【特约专题】
Piers硼烷的应用研究进展
谭敬杰1，罗永安1，吴翊乐*1，赵玉芬1,2
(1.宁波大学 新药技术研究院 天体化学与空间生命-钱学森空间科学协同研究中心，浙江 宁波 315211；2. 厦门大学 化学化工学院 福建省化学生物学重点实验室，福建 厦门 361005)
摘要：基于主族元素的化学试剂和催化剂是当前研究的热点之一。HB(C6F5)2具有强路易斯酸性的硼中心，因此在小分子活化中具有特殊地位，可以活化包括一氧化碳在内的多种惰性小分子和化学键。同时，由于HB(C6F5)2具有可衍生化的硼氢键，因此也被用于构建含硼催化剂以及受阻路易斯酸碱对。经过多年的发展和使用，HB(C6F5)2被广泛应用于合成化学，并且以其发现者命名为Piers' Borane即Piers硼烷。综述了Piers硼烷近年来的应用进展，旨在为硼化合物在有机催化和小分子活化等领域的研究提供参考。
关键词：路易斯酸；有机硼化合物；有机催化；小分子活化；受阻路易斯酸碱对
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
Research Progress of Piers’ Borane TAN Jing-jie1, LUO Yong-an1 , WU Yi-le*, ZHAO Yu-fen1,2 (1. Institute of Drug Discovery Technology, and Qian Xuesen Collaborative Research Center of Astrochemistry and Space Life Sciences, Ningbo University, Ningbo 315211, China; 2. College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Boology of Fujian Province, Xiamen University, Xiamen 361005, China)
Abstract：Main group compounds play important roles in the modern chemistry including catalysis and small molecule activation. The strong Lewis acid HB(C6F5)2, known as Piers’ boraneprompts activation of inert gas molecules such as carbon monoxide and nitrogen monoxide. Meanwhile, the B-H moiety is highly reactive and effect the introduction of a B(C6F5)2 moiety to variety unsaturated compounds via hydroboration. Thus, a series of boron-containing chiral catalysts and frustrated Lewis pairs have been synthesized from HB(C6F5)2. In this review, the use of Piers' borane in organic catalysis and small molecule activation is discussed.
Key words：Lewis acid ; organic boron compound ; organic catalysis ; small molecule activation ; frustrated Lewis pair
引用本文：谭敬杰, 罗永安, 吴翊乐, 等. Piers硼烷的应用研究进展[J]. 化学试剂，2023，45(1)：1-11.
【综述与专论】
Cu-MOF基材料应用研究进展
高春1，王嘉婧2，郭笑天2，李文婷2，张松涛*2,3，庞欢*2
（1. 江苏商贸职业学院 继续教育学院，江苏 南通 226011；
2. 扬州大学 化学化工学院，江苏 扬州 225009；
3. 南京大学 配位化学国家重点实验室，江苏 南京 210023）
摘要：近年来，MOF材料由于具有独特的电子结构、易调节的规则孔道和高比表面积等优点被广泛应用于电化学、生物医药、吸附分离等领域，但MOF材料较差的导电性限制了其应用。因此通过对MOF材料改性思路和复合策略的整合与比较可以为MOF材料的广泛应用提供参考价值。以经典的Cu-MOF为例，重点回顾了近年来文献中报道的Cu-MOF基材料的制备路线及其在电化学储能领域的最新应用进展，主要包括电池、超级电容器、电催化等。最后，总结了Cu-MOF基材料研究中存在的问题和机遇，并对其未来发展方向进行了展望，旨在为MOF材料的设计策略与实际应用提供理论参考。
关键词: Cu-MOF；制备策略；材料；电储能
中图分类号：TB331 文献标识码：A 文章编号：0258-3283（2023）
Recent Progress in the Applications of Cu-MOF-based Materials GAO Chun1, WANG Jia-jing2, GUO Xiao-tian2, LI Wen-ting2, ZHANG Song-tao*2,3, PANG Huan*2 (1. Jiangsu Commercial Vocational College, Nantong, 226011, China; 2. College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225009, China; 3. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210023, China)
Abstract: In recent years, MOF materials had been widely used in many fields such as electrochemistry, biomedicine, adsorption and separation due to their unique electronic structure, easily adjustable and regular pore channels and high specific surface area. However, the poor electrical conductivity of MOF materials has limited their applications. Therefore, the integration and comparison of MOF material modification ideas and compounding strategies can provide a reference value for the wide application of MOF materials. Taking classical Cu-MOF as an example, this paper focuses on reviewing the preparation routes of Cu-MOF-based materials reported in the literature in recent years and their latest application progress in the field of electrochemical energy storage, mainly including batteries, supercapacitors, electrocatalysis, and so on. Finally, the problems and opportunities in the research of Cu-MOF-based materials are summarized, and their future development directions are prospected, aiming to provide theoretical references for the design strategies and practical applications of MOF materials.
Key words: Cu-MOF; preparation strategy; material; energy storage
引用本文：高春, 王嘉婧, 郭笑天, 等. Cu-MOF基材料应用研究进展[J]. 化学试剂, 2023, 45(1), 12-23.
多肽药物口服给药稳定性研究进展
王彬a，段丛雪a，王珊珊a，陈旺a,b，冯自立*a
（陕西理工大学 a.生物科学与工程学院，b.陕西省资源生物重点实验室，陕西 汉中 723000）
摘要：与小分子药物相比，多肽药物因其高选择性与高效性已在医药领域得到广泛应用。但由于较差的药代动力学与有限的生物屏障渗透性等问题，多肽药物的口服生物利用度较低，其通常通过胃肠外途径给药。主要通过多肽药物的口服给药进行综述、介绍了多肽类药物面临的挑战及改善其口服稳定性的策略，如酸碱度调节、酶抑制剂、渗透促进剂及化学法修饰，并对纳米粒载体给药系统进行阐述，以期为未来开发设计临床多肽类口服药物提供参考。
关键词：多肽药物；口服给药；稳定性；纳米粒子；吸收机制
中图分类号：TQ464.7 文献标识码：A 文章编号：0258-3283（2023）--
Progress in Stability of Oral Administration of Peptide Drugs WANG Bina, DUAN Cong-xuea, WANG Shan-shana, CHEN Wanga,b, FENG Zi-li*a (a. School of Biological Science and Engineering, b. Key Laboratory of resource biology of Shaanxi Province, Shaanxi University of Technology, Hanzhong 723000, China)
Abstract: Compared with small molecule drugs, peptide drugs had been widely used in the pharmaceutical field because of their high selectivity and efficiency. However, due to their poor kinetics and limited biological barrier permeability, peptide drugs had low oral bioavailability and were usually administered by the parenteral route. This review focused on the oral administration of peptide drugs, introduced the challenges faced by peptide drugs and strategies to improve their oral stability, such as pH regulation, enzyme inhibitors, penetration enhancers and chemical modifications, and elaborates on the nanoparticle carrier delivery system. To provide a reference for the future development and design of clinical peptide oral drugs.
Key words: peptide drugs; oral administration; stability; nanoparticles; absorption mechanism
引用本文：王彬，段丛雪，王珊珊，等. 多肽药物口服给药稳定性研究进展[J]. 化学试剂,2023,45(1): 24-32。
浅谈化学试剂产业的创新发展之路
王刚
（国药集团化学试剂有限公司, 上海 200002）
摘要：化学试剂的研发与生产，不仅对于科学研究、科技创新具有先导和支撑作用，同时也影响着国民经济的各个领域。着眼创新型国家建设，实现高水平科技自立自强，化学试剂行业应更多围绕重点领域，遵循国家战略发展需求，开展关键核心技术攻关，进一步发展高端试剂，通过企业牵头、产学研合作的创新模式，进行科技成果转化。同时加强创新型、应用型、技能型科技人才队伍建设，完善多元化考核激励机制。作为创新的主体，这是国有化学试剂企业在新时代创建创新型国家建设的新征程上需要肩负的重要使命和责任担当。
关键词：化学试剂；创新发展；高端试剂；生物医药；科技人才
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0856
Discussion on the Innovative Development of Chemical Reagent Industry WANG Gang (Sinopharm Chemical Reagent Co., Ltd., Shanghai 200002, China)
Abstract：The research and development, as well as production of chemical reagents not only play a leading and supporting role in scientific research and technological innovation, but also affect various fields of the national economy. Aiming at the construction of an innovative country and realizing advanced scientific and technological self-reliance, the chemical reagent industry should focus more on key areas, follow the national strategic development needs, promote core technology research, further develop high-end reagents, and adopt an innovative model of enterprise-led, industry-university-academy collaboration, to transform scientific and technological achievements. At the same time, it is critical to strengthen the development of innovative, application-oriented, and skilled scientific and technological talents, and improve the diversified assessment and incentive mechanism. These are important missions and responsibilities for state-owned chemical reagent enterprises, as the innovation subject, in the new era and the new journey of creating an innovative country.
Key words：chemical reagents; innovation development; high-end reagents; biomedicine; technological talents
引用本文：王刚. 浅谈化学试剂产业的创新发展之路[J]. 化学试剂，2023，45（1）：33- 36 .
【生化与药用试剂】
溴代苯酚与牛血清白蛋白的相互作用研究
梁雯洁a，蚁嘉颖a，张振轩*a,b，杨梦婷*a
（深圳大学 a.化学与环境工程学院，b.机电与控制工程学院，广东 深圳 518060）
摘要：消毒副产物（disinfection by-products, DBPs）是水环境中一类重要的污染物，因其检出频率高与对人的健康风险而引起广泛关注。牛血清白蛋白（BSA）作为水溶性最大的蛋白，可通过与水中DBPs发生结合作用而影响其环境行为。选取溴代芳香族DBPs 4-溴苯酚（4BPh）和2,4-二溴苯酚（24DBPh），运用荧光光谱法、紫外可见光谱法和分子对接法，研究了其与BSA的相互作用机制。结果显示，两种溴代DBPs均能与BSA结合而猝灭BSA的内源荧光，并使BSA构象发生改变，且溴化程度越高结合作用越强；290 K条件下，4BPh和24DBPh对BSA的结合常数分别为5.391×102、2.644×104 L/mol。分子对接结果显示4BPh和24DBPh与BSA的结合位点均在结构域IIIA中，氢键是结合的主要作用力。研究结果有助于深入探明水环境中大分子如BSA对DBPs环境行为的影响机制。
关键词：消毒副产物；溴代苯酚；牛血清白蛋白；相互作用；分子对接
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2023）
Study on the Binding Interactions between Bromophenols and Bovine Serum Albumin LIANG Wen-jiea, YI Jia-yinga, ZHANG Zhen-xuan*a,b, YANG Meng-ting*a (a. College of Chemistry and Environmental Engineering, b. College of Mechatronics and Control Engineering, Shenzhen University, Shenzhen 518060, China)
Abstract: Disinfection byproducts (DBPs) in water environments received great attention due to the frequent detection of various water matrix and potential health risks to human beings. Interactions between bovine serum albumins (BSA), the most abundant water-soluble protein, and DBPs possibly occur, which as a result influence the environmental behaviors of DBPs. The binding interactions of 4-bromophenol (4BPh) and 2,4-dibromophenol (24DBPh) with BSA were investigated systematically in this study by using fluorescence spectrometry, UV spectrometry and molecular docking. The results indicated that both 4BPh and 24DBPh could quench the intrinsic fluorescence of BSA through binding interactions, accompanied with the conformation changes of BSA. The binding effects increased with the degree of bromination. 24DBPh (Kb = 2.644 × 104 L/mol) showed higher binding affinity than 4BPh (Kb =5.391×102 L/mol), which determined by the binding constants (Kb) at T = 290 K. The docking analysis suggested that hydrogen bonding was the primary interaction forces and both of 4BPh and 24DBPh were located in the subdomain IIIA of BSA. The results of the present study are helpful in further understanding of influence mechanisms of macromolecules such as BSA on the environmental behaviors of DBPs in water environments.
Key words: disinfection by-products; bromophenol; bovine serum albumin; binding interaction; molecular docking
引用本文：梁雯洁, 蚁嘉颖, 张振轩, 等. 溴代苯酚与牛血清白蛋白的相互作用研究[J]. 化学试剂, 2023, 45(1)：37-45.
刺糖多糖脱色脱蛋白工艺及抗氧化活性研究
陈盈盈1，李杰1，宋建忠1,2，陈章浩1，李改茹1，常军民*1
（1. 新疆医科大学 药学院，新疆 乌鲁木齐 830000；2. 新疆医科大学附属肿瘤医院药学部，新疆 乌鲁木齐 830011）
摘要：为优化刺糖多糖脱色脱蛋白的最佳工艺，运用静动态吸附-解吸的方法，从8种极性不同的树脂中筛选最佳纯化效果的树脂，并通过单因素实验结合响应面法设计优化树脂的最佳纯化工艺。对比纯化前后多糖紫外、红外图谱特征及清除DPPH自由基的能力。结果表明XDA-1型树脂脱色脱蛋白的效果最佳，最优工艺条件为：上样质量浓度为0.03 g/mL，洗脱流速为2 mL/min，上样量为0.5 BV（1 BV＝100 mL）；在此条件下脱色率为（72.93±0.54）%，脱蛋白率为（74.72±0.37）%，多糖的保留率为（88.89±0.84）%；纯化后紫外谱图中蛋白质等杂质的特征吸收峰消失，多糖的红外特征吸收峰未发生变化，纯化后获得的刺糖多糖抗氧化活性增强。XDA-1型大孔吸附树脂可用于刺糖多糖的高效纯化，优选的脱色脱蛋白工艺条件稳定可行。
关键词：刺糖多糖；脱色；脱蛋白；大孔吸附树脂；抗氧化
中图分类号：TQ9 文献标识码：A 文章编号：0258-3283（2023）
Study on Decolorization and Deproteinization Process and Antioxidant Activity of Alhagi-HoneyPolysaccharide CHEN Ying-ying1, LI Jie1, SONG Jian-zhong1,2, CHEN Zhang-hao1, LI Gai-ru1, CHANG Jun-min*1(1. School of Pharmacy, Xinjiang Medical University, Urumqi 830000,China; 2. Department of Pharmacy, Tumor Hospital Affiliated to Xinjiang Medical University, Urumqi 830011,China)
Abstract: To optimize the best process for decolorization and deproteinization of Alhagi-honey polysaccharide, the static and dynamic adsorption-desorption method was used to screen the resin with the best purification effect from eight resins with different polarities, and the best purification process was optimized by the single-factor experiment combined with the response surface methodology. The characteristics of UV and IR spectra of polysaccharides before and after purification and their ability to scavenge DPPH free radicals were compared. The results show that XDA-1 resin has the best decolorization and deproteinization effect, and the optimal process conditions are: the concentration of the sample is 0.03 g/mL, the elution flow rate is 2 mL/min, and the amount of the sample is 0.5 BV (1 BV= 100 mL); under these conditions, the decolorization rate was (72.93±0.54)%, the deproteinization rate was (74.72±0.37)%, and the polysaccharide retention rate was (88.89±0.84)%; the characteristic absorption peaks of proteins and other impurities disappeared after purification, the infrared characteristic absorption peak of the polysaccharide did not change, and the antioxidative activity of the purified Alhagi-honey polysaccharide was enhanced. XDA-1 macroporous adsorption resin can be used for efficient purification of Alhagi-honey polysaccharide, and the preferred decolorization and deproteinization process conditions are stable and feasible.
Key words: Alhagi-honey polysaccharide; decolorization; deproteinization; macroporous adsorption resin; antioxidant
引用本文：陈盈盈，李杰，宋建忠，等. 刺糖多糖脱色脱蛋白工艺及抗氧化活性研究[J]. 化学试剂, 2023, 45(1): 46-53。
上转换@聚多巴胺纳米光热剂的制备及载药与抗菌性能
陈文雪，靳丹丹，朱良亮，袁善蓉，王浩，俞彬，宫培军*
（浙江师范大学 化学与生命科学学院“先进催化材料”教育部重点实验室，浙江 金华 321004）
摘要：癌症和致病菌感染成为公共安全健康的严重威胁。采用反相微乳液法对上转换粒子NaYF4:Yb,Nd,Er@NaGdF4:Nd,Yb包裹聚多巴胺（PDA）并接枝聚乙烯亚胺（PEI），制备了核-壳结构纳米光热剂NaYF4:Yb,Nd,Er@NaGdF4:Nd,Yb@PDA-PEI，表征了产物的形貌、化学组成、光学性质、光热和药载/释药性能。结果表明，光热剂的光热能力随PDA壳的增厚而增强。在PEI接枝后，光热剂在水中的分散效果获得改善，但光热性能轻微减弱，对盐酸阿霉素（DOX）的载药量高达26.6%，体外药物释放过程具有pH依赖和近红外光响应特征。载带盐酸四环素的纳米光热剂在808 nm激光照射下对大肠杆菌的抗菌活性优于光热剂或盐酸四环素。研究结果为发展应用于抗肿瘤或抗感染治疗的纳米光热剂提供了新思路。
关键词：上转换；聚多巴胺；光热治疗；药物负载；pH响应；抗菌性能
中图分类号：TB34, O644.1 文献标识码：A 文章编号：0258-3283（2023）--
Preparation, Drug Loading and Antibacterial Performance of Upconversion@polydopamine Photothermal Nanoagents CHEN Wen-xue, JIN Dan-dan, ZHU Liang-liang, YUAN Shan-rong, WANG Hao, YU Bin, GONG Pei-jun* (Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004, China)
Abstract: Cancer and pathogenic bacterial infection have become serious threats to public safety and health. Core-shell photothermal nanoagents NaYF4:Yb,Nd,Er@NaGdF4:Nd,Yb@PDA-PEI, were prepared by coating NaYF4:Yb,Nd,Er@NaGdF4:Nd,Yb with polydopamine (PDA) via reverse phase microemulsion method and grafting with polyethyleneimine (PEI) subsequently. The morphology, chemical composition, optical properties, photothermal and drug loading/release performance of the obtained products were characterized. The results showed that the photothermal nanoagents with thick PDA shells had enhanced photothermal performance. After grafted with PEI, the nanoagents showed improved particle dispersion in water and slightly decreased photothermal performance. The drug loading of doxorubicin hydrochloride (DOX) for the nanoparticles was up to 26.6% and the in vitro drug release from nanoparticles was pH-dependent and near-infrared light-responsive. Moreover, the tetracycline hydrochloride-loaded photothermal nanoagents exhibited better antibacterial activities against Escherichia coli compared to both the nanoagent and tetracycline hydrochloride under 808 nm laser irradiation. These results provided new insight into the development of photothermal nanoagents for anticancer and anti-infection treatment.
Key words: upconversion; polydopamine; photothermal therapy; drug loading; pH-responsive; antibacterial activity
引用本文：陈文雪，靳丹丹，朱良亮，等. 上转换@聚多巴胺纳米光热剂的制备及载药与抗菌性能[J]. 化学试剂, 2023, 45(1): 54-61。
【功能材料】
共价有机框架材料在药物递送中的应用进展
高嘉1，丁宣凯1，胡嘉欢2，王宜峰3，王燕飞4，付永前2*
（1.浙江理工大学 生命科学与医药学院，浙江 杭州 310018；
2.台州学院 生命科学学院，浙江 台州 318000；3.南京师范大学 食品与制药工程学院，江苏 南京 210023; 4.台州市产品质量安全检测研究院，浙江 台州 318000）
摘要：共价有机框架（Covalent organic frameworks，COFs）是一类通过共价键连接形成的新兴多孔结晶有机聚合物，具有比表面积大、孔隙高度可调及易于化学修饰等特点，是近年来多孔材料领域的研究热点。载药量高、细胞毒性低、生物相容性良好和药物释放能力高效等特点为COFs材料在药物递送领域提供了良好的应用潜力。简要总结了近年来药物递送载体的研究进展，介绍了COFs及其复合材料的合成方法及表征，列举了COFs作为几种模型药物（如阿霉素、5-氟尿嘧啶等）的载体在药物递送中的应用，提出了COFs材料在药物递送领域中的优势，最后对目前COFs材料在药物递送领域所面临的挑战和未来发展的机遇进行了总结和展望。
关键词：共价有机框架；药物递送；抗肿瘤药物；生物相容性；合成方法
中图分类号：Q819 文献标识码：A 文章编号：0258-3283（2023）
Application of Covalent Organic Framework Materials in Drug Delivery GAO Jia1, DING Xuan-kai1, HU Jia-huan2, WANG Yi-feng3, WANG Yan-fei4, FU Yong-qian*2 (1. College of Life Science and Medicine, Zhejiang Sci-tech University, Hangzhou 310018, China; 2. College of Life Science, Taizhou University, Taizhou 318000, China; 3. School of Food Science and Pharmaceutical Engineering, Nanjing Normal University, Nanjing 210023, China; 4. Taizhou Institute of Product Quality and Safety Inspection, Taizhou 318000, China)
Abstract: Covalent organic frameworks (COFs) are a new class of porous crystalline organic polymers formed by covalent bonding. They have the characteristics of a large specific surface area, adjustable pore height, and easy chemical modification, which are the research hotspots in the porous material field. The characteristics of high drug loading, low cytotoxicity, good biocompatibility, and high drug release ability provide COFs with good application potential in the field of drug delivery. In recent years, the research progress of drug delivery carriers is briefly summarized, the synthesis methods and characterization of COFs and their composites are introduced, and COFs are listed as carriers of several model drugs (such as doxorubicin, 5-fluorouracil, etc). The application of COFs materials in the field of drug delivery is proposed, and finally the challenges and future development opportunities are summarized and prospected.
Key words: covalent organic frameworks; drug delivery; anti-tumor drugs; biocompatibility; synthetic method
引用本文: 高嘉, 丁宣凯, 胡嘉欢, 等. 共价有机框架材料在药物递送中的应用进展[J]. 化学试剂, 2023, 45（1）：62-74.
赵一鸣，谭伟强，关静，李钰杰，马雨欣，柴会宁*
（青岛理工大学 环境与市政工程学院，山东 青岛 266520）
摘要：随着工业化、农业化水平的提高，大量污染物的产生严重危害了自然界生态平衡，并且增加了人类面临各种健康问题的风险。开发一种灵敏、稳定、快速、便捷的新型检测方法，对于环境监测具有重要意义。发光金属有机框架材料（Luminescent metal-organic frameworks，LMOFs）兼具了MOFs材料孔隙率高、比表面积大、易于结构修饰等特点和光致发光特性，在荧光传感方面展现出灵敏度高、选择性好、检测范围宽和抗干扰性能强等优点，因而在环境检测领域表现出良好的应用前景。主要介绍了LMOFs的发光类型和发光机理，然后评述了近年来LMOFs对环境中金属离子、无机物、有机物的荧光传感的研究进展，并对LMOFs的发展前景进行了展望。
关键词：发光金属有机框架；荧光传感；发光类型；发光机理；环境检测
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2022）--
Research Progress of Luminescent Metal-Organic Framework Materials in Environmental Detection ZHAO Yi-Ming, TAN Wei-Qiang, GUAN Jing, LI Yu-Jie, MA Yu-Xin, CHAI Hui-Ning* (Department of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520, China)
Abstract: With the improvement of industrialization and agriculturalization, the resulting pollutants have seriously harmed the ecological balance of nature and risked human health. Developing rapid, sensitive, and accurate detection methods to strengthen environmental monitoring are of significant meaning. Luminescent metal-organic frameworks (LMOFs) combines the characteristics of MOFs materials, such as large high porosity, surface area, structural modification and photoluminescence characteristics, which shows the good application prospect in the field of environmental testing because of the advantages of high sensitivity, good selectivity, wide detection range and strong anti-interference performance in fluorescence sensing. The luminescence types and luminescence mechanism of LMOFs were introduced, and then the research progress of LMOFs in fluorescence sensing of metal ions, inorganic and organic pollutants in the environment was reviewed. Finally, the future development of LMOFs in environmental detection was look forward.
Key words: luminous metal-organic frameworks; fluorescent sensing; luminescence types; luminescence mechanism; environmental detection
引用本文：赵一鸣, 谭伟强, 关静, 等. 发光金属有机框架材料在环境检测中的研究进展[J]. 化学试剂, 2023, 45(1):75-84.
硫化镉/金属-有机框架复合材料的制备及光催化应用
陈莲芬1，凌扬1，李耿扬1，刘子建1，徐晓磊2，康健1*
（1.肇庆学院 环境与化学工程学院，广东 肇庆 526061；2.平煤高级中学，内蒙古 赤峰 024076）
摘要：金属-有机框架（Metal-Organic Frameworks，MOFs）是一类近年来受到广泛关注的多孔材料，具有比表面积大、孔隙率高、结构多样、易于调节和修饰等优点。受可见光吸收效果差、光生电子利用效率低等问题影响，纯MOFs在光催化领域的应用比较局限。将MOFs与硫化镉半导体结合，不仅可以拓宽MOFs材料的吸光范围和避免硫化镉纳米粒子聚集，也能促进光生电子的传输，减少电子-空穴复合，从而提升光催化活性。综述了硫化镉/金属-有机框架复合材料的制备方法及其在光催化领域的应用进展，指出了存在的问题和可能的发展方向。
关键词：金属-有机框架；半导体；硫化镉；制备；光催化
中图分类号：O64 文献标识码：A 文章编号：0258-3283（2023）
Preparation and Photocatalytic Application of Cadmium Sulfide/Metal-Organic Framework Composites Chen Lian-fen1, Ling Yang1, Li Geng-yang1, LIU Zi-jian1, Xu Xiao-lei2, Kang Jian1*(1. School of Environmental and Chemical Engineering，Zhaoqing University, Zhaoqing 526061, China; 2. Pingmei Senior Middle School, Chifeng 024076, China)
Abstract: Metal-Organic Frameworks (MOFs) are a kind of porous material that has attracted wide attention in recent years. They have the advantages of large specific surface area, high porosity, diversified structure, and easy adjustment and modification. Due to the poor absorption of visible light and low utilization efficiency of photo-generated electrons, the application of MOFs in the field of photocatalysis is relatively limited. Combining MOFs with Cadmium sulfide semiconductor can not only broaden the light absorption range of MOF materials and avoid the accumulation of CdS nanoparticles, but also promote the transmission of photogenerated electrons and reduce the electron-hole recombination, thus improving the photocatalytic activity. Preparation methods of cadmium sulfide/metal-organic framework composites and their applications in the field of photocatalysis are reviewed, the existing problems are pointed out, and the possible development direction is forecasted.
Key words: metal-organic frameworks; semiconductor; cadmium sulfide; preparation; photocatalysis
引用本文：陈莲芬，凌扬，李耿扬，等. 硫化镉/金属-有机框架复合材料的制备及光催化应用[J]. 化学试剂, 2022, 45(1)：85-91.
共价有机框架材料TpPa-NH2-D-(-)-α-苯甘氨酸用作高效液相色谱手性固定相研究
陈政，禹紫云，段爱红*，刘华林，袁黎明*
（云南师范大学 化学化工学院，云南 昆明 650500）
摘要：共价有机框架(COFs)是通过共价键连接多齿有机结构单元而形成的一类新兴的多孔晶体材料，其成分、结构和功能均具有可调性。由于对手性多孔材料的需求不断增加，且COFs材料拥有比表面积大、有序和永久的孔隙率等优点，COFs材料在不对称催化和分离领域越来越受到人们的重视。对映体之间通常因具有相类似的物理性质和化学性质，一直以来都是分离领域想要突破的难点。通过溶剂热法合成一种具有高结晶度和孔隙率以及在强酸和强碱中具有高化学稳定性的手性共价有机骨架(CCOF)材料的手性衍生物TpPa-NH2-D-(-)-α-苯甘氨酸。采用“网包法”制备TpPa-NH2-D-(-)-α-苯甘氨酸手性固定相，并用其制备高效液相色谱手性柱，考察其对外消旋体拆分和苯系位置异构体的分离能力。TpPa-NH2-D-(-)-α-苯甘氨酸色谱柱分开了11种手性化合物和7种苯系位置异构体，还具有较好的重现性，表明其分离效果良好。
关键词：共价有机骨架；高效液相色谱；手性分离；手性固定相
中国分类号：0657.7 文献标识码：A 文章编号：0258-3283（2023）
Covalent Organic Framework Material TpPa-NH2-D-(-)-α-Phenylglycine as Chiral Stationary Phase for High Performance Liquid Chromatography CHEN Zheng, YU Zi-yun, DUAN Ai-hong*, LIU Hua-Lin, YUAN Li-ming* (School of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China)
Abstract: COFs are an emerging class of porous crystalline materials formed by covalently linking multidentate organic building blocks with tunable composition, structure, and function. Due to the increasing demand for chiral porous materials and the many advantages of COFs such as large specific surface area, and ordered and permanent porosity, COFs have attracted more and more attention in the field of asymmetric catalysis and separation. Enantiomers usually have similar physical and chemical properties, which has always been a difficult point in the separation field. In this paper, a CCOF material TpPa-NH2-D-(-)-α-phenylglycine with high crystallinity and porosity and high chemical stability in strong acids and bases was synthesized by the solvothermal method. TpPa-NH2-D-(-)-α-phenylglycine chiral stationary phase was prepared by "net-encapsulation method", and it was used to prepare high-performance liquid chromatography chiral column, and its racemate resolution and benzene series position were investigated Separation ability of isomers. The TpPa-NH2-D-(-)-α-phenylglycine chromatographic column separated 11 chiral compounds and 7 benzene-based positional isomers with good reproducibility, indicating that the separation effect was well.
Key words: covalent organic framework; high-performance liquid chromatography; chiral separation; chiral stationary phase
引用本文：陈政，禹紫云，段爱红，等. 共价有机框架材料TpPa-NH2-D-(-)-α-苯甘氨酸用作高效液相色谱手性固定相研究[J].化学试剂, 45(1)：92-98.
Bi2S3/BaTiO3复合光催化剂的制备及其光催化性能的研究
董玮*a,b，林莉c，李向阳c，顾怀章a,b，王雷a,b，梁春华a,b，付定梅a
（凯里学院 a.理学院，b.先进功能材料重点实验室，c.大健康学院，贵州 凯里 556011）
摘要：由于BaTiO3(BTO)面临着太阳能利用率低、光生载流子快速重组和稳定性差的问题，严重限制其在可见光下降解有机污染物。以BaTiO3为基体采用简单的水热法在其周围制备了不同物质的量比的Bi2S3/BTO p-n异质结，以改善BaTiO3的光催化性能。分别采用XRD、SEM、EDS、TEM、XPS、PL、UV-vis DR、EIS、瞬态光电流响应等表征手段对样品的结构、形貌、表面价态以及光电性能进行分析。以RhB为模拟污染物，测试了复合材料的光催化活性和稳定性。结果表明，与单组分催化剂相比，Bi2S3/BTO复合材料的催化性能得到了显著提升。在可见光下照射150 min后，对RhB的降解率高达98.7%；经5个循环，降解率仍为86%。通过对光催化剂的机理研究表明羟基自由基、超氧自由基、光生空穴均在光催化反应中起作用，并提出了一种可能的p-n异质结光催化机理。
关键词：Bi2S3；BaTiO3；p-n异质结；光催化
中图分类号：TQ579 文献标识码：A 文章编号：0258-3283（2023）
Synthesis and Photocatalytic Properties of Bi₂S₃/BaTiO3 Composite Photocatalysts DONG Wei*a,b, LIN Lic, , LI Xiang-yangc, GU Huai-zhanga,b, WANG Leia,b, LIANG Chun-huaa,b, FU Ding-meia (a. College of Science; b. Key Laboratory of Advanced Functional Materials; c. College of Big Health, Carey College, Carey 556011, China)
Abstract: BaTiO3 (BTO) faces the problems of low solar energy utilization, rapid recombination of photogenerated carriers and poor stability, which seriously limits the degradation of organic pollutants under visible light. To improve the photocatalysis performance of BaTiO3, Bi2S3/BTO p-n heterostructures with different molar ratios were prepared around BaTiO3 in simple hydrothermal method. XRD, SEM, EDS, TEM, XPS, PL, UV-Vis Dr, EIS, transient photocurrent response and other characterization methods were used to analyze the structure, morphology, surface valence, and photoelectric properties of the samples. The photocatalytic activity and stability of the composites were tested with RhB as a simulated pollutant. The results showed that the catalytic performance of Bi2S3/BTO composite had been significantly improved compared with the single component catalyst. After irradiation by visible light for 150 min, the degradation rate of RhB reached 98.7%. After 5 cycles, the degradation rate was still 86%. Through the mechanism study of photocatalyst, it was showed that hydroxyl radical, superoxide radical and photogenerated hole all played a role in the photocatalysis reaction, and a possible photocatalysis mechanism of p-n heterojunction was proposed.
Key words: Bi₂S₃; BaTiO₃; p-n heterojunction; photocatalysis
引用本文：董玮，林莉，李向阳，等. Bi2S3/BaTiO3复合光催化剂的制备及其光催化性能的研究[J]. 化学试剂，2023，45（1）：99-107.
【电化学和新能源】
王若钰a，梁斌a,b，朱英明b，鲁厚芳a,b，吴可荆*a,b
（四川大学 a. 化学工程学院，b. 新能源与低碳技术研究院，四川 成都 610207）
摘要：针对相变蓄能材料的相变点调节和热导率增强的问题，本文通过熔融混合法制备了一种低相变温度、高潜热的C14～C18石蜡基共熔相变材料，通过DSC和塔曼图对C14～C18混合物进行了分析，确定了共熔物的组成为84.4 wt% C14～15.6wt% C18，熔点和相变焓分别为1.0 ℃和20 5kJ/kg。基于C14～C18石蜡共熔物作为相变储能材料，以5种不同压缩密度的膨胀石墨作为吸附基质，制备了C14～C18/EG复合材料。通过SEM、FT-IR、XRD表征了微观结构和形貌，通过DSC和HOT-DISK热常数分析仪测试了储能性能和导热性能，并探讨了不同压缩密度的膨胀石墨与复合材料的相变焓以及热导率的关系。实验结果表明：在实验条件范围内，相变焓与压缩密度成正比，热导率与压缩密度成反比；在100次吸放热试验后，样品形貌和热性质未发生变化，复合材料具有良好的循环稳定性和热稳定性。复合相变储能材料在低温储存领域具有应用潜力。
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2023）--
Preparation of paraffin-based high thermal conductivity phase change materials WANG Ruo-yua, LIANG Bina,b, ZHU Ying-mingb, LU Hou-fanga,b, WU Ke-jing* a,b (a. School of Chemical Engineering, b. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China)
Abstract: Aiming at the problems of phase change point adjustment and thermal conductivity enhancement of phase change energy storage materials, a kind of C14～C18 paraffin-based eutectic phase change material with low phase transition temperature and high latent heat was fabricated by melt mixing method. The C14～C18 mixture was analyzed by DSC and Taman diagrams, and the composition of the eutectic was determined to be 84.4 wt% C14 and 15.6 wt% C18, and the melting point and phase change enthalpy were 1.0 °C and 205 kJ/kg, respectively. C14～C18/EG composites were prepared based on C14～C18 paraffin eutectic as phase change energy storage material and five kinds of expanded graphite with different compression densities as adsorption matrix. The microstructures and morphologies were characterized by SEM, FT-IR and XRD, while DSC and HOT-DISK thermal constant analyzer were used to evaluate the energy storage performance and thermal conductivity of the composites. Moreover, the relationship between expanded graphite with different compression densities and the phase change enthalpy and thermal conductivity of the composites was discussed. The experimental results indicated that within the range of the experimental conditions, the phase change enthalpy was proportional to the compressive density, while the thermal conductivity was inversely proportional to it. After 100 endothermic and exothermic tests, the sample morphology and thermal properties had not changed, evidencing good cycling and thermal stability of the composite material. Composite phase change energy storage materials have potential applications in the field of low temperature storage.
Key words: paraffin eutectics; phase-change energy storage material; expanded graphite; thermal conductivity
引用本文：王若钰，梁斌，朱英明，等. 石蜡基高热导率相变储能材料的制备[J]. 化学试剂,2023, 45(1): 108-113。
【化学品与环境】
陈晓青1，李亚1，巩冠群1,2*
（1.中国矿业大学 化工学院，江苏 徐州 221116；2.煤炭加工与高效洁净利用教育部重点实验室，江苏 徐州 221116）
摘要：生物炭因其优越的吸附能力、原料广泛和制备工艺简单等特点在重金属污染土壤修复领域具有广泛的研究。然而，生物炭对重金属的固定化效果受到原料类型、制备工艺和其他外在条件的影响。此外，生物炭中含有的重金属存在着对土壤生态系统、环境安全和农业生产造成潜在危害的风险。这些挑战和风险严重阻碍了生物炭的实际应用进程。因此，本综述详细梳理了当前生物炭在固定土壤重金属领域所面临的问题和挑战，深入探索造成生物炭应用局限性的作用机制，从而为未来的生物炭研究方向提供建议，以期促进生物炭的高效生产和安全应用。
关键词：生物炭；重金属污染；负效应；土壤；环境行为
中图分类号：X53 文献标识码：A 文章编号：0258-3283（2023）
Challenges and Potential Negative Effects of Biochar Fixation of Heavy Metals CHEN Xiao-qing, LI Ya, GONG Guan-qun*a,b (1.School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116, China; 2.Key Laboratory of Coal Processing and Efficient Clean Utilization, Ministry of Education, Xuzhou 221116, China)
Abstract：Biochar has been widely studied in the field of remediation of heavy metals contaminated soils due to its superior adsorption capacity, wide range of raw materials and simple preparation process. However, the immobilization effect of biochar on heavy metals is influenced by the type of feedstock, preparation process and other external conditions. In addition, the heavy metals contained in biochar carry the risk of causing potential harm to soil ecosystems, environmental safety and agricultural production. These challenges and risks have seriously hindered the practical application of biochar. Therefore, this review provides a detailed overview of the current problems and challenges faced by biochar in the field of fixing heavy metals in soil, explores in depth the mechanisms of action that contribute to the limitations of biochar, to provide suggestions for future research directions of biochar, in order to realize the efficient production and safe application of biochar.
Key words: biochar; heavy metal pollution; soil remediation; negative effect; environmental behavior
引用本文：陈晓青，李亚，巩冠群. 生物炭固定重金属的挑战及潜在负面效应研究[J]. 化学试剂,2023, 45(1): 114-121。
二乙烯三胺改性磁性生物炭对Cr（VI）吸附性能研究
杨鑫宇1,2，张全悦2，武中豪2，张娜1,2，赵俭波1,2，胡立兵*1,2
（1. 新疆兵团南疆化工资源利用工程实验室，新疆 阿拉尔 843300；2. 塔里木大学 化学化工学院，新疆 阿拉尔 843300）
摘要：为解决水体重金属Cr（VI）的环境污染问题，以棉秆为原料制备生物炭（BC），再采用液相沉淀法将BC赋磁，得到磁性生物炭（MBC）。以二乙烯三胺（DETA）为改性试剂，对MBC进行氨基改性，制备出氨基改性磁性生物炭吸附剂DETA@MBC。用XRD、SEM、FT-IR、VSM对DETA@MBC进行表征，证实了Fe3O4成功负载在BC表面，MBC的氨基改性没有破坏Fe3O4的晶体构型，DETA@MBC表面有丰富的氨基功能团，且饱和磁强度良好。研究其作为吸附剂在不同条件下对Cr（Ⅵ）的吸附性能。结果表明：溶液pH值、吸附剂投加量、竞争性离子和温度等因素均会影响吸附效果；DETA@MBC对Cr（Ⅵ）的吸附更符合准二级动力学方程，等温吸附过程符合Freundlich模型，KF = 25.287 mg1-(1/n)·L1/n/g，n = 2.538，吸附容易进行，对Cr（Ⅵ）的吸附为自发的吸热过程。
关键词：生物炭；氨基改性；吸附；Freundlich模型；动力学
中图分类号：TQ424.3 文献标识码：A 文章编号：0258-3283（2023）--
Study on Adsorption of Cr (VI) on Magnetic Biomass Carbon Modified by Diethylenetriamine YANG Xin-yu1,2, ZHANG Quan-yue2, WU Zhong-hao2, ZHANG Na1,2, ZHAO Jian-bo1,2, HU Li-bing*1,2 (1. Engineering Laboratory of Chemical Resources Utilization in South Xinjiang, Xinjiang Production &Construction Corps, Alar 843300, China; 2. College of Chemistry and Chemical Engineering, Tarim University, Alar 843300, China)
Abstract：In order to solve the problem of environmental pollution caused by heavy metal Cr (VI) in water, biochar (BC) derived from cotton stalk was prepared, and then magnetic biochar (MBC) was synthesized using the precipitation methods. Diethylenetriamine (DETA) was used as modification reagent to aminate the surface of magnetic biochar (MBC), so that amino modified magnetic biomass carbon material DETA@MBC was prepared. DETA@MBC was characterized by XRD, SEM, FT-IR and VSM techniques, which confirmed that Fe3O4 was successfully loaded on the surface of BC. The amino modification of MBC did not destroy the crystal configuration of Fe3O4. There were abundant amino functional groups on the surface of DETA@MBC with high saturation magnetization. The adsorption properties of DETA@MBC on Cr (Ⅵ) under different conditions were studied, which showed that the pH value of solution, the amount of adsorbent, competitive ions and temperature all affected the adsorption effect. The adsorption of Cr (VI) by DETA@MBC was more consistent with the quasi-second-order kinetic equation. The isotherm adsorption process accorded with Freundlich model, KF = 25.287 mg1-(1/n) ·L1/n/g, n = 2.538, adsorption process was easy to proceed, and the adsorption of Cr (VI) was a spontaneous endothermic process.
Key words：biochar; amino modification; adsorption; Freundlich model; kinetics
引用本文：杨鑫宇，张全悦，武中豪，等. 二乙烯三胺改性磁性生物炭对Cr（VI）吸附性能研究[J]。化学试剂，2023，45(1)：122-128.
【分析与测试】
加味桃红四物汤含量测定、指纹图谱以及抗氧化活性研究
张昊祯1，杨爱岗*2，张岩1，吴嘉佳1，陈跃龙2，严诗楷1，金慧子*1
(1.上海交通大学药学院，上海 200240；2.上海松皓生物科技有限公司，上海 200331)
摘要：建立加味桃红四物汤（白及、桃仁、红花等）HPLC指纹图谱，测定其中没食子酸、苦杏仁苷、绿原酸、芍药内酯苷、羟基红花黄色素A、芍药苷、阿魏酸、洋川芎内酯I、毛蕊花糖苷、1,4-二[4-(葡萄糖氧)苄基]-2-异丁基苹果酸酯、苯甲酰芍药苷和藁本内酯共12种成分的含量。色谱柱采用（250 mm×4.6 mm，5 μm）Shim-pack VP-ODS柱，柱温30 ℃；以0.05%磷酸-甲醇为流动相梯度洗脱，体积流量为1.2 mL/min，检测波长分别为210、225、280 nm。10批加味桃红四物汤样品指纹图谱中，共标定26个共有峰，不同批次间相似度均大于0.96，且所有成分在各自范围内线性关系良好（R2≥0.998），平均回收率98.03%～101.43%，RSD 0.72%～1.93%。同时，对加味桃红四物汤的抗氧化活性进行测定，结果显示其清除DPPH、ABTS及羟基自由基的IC50分别为为51.11、44.13、275.39 μg/mL。该方法准确、简便、快速，可用于抗氧化活性良好的加味桃红四物汤的质量控制。
关键词：桃红四物汤；指纹图谱；高效液相色谱；含量测定；抗氧化活性
中图分类号：R284.1; R917.101 文献标识码：A 文章编号：0258-3283（2023）
HPLC Fingerprint and Multi Components Determination in Modified Taohong Siwu Decoction and its Antioxidant Activity ZHANG Hao-zhen1, YANG Ai-gang2, ZHANG Yan1, WU Jia-jia1, CHEN Yue-long2, YAN Shi-kai1, JIN Hui-zi1* (1. School of Pharmacy, Shanghai Jiaotong University, Shanghai 200240, China; 2. Shanghai Songhao Biotechnology Company, Shanghai 200331, China)
Abstract: To establish a method for HPLC fingerprints and simultaneous content determination of gallic acid, amygdalin, chlorogenic acid, albiflorin, hydroxysafflor yellow A, paeoniflorin, ferulic acid, senkyunolide I, verbascoside, militarine, benzoylpaeoniflorin and ligustilide in Modified Taohong Siwu Decoction. Shim-pack VP-ODS column (250 mm×4.6 mm, 5 μm) was used and the column temperature was 30 ℃. The analysis was performed with methanol-0. 05% phosphoric acid, flowing at 1.2 mL/min and the detection wavelengths were set at 210, 225, and 280 nm．Among 10 batches of samples, 26 common peaks were identified in the HPLC fingerprints with similarities of more than 0.96. Twelve constituents showed good linear relationships (R2≥0.998), whose average recoveries were 98.03%～101.43% with the RSDs between 0.72%～1.93%. The antioxidant activity was evaluated by the scavenging ability of DPPH, ABTS and hydroxyl free radicals. The IC50 of DPPH, ABTS and hydroxyl free radicals were 51.11, 44.13, and 275.39 μg/mL. This rapid, simple and precise method can be used for the quality control of Modified Taohong Siwu Decoction with good antioxidant activity.
Key words: Taohong Siwu Decoction; fingerprint; high performance liquid chromatography (HPLC); content determination; antioxidant activity
引用本文：张昊祯，张岩，吴嘉佳，等.加味桃红四物汤含量测定、指纹图谱以及抗氧化活性研究[J]. 化学试剂, 2023, 45(1): 129-135。
高光谱结合图分割算法快速鉴别不同尺度产地陈皮
张悦1,4，王游游4，张婷1，覃驭楚2,3，南铁贵4，杨健4，吕炎杰*2,3
（1.云南中医药大学 中药学院，云南 昆明 650500；2.可持续发展大数据国际研究中心，北京 100094；3.中国科学院 空天信息创新研究院数字地球重点实验室，北京 100094；4.中国中医科学院中药资源中心 道地药材国家重点实验室培育基地，北京 100700）
摘要：以中药材陈皮为研究对象，建立一种高光谱技术结合图分割算法实现不同尺度产地陈皮样本快速无损鉴别的方法。采集可见-近红外波段（VNIR, 400 ~ 1000 nm）及短波红外（SWIR, 950 ~ 2500 nm）波段范围内不同尺度产地陈皮样品的高光谱图像，使用自研图分割算法快速获得样品相对反射率数据集，多种预处理算法对光谱数据进行降噪处理后，结合偏最小二乘判别分析（Partial least square-discriminant analysis，PLS-DA)、随机森林（Random Forests，RF）和支持向量机（Support vector machine，SVM）方法建立分类鉴别模型，将预测结果的准确率作为评价指标筛选最佳模型，使用混淆矩阵（Confusion matrix）评估模型性能。图分割算法与常规人工提取方法相比，时间减少80%。VNIR和SWIR波段的融合光谱一阶导结合PLS-DA模型是不同尺度产地陈皮样品的最优鉴别模型，省级行政区域产地的陈皮样品的鉴别准确率为98.41%；新会不同区域陈皮样品的鉴别准确率为99.05%。广东、山东、四川的陈皮样品鉴别模型的灵敏度可达100%，广东新会不同区域陈皮鉴别模型的灵敏度可达97%以上。该新型图分割算法能够实现高光谱兴趣区域信息的快速、准确获取，结合高光谱技术可实现不同尺度产地陈皮样品的快速鉴别。，
中图分类号：TS272.7 文献标识码：A 文章编号：0258-3283（2023）
Identification of Citri Reticulatae Pericarpium Form Different Scales Geographical Origin by Hyperspectral Imaging Combined with Image Segmentation Algorithm ZHANG Yue1,4, WANG You-you4, ZHANG Ting1, QIN Yu-chu2,3, NAN Tie-gui4, YANG Jian4, LV Yan-jie*2,3 (1.School of Traditional Chinese Medicine, Yunnan University of Chinese Medicine, Kunming 650500, China; 2.International Research Center of Big Data for Sustainable Development Goals, Beijing 100094, China; 3.Key Laboratory of Digital Earth Science, Aerospace Information Research Institute, Chinese Academy Science, Beijing 100094, China; 4. State Key Laboratory Breeding Base of Dao-di Herbs, National Resource Center for Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China)
Abstract: A hyperspectral imaging method combined with an image segmentation algorithm was developed for rapid nondestructive identification of Citri Reticulatae Pericarpium samples from different scales. Hyperspectral imaging of Citri Reticulatae Pericarpium samples from different scales was collected in the visible-near-infrared (VNIR, 400 ~ 1000 nm) or shortwave infrared (SWIR, 950 ~ 2500 nm) bands, and the relative reflectance data set of samples was quickly obtained by using self-developed image segmentation algorithm. After denoising the spectral data by various pre-processing algorithms, the classification and discrimination model was established by combining partial least squares discriminant analysis (PLS-DA), random forest (RF) and support vector machine (SVM). The accuracy of prediction results was used as an evaluation index to screen the best model, and the performance of the model was evaluated by Confusion matrix. Compared with the conventional manual extraction method, the time of the image segmentation algorithm was reduced by 80%. The PLS-DA model based on the fusion spectra of VNIR and SWIR bands was the optimal identification model for Citri Reticulatae Pericarpium samples from different scales. The identification accuracy of Citri Reticulatae Pericarpium samples from provincial administrative regions was 98.41%. The identification accuracy of Citri Reticulatae Pericarpium samples from different areas in Xinhui was 99.05%. The sensitivity of identification models of Citri Reticulatae Pericarpium samples from Guangdong, Shandong and Sichuan could reach 100%, and the sensitivity of identification models of Citri Reticulatae Pericarpium samples from Xinhui of Guangdong could reach over 97%. The new image segmentation algorithm can achieve rapid and accurate acquisition of hyperspectral region of interest information, combined with hyperspectral imaging can achieve rapid identification of Citri Reticulatae Pericarpium samples from different scales.
Key words: hyperspectral imaging; graph separation algorithm; Citri Reticulatae Pericarpium; origin classification
引用本文：张悦，王游游，张婷，等. 高光谱结合图分割算法快速鉴别不同尺度产地陈皮[J]. 化学试剂，45（1）：136-143.
乳蛋白高效液相色谱检测方法的优化及甘南牦牛乳指纹图谱的建立
张琪玮*，乔志刚，葛静微，马芮萍
(甘肃省产品质量监督检验研究院，甘肃 兰州 730050)
摘要：建立多种乳蛋白同时检测的高效液相色谱法，为乳及乳制品乳蛋白的分离检测提供方法，并建立甘南牦牛乳的指纹图谱。样品采用含Bis-Tris、盐酸胍、柠檬酸钠、二硫苏糖醇等的缓冲液使蛋白溶解变性，采用高效液相色谱二极管检测器检测，选择ZORBAX 300SB-C8色谱柱(4.6 mm×150 mm，3.5 µm)，检测波长为215 nm，柱温40 ℃，流速0.6 mL/min，进样量10 µL，流动相为0.1%三氟乙酸水溶液-0.1%三氟乙酸乙腈进行梯度洗脱。应用中药色谱指纹图谱相似度评价软件对甘南牦牛乳进行相似度分析。所建方法能够分离乳中的κ-酪蛋白（κ-CN1、κ-CN2、κ-CN3）、α-酪蛋白（αs2-CN、αs1-CN）、β-酪蛋白（β-CN B型、β-CN A1型、β-CN A2型）、α-乳白蛋白、β-乳清蛋白（β-Lg B、β-Lg A），重复性、精密度结果为峰保留时间RSD＜1.3%，峰面积RSD＜3.3%。10批甘南牦牛乳样品得到的指纹图谱相似度大于0.99，有12个共有峰，指认了其中9个乳蛋白色谱峰。该方法操作简便、具有良好的重现性和专属性，适用于乳及乳制品中多种乳蛋白的分离检测。所建立的甘南牦牛乳指纹图谱为牦牛乳的质量控制提供参考依据。
关键词：乳蛋白；高效高效液相色谱；牦牛乳；指纹图谱
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）
Optimization of Detection Method of Milk Protein by High-Performance Liquid Chromatography and Establishment of Fingerprint of Gannan Yak Milk ZHANG Qi-wei*,QIAO Zhi-gang, GE Jing-wei, MA Rui-ping (Gansu Provincial Institute of Product Quality Supervision and Inspection, Lanzhou 730050, China)
Abstract: A high-performance liquid chromatography method for the simultaneous detection of multiple milk proteins was established to provide a method for the separation and detection of milk and dairy products, and to establish the fingerprint of Gannan yak milk for the quality control of Gannan yak milk. The sample was dissolved and denatured by buffer solution containing Bis-Tris, guanidine hydrochloride, sodium citrate, dithiothreitol, and so on, and detected by a high-performance liquid chromatography diode detector. ZORBAX 300SB-C8(4.6 mm×150 mm,3.5 µm) chromatographic column, the detection wavelength was 215 nm, the column temperature was 40 ℃, the flow rate was 0.6 mL/min, the injection volume was 10 µL, and the mobile phase was 0.1% trifluoroacetic acid aqueous solution-0.1% trifluoroacetic acid acetonitrile for gradient elution. The similarity analysis of Gannan yak milk was carried out using the similarity evaluation software of traditional Chinese medicine chromatographic fingerprints. The established method can separate κ-casein (κ-CN1, κ-CN2, κ-CN3), α-casein (αs2-CN, αs1-CN), β-casein (β-CN B, β-CN A1, β-CN A2), α-lactalbumin, β-lactalbumin(β-Lg B, β-Lg A). The repeatability and precision results showed that the peak retention time RSD<1.3%, and the peak area RSD<3.3%. The similarity between the characteristic chromatogram and chromatograms of 10 batches of Gannan yak milk was greater than 0.99. There were altogether 12 common peaks, and nine of them were identified. The method is easy to operate, has good reproducibility and specificity, and is suitable for the separation and detection of various milk proteins in milk and dairy products. The fingerprint of Gannan yak milk can provide a reference for the quality control of yak milk.
Key words: milk protein; high-performance liquid chromatography; yak milk; fingerprint
引用本文：张琪玮, 乔志刚, 葛静微, 等. 乳蛋白高效液相色谱检测方法的优化及甘南牦牛乳指纹图谱的建立[J]. 化学试剂, 2023, 45(1)：144-149.
【标准物质与标准品】
机动车排放监测用四元气体标准物质的研制
张体强1,2，胡树国1,2，周枫然1，杨扬仲夫3，冯和平1,2，刘智勇1,2，王德发*1,2
(1.中国计量科学研究院，北京 100029；2.国家气体产品质量检验检测中心，北京 100029；3. 中国计量测试学会，北京 100029)
摘要：随着我国第六阶段机动车污染物排放标准的出台，对机动车的排放要求更加严格，其尾气检测需要有合适的标准物质作为测量依据。通过开展一种四元气体标准物质的研制，将气体逐步充装至气瓶中混合制备，采用称量法定值。该标准物质包含二氧化碳（100 ~ 18.0×104）μmol/mol、一氧化碳（100 ~ 10.0×104）μmol/mol、丙烷（50.0 ~ 1.20×104）μmol/mol、一氧化氮（50.0 ~ 0.40×104）μmol/mol，氮气为平衡气。对4种主要组分的分析方法进行了开发，方法精密度较好。对标准气体特性量值的均匀性、稳定性、不确定度进行了评价。结果显示：该气体标准物质在12个月内稳定性良好，特性量值的相对扩展不确定度为1%（k=2）。
关键词：机动车；排放；气体；标准物质；二氧化碳；一氧化碳；丙烷；一氧化氮
中图分类号：O657.71 文献标识码：A 文章编号：0258-3283（2023）
Development of A Certified Reference Material with Four Gaseous Components for Automotive Exhaust Monitoring ZHANG Ti-qiang1,2, HU Shu-guo1,2, ZHOU Feng-ran1,2, YANG-YANG Zhong-fu3, FENG He-ping1,2, LIU Zhi-yong1,2, WANG De-fa*1,2 (1. National Institute of Metrology, Beijing 100029, China; 2. National Quality Inspection and Testing Center for Gas Products，Beijing 100029，China; 3. Chinese Society For Measurement, Beijing 100029)
Abstract: With the introduction of China's Ⅺ vehicle pollutant emission limits standards, exhaust detection requires more stringent, which rely on the appropriate reference materials to make more precise measurement results. In this paper, the development of a 4-component gaseous certified reference material is carried out, the certified value of gas concentration is assigned by the gravimetric method, and the preparation of the mixture is achieved by filling parent gas into cylinders step by step. The mixtures contain carbon dioxide (100~18.0×104) μmol/mol, carbon monoxide (100 ~ 10.0×104) μmol/mol, propane (50.0 ~ 1.20×104) μmol/mol and nitric oxide (50.0 ~ 0.400×104) μmol/mol, nitrogen does as balance gas. The analysis methods of the four main components were developed, which gave good precisions. The homogeneity, stability and uncertainty of the characteristic values of the standard gas were evaluated. The results showed that the gas reference material had good stability within 12 months, and the relative expansion uncertainty of the characteristic quantity value was 1% (k=2).
Key words: vehicle; emission; gas; certified reference material; carbon dioxide; carbon monoxide; propane; nitric oxide
引用本文：张体强，胡树国，周枫然，等. 机动车排放监测用四元气体标准物质的研制[J]. 化学试剂, 2023, 45(1):150-156.
【合成与工艺技术】
聚芳硫醚新型中间体4-（苯硫基）苯甲亚砜（PSO）的合成
吴炳辉1a，马晓明1b,2，陈康3，刘建武1b,2，严生虎1b,2，张跃*1a,2
（1.常州大学 a.石油化工学院，b.药学院，江苏 常州 213164；2.石油和化工行业连续流技术工程实验室，江苏 常州 213164；3.江苏苏化集团有限公司，江苏 苏州 215006)
摘要：以廉价的二苯硫醚为起始原料，经氯磺化（Reed）反应并还原芳基磺酰氯合成了4-（苯硫基）苯硫醇，进一步以四丁基碘化铵（TBAI）催化端基硫醇，再与硫酸二甲酯发生甲基化反应，最终将甲基苯基硫醚高选择性地氧化成亚砜，得到聚芳硫醚合成的关键中间体4-（苯硫基（苯甲亚砜（PSO）；考察了磺化试剂、磺酰氯还原体系（二氯二甲基硅烷-锌）、甲基化试剂、催化剂、溶剂和反应时间等对产率的影响，并对工艺进行了优化。该方法与其他路线相比，解决了使用液溴、硝酸等物质导致设备腐蚀问题的同时，大大提高了产率与纯度。
关键词：聚芳硫醚；硫鎓离子；PSO；硫醇氧化；端基硫醚
中图分类号：TQ612.9 文献标识码：A 文章编号：0258-3283（2023）
Synthesis of a New Intermediate of Poly Aryl Sulfide 4-(Phenylthio)Benzyl Sulfoxide(PSO) WU Bing-hui1a, MA Xiao-ming1b,2, CHEN Kang3, LIU Jian-wu1b,2, YAN Sheng-hu1b,2, ZHANG Yue*1a,2(1a. School of Petrochemical Engineering, 1b.School of Pharmacy, Changzhou University, Changzhou 213164, China; 2.Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry, Changzhou 213164, China; 3.Jiangsu Suhua Group Co., Ltd., SuZhou 215006, China)
Abstract: Using inexpensive diphenyl sulfide as a starting material, the 4-(thiophenyl)benzenethiol was synthesized by chlorosulfonation (Reed reaction) and reduction of benzenesulfonyl chloride. Further, the terminal thiols were catalyzed by tetrabutylammonium iodide (TBAI), followed by methylation with dimethyl sulfate. Ultimately, 4-(thiophenyl) benzyl sulfoxide (PSO), a key intermediate in the synthesis of Poly (arylene sulfide), was obtained by highly selective oxidation of the Methyl phenyl sulfide to sulfoxide. The article investigated the effects of sulfonation reagent, sulfonyl chloride reduction system (dichlorodimethylsilane-Zn), methylation reagent, catalyst, solvent and reaction time on the yield, and determined the optimal reaction conditions, as well as optimized the reaction process. Compared with other routes, this method solved the problem of equipment corrosion caused by using liquid bromine and nitric acid, while greatly improving the yield and purity.
Key words: poly(arylene sulfide); sulfonium ion; PSO; thiol oxidation; terminal thioether
引用本文：吴炳辉，马晓明，陈康，等. 聚芳硫醚新型中间体4-（苯硫基）苯甲亚砜（PSO）的合成[J]. 化学试剂, 2023, 45(1): 157-162。
李熹2，李渺1，魏娴1，柏松*1
（1. 贵州理工学院 化学工程学院，贵州 贵阳 550003；2. 贵州省煤田地质局实验室，贵州 贵阳 550008）
摘要：以离子液体1-丁基-3-甲基咪唑氯盐（[BMIM]Cl）为催化剂，合成了嘧啶氨基酸酯类化合物。研究了不同的常规溶剂和离子液体溶剂对嘧啶氨基酸酯类化合物产率的影响，以离子液体1-丁基-3-甲基咪唑溴盐（[BMIM]Cl）为催化剂，在温度为90 ℃的最优反应条件下一锅法合成了8个嘧啶氨基酸酯衍生物（4a ~ 4h），具有较高的收率（82% ~ 93%）。通过离子液体回收利用实验结果表明，重复使用5次后活性无明显下降，此外，生物活性测试结果表明，该类衍生物对猕猴桃溃疡病菌、柑橘溃疡病菌、水稻白叶枯病菌具有一定的活性，其中，2-(((5-氯-4-甲氧基-6-甲基嘧啶-2-基)氨基)(4-氯苯基)甲基)丙二酸二乙酯对猕猴桃溃疡病菌、柑橘溃疡病菌、水稻白叶枯病菌活性分别为71.5%、63.0%、55.4%，优于对照药剂叶枯唑对3种病菌的抑制活性。
关键词： 嘧啶氨基酸酯；离子液体催化剂；抗菌活性；精细化工中间体
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2023）
Catalytic Synthesis of Pyrimidine Amino Acid Ester Derivatives by Ion Liquid LI Xi2，LI Miao1，WEI Xian1，BAI Song*1 (1. School of Chemical Engineering, Guizhou Institute of Technology, Guiyang 550003, China; 2. Laboratory of Coalfield Geology Bureau of Guizhou Province, Guiyang 550008, China)
Abstract: Pyrimidine amino acid ester derivatives were synthesized by using ionic liquid 1-butyl-3- methylimidazolium chloride ([BMIM]Cl) as catalyst. The effects of different common solvents and ionic liquid solvents on the yield of pyrimidine amino acid ester derivatives were investigated. Eight pyrimidine amino acid ester derivatives (4a ~ 4h) were synthesized by one-pot method using ([BMIM]Cl) as the catalyst under the optimal reaction conditions at 90 °C. The reaction has high yield (82% ~ 93%). The experimental result of ionic liquid recycling showed that the activity did not decrease significantly after repeated use for 5 times. In addition, the biological activity test results showed that the derivatives had certain activities against Pseudomonas syringae pv. actinidiae (Psa), Xanthomonas citri pv. citri (Xac) and Xanthomonas oryzae pv. oryzae (Xoo). Among them, the activity of compound 4b against Psa, Xac, Xoo were 71.5%, 63.0%, and 55.4%, respectively, which were better than that of the control antibacterial agent Bismerthiazol.
Key words: pyrimidine amino acid ester; ionic liquid catalyst; antibacterial activity; fine chemical intermediate
引用本文：李熹，李渺，魏娴，等. 离子液体催化合成嘧啶氨基酸酯类化合物[J]. 化学试剂，2023，45(1):163-168.
磷酰化苯并咪唑[2,1-a]并异喹啉衍生物的合成
唐裕才*，黎敏，杨梦娜，黄鸿鑫
(湖南文理学院 化学与材料工程学院，水处理功能材料湖南省重点实验室，电镀废水回用技术湖南省工程技术研究中心，湖南 常德 415000)
摘要：苯并咪唑[2,1-a]并异喹啉衍生物是一类重要的生物医药和导电高分子材料。开发其绿色的合成新方法具有重要的意义。在硝酸银为催化剂，空气为氧化剂的条件下实现了磷自由基的温和引发并应用于构建苯并咪唑[2,1-a]并异喹啉衍生物。在最佳反应条件下，以40% ~ 65%收率合成了17种不同磷酰化苯并咪唑[2,1-a]并异喹啉化合物，采用1HNMR、13CNMR对终产物进行了结构鉴定。机理验证实验表明，该反应经历了磷自由基生成、对碳碳双键加成/环化、氧化脱氢历程。该方法具有绿色环保、条件温和等优势。
关键词：银催化；空气氧化；苯并咪唑[2,1-a]并异喹啉；绿色合成
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2023）
Synthesis of Phosphorylated Benzimidazo[2,1-a]Isoquinolin-6(5H)-one Derivatives TANG Yu-cai*1, LI Min1, YANG Meng-na1, HUANG Hong-xin1 (College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Hunan Provincial Key Laboratory of Water Treatment Functional Materials, Hunan Province Engineering Research Center of Electroplating Wastewater Reuse Technology, Changde 415000, China)
Abstract: Benzimidazo[2,1-a]isoquinolin-6(5H)-one derivative is an important class of pharmaceutically active compounds and functional materials. It is of great scientific significance to develop a new efficient and green method for the synthesis of benzimidazo[2,1-a]isoquinolin-6(5H)-ones. In this paper, a silver catalyzed radical coupling reaction has been developed for the synthesis of benzimidazo[2,1-a]isoquinolin-6(5H)-ones under oxygen as an oxidant. Under the optimized reaction conditions, seventeen phosphorylated benzimidazo[2,1-a]isoquinolin-6(5H)-ones were obtained with a yield of 40% ~ 65%. Their structures were determined by 1HNMR and 13CNMR. Control experiments showed that the present reaction underwent generating phosphorus radical、radical addition/ cyclization and deprotonate process. This protocol has the advantages of mild condition, green and simple operations.
Key words：silver; oxygen; benzimidazo[2,1-a]isoquinolin-6(5H)-one derivative; green synthesis
引用本文：唐裕才，黎敏，杨梦娜，等. 磷酰化苯并咪唑[2,1-a]并异喹啉衍生物的合成[J].化学试剂，2023，45（1）：169-176.
2023化学试剂第1期PDF文档.pdf
