毛细管气相色谱法研究对环芳烷二氯化产物的组成

在选定毛细管柱温,载气流量、分流比、注入口和ＦＩＤ的温度等色谱条件下,分析了对环芳烷（ＰＣＰ）二氯化产物的组成。定性分析结果表明,ＰＣＰ二氯化产物除主要组分是二氯对环芳烷（ＤＣＰＣＰ）外,还含少量的一氯对环芳烷（ＭＣＰＣＰ）和三氯对环芳烷（ＴＣＰＣＰ）;ＤＣＰＣＰ的色谱图上出现了３个明显的色谱峰,证明３种异构体相对含量较高。用丙酮－石油醚混合溶剂分离去除 物得到了纯度为９９．１％的ＤＣＰＣＰ。以邻苯二甲酸二丁酯为内标物,测定了ＤＣＰＣＰ对内标物的相对质量校正因子。按内标法定量分析了ＰＣＰ二氯化产物各组分的含量,对ＤＣＰＣＰ分析的相对标准偏差小于３％。     

3,6-二取代-5,6-二氢-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

以３－芳基－４－氨基－５－巯基－１,２,４－三唑为原料,在酸催化下与醛类发生分子内的Ｍａｎｎｉｃｈ反应,合成了１４个标题化合物,其结构经元素分析、ＩＲ、＾１ＨＮＭＲ和ＭＳ确证。研究了反应条件。生物活性测定结果表明,部分化合物具有较强的生物活性。     

测定粮食、水果、蔬菜稀土总量的

以一定比例的镧、铈、镨、钕、钐的氧化物配制的混合标准溶液在酸性条件下与二溴羧基偶氮胂反应,632nm处的吸光光度在0－1．5mg/L范围内符合比耳珲律,检出限为1．5μg/L,相关系数为0．9995。方法不需加掩蔽剂。试样实测结果的相对标准偏差＜7％（n＝5）,加标回收率在84％－108％之间。     

两个二亚胺-铜(Ⅰ)-膦配合物的合成、结构和太赫兹时域光谱（英文）

本文报道了2个新的Cu(Ⅰ)配合物:[Cu(PPh3)2(dppz)]I(1)(PPh3=三苯基膦,dppz=二吡啶并[3,2-a∶2′,3′-c]吩嗪)和[Cu2(dppm)2(dppz)2]Cl2(2)(dppm=双(二苯基膦)甲烷)的合成,并通过X射线单晶衍射、元素分析、核磁共振氢(膦)谱、荧光光谱和太赫兹时域光谱对其进行了分析和表征。分析结果显示配合物1是一个单核配合物,中心Cu(Ⅰ)离子与2个含膦配体(PPh3)和1个含氮配体(dppz)进行配位,形成了一个扭曲的四面体结构。与1不同的是,配合物2是由CuCl,dppm和dppz以1∶1∶1的比例混配得到的双核配合物。其中,双膦配体dppm作为桥联配体,连接了2个Cu(Ⅰ)离子。荧光光谱表明所有的发射峰均源于金属到配体的电荷转移跃迁(MLCT)。同时,使用太赫兹时域光谱技术表征了2种配合物以及相应的配体。     

Reviving chloroquine for anti-SARS-CoV-2 treatment with cucurbit[7]uril-based supramolecular formulation

The wide-spreading SARS-CoV-2 virus has put the world into boiling water for more than a year, however pharmacological therapies to act effectively against coronavirus disease 2019 (COVID-19) remain elusive. Chloroquine (CQ), an antimalarial drug, was found to exhibit promising antiviral activity in vitro and in vivo at a high dosage, thus CQ was approved by the FDA for the emergency use authorization (EUA) in the fight against COVID-19 in the US, but later was revoked the EUA status due to the severe clinical toxicity. Herein, we show that supramolecular formulation of CQ by a macrocyclic host, curcurbit[7]uril (CB[7]), reduced its non-specific toxicity and improved its antiviral activity against coronavirus, working in synergy with CB[7]. CB[7] was found to form 1:1 host-guest complexes with CQ, with a binding constant of ∼10⁴ L/mol. The CQ-CB[7] formulation decreased the cytotoxicity of CQ against Vero E6 and L-02 cell lines. In particular, the cytotoxicity of CQ (60 μmol/L) against both Vero E6 cell line and L-02 cell lines was completely inhibited in the presence of 300 μmol/L and 600 μmol/L CB[7], respectively. Furthermore, the CB[7] alone showed astonishing antiviral activity in SARS-CoV-2 infected Vero E6 cells and mouse hepatitis virus strain A59 (MHV-A59) infected N2A cells, and synergistically improved the antiviral activity of CQ-CB[7], suggesting that CB[7]-based CQ formulation has a great potential as a safe and effective antiviral agent against SARS-CoV-2 and other coronavirus.     

[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪类衍生物的合成及生物活性研究进展

[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪作为极具前景的活性基团,在抗菌、抗肿瘤等方面具有多种药理活性,在药物和化学领域受到了广泛的关注。本文以含三唑并噻二嗪结构化合物的合成及其在抗肿瘤、抗菌等方面的生物活性为依据,对近几年国内外关于[1,2,4]三唑并[3,4-b][1,3,4]噻二嗪类化合物的研究进行分析总结,以期为后续该类新型抗肿瘤化合物的设计合成提供参考。     

新型六氢吡啶-2,3-并吲哚化合物的合成及其抗肿瘤活性

以3-取代氧化吲哚与丙烯酸酯为原料,经Michael加成反应制得中间体--3-丙酸酯取代氧化吲哚（3a~3d）; 3a~3d与甲胺发生酰胺化反应制得3 丙酰胺取代氧化吲哚（4a~4d）; 4a~4d用氢化铝锂还原-环化,合成了4个六氢吡啶-2,3-并吲哚化合物(5a~5d）; 5a和5b用氢化铝锂还原合成了2个六氢吡啶-2,3-并吲哚化合物（6a和6b）, 5a～5d, 6a和6b均为新化合物,总产率42%～61%,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。采用MTT法研究了5a～5d, 6a和6b对人肺癌细胞（A549）,人前列腺（PC-3）和人白血病细胞（K562）的体外抗肿瘤活性。结果表明：5b对A549, PC 3和K562的抑制活性均较好,其IC₅₀分别为27.2μmol·L^-1, 37.5 μmol·L^-1和21.7 μmol·L^-1。     

亚稳态分子间复合物反应机理研究

亚稳态分子间复合物（metastable intermolecular composite,MIC）由于具有超高反应燃烧速率及能量释放速率、高体积能量密度、低扩散距离和绿色环保等优点,在微型含能器件、火箭推进剂和绿色火工药剂等军用领域展现了很好的应用潜力。其反应机制与传统的含能材料不同,且具有超高速反应的瞬时性及复杂性,对其反应机理仍然缺乏清晰的认识,这限制了其应用研究的进展。本文对近年来亚稳态分子间复合物的反应机理研究进行综述,重点讨论具有代表性的“金属-氧翻转机理”和“预点火-熔结机理”。对于MIC材料的反应机理研究,本文主要从实验研究、理论模型研究和数值模拟研究三个方面进行分析。改性MIC材料是对材料性能进行调控的重要手段,是目前及未来的重要发展趋势之一,在论文最后对其反应机理做了重点叙述。通过对当前研究现状的归纳与分析,给出了当前的重要研究成果以及研究中出现的问题,并对未来的研究发展趋势进行了展望。     

Ni(II), Co(II), and Cu(II) complexes incorporating 2-pyrazinecarboxylic acid：Synthesis,characterization, electrochemical evaluation,and catalytic activity for the synthesis of 2H-indazolo[2,1-b]phthalazine-triones

Three complexes containing 2-pyrazinecarboxylate (pzca–), including [Ni(pzca)2(H2O)2], [Co(pzca)2(H2O)2], and [Cu(pzca)2(H2O)2], have been synthesized and characterized using physico-chemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complex-es were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.     

Syntheses,Structures, Electrochemistry,and Electrocatalysis of Three Copper(II) Coordination Polymers constructed from 5‐[4‐(1H‐Imidazol‐1‐yl)phenyl]‐1H‐tetrazole

Three coordination polymers (CPs) based on the 5‐[4‐(1H‐imidazol‐1‐yl)phenyl]‐1H‐tetrazole ( HL ) ligand, namely, [Cu(μ₂‐ L )(μ₄‐pbda)(H₂O)] ( 1 ), [Cu₂(μ‐Hbtc)(H₂btc)(μ₃‐OH)(μ₄‐ HL )] ( 2 ) and [Cu₅(μ₃‐ L )(μ₄‐ L )(μ₃‐ip)(μ₃‐OH)(H₂O)₂] · 2H₂O ( 3 ) (H₂pbda = 1,4‐benzenedicarboxylic acid, H₃btc = 1,3,5‐benzenetricarboxylic acid, H₂ip = isophthalic acid) were hydrothermally synthesized and structurally characterized. Complex 1 represents “weave”‐type 2D layers consisting of wave‐like 1D chains and 1D straight chains, which are further connected by hydrogen bonds to form a 3D supramolecular structure. Complex 2 exhibits a uninodal (4)‐connected 2D layer with a point symbol of {4⁴ · 6²}, in which the L ligand can be described as μ₅‐bridging and the H₂btc^– ions display multiple kinds of coordination modes to connect Cu^II ions into 1D “H”‐type Cu‐H₂btc chains. In complex 3 , 2D Cu‐ L layers with two kinds of grids and 1D “stair”‐type Cu‐ip chains link each other to construct a 3D {4¹² · 6³} framework, which contains the pentanuclear subunits. Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1 – 3 . Furthermore, electrochemical behaviors and electrocatalytic activities of the title complexes were analyzed at room temperature, suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions, respectively.