标准物质领域发展现状及趋势
卢晓华*，薄梦，吴雪，陆琳，汪斌
（中国计量科学研究院，北京 100029）
摘要：对标准物质领域国内外发展现状和趋势进行了总结。在介绍标准物质和有证标准物质基本概念及其演变的基础上，以我国国家一级、二级标准物质和国外以各国计量院为主的标准物质研发活动为重点，对标准物质研发现状、关键研发领域以及近年来推出的标准物质典型新品种等进行了分析，对国际和国内标准物质相关技术标准与规范体系的最新情况进行了介绍，并对标准物质领域重大需求与发展趋势进行了展望。
关键词：标准物质；现状；趋势；概念；标准；规范
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283（2022）--
Current situation and trends on the development of reference materials LU Xiao-hua*，BO Meng，WU Xue，LU Lin，WANG Bin(National Institute of Metrology，Beijing 100029, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: This paper gives an overview on the development status and trend of reference materials at home and abroad. Based on the introduction of basic concept evolution of reference material and certified reference material, the R & D status, key R & D fields, new and representative varieties of reference materials are analyzed, mainly focusing on China's first class and second class national certified reference materials and the R & D activities of reference materials by mainly national metrology institutes in other countries. The paper also summarizes the latest situation on related international and domestic technical standards and specification system, prospects the future important needs and developing trends of reference materials.
Key words: reference material; status; trend; concept; standard; specification
引用本文：卢晓华，薄梦，吴雪，等. 标准物质领域发展现状及趋势[J]. 化学试剂，2022, 44(10):1403 -1410 .
抗菌肽的结构修饰及活性研究进展
段丛雪1，王彬1，王珊珊1，陈旺1,2，冯自立*1,2
（1. 陕西理工大学 生物科学与工程学院，陕西 汉中 723000；
2. 秦巴生物资源与生态环境省部共建国家重点实验室，陕西 汉中 723000）
摘要：抗生素耐药性是目前急需解决的医疗问题之一，寻找新的有效抗菌药物是解决耐药性的一种有效途径。抗菌肽（Antimicrobial peptides，AMPs）是广泛存在于生物体内的一类重要的多肽活性物质，具有广谱抗菌活性，并且部分抗菌肽还具有一定的抗肿瘤活性。因为抗菌肽具有独特的破膜作用机制，传统的耐药机制难以对其产生影响，在治疗细菌感染方面有广阔的应用前景，因此得到了研究者的广泛关注。本文主要通过总结相关研究文献，对抗菌肽的研究现状以及结构改造的研究加以综述，为抗菌肽在临床上的进一步研究和开发提供参考。
关键词：抗生素；耐药性；抗菌肽；结构修饰；抗菌活性
中图分类号：TQ465.6 文献标识码：A 文章编号：0258-3283（2022）
Research Progress on Structural Modification and Activity of Antimicrobial Peptides DUAN Cong-xue1, WANG Bin1, WANG Shan-shan1, CHEN Wang1,2, FENG Zi-li*1,2 (1. College of Biological Science and Engineering, Shanxi University of Technology, Hanzhong 723000, China; 2. State Key Laboratory of Qinba Bioresources and Eco-Environment, Hanzhong 723000, China), Huaxue Shiji, 2022,
Abstract: Antibiotic resistance is one of the medical problems that need to be solved urgently. Finding new effective antibiotics is an effective way to solve drug resistance. Antimicrobial peptides (AMPs) are a kind of important polypeptide active substances widely existing in organisms. They have broad-spectrum antibacterial activity, and some antimicrobial peptides also have certain antitumor activity. Because antimicrobial peptides have a unique membrane breaking mechanism, the traditional drug resistance mechanism is difficult to affect them. They have broad application prospects in the treatment of bacterial infection, so they have attracted extensive attention of researchers. This paper mainly summarizes the relevant research literatures, the research status of antimicrobial peptides and the research of structural transformation, so as to provide reference for the further research and development of antimicrobial peptides in clinic.
Key words: antibiotics; drug resistance; antimicrobial peptides; structural modification; antibacterial activity
引用本文：段丛雪, 王彬, 王珊珊, 等. 抗菌肽的结构修饰及活性研究进展[J]. 化学试剂, 2022,44（10）：1411-1420.
Gd(III)-DOTA类磁共振成像造影剂的合成策略与进展
张元红，王艳芳，万福贤*
(山东农业大学 化学与材料科学学院，山东 泰安 271018)
摘要：近年来，基于钆(III)的磁共振成像造影剂(GBCAs)受到了前所未有的挑战，迫切需要开发更安全、更惰性、靶向性、生化响应性钆(III)基造影剂。由于环状多胺多羧类配体(如DOTA)更易于被功能性基团修饰，且其钆(III)配合物比线性多胺多羧类钆(III)配合物(如Gd-DTPA)具有更高的热力学稳定性和动力学惰性，因此在研发新型钆(III)基造影剂领域备受青睐。本文以典型的DOTA类双功能造影剂配体(BFCAs)的设计、合成及应用为主线，重点介绍Gd-DOTA类造影剂的合成策略与进展。
关键词：磁共振成像(MRI)；DOTA；钆(III)配合物；双功能螯合试剂；合成策略
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2022）--
Synthetic strategies and progress of Gd(III)-DOTA derivatives used as MRI contrast agents ZHANG Yuan-hong, WANG Yan-fang, WAN Fu-xian* (College of Chemistry and Material Science, Shandong Agricultural University, Taian 271018, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：In recent years unprecedented challenges have arisen for gadolinium(III)-based contrast agents (GBCAs), and there is an urgent need to develop safer, more inert, targeted, and bioresponsive GBCAs. Macrocyclic polyamine polycarboxylic ligands (e.g., DOTA) are more easily modified by functional groups（e.g., antibodies, peptides, aptamers) and their gadolinium(III)-based complexes have higher thermodynamic stability and kinetic inertia when they are compared with those of gadolinium(III)-based complexes with linear polyamine polycarboxylic ligands (e.g., DTPA). Therefore, gadolinium(III)-based complexes with macrocyclic polyamine polycarboxylic ligands are favored in the field of developing novel GBCAs. In this review, the synthetic strategies and recent progress of Gd(III)-DOTA contrast agents are summarized by introducing the design and application of typical DOTA bifunctional contrast agent ligands (BFCAs).
Key words：magnetic resonance imaging; DOTA; gadolinium(III)-complexes; bifunctional chelating agents ligands (BFCAs); synthetic strategy
引用本文：张元红，王艳芳，万福贤. Gd(III)-DOTA类磁共振成像造影剂的合成策略与进展[J]. 化学试剂，2022, 44( ):1421 -1432.
有机铋化合物参与的氧化还原反应
贾自自，吴孝兰*
(国药集团化学试剂有限公司，上海 200002)
摘要：金属铋化合物在有机化学反应中具有重要的应用。其中，无机铋化合物通常作为路易斯酸来参与反应，有机铋化合物通常作为氧化剂、转金属试剂和芳基化试剂等来参与反应。有机铋化合物是指含有C-Bi键的一类有机金属试剂，它们易于由价廉低毒的无机铋盐制得。该类化合物具有独特的化学性质和反应性，因而在有机合成中具有广泛的吸引力。本文综述了该类金属试剂近年来所参与的氧化还原反应，并展望了未来发展趋势。
关键词：有机铋化合物；金属试剂；氧化还原反应；催化；机理
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2022）--
The redox reactivity of organobismuth compounds JIA Zi-zi, WU Xiao-lan* (Sinopharm Chemical Reagent Co., LTD., Shanghai 200002, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：Bismuth compounds are important in organic synthesis. Among them, inorganic bismuth compounds are usually acted as Lewis acids, organobismuth compounds are typically involved in the reaction as an oxidant, a metal reagent, arylation reagent, or the like. Organobismuth compounds are organometallic reagents containing a C-Bi bond which are easily accessed from inexpensive and low-toxicity inorganic bismuth salts and are highly attractive in synthesis due to their unique properties and reactivity. This article reviews the redox reactivity of organobismuth compounds in recent years and prospects the development tendency in the future.
Key words：organobismuth compounds; redox reactivity; metal reagent; catalysis; mechanism
引用本文：贾自自，吴孝兰. 有机铋化合物参与的氧化还原反应[J]. 化学试剂，2022, 44(10):1433-1438.
pH敏感型二氧化硅纳米载体的制备研究
赵宇，梁旭阳，刘超，尹付琳，周国勇*
(贵州民族大学 化学工程学院 贵州 贵阳 550000)
摘要：利用肿瘤弱酸环境引发功能化中空介孔纳米载体的电荷反转，使其具有pH刺激敏感。通过CTAB制备软模版并在其表面沉积TEOS和Si-69硅烷偶联剂制备得到多腔介孔纳米载体，并对其功能化修饰修饰。软模版是粒径约为180 nm的实心球体，DLS、TEM、BET数据显示最终制备得到介孔为3.1 nm粒径约为200 nm的多腔介孔纳米载体，红外光谱和拉曼光谱说明成功的进行功能化修饰，最后通过在不同pH的PBS中表征纳米载体的Zeta电位数据，显示pH 7.4、8.0、9.0条件中该纳米载体的Zeta电位分别(-21.5±0.32)、(-23.8±0.21)、(-25.3±0.33) mV，但是在pH 6.0、5.0条件下电位反转为(+6.2±0.41) mV、(+7.1±0.4) mV。多腔介孔纳米载体的空腔使其具有更大的载药量，带负电荷的纳米载体具有更长的血液循环时间，而该纳米粒子在弱酸环境下的电荷反转能力，使其能够在肿瘤组织富集，从而具有靶向功能提高药效。
关键词：多腔介孔纳米载体；功能化修饰；弱酸环境；电位反转；靶向功能
中图分类号：TQ460.4 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of ph-sensitive silica nanocarriers ZHAO Yu, LIANG Xu-yang, LIU Chao，YIN Fu-lin， ZHOU Guo-yong* (College of Chemical Engineering, Guizhou Minzu University, guiyang 550000, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：Charge reversal of functionalized hollow mesoporous nanoccarriers in tumor weak acid environment and make them sensitive to pH stimulation. The soft template was prepared by CTAB, TEOS and Si-69 silane coupling agent were deposited on the surface of the soft template to prepare the multi-cavity mesoporous nanoccarriers, and its functionalization was modified. The soft template was a solid sphere with a particle size of about 180 nm. DLS, TEM and BET data showed that a multi-cavity mesoporous nano-carrier with a mesopore of 3.1 nm and a particle size of about 200nm was finally prepared. IR and Raman spectra indicated that the functional modification was successfully carried out. Finally, the Zeta potential data of the nanocarrier were characterized in PBS with different pH values. It was shown that the Zeta potential of the nanocarrier was (-21.5±0.32), (-23.8±0.21), (-25.3±0.33) mV at pH 7.4, 8.0, 9.0, respectively. But at pH 6.0, 5.0, the potential changes to (+6.2±0.41), (+7.1±0.4) mV. The cavity of the multi-cavity mesoporous nanocarrier enables it to have a larger drug load, and the negatively charged nanocarrier has a longer blood circulation time. Moreover, the charge reversal of the nanoparticle in the weak acid environment enables it to accumulate in the tumor tissue, and thus has the targeting function to improve the drug efficacy.
Key words：HMSNs; functional modification; TME; potential reversal; target function
引用本文：赵宇，梁旭阳，刘超，等. pH敏感型二氧化硅纳米载体的制备研究[J]. 化学试剂，2022, 44(10):1439-1444.
硅钨酸盐-双氢氧化物复合材料选择性分离人全血中血红蛋白
陈晴,王蒙蒙,张杨,张丹丹*
（沈阳医学院 公共卫生学院 卫生化学教研室，辽宁 沈阳 110034）
摘要：在中性条件下，利用静电和氢键相互作用，制备了多金属氧酸盐-双氢氧化物复合材料ZnAl-SiW10Zr，并采用扫描电镜（SEM）、能谱（EDXS）、傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）手段对ZnAl-SiW10Zr复合材料进行表征。复合材料ZnAl-SiW10Zr中的金属离子与血红蛋白（Hb）之间存在亲和相互作用，因此，ZnAl-SiW10Zr可以高选择性吸附Hb。ZnAl-SiW10Zr复合材料（0.5 mg）对血红蛋白（100 μg/mL，1 mL）的吸附效率在pH 7.0时达到最大，为92%。血红蛋白在材料表面的吸附行为符合Langmuir模型，最大吸附容量为760 mg/g。采用0.1 mol/L SDS溶液作为洗脱剂将固相材料表面吸附的血红蛋白洗脱下来，洗脱回收率为91%。将复合材料ZnAl-SiW10Zr用于实际样品中血红蛋白的分离纯化，并采用SDS-PAGE凝胶电泳验证血红蛋白的纯度，结果表明经复合材料ZnAl-SiW10Zr分离出来的血红蛋白纯度较高。将多金属氧酸盐-双氢氧化物复合材料用于蛋白质的吸附分离，拓宽了多金属氧酸盐在生物分离中的应用。
关键词：血红蛋白；固相萃取；硅钨酸盐；复合材料；双氢氧化物
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2022）--
Selective Adsorption of Hemoglobin in Human Whole Blood with Silicotungstate-Layered Double Hydroxides Composite CHEN Qing, WANG Meng-meng, ZHANG Yang, ZHANG Dan-dan* (Department of Sanitary Inspection, School of Public Health, Shenyang Medical College, Shenyang 110034, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: A compositie of silicotungstate-layered double hydroxides ZnAl-SiW10Zr was prepared by using electrostatic and hydrogen bonding interactions at neutral conditions. The ZnAl-SiW10Zr composite was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectra (EDXS), fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). On the basis of the affinity interaction between metal ion of ZnAl-SiW10Zr composite and hemoglobin (Hb), the ZnAl-SiW10Zr composite could adsorb Hb selectivity. At pH 7.0, 0.5 mg ZnAl-SiW10Zr resulted in the adsorption efficiency of 92% for 1 mL 100 μg/mL hemoglobin. The adsorption behavior of Hb on the composite fitted the Langmuir model with an adsorption capacity of 760 mg/g. The adsorbed Hb could be eluted by the SDS solution (0.1 mol/L) providing recoveries of 91%. The ZnAl-SiW10Zr composite has been used for selectivity separating Hb from human whole blood, and the results of SDS-polyacrylamide gel electrophoresis assay indicated that the Hb with high purity was obtained. It could be expanded the application of polyoxometalates in bioseparation attributing to the application of polyoxometalates composite in protein separation and purification.
Key words: hemoglobin; solid phase extraction; silicotungstate; composite; layered double hydroxides
引用本文：陈晴, 王蒙蒙, 张杨, 等. 硅钨酸盐-双氢氧化物复合材料选择性分离人全血中血红蛋白[J]. 化学试剂, 2022, 44(10):1445 -1450 .
基于二氧化锰纳米片-纳米金共振光散射法测定碱性磷酸酶
邹明静*，马凯霞，马雪峰
（菏泽医学专科学校 中心实验室，山东 菏泽 274030）
摘要：建立了检测血清碱性磷酸酶（ALP）活性的新方法。以ALP催化底物L-抗坏血酸-2-磷酸三钠盐（AAP）水解可生成抗坏血酸（AA），AA可将二氧化锰（MnO2）纳米片还原为Mn2+，导致聚集在MnO2纳米片表面的纳米金释放至溶液中，体系在620 nm处的共振光散射强度减弱。结果表明，ALP浓度在0.25～35 mIU/mL范围内与散射光强度的降低值Δ I620nm呈现对数相关，检出限（3σ）为0.19 mIU/mL，已用于血清碱性磷酸酶的检测，检测结果与临床检验分光光度法呈现良好的相关性。
关键词：纳米金；二氧化锰；纳米片；碱性磷酸酶；共振光散射
中图分类号：O656.3 文献标识码：A 文章编号：0258-3283（2022）--
Resonance Light Scattering Spectral Assay of Alkaline Phosphatase Based on Manganese Dioxide Nanosheets and Gold Nanoparticles ZOU Ming-jing*, MA Kai-xia, MA Xue-feng (Central Laboratory, Heze Medical College, Heze 274030, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：The new method was used to detect alkaline phosphatase (ALP) in the serum. ALP catalyzed the hydrolysis of L-ascorbate-2-phosphate (AAP) to ascorbic acid (AA), which reduced manganese dioxide (MnO2) to Mn2 +, resulting in the release of gold nanoparticles on the surface of nanosheets into the solution and the decreasing resonance light scattering intensity at 620 nm. Furthermore, the decreasing intensity Δ I620nm was logarithmically related to the concentration of ALP in the range of 0.25 to 35 mIU/mL, with the detection limit (3σ) of 0.19 mIU·mL-1, which was used to detect ALP in the serum, a good correlation with spectrophotometry in the clinical laboratory.
Key words：gold nanoparticles; manganese dioxide; nanosheets; alkaline phosphatase; resonant light scattering
引用本文：邹明静，马凯霞，马雪峰. 基于二氧化锰纳米片-纳米金共振光散射法测定碱性磷酸酶[J]. 化学试剂，2022, 44(10):1451 -1456 .
海藻酸钠/聚乙烯亚胺复合材料对Pb(II)的吸附性能研究
付秋平，张海润，罗云，娄杰，石登红，莫昌琍，罗军，严伟*
（贵阳学院 化学与材料工程学院，贵阳 550005）
摘要：以海藻酸钠和聚乙烯亚胺为原料，制备海藻酸钠/聚乙烯亚胺（SA/PEI）复合材料，研究其对水中Pb(II)的吸附去除性能。系统研究了各因素对SA/PEI吸附Pb(II)效果的影响。结果表明，SA/PEI对Pb(II)的吸附量与Pb(II)初始浓度正相关，在360 min达到吸附平衡。吸附过程符合拟二级动力学和Langmuir等温吸附模型。在303.15 K时，Langmuir等温吸附模型拟合得到的最大吸附量为316.46 mg/g。第6次使用的SA/PEI对Pb(II)仍表现出较好的去除效果。
关键词：海藻酸钠；聚乙烯亚胺；吸附；Pb(II)；水处理
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2022）--
Adsorption of Pb(II) by Sodium Alginate/Polyethyleneimine Composite Materials FU Qiu-ping, ZHANG Hai-run, LUO Yun, LOU Jie, SHI Deng-hong, MO Chang-li, LUO Jun, YAN Wei* (College of Chemistry and Materials Engineering, Guiyang University, Guiyang 550005, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: Sodium alginate/polyethyleneimine (SA/PEI) composite materials were prepared with sodium alginate (SA) and polyethyleneimine (PEI) as raw materials. The adsorption and removal performance of Pb(II) from water by gel spheres was studied. The effects of various factors on the adsorption of Pb(II) by SA/PEI were systematically studied. The results showed that the adsorption capacity of Pb(II) on SA/PEI were positively correlated with the initial concentration of Pb(II), and the adsorption equilibrium was reached in 360 min. The adsorption process accords with pseudo-second-order kinetics and Langmuir isothermal adsorption model. At 303.15 K, the maximum adsorption capacity fitted by Langmuir isothermal adsorption model was 316.46 mg/g. The sixth application of SA/PEI still showed a good removal effect on Pb(II).
Key words: sodium alginate; polyethyleneimine; adsorption; Pb(II)
引用本文：付秋平, 张海润, 罗云, 等. 海藻酸钠/聚乙烯亚胺复合材料对Pb(II)的吸附性能研究[J]. 化学试剂, 2022, 44（10）：1457 -1462 .
基于1,4-萘二膦酸钴化合物的合成、晶体结构及磁性质
徐艳*，王宣，王肖阳，崔磊*
(宿迁学院 信息工程学院 材料工程系，江苏 宿迁 223800)
摘要：采用水热法合成了基于1,4-萘二膦酸的新颖钴化合物：[Co4(1,4-ndpaH)2(1,4-ndpaH2)(1,4-ndpa)](1,3-dpp)2·6H2O (1) （1,4-ndpaH4 = 1,4-萘二膦酸，1,3-dpp = 1, 3- 二（4-吡啶）丙烷）。并通过单晶X-射线衍射、元素分析、红外光谱、粉末X-射线衍射及热重分析表征了化合物的结构和热稳定性。单晶结构分析表明，化合物1具有三维开放骨架结构，其中包含有一维孔道，孔道壁由萘环连接共用顶点的四面体{CoO4}和{PO3C}所组成，辅助配体1,3-二（4-吡啶）丙烷未参与配位，填充在一维孔道中，并和结晶水分子产生氢键作用，再通过范德华分子间作用力固定于三维骨架中。化合物1的磁性研究表明CoII离子之间存在反铁磁相互作用。
关键词：钴膦酸盐；晶体结构；磁性质；水热法；开放结构
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2022）--
Cobalt phosphonates based on 1,4-naphthalenediphosphonic acid: Synthesis, Structure and Magnetic Properties XU Yan*, WANG Xuan, WANG Xiao-yang, CUI Lei* (Department of Materials Engineering, Institute of Information Engineering, Suqian University, Suqian 223800, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：A new cobalt phosphate based on 1,4-naphthalene diphosphonic acid was synthesized by hydrothermal method: [Co4(1,4-ndpaH)2(1,4-ndpaH2)(1,4-ndpa)](1,3-dpp)2·6H2O (1) (1,4-ndpaH4 = 1,4-naphthalene diphosphonic acid, 1,3-dpp = 1,3-bis (4-pyridyl) propane).The crystal structure and thermal stability of the compound 1 was characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis. Single crystal structure analysis showed that compound 1 had a three-dimensional open framework structure, which contained a one-dimensional channel. The channel wall was composed of corner-sharing {CoO4} and {PO3C} tetrahedra connected by naphthalene rings. The auxiliary ligand 1, 3-bis (4-pyridyl) propane filled in the one-dimensional channel without participating in coordination, and formed hydrogen bond with lattice water molecules. The van der Waals intermolecular forces are fixed in the three-dimensional skeleton. Magnetic studies of compound 1 indicate that antiferromagnetic interactions exist between CoII ions.
Key words：Cobalt phosphonate; crystal structure; magnetic properties
引用本文：徐艳，王宣，王肖阳，等. 基于1,4-萘二膦酸钴化合物的合成、晶体结构及磁性质[J]. 化学试剂，2022，44(10): 1463-1467.
铁酸钴纳米团簇模拟酶的制备及其应用研究
宋玉哲1,2，左显维*1,2，何永成1,2，刘一丹1,2，王焱1,2，何欣1,2，韩根亮1,2
（(甘肃省科学院 传感技术研究所 甘肃省传感器与传感技术重点实验室ꎬ甘肃 兰州 730000）
摘要：利用微波多元醇法制备了具有大比表面积的铁酸钴纳米团簇，通过透射电子显微镜（TEM）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、振动样品磁强计（VSM）等表征手段对其形貌、结构和性能进行了表征和分析，深入研究了其模拟氧化物酶的催化性能，并利用该性能建立了一种简单灵敏且能可视化检测食品添加剂亚硫酸盐的新方法。在最优条件下，该方法对亚硫酸根离子（SO32-）的检测线性范围在10.0 ~ 500.0 µmol/L之间，检测限为0.8 µmol/L，实际食品样品的加标回收率为96.9% ~ 103.9%，能够满足快速简便和可视化检测食品添加剂的实际要求，其有望在食品安全领域得到广泛应用。
关键词：纳米模拟酶；铁酸钴纳米团簇；模拟氧化物酶；亚硫酸盐；食品添加剂
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of Cobalt Ferrite Nano-Enzyme Mimetics and Its Application SONG Yu-zhe1,2, ZUO Xian-wei*1,2, HE Yong-cheng1,2, LIU Yi-dan1,2, WANG Yan1,2, He Xin1,2, HAN Gen-liang1,2 (1. Key Laboratory of Sensor and Sensing Technology of Gansu Province, Lanzhou 730000, China; 2. Institute of Sensor Technology, Gansu Academy of Sciences, Lanzhou 730000, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: In this work, cobalt ferrite nanoclusters (CoFe2O4NCs) with large specific surface area were prepared by microwave-assisted polyol method, which have intrinsic oxidase-like activity. The obtained samples were characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM) and X-Ray powder diffraction (XRD) in the morphology and structure, and by vibrating samples magnetometer (VSM) in magnetism. The intrinsic oxidase-like activity of the samples was investigated, and then a colormelric approach to detect sulfite in food was established base on the oxide enzyme catalytic property of CoFe2O4NCs. Under the optimal detection conditions, the concentration of sulfite (SO32-) in the range of 10.0~500.0 µmol/L has a good linear relationship with the change of absorbance of the detection system, and the detection limit is 0.8 µmol/L.The recovery for food samples was in the range of 96.9~103.9%. The main advantage of this method could meet the practical requirements of fast, convenient and visual detection of food additives. It is expected to be widely used in the field of food safety.
Key words: nano-enzyme mimetics; cobalt ferrite nanoclusters; oxidase-like activity; sulfites; food addition.
引用本文：宋玉哲, 左显维, 何永成, 等.铁酸钴纳米团簇模拟酶的制备及其应用研究[J]. 化学试剂, 2022, 44(10 ):1468 -1474 .
赤芝、紫芝孢子粉总三萜的提取工艺优化
崔馨戈1a,b,c，张静1a,b,c，袁抒捷1a,b,c，李思雨1a,b,c，祝朋玲1a,b,c，王雯1a,b,c，阚家义2，周俊3，彭灿*1
（1. 安徽中医药大学 a.药学院；b. 安徽道地中药材品质提升协同创新中心；c. 中药复方安徽省重点实验室；d. 安徽省中医药科学院药物制剂研究所；e. 药物制剂技术与应用安徽省重点实验室；f. 现代药物制剂安徽省工程技术研究中心 安徽中医药大学，安徽 合肥 230012；2. 安徽省食品药品检验研究院，安徽 合肥 230051；3. 安徽黄山云乐灵芝有限公司，安徽 宣城 242600）
摘要：采用响应面法优化赤芝、紫芝孢子粉超声提取工艺。以孢子粉中总三萜得率为评价指标，运用紫外-可见分光光度法，考察溶剂、料液比、提取时间、提取温度、乙醇体积分数五个因素对赤芝、紫芝孢子粉超声提取总三萜的影响，以单因素试验为基础，采用Box-Behnken响应面法优化得到最优提取工艺。赤芝孢子粉超声提取最优方案：提取溶剂为无水乙醇，料液比1:65（g/mL），提取时间60 min，提取温度42 oC；紫芝孢子粉超声提取最优方案：无水乙醇为提取溶剂，料液比1:50（g/mL），提取时间42 min，提取温度40 oC；且二者三萜类成分含量有明显差别。验证实验结果表明，赤芝、紫芝孢子粉中总三萜得率的平均值分别为14.03%、10.20%，与模型预测值的RSD仅为0.94%、1.24%，表明优化所得的提取工艺真实可靠。优化得到的提取工艺操作简单，合理可靠，为赤芝、紫芝孢子粉三萜类成分的进一步研究以及食品药品的开发利用提供理论依据和参考。
关键词：赤芝孢子粉；紫芝孢子粉；超声提取；总三萜得率；响应面法
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2022）--
Optimization of Total Triterpenoids Extraction from Ganoderma Lucidum and Ganoderma Sinense Spore Powder CUI Xin-ge1a,b,c, ZHANG Jing1a,b,c, YUAN Shu-jie1a,b,c, LI Si-yu1a,b,c, ZHU Peng-ling1a,b,c, WANG Wen1a,b,c, KAN Jia-yi2, ZHOU Jun3, PENG Can*1 (1a. School of Pharmacy, Anhui University of Chinese Medicine; 1b. Synergetic Innovation Center of Anhui Authentic Chinese Medicine Quality Improvement; 1c. Anhui Province Key Laboratory of Chinese Medicinal Formula; 1d. Institute of Pharmaceutics, Anhui Academy of Chinese Medicine; 1e. Anhui Province Key Laboratory of Pharmaceutical Preparation Technology and Application; 1f. Engineering Technology Research Center of Modern Pharmaceutical Preparation, Anhui Hefei 230012, China; 2. Anhui Institutes for Food and Drug Control, Anhui Hefei 230051, China; 3. Anhui Huangshan Yunle Ganoderma Lucidum Co., Ltd, Anhui, Xuancheng 242600, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: To optimize the ultrasonic extraction method of total triterpenoids from Ganoderma lucidum and Ganoderma sinense spore powder by Response Surface Methodology. With the extraction rate of total triterpenoids in spore powder as the evaluation index, the effects of five factors including extraction solvent type, solid-liquid ratio, extraction time, extraction temperature and ethanol volume fraction on the ultrasonic extraction of total triterpenoids from Ganoderma lucidum and Ganoderma sinense spore powder were studied by UV-vis spectrophotometry. On the basis of single factor experiment, the ultrasonic extraction method was optimized by Box-Behnken Response Surface Methodology. The best ultrasonic extraction conditions of Ganoderma lucidum spore powder were as follows: ethanol volume fraction of 100%, solid-liquid ratio of 1:65, extraction time of 60 min and extraction temperature of 42 °C. For Ganoderma sinense spore powder, the best ultrasonic extraction methods were as follows: ethanol volume fraction of 100%, solid-liquid ratio of 1:50, extraction time of 42 min and extraction temperature of 40 °C. In addition, the content of total triterpenoids between this two varieties was significantly different. In the verification experiment, the average extraction rate of total triterpenoids in Ganoderma lucidum and Ganoderma sinense spore powder were 14.03% and 10.20%, and the RSD with the predicted value of the model was only 0.94% and 1.24%, indicating that the optimized extraction process was reliable. The optimized extraction method was simple, reasonable and reliable, which provided a theoretical basis and reference for further research on triterpenoids and the development of utilization Ganoderma lucidum and Ganoderma sinense spore powder for food and drug.
Key words: Ganoderma lucidum spore powder; Ganoderma sinense spore powder; ultrasonic extraction; extraction rate of total triterpenoids; response surface methodology
引用本文：崔馨戈, 张静, 袁抒捷, 等. 赤芝、紫芝孢子粉总三萜的提取工艺优化[J]. 化学试剂, 2022, 44(10):1475-1481.
金属-有机骨架/石墨烯基复合材料在电化学领域的应用
高春1，张松涛*2，庞欢*2,3
（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：金属有机骨架材料(Metal-organic frameworks，MOFs)作为一种新型多孔晶体材料，具有大比表面积、高孔隙率、孔结构和形态特征可调等优点。但是传统MOFs的稳定性和导电性较差，限制了其应用。利用具有丰富官能团的石墨烯基材料作为模板生长MOF颗粒，不仅可以缓解MOF导电性能差和结构不稳定的问题，而且可以避免石墨烯片间的聚集和堆积现象。由于衍生物的结构和组成可调，MOF衍生物/石墨烯材料可以广泛应用于多个领域。本文综述了近年来MOF/石墨烯复合材料在电化学领域的应用，并指出了存在的问题及以后的发展方向。
关键词: 金属有机骨架；石墨烯；复合材料；性能；应用
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2022）--
Application of metal-organic framwork/graphene-based composites in electrochemical fields GAO Chun1, ZHANG Song-tao*2, PANG Huan *2,3 (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), Huaxue Shiji, 2022, 44( ), ～
Abstract: As a new kind of porous crystal materials, metal-organic frameworks (MOFs) have the advantages of large specific surface area, high porosity, adjustable pore structure and morphological characteristics. However, the poor stability and conductivity of traditional MOFs limit their application. Using graphene-based materials with rich functional groups as templates to grow MOF particles can not only alleviate the problems of poor electrical conductivity and unstable structure of MOF, but also avoid aggregation and accumulation between graphene sheets. Due to the adjustable structure and composition of the derivatives, MOF/graphene-derived materials can be widely used in many fields. In this paper, the recent application of MOF/graphene composites in the field of electrochemistry are reviewed, and the existing problems and future development are pointed out.
Key words: metal-organic frameworks; graphene; composites; properties; application
引用本文：高春，张松涛，庞欢. 金属-有机骨架/石墨烯基复合材料在电化学领域的应用[J]. 化学试剂,2022,44(10):1482-1490.
MnOOH@g-C3N4的制备及其活化PMS降解苯酚的研究
陈文凯，曹宇，赵焕新*，刘欣悦，刘宇琪，王妍，张志傲
（沈阳化工大学 环境与安全工程学院，辽宁 沈阳 110142）
摘要：采用水热法制备了MnOOH@g-C3N4复合催化剂用于活化PMS降解苯酚。当MnOOH的负载量为50 wt.%时复合催化剂表现出最佳的催化活性。当MnOOH@g-C3N4投加量为0.5 g/L，PMS浓度为1.25 mmol/L时MnOOH@g-C3N4/PMS体系在30 min对23.5 mg/L苯酚去除率可达100%，反应活化能为31.1 kJ/mol。MnOOH@g-C3N4在弱酸或弱碱性(pH 5或pH 9)环境下具有最佳的催化性能，且在pH 3～11范围内表现出良好的活性。Cl-、HCO3-、NO3-以及H2PO4-四种常见的无机阴离子对MnOOH@g-C3N4/PMS体系降解苯酚的影响较小。自由基猝灭实验证实高价金属氧物种MnⅤ(O)/MnⅣ(O)为MnOOH@g-C3N4/PMS体系的主要活性氧物种，O2·-和1O2也是参与苯酚降解的活性物种。
关键词：高级氧化技术；MnOOH@g-C3N4；PMS；苯酚；高价金属氧物种
中图分类号：X703.1 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis and application of MnOOH@g-C3N4 composite as activator of peroxymonosulfate for phenol degradation CHEN Wen-kai, CAO Yu, ZHAO Huan-xin*, LIU Xin-yue, LIU Yu-qi, WANG Yan, ZHANG Zhi-ao (College of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: Composite catalyst MnOOH@g-C3N4 was synthesized by hydrothermal reaction, and it was used to activate PMS for phenol degradation. MnOOH@g-C3N4 exhibited the best catalytic activity when the loading of MnOOH was 50 wt%. 23.5 mg/L Phenol could be completely degraded in 30 min by MnOOH@g-C3N4/PMS system with the activation energy of 31.1 kJ/mol under conditions of 0.5 g/L MnOOH@g-C3N4 and 1.25 mmol/L PMS. MnOOH@g-C3N4 has the best catalytic performance in weak acid or weak alkaline environment (pH 5 or pH 9), and shows great activity in the range of pH 3～11. Four common inorganic anion Cl-, HCO3-, NO3- and H2PO4- have little influence on the degradation of phenol by MnOOH@g-C3N4/PMS systems. The radical quenching experiments confirmed that the high-valence metal oxygen species MnⅤ(O)/MnⅣ(O) was the main reactive oxygen species in the MnOOH@g-C3N4/PMS system, and O2·- and 1O2 also played a significant role in the degradation of phenol.
Key words: advanced oxidation processes; MnOOH@g-C3N4; PMS; phenol; high-valence metal oxygen species
引用本文：陈文凯，曹宇，赵焕新，等. MnOOH@g-C3N4的制备及其活化PMS降解苯酚的研究[J]. 化学试剂，2022, 44(10 ):1491-1499.
高温灰化-酸溶-离子选择性电极法测定生态地球化学评价生物样品中的痕量氟
双龙
（内蒙古岩石矿物综合分析重点实验室 内蒙古自治区矿产实验研究所，内蒙古 呼和浩特 010031）
摘要：建立了高温灰化、酸溶去除生物样品中的复杂有机组分、离子选择性电极法测定生态地球化学评价生物样品中的痕量氟的方法。讨论了样品氟固定试剂的选择和用量、灰化温度、灰化时间等对氟元素测定结果的影响，试样经5 mL、100 g/L硝酸镁溶液固定，电热板蒸干和炭化，再经箱式电阻炉在600 ℃，灼烧1.5 h灰化后，采用盐酸（1+10）酸解提取，加入乙酸钠溶液和柠檬酸钠溶液，在该体系中以离子选择性电极法对样品中的氟元素进行测定。以电极电位值为纵坐标，标准系列溶液中氟离子浓度对数的负数为横坐标，绘制标准曲线，氟标准系列溶液浓度在0.02～4.0 μg/mL范围内呈现良好的线性关系，氟标准曲线方程为y=56.449x+219.05，相关系数(R2) =0.9998，根据试样电位值求得试样中的氟含量。方法检出限0.85 μg/g。选用12种不同种类国家一级标准物质进行验证，测定值与认定基本一致，相对标准偏差(RSD)均≤8.9%,(n=12)，相对误差(RE)均≤2.9%，各种标准物质氟元素测定t值均小于2.20（t0.05,11值），该方法测定结果与标准物质标准值具有较好的一致性，且无显著性差异，该方法可用于生态地球化学评价项目中不同种类生物样品中氟元素的测定。
关键词：高温灰化；酸溶；离子选择性电极法；氟；生态地球化学；生物样品
中国分类号：O657.15 文献标识码：A 文章编号：0258-3283（2022）--
Determination of trace fluorine in biological samples for eco-geochemical assessment by ion selective electrode method with high temperature ashing acid digestion SHUANG Long（Inner Mongolia Minerals Experiment Research Institute, Inner Mongolia Key Laboratory of Rock Mineral Comprehensive Analysis, Hohhot 010031,China）, Huaxue Shiji, 2022, 44( ), ～
Abstract: The method for determining trace fluorine in biological samples for eco-geochemical assessment based on high temperature ashing, acid dissolution and ion selective electrode was established. The effects of the selection and dosage of sample fluorine fixing reagent, ashing temperature and ashing time on the determination results of fluorine were discussed. The sample was fixed with 5 mL and 100 g/L magnesium nitrate solution, evaporated and carbonized by electric heating plate, and then burned in a box resistance furnace at 600 ℃ for 1.5 h. After ashing, it was extracted by hydrochloric acid (1+10), and sodium acetate solution and sodium citrate solution were added, in this system, the fluorine element in the sample was determined by ion selective electrode method. Take the electrode potential value as the ordinate and the negative number of the logarithm of fluorine ion concentration in the standard series solution as the abscissa to draw the standard curve. The concentration of fluorine standard series solution showed a good linear relationship in the range of 0.02 ～ 4.0 μg/mL. The fluorine standard curve equation is y = 56.449x + 219.05, and the correlation coefficient (R2) = 0.9998. The fluorine content in the sample is obtained according to the potential value of the sample. The detection limit of the method is 0.85 μg/g.12 different kinds of national first-class reference materials are selected for verification. The measured values were basically consistent with the certified values, the relative standard deviation (RSD) were less than 8.9%, (n=12), the relative error (RE) were less than 2.9%, and the measured T values of fluorine elements of various reference materials were less than 2.20 (t0.05,11). The measured results of this method are in good agreement with the certified values of reference materials, and there is no significant difference. The method can be used for the determination of fluorine in different kinds of biological samples in the ecological geochemical assessment projects.
Key words：high temperature ashing; acid soluble; ion selective electrode method; fluorine; ecological geochemistry; biological sample
引用本文：双龙. 高温灰化-酸溶-离子选择性电极法测定生态地球化学评价生物样品中的痕量氟[J]. 化学试剂,2022，44（10）：1500-1505..
QuEChERS-GC-MS/MS法测定新疆伽师瓜中74种农药残留
阿不力米提·玉麦尔1，曹续2，崔智超1，阿卜杜拉·玉苏普*1
（1. 喀什大学 化学与环境科学学院，新疆特色药食用植物资源化学实验室，新疆 喀什 844000；
2. 新疆维吾尔自治区分析测试研究院，新疆 乌鲁木齐 830000）
摘要：建立新疆伽师瓜中74种农药残留的快速测定方法。新疆伽师瓜经优化后的QuEChERS技术提取和净化，根据70种农药残留特征碎片离子建立气质联用条件，在多反应监测模式（SRM）下进行检测，基质匹配外标法定量分析。结果表明：在0～1.0 μg/mL浓度范围内，线性关系良好（R2 ＞ 0.995），检出限为：0.005～0.02 mg/kg，回收率为70.1%～110.2%，相对标准偏差（RSD）为0.3%～12.6%（n = 5），采用SPSS 19.0软件，以P ＜ 0.05为差异有统计学意义。研究表明，该方法简便、快捷，溶剂消耗量少，灵敏度高，适用于新疆伽师瓜此类多色素含糖量高、干扰大的物质中农药残留检测。
关键词：新疆伽师瓜；QuEChERS；三重四极杆-气质联用；外标法；农药残留
中图分类号: O657.99 文章标识码：A 文章编号：0258-3283（2022）--
Determination of 74 Types of Pesticide Residues in Xinjiang Jiashi Melon by QuEChERS Gas Chromatography-Triple Quadrupole Mass Spectrometry YUMAIER Abulimiti1, CAO Xu2，CUI Zhi-chao1，YUSUF Abdullah*1 (1. Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry, College of Chemistry and Environmental Science, Kashi University, Kashi 844000, China; 2. Xinjiang Academy of Analysis and Testing, Urumqi, 830000, China), Huaxue Shiji, 2022, 44（ ），～
Abstract: In this paper we established a rapid method for the determination of 74 types of pesticide residues in Xinjiang Jiashi melon. Xinjiang Jiashi melon was extracted and purified by the optimized QuEChERS technology. The GC-MS conditions were established according to the characteristic fragment ions of 70 pesticide residues. The detection was carried out under the multi reaction monitoring mode (SRM), and the matrix matching external standard method was used for quantitative analysis. The results showed that in the concentration range of 0~1.0 μg·mL-1, the linear relationship was good (R2 > 0.995), the detection limit was 0.005 ~ 0.02 mg·kg-1, the recovery was 70.1% ~ 110.2%, and the relative standard deviation (RSD) was 0.3%~12.6% (n = 5). Using SPSS 19.0 software, the difference was statistically significant with P < 0.05. The method is simple, rapid, low solvent consumption and high sensitivity. It is suitable for the detection of pesticide residues in Xinjiang Jiashi melon, which has high sugar content and large interference.
Key words: Xinjiang Jiashi melon; QuEChERS; gas chromatography-triple quadrupole mass spectrometry; pesticide residues
引用本文：阿不力米提·玉麦尔, 曹续, 崔智超, 等. QuEChERS-GC-MS/MS法测定新疆伽师瓜中74种农药残留[J]. 化学试剂, 2022, 44（10）：1506 -1512 .
高效液相色谱法同时测定白芷药材中的9种香豆素成分及其质量分析
刘志荣1,2，张明童*1,2，张平1,2，李冬华1,2，马潇1,2,3，谢楠1,2,3，郭朝晖1,2,3
(1. 甘肃省药品检验研究院，甘肃 兰州 730070；2. 甘肃省中藏药检验检测技术工程实验室，甘肃 兰州 730070；3. 中药材及饮片质量控制重点实验室，甘肃 兰州 730070)
摘要：建立了白芷9种香豆素成分的定量测定方法，并用于化学统计分析，为白芷药材的质量控制提供参考。采用高效液相色谱法（HPLC）同时分析4个不同省份的23批白芷样品中9种香豆素成分，采用单因素方差分析（ANOVA）分析未硫熏和硫熏样品中9种香豆素成分的差异。采用系统聚类分析（HCA）和主成分分析（PCA）进行化学模式识别分析，对不同产地白芷药材和硫磺熏蒸情况进行分析。ANOVA结果表明硫熏和未硫熏样品中8种化学成分含量差异显著（P < 0.05），硫磺熏蒸对白芷药材质量有较大影响。HCA和PCA结果均显示，23批白芷可分为3类，其中，硫熏样品聚为一类，河南、河北未硫熏样品聚为一类，四川、安徽未硫熏样品聚为一类。该实验所建立的含量测定结合化学统计学分析方法可用于白芷药材的综合质量评价。
关键词：高效液相色谱；白芷；化学统计学；单因素方差分析；系统聚类分析；主成分分析
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2022）--
Simultaneous Determination and Quality Analysis of Nine Coumarins in Angelica Dahurica by High Performance Liquid Chromatography LIU Zhi-rong1,2, ZHANG Ming-tong*1,2, ZHANG Ping1,2, LI Dong-hua1,2, MA Xiao1,2,3, XIE Nan1,2,3, GUO Zhao-hui1,2,3 (1. GanSu Provincial Institute of Drug Control, Lanzhou 730070, China; 2. GanSu Tibetan Medicine Examination Engineering Laboratory, Lanzhou 730070, China; 3. NMPA Key Laboratory for Quality Control of Traditional Chinese Medicine (Chinese Materia Medica and Prepared Slices), Lanzhou 730070, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：To develop a quantitative method for simultaneous determination of nine coumarins of Angelica dahurica, which was used for chemical statistical analysis, so as to provide reference for the quality control of Angelica dahurica. Nine coumarins of 23 batches of Angelica dahurica originated from four provinces were analyzed by high performance liquid chromatography (HPLC). Then one-way analysis of variance (ANOVA) was used to analyze the differences of nine coumarins between sulfur fumigation and no-sulfur fumigation samples. Hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to identify chemical patterns, which were able to identify the origins and smouldering sulphur of samples. The results of ANOVA showed that the contents of 8 chemical components were significant different (P < 0.05) between the sulfur fumigated samples and unfumigated samples, so sulfur fumigation had a great influence on the quality of Angelica dahurica based on the results of ANOVA. Furthermore, the results of HCA and PCA showed that 23 batches of Angelica Dahurica could be divided into three categories, and sulfur fumigate samples were clustered into one category, no-sulfur fumigate samples collected from Henan Province and Hebei Province were clustered into one category, and no-sulfur fumigate samples collected from Sichuan Province and Anhui Province were clustered into one category. The quantitative determination combined with chemical statistics method can be used in the quality control and evaluation of Angelica dahurica.
Key words: high performance liquid chromatography (HPLC); Angelica dahurica; chemical statistics; one-way analysis of variance (ANOVA); hierarchical cluster analysis (HCA); principal component analysis (PCA)
引用本文：刘志荣, 张明童, 张平, 等. 高效液相色谱法同时测定白芷药材中的9种香豆素成分及其质量分析[J]. 化学试剂, 2022, 44(10):1513 -1518 .
高华a，刘正a，李舂龙*a,b,c
（北方民族大学 a.化学与化学工程学院，b.国家民委化工技术基础重点实验室，c.宁夏太阳能化学转化技术重点实验室，宁夏 银川 750021）
摘要：以环己二胺为起始原料，设计并合成了一种侧基含有环己二胺衍生物的新型螺旋聚合物，这种螺旋负载催化剂用于催化Aldol反应，显示出较好的催化效果。当以氯仿为溶剂，4-甲基苯磺酸为助催化剂时，环己酮与2-三氟甲基苯甲醛反应的对映体过量（e.e.）值最高为92%，非对映异构体比率（dr）值为24/1，显示了环己二胺类负载催化剂具有较高的催化活性，为后续其他反应类型的探索提供了思路，并且这种螺旋聚合物催化剂表现出增强的立体选择性，在不对称催化方面具有很大的前景。
关键词：环己二胺；螺旋聚合物；负载催化剂；不对称催化；Aldol反应
中图分类号: O629 文献标识码: A 文章编号：0258-3283（2022）--
Preparation and Performance of Cyclohexanediamine Supported Catalyst GAO Huaa, LIU Zhenga, LI Chong-long*a,b,c (a. College of Chemistry and Chemical Engineering; b. National Civil Affairs Commission Key Laboratory of Chemical Technology; c. Ningxia Key Laboratory of Solar Energy Chemical Conversion Technology, North Minzu University, Yinchuan 750021, China), Huaxue Shiji, 2022, 44( ), ～
Abstract: In this paper, a novel helical polymer with a pendant cyclohexanediamine derivative in side group using Cyclohexanediamine as a starting material was designed and synthesized, which was used to catalyze Aldol reaction and showed good catalytic effect. When chloroform was used as solvent and 4-methylbenzenesulfonic acid was used as cocatalyst, the highest enantiomeric excess (e.e.) value of 92% and diastereomeric ratio (dr) value of 24/1 for cyclohexanone and 2-(trifluoromethyl)benzaldehyde reaction revealed that the cyclohexanediamine supported catalyst possessed high catalytic activity, which provided ideas for the subsequent exploration of other reaction types, and the helical polymer catalyst exhibited enhanced stereoselectivity and was highly promising in asymmetric catalysis.
Key words: cyclohexanediamine; helical polymers; supported catalyst; asymmetric catalysis; Aldol reactions
引用本文：高华, 刘正, 李舂龙. 环己二胺类负载催化剂的制备及性能研究[J]. 化学试剂, 2022, 44(10):1519 -1524 .
电化学合成C-3位芳酰基取代的咪唑并[1,2-a]吡啶衍生物
张杰1，耿梦囡，张玉凤，孙茹萍，张建
（江苏农牧科技职业学院 动物药学院，江苏 泰州 225300）
摘要：以廉价易得的芳酰基甲酸作为芳酰基源，2-芳基咪唑并[1,2-a]吡啶为底物，无需过渡金属催化剂和氧化剂，在电化学条件下，通过脱羧实现了咪唑并[1,2-a]吡啶C-3位碳氢键的芳酰基化反应，以良好的产率成功构建了一系列C-3位芳酰基取代的咪唑并[1,2-a]吡啶化合物。利用核磁氢谱、核磁碳谱、高分辨质谱对产物进行了结构表征。该方法条件温和绿色，简便高效，底物适用范围广，官能团耐受性较好，为C-3位芳酰基取代的咪唑并[1,2-a]吡啶衍生物的合成提供了新途径。
关键词：电化学合成；芳酰基化；咪唑并[1,2-a]吡啶；脱羧；绿色方法
中图分类号：O621.25 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis of C-3 Aroyl Substituted Imidazo[1,2-a]pyridines via Electrochemical Oxidative ZHANG Jie*, GENG Meng-nan, ZHANG Yu-feng, SUN Ru-ping, ZHANG Jian (School of Animal Pharmaceutical, Jiangsu Agri-animal Husbandry Vocational College, Taizhou 225300, China), Huaxue Shiji, 2022, 44（ ），～
Abstract: Using cheap and readily available arylglyoxylic acids as aroyl source, a series of C-3 aroyl substituted imidazo[1,2-a]pyridines were successfully synthesized through electrochemical decarboxylation and oxidative C-H aroylation of imidazo[1,2-a]pyridines under transition-metal-free and oxidant-free conditions. The characterization analysis of product structures was depended on NMR and HRMS spectra analyses. This method used electricity as the reaction driving force and has advantages of high yields, mild reaction conditions, simple operation, broad substrate range and good tolerance of functional groups, which provides a new approach for constructing C-3 aroyl substituted imidazo[1,2-a]pyridines.
Key words: electrochemical synthesis; aroylation; imidazo[1,2-a]pyridines; decarboxylation; green method
引用本文：张杰, 耿梦囡, 张玉凤, 等. 电化学合成C-3位芳酰基取代的咪唑并[1,2-a]吡啶衍生物[J]. 化学试剂, 2022, 44（10）：1525-1531 .
非均相条件下茴脑氧化制备4-甲氧基肉桂醛
贾均松，唐海涛，潘英明*
(广西师范大学 化学与药学学院 省部共建药用资源化学与药物分子工程国家重点实验室，广西 桂林 541004)
摘要：为了开发天然产物反式茴脑的绿色化利用，实现将反式茴脑转化为更有价值的产品。我们报道了一种高度稳定且具有高活性的非均相催化剂PdCl2@POL-PPh3，在非均相条件下实现了天然产物反式茴脑以88%的分离产率选择性氧化为4-甲氧基肉桂醛。避免了副产物茴香醛和茴香酸的生成，使得该转化更具有原子经济性。同时在标准条件下实现该反应的克级转化。实验证明非均相催化剂PdCl2@POL-PPh3至少可以循环使用5次，表征数据证明了催化剂在循环5次无明显失活现象，为天然产物茴脑的开发应用打下了基础。
关键词：非均相催化；反式茴脑；选择性氧化；循环利用；克级转化
中图分类号：O6 文献标识码：A 文章编号：0258-3283（2022）--
Preparation of 4-methoxycinnamaldehyde by oxidation of trans-Anethole under heterogeneous conditions JIA Jun-song, TANG Hai-tao, PAN Ying-ming* (State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：In order to develop the green utilization of natural product trans-anethole, and realize the conversion of trans-anethole into more valuable products. We report a highly stable and highly active heterogeneous catalyst, PdCl2@POL-PPh3, which enables the selective oxidation of the natural product trans-anethole to 4-methoxycinnamaldehyde in an isolated yield of 88% under heterogeneous conditions. The formation of by-products anisaldehyde and anisic acid is avoided, making the transformation more atom-economical. At the same time, gram-scale conversion of the reaction was achieved under standard conditions. Experiments show that the heterogeneous catalyst PdCl2@POL-PPh3 can be recycled for at least 5 times, and the characterization data proves that the catalyst has no obvious deactivation after 5 cycles, which lays the foundation for the development and application of natural product anethole.
Key words：heterogeneous catalysis; trans-anethole; selective oxidation; recycling; gram scale conversion
引用本文：贾均松，唐海涛，潘英明. 非均相条件下茴脑氧化制备4-甲氧基肉桂醛[J]. 化学试剂,2022, 44(10):1532-1536 .
硒粉催化合成N-乙烯基双苯磺酰胺类化合物
鲍峰玉*，祁成龙，张婉，梁城铭
（河南农业大学 理学院，河南 郑州 450002）
摘要：烯胺有广泛的应用价值，烯烃和胺反应合成烯胺的方法存在重金属残留或不能循环催化的局限性。以硒粉为催化剂，以取代苯乙烯和N-氟代双苯磺酰胺为原料，通过研究催化剂、溶剂、温度、添加物对产物N-(苯磺酰)-N-(1-(对甲苯基)乙烯基)苯磺酰胺产率的影响，得到最佳反应条件：10 mol%硒粉为催化剂，空气气氛中，在V（对二甲苯）：V（氯苯） = 1:1的混合溶剂中80 °C反应，用三乙基铵苯磺酰亚胺[Et3NH][N(SO2Ph)2]为添加物。硒粉可循环催化对甲苯乙烯和N-氟代双苯磺酰胺的氧化胺化反应。对烯烃底物进行拓展，得到5种目标产物，并通过1HNMR、13CNMR和HRMS对产物的结构进行表征。
关键词：硒粉；催化；烯烃；N-氟代双苯磺酰胺；氧化胺化反应；烯胺
中图分类号：O622.6 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis of N-Vinylbenzenesulfonimides Catalyzed Selenium Powder BAO Feng-yu*, QI Cheng-long, ZHANG Wan, LIANG Cheng-ming (College of Science, Henan Agricultural University, Zhengzhou 450002, China), Huaxue Shiji, 2022, 44( ), ～
Abstract：Enamines show a wide range of applications. The synthetic methods of enamines by the reactions of alkenes with amines suffer from limitation of heavy metal residues or unrecyclable catalysis. Selenium powder was used as catalyst, substituted styrenes and N-fluorobenzenesulfonimide were used as the starting materials. The effects of catalysts, solvents, temperature and additives on the yield of product N-(phenylsulfonyl)-N-(1-(p-tolyl)vinyl)benzenesulfonamide were studied. The best reaction conditions were as follows: 10 mol% of selenium powder was used as catalyst, the reaction was conducted in the mixture of p-xylene and chlorobenzene (volume ratio is 1:1) at 80 °C in an air atmosphere, and triethylammonium benzenesulfonimide was used as additive. Selenium powder can circularly catalyze oxidative amination of p-methylstyrene with N-fluorobenzenesulfonimide. The olefin substrates were studied, and five target products were obtained. The structures of the products were confirmed by 1HNMR, 13CNMR and HRMS.
Key words：selenium powder; catalysis; alkene; N-fluorobenzenesulfonimide; oxidative amination reaction; enamine
引用本文：鲍峰玉, 祁成龙, 张婉, 等. 硒粉催化合成N-乙烯基双苯磺酰胺类化合物[J]. 化学试剂, 2022, 44(10)：1537-1541.
