高性能Pt-Mo/AC催化剂：煅烧条件的探索及在催化硬脂酸甲酯原位加氢中的应用
杨微1，郑雨欣1，吴可荆*2，朱英明2，刘颖颖2，鲁厚芳1,2，梁斌1,2
（1. 四川大学化学工程学院，四川成都 610065；2. 四川大学新能源与低碳技术研究院，四川成都 610207）
摘要：由于能源危机和温室效应，生物燃料作为化石燃料的替代品已经引起了全世界的广泛关注。以硬脂酸甲酯为模型化合物和甲酸（FA）为氢供体，探索了活性碳（AC）负载的Pt-Mo双功能催化剂的煅烧条件及其在催化硬脂酸甲酯原位加氢反应中的应用。结果表明：N2煅烧气氛能够增强Pt和Mo的相互作用，从而促进低氢供体用量条件下的反应活性；煅烧温度主要影响Mo组分的晶相和Pt-Mo相互作用，在750 ℃煅烧的Pt-Mo/AC-750催化剂在低氢供体用量（n（FA）∶n（硬脂酸甲酯）=3.9）下目标产物总收率达到95.4%，TON达到59.96 h-1。MoOxCy的存在和强烈的Pt-Mo相互作用是Pt-Mo/AC-750催化剂高活性的原因。循环实验表明，催化剂表面活性位掩盖是导致活性降低的主要原因，将重复四次的催化剂通过750 ℃煅烧4 h再生后，目标产物总收率从45.8%恢复到86.2%。
关键词：Pt-Mo/AC；制备；原位加氢；硬脂酸甲酯；甲酸；烷烃
中图分类号：TK6文献标识码：A文章编号：0258-3283（2021）--
High Performance Pt-Mo/AC Catalyst: Exploration of Calcination Conditions and its Application in in-situ Hydrogenation of Methyl Stearate YANG Wei1, ZHENG Yu-xin1, WU Ke-jing*2, ZHU Ying-ming2, LIU Ying-ying2, LU Hou-fang1,2, LIANG Bin1,2 (1. Sichuan University, School of Chemical Engineering, Chengdu 610065,China; 2. Sichuan University, Institute of New Energy and Low-Carbon Technology, Chengdu 610207, China), Huaxue Shiji, 2021, 43(11), ～
Abstract: Biofuel as an alternative to fossil fuel has attracted worldwide attention due to energy crisis and greenhouseeffect. The calcination conditions of activated carbon (AC) supported Pt-Mo bifunctional catalyst and its application in in-situ hydrogenation of methyl stearate were investigated by using methyl stearate as model compound and formic acid (FA) as hydrogen donor. The results show that N2 calcination atmosphere can enhance the interaction between Pt and Mo, thus promoting the reactivity under the condition of low hydrogen donor dosage. The calcination temperature mainly affects the crystal phase of Mo component and the Pt-Mo interaction. The total yield and TON of Pt-Mo/AC-750 catalyst calcined at 750 ℃ reached 95.4% and 59.96 h-1 at low hydrogen donor dosage (n(FA)∶n(methyl stearate)=3.9), respectively. The presence of MoOxCy and the strong Pt-Mo interaction are the reasons for the high activity of Pt-Mo/AC-750 catalyst. The cycle experiments show that the main reason for the decrease of activity was the covering of the active sites on the surface of the catalyst. The total yield of the target product recovers from 45.8% to 86.2% afterthe catalyst, which was repeated four times, was regenerated by calcining at 750 ℃ for 4 h
Keywords: Pt-Mo/AC; preparation; in-situ hydrogenation; methyl stearate; formic acid; alkane
引用本文：杨微，郑雨欣，吴可荆，等.高性能Pt-Mo/AC催化剂：煅烧条件的探索及在催化硬脂酸甲酯原位加氢中的应用[J]. 化学试剂，2021，43(11):1457-1465.
MOF(Ni)-74对废水中偶氮染料刚果红的吸附性能研究
娄杰a,b，付秋平*c，余磊a,b，严伟c，黄伟江c，王琪c
（贵阳学院 a.教学设备及实验管理中心，b.贵州生态环境中优势农产品残留农药降解关键技术研究重点实验室，c.化学与材料工程学院，贵州 贵阳 550005）
摘要：以2,5-二羟基对苯二甲酸为有机配体、Ni(Ⅱ)为中心金属，采用溶剂热法合成了金属有机骨架材料MOF(Ni)-74，通过XRD和FT-IR对其结构进行了表征。用MOF(Ni)-74吸附偶氮染料刚果红，考察了溶液初始浓度和接触时间、吸附剂投加量、pH值、Na+浓度及温度对吸附的影响，并对其等温吸附过程、吸附动力学和吸附热力学进行了研究。实验结果表明，随着刚果红初始浓度增大，MOF(Ni)-74的吸附量增大；吸附剂投加量增大，去除率提高，吸附量减小；Na+浓度增大，吸附量减少。等温吸附模型更符合Freundlich方程，动力学更符合双常数模型。热力学参数∆G < 0、∆H > 0、∆S > 0，表明MOF(Ni)-74对刚果红的吸附是自发的、吸热的过程。
关键词：金属有机骨架材料；刚果红；偶氮染料；吸附
中图分类号：X703 文献标志码：A 文章编号：0258-3283（2021）
Adsorption Performance of Azo Dyes Congo Red in Wastewater by MOF(Ni)-74 LOU Jiea, b, FU Qiu-ping*c, YU Leia, b, YAN Weic, HUANG Wei-jiangc, WANG qic (a. Teaching Equipment and Laboratory Management Center; b. Key Laboratory of Critical Technology for Degradation of Pesticide Residues in Agro-products in GuiZhou Ecological Environment; c. College of Chemistry and Materials Engineering, Guiyang University, Guiyang 550005, China), Huaxue Shiji, 2021
Abstract: The metal-organic framework MOF(Ni)-74 was synthesized by solvothermal method with 2, 5-dihydroxy terephthalic acid as the organic ligands, metal Ni (Ⅱ) as the center. The structure of MOF(Ni)-74 was characterized by XRD and FT-IR. The effects of initial concentration of Congo red, contact time, dosage of adsorbent, pH, Na+ concentration and temperature on the adsorption of azo dye Congo red by MOF(Ni)-74 were investigated. The isothermal adsorption process, adsorption kinetics and adsorption thermodynamics were also studied. The results show that the adsorption capacity increases with increasing of initial concentration of Congo red. When the amount of adsorbent increased, the removal rate increased, and the adsorption amount decreased. In addition, with the increase of Na+ concentration, the adsorption amount decreased. The isothermal adsorption model is in consistent with the Freundlich equation, and the kinetics is in consistent with the Double constant equation model. Thermodynamic parameters ∆G<0, ∆H>0, ∆S>0, which indicates that the adsorption of Congo red by MOF(Ni)-74 is a spontaneous and endothermic process.
Key words: metal-organic frameworks（MOFs）; Congo red; azo dyes; adsorption
引用本文：娄杰 ，付秋平，余磊，等. MOF(Ni)-74对废水中偶氮染料刚果红的吸附性能研究 [J]. 化学试剂，2021，43（11）：1466-1472.
双金属Co/Pd纳米催化剂催化乙炔双羰化反应的性能研究
赵晶璨，杨启亮，张雨晨，罗迎春，王环江*
(贵州民族大学 化学工程学院，贵州 贵阳 550025)
摘要：采用一步还原法制备了一系列双金属纳米Pd基合金催化剂，以获得优秀的乙炔双羰化反应催化剂。利用透射电子显微镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、原位红外光谱（In-situ IR）等手段对催化剂的性质进行了研究。考察了掺杂金属、溶剂、助剂种类及用量、一氧化碳压力、温度对反应收率的影响。结果表明：以乙腈为溶剂，乙炔、一氧化碳和甲醇为原料合成丁烯二酸二甲酯，Co/Pd双金属纳米催化剂的活性最高，在低温低压条件下丁烯二酸二甲酯的总收率可达97.99%。Co元素的引入，有助于降低Pd对一氧化碳吸附强度，使更多的吸附于催化剂表面的CO分子能参与反应，提高了Pd基纳米双金属催化剂催化乙炔双羰化反应的活性。
关键词：Pd基双金属；纳米合金催化剂；乙炔双羰化；助剂
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2021）--
Access to Highly Active Co/Pd Bimetallic Nanoparticle Catalysts for Acetylene Dicarbonylation Reactions ZHAO Jing-can, YANG Qi-liang, ZHANG yu-chen, LUO Ying-chun, WANG Huan-jiang * (School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China) , Huaxue Shiji, 2021, 43(11), ～
Abstract: A series of bimetallic nano Pd-based alloy catalysts were prepared by one-step reduction method and used to obtain excellent catalysts for acetylene dicarbonylation reactions. The transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and in situ infrared spectroscopy (In-situ IR) were used to investigate the composition and structure of Co/Pd catalysts. The effects of doping metal, solvent, type and dosage of promoter, carbon monoxide pressure and temperature on the reaction yield were investigated. The results show that the Co/Pd bimetallic nano-catalysts have excellent catalytic activity in the reaction of acetonitrile, acetylene, carbon monoxide, and methanol, and the total yield of acetylene dicarbonylation can reach 97.99% at low temperature and low pressure. The introduction of Co reduces the chemisorption strength of CO chemisorption on Pd, so that more CO molecules adsorbed on the catalyst surface can participate in the reaction, and the Pd-based nano-catalysts catalytic activity for acetylene dicarbonylation are improved.
Key words: Pd-based bimetallic nanoparticle; nano-alloy catalyst; acetylene dicarbonylation reaction; promoter
引用本文：赵晶璨，杨启亮，张雨晨，等. 双金属Co/Pd纳米催化剂催化乙炔双羰化反应的性能研究[J]. 化学试剂，2021，43(11):1473-1479.
金属有机骨架衍生的自支撑Co9S8/Ni3S2纳米片阵列用于高效电催化分解水性能研究
覃彪1，郭芬岈2，黎挺挺*2
（1. 遵义师范学院 化学化工学院，贵州 遵义 563006；
2. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211）
摘要：采用简单、可控的阳离子交换法和水热法在导电基底上成功构筑了具有自支撑纳米片阵列结构的Co9S8/Ni3S2电催化剂，在碱性电解液（1 mol/L KOH）中，采用三电极体系分别研究了Co9S8/Ni3S2的电催化析氧和析氢性能。在析氧性能测试中，Co9S8/Ni3S2电催化剂获取50、100 mA/cm2的催化电流密度所需要的过电位仅为230、280 mV。而在析氢性能测试中，Co9S8/Ni3S2电催化剂获取-100 mA/cm2的催化析氢电流密度所需的过电位仅为129 mV，同时该催化剂表现出了优异的电催化稳定性，其优异的电催化性能归因于其自支撑纳米片阵列结构，可提供更多的活性位点。
关键词：电催化；水分解；金属有机骨架前驱体；双金属硫化物；自支撑电极
中图分类号：O643.36 文献标识码：A 文章编号：0258-3283（2021）
MOFs Derived Self-Supported Co9S8/Ni3S2Nanosheet Arrays for Efficient Electrocatalytic
Water Splitting Qin Biao1,Guo Fen-ya2, Li Ting-ting*2(1. College of Chemistry and Chemical Engineering, Zunyi Normal University, Zunyi 563006; 2. School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211), HuaxueShiji, 2021, 43(11)
Abstract： In this work, the combination of cation exchange and hydrothermal method was used to fabricate Co9S8/Ni3S2nanosheet arrays in-situ grown on nickel foam (Co9S8/Ni3S2/NF). 1 mol/L KOH solution was used as the electrolyte, in a three-electrode system, the electrocatalytic performances towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were investigated. As for OER, the overpotentials of Co9S8/Ni3S2/NF to acquire the current densities of 50 and 100 mA/cm2 were only 230 and 280 mV, respectively. And in HER, the overpotential at -100 mA/cm2 is as low as 129 mV. Furthermore, this electrode showed remarkable durability in both reactions. The excellent electrocatalytic performance of Co9S8/Ni3S2/NF is attributed to the free-standing architecture as well as the nanosheet array structure, which can expose more active sites.
Key words：electrocatalysis;water splitting;MOF precursor; bimetallic sulfide;self-supported electrode
引用本文：覃彪，郭芬岈，黎挺挺.金属有机骨架衍生的自支撑Co9S8/Ni3S2纳米片阵列用于高效电催化分解水性能研究[J].化学试剂，2021，43（11）：1480-1485.
烟气中Fe2O3对商用V-Mo/Ti脱硝催化剂的性能影响研究
黄力1，刘洋1，纵宇浩1，王虎1，常峥峰1，李金珂1，姚晔1，韩沛*2
(1. 大唐南京环保科技有限责任公司，江苏 南京 211111；
2. 内蒙古科技大学 分析测试中心，内蒙古 包头 014010)
摘要：为明确燃煤烟气飞灰中Fe2O3对商用脱硝催化剂的影响，采用浸渍法制备了不同Fe2O3负载量的V-Mo-Fe/Ti脱硝催化剂。通过XRF、XRD、N2-吸附脱附、NH3-TPD、H2-TPR、XPS等表征手段对催化剂的物理化学性能进行分析。随后，使用固定床微型反应评价装置对催化剂进行了脱硝性能检测。结果表明，Fe2O3的负载对催化剂的晶型和孔结构影响不大，却能提升催化剂的酸性和还原性能。然而，Fe2O3同时会对催化剂活性位产生覆盖作用，导致催化剂化学吸附氧含量以及脱硝活性的降低。此外，催化剂的老化实验结果表明，Fe2O3会增加硫酸氢铵在催化剂上的沉积，影响催化剂的运行稳定性。
关键词：选择性催化还原法；V-Mo/Ti；Fe2O3；脱硝；催化剂
中图分类号：X511;TQ032.4 文献标识码：A 文章编号：0258-3283（2021）
Investigation of Fe2O3 in Flue Gas on the Catalytic Performance of Commercial V-Mo/Ti De-NOx Catalyst HUANG Li1, LIU Yang1, ZONG Yu-hao1, WANG Hu1, CHANG Zheng-feng1, LI Jin-ke1, YAO Ye1, HAN Pei*2 (1. Datang Nanjing Environmental Protection Technology Co., Ltd, Nanjing 211111, China; 2. Instrumental Analysis Center, Inner Mongolia University of Science & Technology, Baotou, 014010, China), Huaxue Shiji, 2021, 43(11)
Abstract：V-Mo-Fe/Ti de-NOx catalysts with different amounts of Fe2O3 were prepared by impregnation method to investigate the influence of Fe2O3 in fly ashes from coal-fired power stations on the catalytic performance of commercial de-NOx catalyst. The catalysts were characterized by XRD, N2-adsorption, NH3-TPD, H2-TPR, XPS, etc. Furthermore, the denitrification performances of the different catalysts were compared through a fixed-bed micro-reactor. It was found that the doping of Fe2O3 had little impact on the structure and pore property of V-Mo/Ti catalyst but increased its acidity and reducibility. However, Fe2O3 covered the active sites of the catalyst, which led to the decrease of the amount of chemisorbed oxygen and de-NOx activity of the catalyst. Besides, Fe2O3 facilitated the deposition of ammonium bisulfate on the catalyst during the SCR reaction. As a result, the stability of the catalyst declined.
Key words：SCR; V-Mo/Ti catalyst; Fe2O3; De-NOx；catalysts
引用本文：黄力，刘洋，纵宇浩，等. 烟气中Fe2O3对商用V-Mo/Ti脱硝催化剂的性能影响研究[J]. 化学试剂，2021，43（11）：1486-1491.
含磺酰基结构2-苯胺基嘧啶衍生物的合成及抗肿瘤活性研究
韩柳1，刘源1，张奥金1，高连丛1，马艳迪1，殷世亮*2，昌盛*1
(1. 吉林医药学院 药学院，吉林 吉林 132013；2. 沈阳医学院 基础医学院，辽宁 沈阳 110034)
摘要：该文设计、合成含磺酰基结构的2-苯胺基嘧啶衍生物，并评价其体外抗白血病活性。以2-甲基-5-硝基苯胺、3-乙酰基吡啶、N, N二甲基甲酰胺二甲基缩醛为起始原料经加成、缩合、环合、还原、磺酰化等5步反应合成17个新型含磺酰基结构的2-苯胺基嘧啶衍生物。产物结构均经1HNMR、13CNMR和MS表征。以伊马替尼为阳性对照药，采用台盼兰排染法，以慢性粒细胞白血病K562细胞为测试细胞株对目标化合物进行体外抗白血病活性评价。结果表明：对于单取代化合物小体积吸电子基对活性有显著影响，其中3-溴-N-(4-甲基-3-((4-(吡啶-3-基)嘧啶-2-基)胺基)苯基)苯磺酰胺（6e）具有最强的活性，GI50为（9.71±0.37） μmol/L，分子对接结果显示，化合物6e与伊马替尼具有相似的结合模式，伊马替尼和化合物6e均与Met318、Thr315、Asp381形成氢键，可以初步推测目标化合物的作用靶点和伊马替尼相似，可以与c-Abl受体口袋区结合，但相比伊马替尼，化合物6e缺失与Glu286之间的氢键，推测这一氢键作用的缺失是导致目标化合物活性减弱的主要原因。研究同时也证明单取代化合物活性优于双取代化合物活性。本研究为开发2-苯胺基嘧啶衍生物应用于人慢性粒细胞白血病提供了借鉴。
关键词：磺酰基；2-苯胺基嘧啶衍生物；合成；抗肿瘤；分子对接
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis and Antitumor Activity of 2-Aniline Pyrimidine Derivatives with Sulfonyl Structure HAN Liu1, LIU Yuan1, ZHANG Ao-jin1, GAO Lian-cong1, MA Yan-di1, YIN Shi-liang*2, CHANG Sheng*1 (1. School of Pharmacy, Jilin Medical College, Jilin 132013, China; 2. School of Basic Medical Sciences, Shenyang Medical College, Shenyang 110034, China), Huaxue Shiji, 2021, 43(11)
Abstract: A series of 2-aniline pyrimidine derivatives with sulfonyl structure were designed and synthesized to evaluate their anti-leukemia activity in vitro in this paper. Using 2-methyl-5-nitroaniline, 3-acetyl-pyridine, N, N dimethylformamide dimethylacal as the starting materials, 17 new 2-aniline pyrimidine derivatives with sulfonyl structure synthesized through 5 steps of addition, condensation, cyclization, reduction and sulfonylation were reported in this paper. These compounds were tested to inhibit human leukemia cell lines K562 using trypan blue dye exclusion method with imatinib as the positive control. Preliminary pharmacological results showed that the small-volume electron withdrawing group of the monosubstituted compounds has a significant effect on the activity. Among them, the 3-bromo-substituted compound 6e has the strongest activity, with a GI50of 9.71±0.37μmol•L-1. Molecular docking results show that the compound 6e combined with imatinib have similar pattern, imatinib and compound 6e with Met318, Thr315, Asp381 hydrogen bond formation, can be presumed target compounds targets similar to those of imatinib , can combine with c-Abl receptor pocket area, but compared to imatinib, lack of compound 6e and the hydrogen bonding between Glu286.We speculated that the lack of the hydrogen bonding interaction is the main cause weaken the activity of target compounds. It is also proved that the activity of mono-substituted compounds is better than that of di-substituted compounds. This research provides a reference for the development of 2-arylaminopyrimidine derivatives for human chronic myeloid leukemia.
Key words: sulfonyl group; 2-aniline pyrimidine derivatives; synthesis; anti-tumor
引用本文：韩柳，刘源，张奥金，等. 含磺酰基结构2-苯胺基嘧啶衍生物的合成及抗肿瘤活性研究[J]. 化学试剂, 2021, 43(11): 1492-1499.
自由基共聚合制备功能化PVP共聚物及性能研究
刘娜，张金策，刘敏，由晓蕾，马晓雪，房大维 *
(辽宁大学 稀散元素化学研究所，辽宁 沈阳 110036)
摘要：采用简单高效的一锅法合成了一种新型官能化的N-乙烯基吡咯烷酮单体（[TBSE]2-NVP），运用自由基共聚合的方法报道了结构相似的N-乙烯基吡咯烷酮（NVP）和[TBSE]2-NVP单体的共聚合，并对所得共聚物进行了后修饰，利用核磁共振波谱（NMR）、傅里叶变换红外光谱（FT-IR）对修饰前后的共聚物进行了结构表征，结果表明通过调控单体投料比可以较好地控制共聚物的组成。进一步对所合成的共聚物进行了静态接触角（WCA）、热重分析仪（TGA）和差示扫描量热仪（DSC）的性质表征，结果表明随着疏水性单体含量的增加，共聚物的疏水性和热稳定性依次增强；相比于聚乙烯吡咯烷酮（PVP），共聚物的熔点有所降低，在93～103 °C范围内。当对共聚物进行脱保护后，共聚物表现出相似的亲水性和热稳定性，且随着羟基含量的增加，共聚物的熔点逐渐上升。
关键词：N-乙烯基吡咯烷酮；共聚合；功能化聚合物；亲水性；热稳定性
中图分类号：O632 文献标识码：A 文章编号：0258-3283（2021）--
The Preparation and Properties of Functional PVP Copolymers by Free Radical Copolymerization Liu Na, Zhang Jin-ce, Liu Min, You Xiao-lei, Ma Xiao-xue, Fang Da-wei* ( Liaoning University, Institute of Rare and Scattered Elements Chemistry, College of Chemistry, Shenyang 110036, China), Huaxue shiji, 2021, 43(11), ～
Abstract：A novel functional N-vinyl-pyrrolidone monomer ([TBSE]2-NVP) was synthesized by simple and efficient one-pot method. The copolymerization of NVP and [TBSE]2-NVP was studied in detail using free radical copolymerization. The structures of resultant copolymers were characterized by NMR spectroscopy and FT-IR. The results indicated that the composition of the copolymers could be regulated by the feeding ratio of monomers. The properties of copolymers were further certified by static water contact angle (WCA), thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). The results revealed that the hydrophobicity and thermal stability of the obtained copolymers gradually increased with increasing of hydrophobic monomer content. Compared to the PVP polymer, the Tm decreased in the PVP-co-P(TBSE-NVP) copolymers, which was between the 93～103 °C. After the functional group within the copolymers was deprotected, the copolymers exhibited similar hydrophilicity and thermal stability. The Tm increased with the increasing of content of hydroxyl group.
Key words：N-vinyl-pyrrolidone monomer; copolymerization; functional polymers; hydrophilic; hermal stability
引用本文：刘娜，张金策，刘敏，等.自由基共聚合制备功能化PVP共聚物及性能研究[J]. 化学试剂，2021，43(11):1500-1508.
质粒DNA构型分离和分析方法研究进展
王乐乐，闻艳丽，李兰英，杨雪，李妍，刘刚*
(上海市计量测试技术研究院 生物计量实验室，上海 201203)
摘要：作为基因传递的载体，质粒DNA已被广泛应用于DNA疫苗和基因治疗。质粒DNA存在不同的构型，其中超螺旋构型的质粒在细胞中的转染和表达效率最高。美国食品与药品监督管理局在2007年发布了质粒DNA疫苗的工艺指导原则，建议超螺旋构型的比例大于80%，因此建立高灵敏度和高分辨率的方法用于质粒DNA构型分离和分析具有重要意义。本文就近年来质粒DNA构型的分离和分析方法进行了综述，主要包括琼脂糖凝胶电泳法、液相色谱法和毛细管凝胶电泳法，并对未来质粒DNA构型分离和分析方法的发展提出了展望。
关键词：质粒DNA；构型；琼脂糖凝胶电泳法；液相色谱法；毛细管凝胶电泳法
中图分类号： O657.8 文献标识码：A 文章编号：0258-3283（2021）--
Research progress of plasmid DNA conformation separation and analysis methods Wang Le-le, Wen Yan-li, Li Lan-ying, Yang Xue, Li Yan, Liu Gang* (Biometrology Laboratory, Chemical and Ionizing Radiation Metrology Institute, Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China), Huaxue Shiji, 2021, 43(11), ～
Abstract:As a gene delivery vector, plasmid DNA has been widely used in DNA vaccines and gene therapy. Plasmid DNA exists in different conformations, and the supercoiled plasmid has the highest transfection and expression efficiency in cells. The US Food and Drug Administration issued the guidance for plasmid DNA vaccines in 2007, suggesting that the proportion of super coiled conformation should be higher than 80%.Therefore, it is of great significance to establish a high-sensitivity and high-resolution method for plasmid DNA conformation separation and analysis. This article reviews the separation and analysis methods of plasmid DNA conformation in recent years, including agarose gel electrophoresis, liquid chromatography and capillary gel electrophoresis. The prospect for the future development of plasmid DNA conformation separation and analysis methods is also proposed.
Keywords：plasmid DNA; conformations; agarose gel electrophoresis; liquid chromatography; capillary gel electrophoresis
引用本文：王乐乐，闻艳丽，刘刚，等.质粒DNA构型分离和分析方法研究进展[J]. 化学试剂，2021，43(11): 1509-1517。
硫化氢供体衍生物及其抗肿瘤活性研究进展
韦纯永，王合珍，王芝元，徐应淑，王京*，张磊*
(遵义医科大学 贵州省生物催化与手性药物合成重点实验室 药学院，贵州 遵义 563000)
摘要：硫化氢（H2S）是新型内源性气体信号分子，其作为信号和（或）效应分子，在各种生理和病理生理过程中起着关键作用，因而在治疗高血压、心脑疾病、炎症及肿瘤等方面具有潜在的应用价值。目前研究较多的是有机合成的硫化氢供体化合物，如劳森试剂衍生物、茴三硫和过硫化物类化合物。近年来，人们对硫化氢供体化合物进行修饰改造或将硫化氢供体与其它药效基团拼合，制备得到了许多具有研究价值的化合物，这也成为了国内外研究的热点之一。主要综述了近年来硫化氢供体衍生物及其抗肿瘤活性研究进展，为硫化氢供体的研究提供帮助。
关键词：硫化氢供体；衍生物；抗肿瘤；研究进展
中图分类号：O621.29 文献标识码：A 文章编号：0258-3283（2021）--
Advance on the Structural Modifications and Anticancer Activities of H2S Donor Derivatives WEI Chun-yong, WANG He-zhen, WANG Zhi-yuan, XU Ying-shu, WANG Jing*, ZHANG Lei* (Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563000, China) , Huaxue Shiji, 2021, 43(11), ～
Abstract: Hydrogen sulfide (H2S) is a new type of endogenous gas signal molecule. As a signal and / or effector molecule, it plays a key role in various physiological and pathophysiological processes. Many studies have found that H2S has application prospects in the treatment of hypertension, heart and brain diseases, inflammation, and cancer. At present, synthetic H2S donor are mainly studied, such as Lawesson regent, disulfurating and anethole trithione derivatives. Recently, many H2S donor derivatives with potential application have been prepared via structure modifications of H2S donor or combining hydrogen sulfide donors with different pharmacophores, which has become one of the hot topics in the research field at home and abroad. Therefore, this article mainly reviews the research progress of structural modifications and anticancer activities of H2S donor derivatives in recent years, for the further study of H2S donor.
Key words: hydrogen sulfide donor; derivative; anticancer activity; research progress
引用本文：韦纯永，王合珍，王芝元，等. 硫化氢供体衍生物及其抗肿瘤活性研究进展[J]. 化学试剂，2021，43(11):1518-1526.
2,2-二溴-1-苯基乙烯在杂环合成中的应用研究进展
张文生*1，李焱2，周鸿燕1，左国强1，苏小莉1，刘改云1
(1. 济源职业技术学院 冶金化工系，河南 济源 459000；
2. 焦作师范高等专科学校 合成技术研究所，河南 焦作 454100)
摘要：2,2-二溴-1-苯基乙烯是一类重要的有机合成中间体，广泛应用于合成吲哚、苯并呋喃、苯并噻吩、苯并吡喃、喹啉、异香豆素等稠杂环和芳基取代的杂环类化合物。在有关综述的基础上，主要对2013年后该领域的最新研究进展进行综述。该综述主要涉及两类反应：（1）以2,2-二溴-1-苯基乙烯为原料，通过分子内反应构建吲哚、苯并呋喃、苯并噻吩和苯并硒吩类杂环化合物，以及在苯并呋喃类天然产物合成中的应用进展；（2）基于2,2-二溴-1-苯基乙烯，通过分子间环化合成芳基取代噻吩、芳基取代三唑、呋喃和香豆素等杂环化合物。
关键词：2,2-二溴-1-苯基乙烯；杂环；合成；分子内反应；环化
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2021）
Progress in Application of 2,2-Dibromo-1-phenylethylene in Heterocyclic Synthesis ZHANG Wen-sheng*1, Li Yan2, ZHOU Hong-yan1, ZUO Guo-qiang1, SU Xiao-li1, LIU Gai-yun1 (1. Department of Metallurgy and Chemical Engineering, Jiyuan Vocational and Technical College, Jiyuan 459000, China; 2. Institute of Synthetic Technology, Jiaozuo Teachers College, Jiaozuo 454100, China), Huaxue Shiji, 2021, 43(11), ～
Abstract：2,2-dibromo-1-phenylethyleneis an important intermediate in organic synthesis ,which is widely applied in the synthesis of fused heterocycles, including indoles, benzofurans, benzothiophenes, benzopyrans, quinolines, isocoumarins and aryl substituted heterocyclic compounds. Based on the previous reviews, this paper mainly covers the latest research progress in the field since 2013. Two classes of reactions are involved in this review: (1) construction of indoles, benzofurans, benzothiophenes and benzoselenophene derivatives based on 2,2-dibromo-1-phenylethylenes by intramolecular reaction, and the applications of 2,2-dibromo-1-phenylethylenes in the synthesis of benzofuran natural products; (2) synthesis of aryl-substituted thiophenes, aryl-substituted triazolse, furans and coumarins via intermolecular cyclization from 2,2-dibromo-1-phenylethylenes.
Keywords：2,2-dibromo-1-phenylethylenes; heterocycle; synthesis; intramolecular reaction; cyclization
引用本文：张文生, 李焱, 周鸿燕,等. 2,2-二溴-1-苯基乙烯在杂环合成中的应用研究进展[J]. 化学试剂, 2021, 43(11):1527-1535。
免疫磁固相萃取高效液相色谱测定粮油作物产品中黄曲霉毒素B1的含量
汪文花1,2，张奇1,2,3,4，马飞*1,2,3,4,5，李培武1,2,3,4,5
（1. 中国农业科学院油料作物研究所，湖北 武汉 430062；2. 农业农村部油料作物生物学与遗传育种重点实验室，湖北 武汉 430062；3. 农业农村部生物毒素检测重点实验室，湖北 武汉 430062；4. 农业农村部油料产品质量安全风险评估实验室（武汉），湖北 武汉 430062；5. 国家农业检测基准实验室（生物毒素），湖北 武汉 430062）
摘要：采用70%乙腈溶液提取花生、玉米样品，然后用免疫磁珠固相萃取、净化和富集提取液中的黄曲霉毒素B1，高效液相色谱荧光检测仪定量分析。对影响免疫磁固相萃取的条件包括提取剂种类、吸附剂用量、吸附时间、洗脱液类型、洗脱液体积进行优化。结果表明，黄曲霉毒素B1在0.5 ～ 50 μg/kg范围内线性关系良好，相关系数为0.9995，回收率为90.3% ～ 115.7%，相对标准差小于6.9%，检出限和定量限分别为0.1 μg/kg和0.3 μg/kg。方法步骤简单、准确性好、检出限低，能够应用于粮油作物产品中花生、玉米黄曲霉毒素B1的定量检测。
关键词：粮油作物产品；黄曲霉毒素B1；免疫磁珠固相萃取；高效液相色谱
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Aflatoxin B1in Cereal and Oil Products by Immunomagnetic Solid Phase Extraction coupled with HPLC WANG Wen-hua1,2, ZHANG Qi1,2,3,4, MA Fei*1,2,3,4,5, LI Pei-wu1,2,3,4,5 (1. Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Wuhan 430062, China; 2. Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture and Rural Affairs, Wuhan 430062, China; 3. Key Laboratory of Detection for Mycotoxins, Ministry of Agriculture and Rural Affairs, Wuhan 430062, China; 4. Laboratory of Risk Assessment for Oilseeds Products (Wuhan), Ministry of Agriculture and Rural Affairs, Wuhan 430062, China; 5. National Standard Laboratory for Agricultural Testing, Wuhan 430062, China), Huaxue Shiji, 2021, 43(11), ～
Abstract: The peanut and corn samples were extracted with 70% acetonitrile solution, and purified and enriched byimmunomagnetic solid-phase extraction beads (IMSPE).Aflatoxin B1 (AFB1) was determined by high performance liquid chromatographywith fluorescence detector (HPLC-FLD). The IMSPE conditions,including extractant, adsorbentamount, adsorption time, the type and volume of eluent, werestudied. Under the optimized conditions, a good linear relationship was established in the range of 0.5-50 μg/kg and the correlation coefficient was0.9995.The recovery was ranging from 90.3% to 115.7% and RSDs less than 6.9%. The detection limit (LOD) and the quantification limit (LOQ)were 0.1 μg/kg and 0.3 μg/kg, respectively.The IMSPE-HPLC-FLD method wassimple, fast, high accuracy and with low detection limit, whichcould beapplied forthe determinationof AFB1 inagri-products.
Key words: grain and oilseed products; aflatoxin B1; immunomagnetic bead solid phase extraction; HPLC
引用本文：汪文花, 张奇, 马飞, 等.免疫磁固相萃取高效液相色谱测定粮油作物产品中黄曲霉毒素B1的含量[J]. 化学试剂, 2021, 43(11)：1536-1540.
高分辨气体同位素质谱法测定重水的氘同位素丰度
解龙，宋明鸣，雷雯*
（上海化工研究院有限公司，上海 200062)
摘要：基于高分辨气体同位素质谱技术，建立重水的氘同位素丰度测定方法。取10 μL样品与轻金属镁条在200 ℃条件下反应2 h，将生成的氘气（D2）引入高分辨气体同位素质谱仪中检测离子流强度，数据代入推导出的计算公式计算得到氘同位素丰度。测试结果表明：通过精确地配制高、中、低不同氘同位素丰度的重水样品，利用计算公式得出的测量值与配置值偏差均小于0.3 atom% D，标准偏差均小于0.1%，方法适用的氘同位素丰度范围为0.015～99.8 atom% D。该方法可为质谱测定重水中氘同位素丰度提供准确可靠的检测方法。
关键词：高分辨气体同位素质谱仪；重水；氘；同位素丰度；氘气；镁条
中图分类号：TQ421.6 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Deuterium Isotope Abundance in Heavy Water Based on High Resolution Gas Isotope Mass Spectrometry XIE Long, SONG Ming-ming, LEI Wen* (Shanghai Research Institute of Chemical Industry CO.,LTD , Shanghai 200062 , China), Huaxue Shiji, 2021,43(11), ～
Abstract: A method for the determination of deuterium isotope abundance of heavy water was established based on high-resolution gas isotope mass spectrometry. 10μL sample was taken to react with magnesium ribbon at 200 ℃ for 2 hours. The generated deuterium gas (D2) was introduced into the high-resolution gas isotope mass spectrometer to detect the ion current intensity, and the deuterium isotope abundance was finally obtained after putting the data into the derived formula. The test results showed that: based on the accurate preparation of heavy water samples with high, medium, and low deuterium isotope abundances, the deviations between the measured value and the configured value calculated by the formula are all less than 0.3 atom%D, the standard deviation of each result is also less than 0.1%, and the range of deuterium isotope abundance applicable to this method is (0.015～99.8) atom%D. The method has been verified to be accurate and reliable in detecting the abundance of deuterium isotope in heavy water by mass spectrometry.
Key words: high-resolution gas isotope mass spectrometry; heavy water; deuterium; isotope abundance; deuterium gas; magnesium ribbon
引用本文：解龙，宋明鸣，雷雯.高分辨气体同位素质谱法测定重水的氘同位素丰度[J]. 化学试剂，2021，43(11):1541-1545。
超高效液相色谱-串联质谱法测定海螵蛸中9种磺胺类药物 残留量
许晓辉1，徐惠昌2，王小乔*1，张生萍1，朱仁愿1，李赟1
（1. 兰州市食品药品检验检测研究院，甘肃 兰州 730050；2. 民勤县人民医院，甘肃 民勤 733300）
摘要：采用超高效液相色谱-串联三重四级杆质谱（UPLC-MS/MS）法定性和定量测定，建立动物源性中药海螵蛸中9种磺胺类药物残留的检测方法。干燥样品加EDTA溶液复原，以乙腈作为提取溶剂，使用萃取盐盐析分层，以增强型脂质去除分散固相萃取（EMR-Lipid dSPE）净化，以ACQUITY BEH C18柱（2.1 mm×100 mm，1.7 μm）为分离色谱柱进行分离分析，以动态多反应监测模式（d-MRM）进行检测，外标法定量。9种磺胺类药物在0～30 ng/mL范围内呈良好的线性关系，相关系数（R2）均大于0.9973，方法检出限和定量限分别在0.0136～0.1283 µg/kg和0.0455～0.4326 µg/kg之间，各加标水平的回收率在63.3%～91.9%之间，相对标准偏差为1.7%～5.7%。该方法简单、快速、准确，适合于中药海螵蛸中9种磺胺类药物残留的快速筛查。
关键词：海螵蛸；磺胺；超高效液相色谱串联三重四级杆质谱法；QuEChERS
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2021）
Ultra-Performance Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry for Determination of Nine Kinds of Sulfonamides Residues in Cuttlebone XU Xiao-hui1, XU Hui-chang2, WANG Xiao-qiao*1, ZHANG Sheng-ping1, ZHU Ren-yuan1, LI Yun1 (1. Lanzhou Institute for Food and Drug Control, Lanzhou 730050, China; 2. Minqin People's Hospital, Minqin 733300, China), Huaxue Shiji, 2021, 43(11),
Abstract: A comprehensive analytical method was developed for qualitative and quantitative determination of nine kinds of sulfonamides in Cuttlebone by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry(UPLC-MS/MS). The dry sample was restored with EDTA solution, then extracted by acetonitrile with salting-out separation under the condition of salt, secondly purified with enhanced matrix removal lipid-dispersed solid phase extraction(EMR-Lipid dSPE), separation was performed on an ACQUITY BEH C18 column(2.1 mm×100 mm, 1.7 μm). The dynamic multiple reaction monitoring acquisition mode(d-MRM) was used for detection, and external standard method was used for quantitative detection. The analytes of sulfonamides showed good linearities in the concentration range of 0 ～30 ng/mL with correlation coefficients(R2) no less than 0.9973. The limits of detection and quantitation were in the ranges of 0.0136 ～ 0.1283 µg/kg and 0.0455 ～ 0.4326 µg/kg, respectively. The spiked recoveries for analytes at their spiked levels were in the range of 63.3% ～ 91.9%, RSD were 1.7% ～ 5.7%. The method is simple, reproducible, sensitive, and suitable for rapid screening of nine kinds of sulfonamides residues in Cuttlebone.
Key words: Cuttlebone; sulfonamides; UPLC-MS/MS; QuEChERS
引用本文：许晓辉，徐惠昌，王小乔，等. 超高效液相色谱-串联质谱法测定海螵蛸中9种磺胺类药物残留量[J]. 化学试剂, 2021, 43(11):1546-1550。
罐采样-预浓缩-气相色谱质谱法测定环境空气中10种消耗臭氧层物质
杜明月*,郭龙,林勇,葛璇,张厚勇
（山东省济南生态环境监测中心，山东 济南 250102）
摘要：建立了罐采样-预浓缩-气相色谱质谱联用仪测定环境空气中10种消耗臭氧层物质（ODS）的分析方法。采用硅烷化的苏玛罐采集环境空气，三级冷阱预浓缩富集，色谱柱为Gas-Pro色谱柱（60 m×0.32 mm），采用全扫描模式（SCAN）和选择离子模式（SIM）同时进行测定，内标法定量，优化了色谱柱、初始柱温条件。结果表明：当取样量为400 mL时，10种ODS在35.0 pmol/mol ～ 4.0 nmol/mol范围内具有良好的线性关系，且平均相对响应因子的相对标准偏差为2.5% ～ 14.0%，检出限为9.6 ～ 31.6 pmol/mol，平均加标回收率为71.5% ～112.8%，相对标准偏差为0.4% ～10.9%。该方法操作简单、检出限低、可满足环境空气中ODS pmol/mol ～ nmol/mol 浓度量级的要求，精密度好、准确度高，适用于环境空气中10种ODS的测定。
关键词：消耗臭氧层物质；环境空气；气相色谱质谱；罐采样；预浓缩
中图分类号：X831 文献标识码：A 文章编号：0258-3283（2021）--
Determination of 10 Dzone Depleting Substances in Ambient Air by Summa Canister Sampling with Pre-concentration-gas Chromatography-mass Dpectrometry DU Ming-yue*, GUO Long, Lin Yong, GE Xuan, ZHANG Hou-yong (Jinan Ecology and Environment Monitoring Center of Shandong Province, Jinan 250102, China)
Abstract: A method was established for the determination of 10 ozone depleting substances(ODS) in ambient air by summa canister sampling with pre-concentration-gas chromatography-mass-spectrometry (GC-MS). Ambient air was collected by summa canister with pre-concentration, enrichment, thermal desorption by three-stage cold trap. Gas-Pro column(60 m ×0.32 mm) was used for the separation.Full scan mode and sim mode were adopted in the determination.Internal standard method was used for quantification. The results showed that when the injection volume was 400 mL, the 10 ODS were in good fitting relationship in the range of 35.0 pmol·mol-1~4.0 nmol·mol-1, and average relative response factor’sRSDs of 10 ODS were 2.5% ～14%.The detection limits were in the range of 9.6 pmol·mol-1~31.6 pmol·mol-1.The average of recoveries were in the range of 71.5% ～112.8%, and the RSDs were 0.4% ～10.9%. The method was simple, low detection limit,good precision and high accuracy in qualitative and quantitative analysis. The method can meet the requirements of ODS pmol·mol-1 ~ nmol·mol-1 concentration level in ambient air. It is suitable for the determination of 10 ODS in ambient air.
Keyowrds: ozone depleting substances; ambient air; gas chromatography-mass-spectrometry; summa canister sampling; pre-concentration
引用本文：杜明月，郭龙，林勇，等.罐采样-预浓缩-气相色谱质谱法测定环境空气中10种消耗臭氧层物质[J].化学试剂，2021，43（11）：1551-1555.
奶粉中睾酮和甲睾酮基体标准物质的定值及不确定度评定
肖月婷1,2，刘书妤*2，李晓敏1，田甜1,2，张庆合1，李秀琴*1
（1.中国计量科学研究院，北京100029；2.上海工程技术大学化学化工学院，上海201620）
摘要：建立了奶粉中睾酮和甲睾酮的同位素稀释质谱高准确度测量方法，对样品前处理方法和基质效应进行优化和考察，结果表明同位素稀释质谱和溶液稀释法可以有效减少基质效应对检测的影响，显著提高分析效率。应用该方法对奶粉中睾酮和甲睾酮基体标准物质进行均匀性检验和准确定值，并对不确定度进行详细评估。结果显示，奶粉中睾酮和甲睾酮均匀性良好，特性量值分别为19.4±1.4 μg/kg（k=2）、21.0±1.4 μg/kg（k=2）。本标准物质适用于质量控制、检测方法开发、实验室能力验证等领域。
关键词：基体标准物质；类固醇激素；奶粉；定值方法；不确定度评估
中图分类号：O6 文献标识码：A 文章编号：0258-3283（2021）--
Certification and Uncertainty Evaluationof Testosterone and Methyltestosterone Matrix Reference Material in Milk Powder XIAO Yue-ting1,2, LIU Shu-yu*2, LI Xiao-min1, Tian tian1,2, ZHANG Qing-he1, LI Xiu-qin*1 (1.NationalInstitute of Metrology,Beijing 100029,China;2.College ofChemistry and Chemical Engineering,Shanghai University of Engineering Science, Shanghai 201620, China), Huaxue Shiji, 2021, 43(11), ～
Abstract:In this study, a highly accurate method for the determination of testosterone and methyltestosterone in milk powder by isotope dilution mass spectrometry was developed, and the sample pretreatment methods and matrix effects were optimized. The result shows that isotope dilution mass spectrometry and solution dilution methods can effectively reduce the influence of matrix effects and significantly improve the analytical efficiency. The method was applied to test the homogeneity and accurately, determine the values of testosterone and methyltestosterone in milk powder, and the uncertainties were evaluated in detail. The result shows that the homogeneities of testosterone and methyltestosterone in milk powder are good, with characteristic values of 19.4±1.4μg/kg (k=2) and 21.0±1.4μg/kg (k=2), respectively. This standard is suitable for quality control, assay development, laboratory proficiency testing and other fields.
Key words: matrix reference material; steroids; milk powder; certification method; uncertainty evaluation
引用本文：肖月婷，刘书妤，李晓敏，等. 奶粉中睾酮和甲睾酮基体标准物质的定值及不确定度评定[J]. 化学试剂, 2021, 43(11):1556-1560。
聚乙烯醇微塑料对溶液中Cu2+的吸附
宫婉婷1, 2，李万海1，邹继颖*1，王晓明3，吴天舒2，陈晓彤1，卢山1，张扬1
(1. 吉林化工学院 资源与环境工程学院，吉林 吉林 132022；2. 吉林市产品质量检验院，吉林 吉林 132013；3. 吉林国际旅行卫生保健中心，吉林 吉林 132013)
摘要：微塑料是一种全球新型污染物，环境分布广，易迁移，能吸附环境介质中的其他污染物形成复合污染并通过生物摄食进入食物链。以聚乙烯醇（PVA）微塑料为吸附剂，考察其对Cu2+的吸附能力。采用FTIR、XRD、SEM等手段对吸附前后的PVA进行表征。探讨了吸附时间、铜离子初始浓度、pH、离子浓度、粒径等因素对吸附的影响。结果表明：吸附在12 h达到平衡；PVA对铜的吸附更符合二级动力学模型和Langmuir吸附等温模型；pH 4时吸附量最大；随着溶液中共存离子Na+浓度的增加，吸附量逐渐减小；粒径对吸附量的影响不显著。单分子层的表面吸附为主要吸附机制。PVA微塑料对Cu2+的吸附行为研究结果可为了解微塑料和重金属之间的相互作用机制从而准确评估微塑料的环境风险具有重要意义。
关键词：微塑料；聚乙烯醇（PVA）；重金属；吸附；Cu2+
中图分类号：X131 文献标识码：A 文章编号：0258-3283(2021)
Adsorption of Cu2+ in solution by polyvinyl alcoholmicroplasticLi Wanhai1, Gong Wanting1,2, Zou Jiying*1, Wang Xiaoming3, Wu Tianshu2, Chen Xiaotong1, lu shan1, Zhang Yang1 (1.College of Resources and Environmental Engineering, Jilin Institute of Chemical Technology, Jilin 132013; 2.Jilin City Institute of Testing on product Quality, Jilin 132013; 3.Jilin International Travel Healthcare Center, Jilin 132013)
Abstract: Microplastics are a new type of pollutant in the world, which have a large environmental stock, easily adsorb other pollutants in environmental media to form compound pollution, have a wide migration range, and can enter the food chain through biological feeding. In this paper, polyvinyl alcohol (PVA) microplastic was used as carrier and divalent copper ions as target pollutant, and the adsorption characteristics of PVA with particle size ranging from 0.3~2 mm for Cu2+ in solution were systematically studied. The effects of adsorption time, initial concentration of copper ions, pH, ionic strength and particle size on adsorption capacity were investigated. The PVA before and after adsorption was characterized by FTIR, XRD and SEM. The results showed that adsorption reached equilibrium after 12 h. The adsorption of copper ions by PVA is more in line with the second-order kinetic model and Langumuir adsorption isotherm model. The adsorption capacity is the largest when pH is4. With the increase of the strength of coexisting Na+ions in solution, the adsorption capacity decreases gradually. In this study, the smaller the particle size is, the stronger the adsorption capacity is.The particle size has no significant effect on the adsorption capacity. Chemical adsorption and monolayer adsorption are the main adsorption mechanisms. The research results of adsorption behavior of Cu2+ by PVA microplastic in this paper can provide theoretical basis for further exploring the environmental behavior and influence of microplastics adsorption of Cu ions in fresh water and the migration and transformation law of pollutants in the environment.
Key words: microplastics; polyvinyl alcohol (PVA); heavy metal;adsorption; Cu2+
引用本文：宫婉婷，李万海，邹继颖，等. 微塑料聚乙烯醇对溶液中Cu2+的吸附[J]. 化学试剂，2021，43（11）：1561-1568.
1-(4-甲氧基苯基)-3-(2-噻吩基)-2-丙烯酮与牛血清白蛋白的相互作用研究
王会镇1，赵雨1，姚小军2，刘家琴*1
(1. 西华大学 理学院，四川 成都 610039；2. 兰州大学 化学学院，甘肃 兰州 730000)
摘要：在模拟生理条件下，采用荧光光谱法和分子对接法研究了1-(4-甲氧基苯基)-3-(2-噻吩基)-2-丙烯酮（MOTPO）与BSA的结合机理，结果表明BSA与MOTPO之间为静态荧光淬灭过程，得到了BSA与MOTPO之间相互作用的结合常数和热力学数据，结合常数（Ka）的数量级为104，疏水及静电相互作用在BSA与MOTPO之间的相互作用中起着重要作用。根据共振能量转移的Fӧrster理论计算得MOTPO和BSA之间的结合距离（r）小于7 nm。进一步研究了在280 nm和295 nm激发波长下的荧光淬灭过程：MOTPO的主要结合位点位于BSA的亚结构域IIA（位点I）中；同步荧光光谱研究表明，MOTPO与BSA的结合可以诱导BSA中的构象变化。进一步讨论了常见金属离子对MOTPO-BSA复合物结合常数的影响，表明金属离子的存在可能会影响MOTPO的作用结果。分子对接表明，MOTPO可以与BSA的亚结构域IIA结合，疏水和极性起了关键作用。
关键词: 1-(4-甲氧基苯基)-3-(2-噻吩基)-2-丙烯酮；牛血清白蛋白；结合机理；荧光；金属离子；分子对接
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2021）--
Study on the Binding Mechanism of MOTPO to Bovine Serum Albumin by Fluorescence Technique and Molecular Docking Wang Hui-zhen1, Zhao Yu1, Yao Xiao-jun2, Liu Jia-qin*1 (1. School of Science, Xihua University, Sichuan, Chengdu 610039, China; 2. Department of Chemistry, Lanzhou University, Gansu, Lanzhou 730000, China), Huaxue Shiji, 2021, 43(11)
Abstract: Under imitated physiological conditions1-(4-methoxyphenyl)-3-(2-thienyl)-2- propen-one(MOTPO) can quench the fluorescence of bovine serum albumin (BSA). In this paper, the fluorescence spectrometric methods and molecular docking approach were employed to investigate the binding mechanism of MOTPO to BSA. The static fluorescence-quenching process between BSA and MOTPO was confirmed and the binding constant and thermodynamic data for the interaction between BSA and MOTPO were also obtained. Results showed that the order of magnitude of binding constant (Ka) was 104, and hydrophobic, electrostatic interactions played important role on the conjugation reaction between BSA and MOTPO.Based on the Fӧrster theory of the resonance energy transfer, the binding distance (r) between MOTPO and BSA was less than 7 nm. Comparing the quenching of protein fluorescence excited at 280 nm and 295 nm, it was shown that the primary MOTPO binding site was in the sub-domain IIA (site I) of BSA. Synchronous fluorescence spectra clearly revealed that the binding of MOTPO with BSA can induce conformation changes in BSA. The effects of common metal ions on the binding constants of MOTPO–BSA complex were also discussed, which showed that the presence of metal ions may influence the MOTPO efficacy. The molecule docking results illustrate that MOTPO can bind with the sub-domain IIA of BSA and hydrophobic and polar interactions are the key acting force.
Keywords: MOTPO; bovine serum albumin; binding mechanism; fluorescence; metal ions; molecule docking
引用本文：王会镇，赵雨，姚小军，等.1-(4-甲氧基苯基)-3-(2-噻吩基)-2-丙烯酮与牛血清白蛋白的相互作用研究[J]. 化学试剂，2021，43（11）:1569-1574.
膦酸桥联锰席夫碱化合物的合成、晶体结构及磁性质
徐艳
(宿迁学院 信息工程学院 材料工程系，江苏 宿迁 223800)
摘要：利用溶剂挥发法合成了基于膦酸桥联的新颖MnIII席夫碱三核化合物{[Mn(salen)]3(L)}ClO4 (salen2- = 乙二胺缩双水杨醛), H2L =5-羧酸-1-萘膦酸)，并采用单晶X-射线衍射、元素分析、红外光谱、粉末X-射线衍射表征了化合物的结构。MnIII席夫碱三核化合物的不对称单元中含有一个{[Mn(salen)]3(L)}+三核单元，这些三核单元由来自膦酸配体的O-P-O基团桥联3个MnIII离子中心形成，另外晶体结构中还有一个无序的ClO4- 作为平衡阴离子。这些{[Mn(salen)]3(L)}+ 三核单元之间通过π-π相互作用形成一维超分子链。MnIII席夫碱三核化合物的磁性研究表明MnIII离子之间存在反铁磁相互作用。
关键词：锰；席夫碱；膦酸；晶体结构；磁性质
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2021）--
Phosphonate Bridged MnIII-Schiff Base Compound: Synthesis, Structure and Magnetic Properties XU Yan (Department of Materials Engineering, Institute of Information Engineering, Suqian University, Suqian 223800, China), Huaxue Shiji, 2021, 43(11)
Abstract：A new trinuclear compound consisting of MnIII-Schiff base building block bridged by O-P-O units, namely, {[Mn(salen)]3(L)}ClO4 (salen2- = N,N'-(ethylene)bis-(salicylideneiminato), L = 5-(ethoxycarbonyl- naphthalen-1-yl)phosphonic acid), was synthesized by using solvent evaporation and characterized by single crystal X-ray crystallographic analysis. MnIII-Schiff base compound shows trinuclear structure- {[Mn(salen)]3(L)}+, in which O-P-O groups among the phosphonate ligand bridge three MnIII ions centers, and an additional disordered ClO4- as a balance anion. These {[Mn(salen)]3(L)}+ trimers are assembled by π-π interaction from the neighboring compounds, giving rise to supramolecular one-dimensional chain. Magnetic measurements of MnIII-Schiff base compound indicate that dominant antiferromagnetic interactions are mediated between the MnIII ions centers.
Key words：manganese; Schiff base; phosphonate; crystal structure; magnetic properties
引用本文：徐艳.膦酸桥联锰席夫碱化合物的合成、晶体结构及磁性质[J]. 化学试剂，2021，43（11）:1575-1579.
感应草多糖的化学组成与生物活性研究
廖彭莹*a，孙雪芹a，李务荣a，曾维锦a，吴家明a，杨珍珍a，张淼a,b
(广西中医药大学 a. 药学院，b. 广西壮瑶药重点实验室（壮瑶药协同创新中心），广西南宁 530200）
摘要：对感应草多糖的化学组成与生物活性进行研究。采用水提醇沉法、脱色脱蛋白透析处理，得到粗多糖、脱色多糖和精制多糖，测定多糖的主成分含量，采用薄层色谱法及柱前衍生化-高效液相色谱法（HPLC）分析多糖的单糖组成，测定多糖对DPPH·和ABTS+·的清除能力、还原能力以及对α-葡萄糖苷酶和DPP-IV酶的体外抑制作用。感应草多糖由5种单糖组成，对DPPH·和ABTS+·均有清除作用，具有还原能力，对α-葡萄糖苷酶和DPP-IV酶均有抑制作用。相关性分析表明，多糖的糖含量、糖醛酸含量、还原糖含量和蛋白质含量与其抗氧化活性、α-葡萄糖苷酶抑制活性均无显著相关性。感应草多糖具有抗氧化活性和α-葡萄糖苷酶及DPP-IV酶抑制活性。
关键词：感应草；多糖；单糖组成；抗氧化；α-葡萄糖苷酶；DPP-IV酶
中图分类号：R284.2 文献标识码：A文章编号：0258-3283（2021）
Studies on the Chemical Compositions and Biological Activities of Polysaccharides from Biophytumsensitivum LIAO Peng-ying*a, SUN Xue-qina, LI Wu-ronga, ZENG Wei-jina, WU Jia-minga, YANG Zhen-zhena, ZHANG Miaoa, b (a. College of Pharmacy, b. Guangxi Key Laboratory of Zhuang and Yao Ethnic Medicine Collaborative Innovation Center of Zhuang and Yao Ethnic Medicine, Guangxi University of Chinese Medicine, Nanning 530200, China), Huaxue Shiji, 2021, 43(11), ～
Abstracts: To study the chemical compositions and the biological activities of polysaccharides from Biophytumsensitivum. The polysaccharides were obtained by water extraction and alcohol precipitation, depigmentation, deproteinization and dialysis. The main chemical contents of polysaccharides were determined. TLC and pre-column HPLC were used to analyze the monosaccharides compositions of the polysaccharides. The DPPH· and ABTS+· scavenging abilities and the reducing power of the polysaccharides were evaluated. The α-glucosidase and DPP-IV inhibitory activities were also evaluated in vitro. The monosaccharides in the polysaccharides were mannose, rhamnose, glucose, galactose and xylose. The polysaccharides showed scavenging activities against DPPH· and ABTS+·, also possessed reducing capacity. The polysaccharides showed inhibitory activities against α-glucosidase and DPP-IV enzyme. Correlation analysis showed that the contents of sugar, uronic acid, reducing sugar and protein had no significant correlation with antioxidant activity and α-glucosidase inhibitory activity. The polysaccharides from Biophytumsensitivum showed antioxidant activities and inhibitory effect against α-glucosidase and DPP-IV enzyme.
Keywords: Biophytumsensitivum; polysaccharides; monosaccharide compositions; antioxidant activities; α-glucosidase; DPP-IV enzyme
引用本文：廖彭莹，李务荣，曾维锦，等.感应草多糖的化学组成与生物活性研究[J]. 化学试剂，2021，43（11）：1580-1585.
3-(2-甲氧基吡啶-3-基)喹啉-4(1H)-酮的合成研究
张颖1，胡玟奇1，代凯莉1，于丽芳1，刘婷1，汤杰1, 2，杨帆*1
(1. 华东师范大学 化学与分子工程学院 上海分子治疗与新药创制工程技术研究中心，上海 200062；2. 上海格苓凯生物科技有限公司，上海 200062)
摘要：发展了标题化合物的新合成方法。以2'-硝基吡啶查尔酮环氧化物为底物，经重排反应和分子内还原-环化反应合成目标化合物。通过考察催化剂、还原剂、反应温度对反应的影响，获得最优反应条件。该方法具有良好的官能团兼容性，通过此方法可以高效快速构建系列标题化合物，此外，该系列化合物亦可作为关键中间体经交叉偶联反应进行衍生化，构建结构更丰富的系列杂环化合物以应用于新药发现研究。所有产物均通过1HNMR、13CNMR和HRMS等分析方法进行了结构表征。
关键词：3-(2-甲氧基吡啶-3-基)喹啉-4(1H)-酮；2'-硝基吡啶查尔酮环氧化物；重排反应；分子内还原环化反应；Suzuki交叉偶联反应
中图分类号：O625.8 文献标识码：A 文章编号：0258-3283（2021）
Practical Synthesis of 3-(Methoxypyridin-3-yl)quinolin-4(1H)-ones by Sequential Meinwald Rearrangement/Intramolecular Reduction-cyclization Reactions ZHANG Ying1, HU Min-qi1, DAI Kai-li1, YU Li-fang1, LIU Ting1, TANG Jie1,2, YANG Fan*1 (1. Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China; 2. Shanghai Greenchem & Biotech Co., Ltd., Shanghai 200062, China), Huaxue Shiji, 2021, 43(11)
Abstract: A convenient one-pot method for the synthesis of 3-(2-methoxypyridin- 3-yl)quinolin-4(1H)-ones has been developed. Rearrangment of 2'-nitropyridine chalcone epoxide followed by intramolecular reduction-cyclization reaction afforded the desired 3-(2-methoxypyridin-3-yl)quinolin-4(1H)-ones with high yields. Moreover, further derivation successfully furnished more complicated derivatives by Suzuki cross-coupling reaction which may provide a promising potential application in exploring biological activity of 3-(pyridin-3-yl)quinolin-4(1H)-ones.
Key words: 3-(2-methoxypyridin-3-yl)quinoline-4(1H)-one; 2'-nitropyridine chalcone epoxide; rearrangement reaction; intramolecular reduction-cyclization reaction; Suzuki cross-coupling reaction
引用本文：张颖，胡玟奇，代凯莉，等. 3-(2-甲氧基吡啶-3-基)喹啉-4(1H)-酮的合成研究[J]. 化学试剂，2021，43（11）：1586-1594.
DBU催化2-氟烷基咪唑的合成及其功能化
张家荣b，李珊*a,b，杨勇健b，雷婷婷b，杜如莎b，冼丽清c
（百色学院 a.桂西区域生态环境分析和污染控制重点实验室，b. 化学与环境工程学院，c.材料科学与工程学院，广西百色533000）
摘要：含氟咪唑类化合物的合成方法进展十分缓慢，限制了其在医药、农药等领域中的应用。以20 mol%1,8-二氮杂二环十一碳-7-烯（DBU）为催化剂，含氟炔丙基脒在乙腈中60 ℃空气条件下通过5-exo-dig关环反应以中等至优秀的产率生成2-氟烷基-5-甲基咪唑。2-氟烷基-5-甲基咪唑被二氧化硒氧化生成2-氟烷基咪唑-5-甲醛，提高了产物的反应活性，并进一步尝试了其与邻苯二胺的反应，合成了2-氟烷基咪唑联苯并咪唑化合物。以上反应体系简单、操作简便，可实现大剂量2-氟烷基咪唑类化合物的合成，丰富了含氟咪唑的化合物库，推动含氟咪唑在各个领域中的应用。
关键词：含氟炔丙基脒；DBU催化；2-氟烷基咪唑；关环反应；功能化
中图分类号：O627.7 文献标识码：A 文章编号：0258-3283（2021）--
DBU-Catalyzed Synthesis of 2-Fluoroalkyl Imidazoleand Its Functionalization ZHANG Jia-rongb, LI Shan*a,b, YANG Yong-jianb, LEI Ting-tingb, DU Ru-shab, XIAN Li-qingc(a. Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi, b. School of Chemistry and Environment Engineering, c. School of Materials Science and Engineering, Baise University, Baise 533000, China), Huaxue Shiji, 2021, 43(11), ～
Abstract: The number of biologically active pharmaceuticals and agrochemicals containing fluorinated imidazole motif was still surprisingly limited due to lack of efficient methods. 20 mol% DBU wasused as the catalyst, converted fluorinated propargyl amidineto 2-fluoroalkyl-5-methyl imidazole in CH3CN at 60 ℃ under air by 5-exo-dig cyclization in moderate to excellent yields. In order to functionalize the product, 2-fluoroalkyl imidazole-5-carbaldehydes were obtained by oxidation of SeO2, which could react with o-phenylenediamines to give 2-fluoroalkyl imidazole-benzimidazoles. These simple and easy operationally reactions could be used to realize large scale synthesis of 2-fluoroalkyl imidazoles, enriching the library of fluorinated imidazole-containing compounds and promoting the application of fluorinated imidazoles in various fields.
Key words: fluorinated propargyl amidines; DBU-catalyzed; 2-fluoroalkyl imidazole; cyclization; functionalized
引用本文：张家荣，李珊，杨勇健，等. DBU催化2-氟烷基咪唑的合成及其功能化[J]. 化学试剂, 2021, 43(11): 1595-1603.
钯催化脱氢制备苯并二氢恶嗪酮类化合物研究
冀旋，胥加腾，刘仁华*
（华东理工大学 药学院，上海 200237）
摘要：针对现有合成苯并二氢恶嗪酮的方法大多存在底物范围窄、需要化学计量的氧化剂、副产物多等问题，发展了一种Pd/C催化N-取代水杨酰胺脱氢环化合成苯并二氢恶嗪酮类化合物的方法。该方法在无氧化剂和氢接受体条件下，以较高产率获得苯并二氢恶嗪酮类化合物，氢气为唯一副产物。该方法反应体系简单、原子经济性高、环境友好，符合绿色化学发展的要求。
关键词：苯并二氢恶嗪酮；Pd/C；N-取代水杨酰胺；脱氢；原子经济性
中图分类号：O626.4 文献标识码：A 文章编号：0258-3283（2021）
Synthesis of Benzodihydrooxazinones via Palladium Catalyzed Dehydrogenation JI Xuan, XU Jia-teng, LIU Ren-hua*(School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China), HuaxueShiji, 2021
Abstract: Most of the existing methods for synthesizing benzodihydrooxazinones have problems such as a narrow substrate range, a stoichiometric amount of oxidant, and many by-products. A Pd/C-catalyzed N-substituted salicylamidedehydrocyclization method was developed to synthesize benzodihydrooxazinones. The method, without any oxidants and hydrogen acceptors, obtains benzodihydrooxazinones in a higher yield, and hydrogen is the only by-product. The method has a simple reaction system, high atomic economy, environmental friendliness, and meets the requirements of green chemistry development.
Keywords: benzodihydrooxazinone; Pd/C; N-substituted salicylamide; dehydrogenation; atom economy
引用本文：冀旋，胥加腾，刘仁华.钯催化脱氢制备苯并二氢恶嗪酮类化合物研究[J]. 化学试剂，2021，43（11）：1604-1610.
新型压敏染料的合成与紫外可见光谱性能测定
王利敏，宋晓宇，张倩，陈彤，程森祥*
（河南省科学院高新技术研究中心，河南 郑州 450002）
摘要：合成了新的蓝色压敏染料，以2-甲基吲哚为原料，碳酸二甲酯为甲基化试剂，经条件优化，以97.1% 的转化率合成了N-甲基-2-甲基吲哚，然后与4-氯苯酐在甲苯中反应得到化合物吲哚酮酸，再与3-N,N-二甲氨基苯甲醚在乙酸酐中反应得到氯代吲哚紫（CIL）。整个工艺过程共计三步，每步的转化率均在90%以上。每步的反应不需要纯化处理，直接进行下步反应，工艺简单。利用1H NMR、13C NMR、IR和MS等对CIL进行了结构确认。最后还进行了紫外可见光谱性能测定，并与结晶紫内酯（CVL）进行比较。实验结果表明，CIL摩尔吸光系数大于CVL，且对酸变色稳定。
关键词：压敏染料；2-甲基吲哚；碳酸二甲酯；甲基化；紫外可见光谱
中图分类号：TQ630 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis and Ultraviolet-visible Spectrum of a Novel Pressure Sensitive Dye WANG Li-min, SONG Xiao-yu, ZHANG Qian, CHEN Tong, CHENG Sen-xiang* (High & New Technology Research Center of Henan Academy of Sciences, Zhengzhou 450002, China), Huaxue Shiji, 2021, 43(11), ～
Abstract: A novel pressure sensitive dye was synthesized. N-methylation of 2-methyl indole was synthesized using dimethyl carbonate with a 97.1% conversion, then the carborybenzoyl-indole was synthesized with 4-chlorophthalic anhydride in toluene, the target compound was afforded with m-dimethylamino-methoxybenzene in anhydride acetic acid.The synthetic route consists of three steps, the conversion rate of each step is above 90%. The structure of target compound was confirmed by1H NMR、13C NMR、IR and MS. The ultraviolet spectra of the CIL were investigated and compared with CVL. The experimental results show that the molar absorptivity of CIL is greater than that of CVL, and it is stable to acid discoloration.
Key words: pressure sensitive dye; 2-methyl indole; dimethyl carbonate; ultraviolet spectrum
引用本文：王利敏，宋晓宇，张倩，等. 新型压敏染料的合成与紫外光谱性能测定[J]. 化学试剂, 2021, 43(11): 1611-1614.
