Conversion of 3‐amino‐4‐arylamino‐1H‐isochromen‐1‐ones to 1‐arylisochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐ones: synthesis,spectroscopic characterization and the structures of four products and one ring‐opened derivative

An efficient synthesis of 1‐arylisochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐ones, involving the diazotization of 3‐amino‐4‐arylamino‐1H‐isochromen‐1‐ones in weakly acidic solution, has been developed and the spectroscopic characterization and crystal structures of four examples are reported. The molecules of 1‐phenylisochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐one, C₁₅H₉N₃O₂, (I), are linked into sheets by a combination of C—H…N and C—H…O hydrogen bonds, while the structures of 1‐(2‐methylphenyl)isochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐one, C₁₆H₁₁N₃O₂, (II), and 1‐(3‐chlorophenyl)isochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐one, C₁₅H₈ClN₃O₂, (III), each contain just one hydrogen bond which links the molecules into simple chains, which are further linked into sheets by π‐stacking interactions in (II) but not in (III). In the structure of 1‐(4‐chlorophenyl)isochromeno[3,4‐d][1,2,3]triazol‐5(1H)‐one, (IV), isomeric with (III), a combination of C—H…O and C—H…π(arene) hydrogen bonds links the molecules into sheets. When compound (II) was exposed to a strong acid in methanol, quantitative conversion occurred to give the ring‐opened transesterification product methyl 2‐[4‐hydroxy‐1‐(2‐methylphenyl)‐1H‐1,2,3‐triazol‐5‐yl]benzoate, C₁₇H₁₅N₃O₃, (V), where the molecules are linked by paired O—H…O hydrogen bonds to form centrosymmetric dimers.     

Effect of the position of a methoxy substituent on the antimicrobial activity and crystal structures of 4‐methyl‐1,6‐diphenylpyrimidine‐2(1H)‐selenone derivatives

Derivatives of pyrimidine‐2(1H)‐selenone are a group of compounds with very strong antimicrobial activity. In order to study the effect of the position of the methoxy substituent on biological activity, molecular geometry and intermolecular interactions in the crystal, three derivatives were prepared and evaluated with respect to their antimicrobial activities, and their crystal structures were determined by X‐ray diffraction. The investigated compounds, namely, 1‐(X‐methoxyphenyl)‐4‐methyl‐6‐phenylpyrimidine‐2(1H)‐selenones (X = 2, 3 and 4 for 1 , 2 and 3 , respectively), C₁₈H₁₆N₂OSe, showed very strong activity against selected strains of Gram‐positive bacteria and fungi. Two compounds, 1 and 2 , crystallize in the monoclinic space group P2₁/c, while 3 crystallizes in the space group P2₁/n; 1 has two molecules in the asymmetric unit and the other two ( 2 and 3 ) have one molecule. The geometries of the investigated compounds differ slightly in the mutual orientations of the aromatic and pyrimidineselenone rings. The O atom in 1 stabilizes the conformation of the molecules via intramolecular C—H…O hydrogen bonding. The packing of molecules is determined by weak C—H…N and C—H…Se intermolecular interactions and additionally in 1 and 2 by C—H…O intermolecular interactions. The introduction of the methoxy substituent results in greater selectivity of the investigated compounds.     

Organophosphine bearing multiple hydrogen-bond donors for asymmetric Michael addition reaction of 1-oxoindane-2-carboxylic acid ester via dual-reagent catalysis

Multiple hydrogen bonds containing nucleophilic phosphines derived from dipeptide dual-reagents catalyzed asymmetric Michael addition reactions between indene esters and activated olefins in high yields and good to excellent enantioselectivities under mild reaction conditions. The success of current highly selective reactions should provide inspiration for expansion to other reactions and would open up new paradigms for the synthesis of indanone derivatives bearing chiral quaternary carbon centers.     

Theoretical Investigation on the Hydrogen Evolution,Oxygen Evolution,and Oxygen Reduction Reactions Performances of Two-Dimensional Metal-Organic Frameworks Fe3(C2X)12 (X = NH,O, S)

Two-dimensional metal-organic frameworks (2D MOFs) inherently consisting of metal entities and ligands are promising single-atom catalysts (SACs) for electrocatalytic chemical reactions. Three 2D Fe-MOFs with NH, O, and S ligands were designed using density functional theory calculations, and their feasibility as SACs for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) was investigated. The NH, O, and S ligands can be used to control electronic structures and catalysis performance in 2D Fe-MOF monolayers by tuning charge redistribution. The results confirm the Sabatier principle, which states that an ideal catalyst should provide reasonable adsorption energies for all reaction species. The 2D Fe-MOF nanomaterials may render highly-efficient HER, OER, and ORR by tuning the ligands. Therefore, we believe that this study will serve as a guide for developing of 2D MOF-based SACs for water splitting, fuel cells, and metal-air batteries.     

固相微萃取-气相色谱联用技术分析混合气体中微量氢

制备钯-5A分子筛萃取头,使用固相微萃取-气相色谱联用技术,建立了对混合气体中微量氢气的分析方法.实验结果表明,含氢浓度在0.0011~0.1250 mL/L范围内,具有良好线性关系,检出限为9×10-4mL/L.此方法和气相色谱法比较,有更高的灵敏度和更少的干扰,2种方法的标准偏差为8.7%.     

MALDI-TOF MS和电子光谱技术研究海兔肝铁蛋白亚基电离和释放铁动力学特性

选用肽质量指纹谱(peptide mass fingerprint,PMF)技术鉴定质谱纯海兔肝铁蛋白(liver ferritin ofAplysia,ALF)。来源于基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)仪中的激光和基质芥子酸协同解吸海兔肝铁蛋白(ALF)为带双电荷、单电荷[M H] 和二聚体的亚基离子,并可供质谱分析。ALF亚基的质荷比m/z分别为9784.03[M 2H]2 、19678.42[M H] 和39387.80[2M H] ,其中亚基分子量[M H] 略小于鲨鱼肝铁蛋白(liver ferritin of shark,SLF)。在弱碱介质(pH8.0)条件下,电子光谱技术研究指出,抗坏血酸以1/2级反应方式参与ALF释放铁全过程,同时又使ALF以一级反应动力学方式释放铁,呈现两种不同的速率。推测这一异常现象可能与ALF含低铁量、亚基调节能力和海兔的进化地位有关。     

基于离散小波变换的蛋白质结构、功能与进化关系延时交叉相关分析

基于氨基酸的疏水特性, 将离散小波变换与延时交叉相关分析相结合, 提出了一种分析蛋白质结构、功能和进化关系的新方法——序列小波层次相关法. 以丝氨酸蛋白酶超家族中Trypsin种属为研究对象, 描述了该方法在揭示不同物种的Trypsin蛋白质进化关系中的应用; 以蛋白质酪氨酸磷酸酶、血红蛋白和溶菌酶为例, 采用该方法揭示了蛋白质之间功能与序列的内在关系. 该方法为非参数方法, 具有简单、直观、可视和可操作性强等特点, 且不需要事先知道蛋白质的结构, 仅从蛋白质的氨基酸序列出发即可比较和揭示蛋白质之间的关系.     

Stable Zinc-Based Metal-Organic Framework Photocatalyst for Effective Visible-Light-Driven Hydrogen Production

Herein, a new Zn-MOF material, [Zn(L1)(L2)], 1, was built successfully through a one-pot solvothermal method. The 3D MOF structure was determined by Single X-ray diffraction analysis, IR, and elemental analysis. A series of PXRD tests of 1 after being immersed in different solvents and pH solutions demonstrated the good stability of 1. Interestingly, this material displayed high catalytic activity for the visible-light-driven hydrogen generation under the illumination of white LED in pure water or a mixture of DMF and H₂O without additional photosensitizers and cocatalysts. Besides, the studies also showed that the catalytic activity changed constantly as well as the solvent ratio adjustment of DMF and H₂O from 4:6 to 2:8. Additionally, the catalytic activity reached the best value (743 μmol g⁻¹ h⁻¹) when the solvent ratio was 4:6. The heterogeneous nature and recyclability of the MOF catalyst, as well as several factors that affect the catalytic activity, were investigated and described in detail. Moreover, the photocatalytic mechanism for the hydrogen generation of 1 was also proposed based on the fluorescence spectra and UV-vis absorption.     

基于概率密度演化的输电塔-线体系抗风可靠性分析

以三线两塔直线段输电塔-线体系为工程对象,应用有限元数值模拟,建立了基于概率密度演化的输电塔-线体系抗风可靠性分析方法。首先,应用谱表示-降维方法模拟结构脉动风场,生成风荷载的代表性样本集合。然后,结合概率密度演化理论,分析了输电塔-线体系考虑气弹效应的随机动力反应。最后,应用等价极值思想构建了风荷载作用下输电塔-线体系失效准则,进而对输电塔-线体系的抗风可靠性进行精细化分析。本文结合谱表示-降维方法与概率密度演化理论,实现了仅用较少数量的代表性样本来精细地分析结构的抗风可靠性,为工程实践提供参考。     

高温高压下冲击波淬火的锆基大块金属玻璃的相演化过程研究

 采用同步辐射能散X射线衍射技术,研究了高温高压下利用冲击波淬火技术制备的Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5大块金属玻璃的相演化过程。研究结果发现：在实验压力范围内,在不同压力下试样具有相同的初始析出相Zr₂Be₁₇,但是随后的相演化过程是不同的,根据应用压力的不同,试样的相演化过程可以分为3个不同的区域;另外,试样的晶化温度随着压力的增大而升高,但是在6.0 GPa存在一个突然的下降,在此压力点试样具有不同于其它压力点的相演化过程。相演化过程的不同和晶化温度的突然下降,可能归因于在不同压力下试样具有不同的原子构型。