指标综合分析对不同国家冻肉中的牛肉产地溯源的正确判别率约96.5%。建立的牛肉产地溯源方法可为不同国家冻牛肉或转口牛肉的鉴别提供关键技术支撑。
关键词：动物源性食品；产地溯源；稳定同位素比质谱仪；地域信息；化学计量学分析
Origin traceability of imported beef based on stable isotope ratio mass spectrometry CHEN Geng-chao, YANG Xue-jiao*, WANG Jing, XU Zheng-hua, WU Si-chao, GUO Yuan-yuan, ZHENG Si-hang, HUANG Zhi-juan, FANG Xiao-qing, LI Xing-ying (Technology Center of Huangpu Customs, DongGuan 523000, China), Huaxue Shiji, 2022, 44(8), ～
Abstract: To combat the smuggling of frozen meat effectively and ensure food safety, the technology of elemental analyzer stable isotope ratio mass spectrometry (EA-IRMS) was used to establish a method for tracing animal-derived food in different countries in this paper. The distribution of four stable isotopes in samples from five beef exporting countries in Europe, North America, South America, Oceania, and other regions was systematically analyzed. The changes of 13C、15N、2H and 18O isotopic compositions in beef samples from five regions were studied and discussed by analysis of variance (ANOVA) and principal component analysis (PCA). The results show that the δ 13C, δ15N, δ 2H, δ 18O values of beef from different countries have significant differences, among which δ13C content is mainly highly related to the species of cultivated feed plants, δ15N content is mainly affected by breeding methods and feed plant types, while the δ2H and δ18O are mainly affected by the growth environment and drinking water. Based on the comprehensive analysis of δ 13C、δ15N、δ2H和δ 18O, the correct discrimination rate of beef origin traceability in frozen meat from different countries was about 96.5%. The method of beef origin traceability established in this paper can provide key technical support for the identification of frozen beef or entrepot beef from different countries.
Key words: animal derived food; origin traceability; stable isotope ratio mass spectrometry; regional information; analysis of variance; principal component analysis
引用本文：陈庚超, 杨雪娇, 王静, 等. 基于稳定同位素比质谱技术的进口牛肉产地溯源技术研究[J]. 化学试剂, 2022, 44(8): 1218-1223.
喹喔啉-2-羧酸标准品的制备与表征
时若寒1，刘洪斌2，叶子煜2，雷春娟2，韩雪*1，蔡英华*2
(1. 河北科技大学，河北 石家庄 050018；2. 中国动物疫病预防控制中心，北京 102618)
摘要：根据ISO指南34、35，建立喹喔啉-2-羧酸的有机合成路线并进一步验证，最终研制出高纯度的喹喔啉-2-羧酸标准样品。通过高效液相色谱、红外光谱、紫外光谱、质谱、核磁共振光谱的检测，确定了喹喔啉-2-羧酸的化学结构。研究还使用质量平衡法和定量核磁共振方法联合定值。并进行了均匀性、短期和长期稳定性的评估和特征值的表征。通过单因素方差分析来获得合成不确定度。根据质量平衡理论和定量核磁共振方法，确定“喹喔啉-2-羧酸纯度标准样品”的纯度值为：99.5% ± 0.4%，k=2，P=0.95。该标准品纯度值很高。在4 ℃条件下，喹喔啉-2-羧酸在6个月表现出均匀稳定的特性，可以为我国动物源性产品中关于卡巴氧残留的检测标准提供可靠的标样支撑。
关键词：喹喔啉-2-羧酸；标准物质；稳定性；不确定度
中图分类号： 文献标识码：A 文章编号：0258-3283（2022）
Preparation and Characterization of a New Reference of Quinoline-2-carboxylic SHI Ruo-han1, LIU Hong-bin2, YE Zi-yu2, LEI Chun-juan2, HAN Xue*1, CAI Ying-hua*2 (1. School of Food and Biology, Hebei University of Science and Technology, Hebei 050018, China; 2. China Animal Disease Prevention and Control Center, Beijing 102618, China) , Huaxue Shiji，2022，44 (8)，00 ~ 00
Abstract：An organic synthesis route of quinoxaline-2-carboxylic acid was established and further verified according to the ISO Guides 34 and 35, and finally a high-purity quinoxaline-2-carboxylic acid reference material was developed. The structure of the compound was determined by the detection of high-efficiency liquid chromatography, infrared spectrum, ultraviolet spectrum, mass spectrum, and nuclear magnetic resonance spectrum. This research used the combined value assignment of the mass balance method and the quantitative NMR, evaluation of homogeneity, and short-term and long-term stability, to characterize the certified value. Homogeneity, short-term and long-term stability, and value characterization are summarized in this research. Uncertainty was obtained according to ANOVA. The purity value of mass balance theory and quantitative NMR method for the reference sample of quinoxaline-2-carboxylate purity was determined as 99.5% ± 0.4%, k=2, p=0.95. At 4 ℃ degrees, quinoxaline-2-carboxylic acid was homogenous and stable over 6 months, which can provide reliable sample support for the detection standard of carbadox residue in animal-derived products in China.
Key words: quinoxaline-2-carboxylic acid; reference material; homogeneity; uncertainty
引用本文：时若寒，刘洪斌，叶子煜，等. 喹喔啉-2-羧酸标准品的制备与表征 [J]. 化学试剂, 2022, 44(8): 1224-1232。
β-硫代糖苷的合成方法研究及晶体结构表征
华敏1，熊涛1，陈绍彦2，曹燕来2，姚辉1，黄年玉*1，刘明国*1
(1. 三峡大学 生物与制药学院天然产物研究与利用湖北省重点实验室，湖北 宜昌 443002；2. 湖北广辰药业股份有限公司，湖北 宜昌 443002)
摘要：通过化学方法非对映选择性合成β-硫代糖苷，并对其进行结构分析。以三乙酰基葡萄烯糖为起始原料，经过水解、缩合、酯化后得到葡萄烯糖-3-吡啶酸酯，筛选了钴催化下其与苯亚磺酸钠反应的最佳条件，合成系列β-硫代糖苷衍生物，分析产物的立体化学结构。以三乙酰基葡萄烯糖为起始原料经4步反应合成β-硫代糖苷，总产率为42%～46%；通过X射线单晶衍射分析出(4aR,6S,8aS)-6-((4-氯苯基)硫代)-2-(4-甲氧基苯基)-4,4a,6,8a-四氢吡喃[3,2-d][1,3]二噁英的Flack参数为0.002(6)。该方法使用廉价金属催化剂，无毒无臭，操作简便，为β-硫代糖苷的研究提供理论依据和基础。
关键词：钴催化；硫糖苷；合成；晶体结构；α-葡萄糖苷酶抑制活性
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis and crystal structure characterization of β-thioglycoside HUA Min1, XIONG Tao1, CHEN Shao-yan2, CAO Yan-lai2, YAO Hui1, HUANGNian-yu*1, LIU Ming-guo*1 (1. Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University,Yichang 443002, Hubei, China；2. Hubei Guangchen Pharmaceutical Co. Ltd, Yichang 443002, Hubei China),Huaxue Shiji, 2022, 44(8), ～
Abstract: β-thioglycosides were diastereoselectively synthesized by chemical methods, and their structures were analyzed. The picoloylglucal donor was obtained by hydrolysis, condensation, and esterification from the starting material of commercial tri-O-acetyl-D-glucal. After screening the optimized reaction conditions of picoloylglucal donor and sodium benzene sulfinate, a series of β-thioglycosides was synthesized under the catalysis of cobalt. Then the stereochemical structures of the products were characterized. The β-thioglycosides were synthesized with a total yield of 42%～46% by four-step reaction using tri-O-acetyl-D-glucal as the starting material, and compound 5b was analyzed by X-ray crystallography with a Flack parameter of 0.002(6). This simple methodology using cheap, nontoxic, and odorless metal catalysts would provide a theoretical basis for the study of β-thioglycosides.
Keywords: cobalt catalysis; thioglycoside; synthesis; crystal structure; α-glucosidase inhibitory activity
引用本文：华敏，熊涛，陈绍彦，等. β-硫代糖苷的合成方法研究及晶体结构表征[J]. 化学试剂，2022，44(8): 1233-1240。
新型18F标记的多巴胺正电子发射显影剂前体的合成
陈瑜，李如雯，谢树英，刘中强*
（海南大学 药学院，海南 海口 570228）
摘要：报道了以多巴胺为原料，3种新型18F标记的多巴胺正电子发射显影剂前体的合成方法。在Boc酸酐的作用下，多巴胺转化成全保护的中间体，接着单质碘亲电取代多巴胺6-位的氢，然后与联硼酸频那醇酯发生偶联反应，得到有机硼酸酯。最后，在双氧水的作用下，有机硼酸酯水解，羟基取代多巴胺的6-位；采用三氟甲磺酰基(Tf)或对甲基苯磺酰基(Ts)发生酯化反应，以5～6步和43%～51%的总产率得到3种芳香环上连有Tf或Ts基团的新型前体化合物。3种新型前体的芳香环上连有易离去基团，有利于亲核取代反应，不含重金属离子及避免了繁琐的重金属离子清除步骤，非常适于作为显影剂前体，为进一步研究氟代多巴胺（[18F]FDA）在PD和多种癌症早期显像方面的性能提供了基础。
关键词：多巴胺；正电子发射显影剂；前体；合成；帕金森病
Synthesis of the new precursors of 18F-labeled for dopamine used in positron emission tomography CHEN Y, LI Ru-wen, XIE Shu-ying, LIU Zhong-qiang* (School of Pharmacy, Hainan University, Haikou 570228, China), Huaxue Shiji, 2022, 44(8), ～
Abstract: Using dopamine as a starting material, the synthesis of three new precursors of 18F-labeled dopamine used in positron emission tomography for tumor imaging was reported. Under the action of Boc anhydride, dopamine was converted into a fully protected intermediate, which was then reacted with iodine electrophilically to replace the hydrogen at position 6 of dopamine. Next, organic borate ester was obtained by coupled with bis (pinacolato) diboron. Finally, under the action of hydrogen peroxide, the organic borate ester was hydrolyzed and the hydroxyl group replaced the 6-position of dopamine. Trifluoromethanesulfonate (Tf) or p-methyl benzenesulfonate (Ts) were esterified to obtain three new precursor compounds with Tf or Ts groups attached to aromatic rings, which went through 5～6 steps with a total recovery of 43%～51%. The aromatic rings of the three new precursors were attached with easy leaving groups, which were conducive to nucleophilic substitution reactions. In addition, without heavy metal ions, they avoided the tedious heavy metal ion removal steps. Given all this, the synthesized three new precursors were very suitable as the developer precursors, providing a basis for further research on the performance of fluorinated dopamine ([18F] FDA) in PD and early imaging of various cancers.
Key words: dopamine; positron emission developer; precursor; synthesis; Parkinson's disease
引用本文：陈瑜，李如雯，谢树英，等. 新型18F标记的多巴胺正电子发射显影剂前体的合成[J]. 化学试剂，2022，44(8): 1241-1247。
