2,4-二氨基喹唑啉和2,4-二氨基吡啶并[2,3-d]嘧啶衍生物的合成

以6-氯-5-氰基烟酸、3-氰基-4-氟苯甲酸、4-氰基-3-氟苯甲酸和6-氯-5氰基-2-吡啶甲酸为原料,经过酰胺化和关环两步反应合成了2,4-二氨基喹唑啉和2,4-二氨基吡啶并[2,3-d]嘧啶衍生物,该方法操作简便,除6-氯-5-氰基-2-吡啶甲酸外,其它三种酸的反应收率可达65%以上.采用氢核磁(1H NMR)、碳核磁(13C NMR)和高效液质联用(LC-MS)分析对目标产物进行了表征.采用四甲基偶氮唑盐(MTT)法考察所合成化合物的体外抗肿瘤活性测性,结果表明部分化合物对所选肿瘤细胞的增殖有一定的抑制活性,化合物4c,4d,4e和4f对人白血病细胞(K562)和人肝癌细胞(HepG2)的抑制活性强于阳性对照药5-氟尿嘧啶(5-Fu).     

Metal‐Organic Gels Based on Carboxyl‐Functionalized Benzimidazole and Their Stimuli Responsivenesses

Three multi‐responsiveness supramolecular metal‐organic gels (MOGs) have been prepared upon Ba(OAc)₂, CdSO₄·8H₂O and Pb(NO₃)₂ with a simple ligand (G17) based on a carboxyl‐functionalized benzimidazole derivative in alcoholic‐water solutions. The MOGs display the formation of well‐developed nanofibrillar networks composed of intertwined fibers which provide stability to gels structures through coordination, hydrogen bonding and π‐ π interactions characterized by using field emission scanning electron microscopy (FESEM), the fourier transform infrared (FT‐IR) spectroscopy and powder X‐ray diffraction (XRD) techniques. MOG‐1 shows good stimuli responsiveness toward the changes in K₂CrO₄, both MOG‐2 and MOG‐3 do good job toward the changes in Na₂S. Moreover, because these MOGs were formed easily by gelator with some heavy metal ion, such as Cd(II) and Pb(II), it might provide the basis for heavy metal ion capture and removal.     

Syntheses,Structures, and Properties of the 3D Lanthanide Organic Frameworks with N‐Heterocyclic Polycarboxylic Acids

Four 3D lanthanide organic frameworks from potassium pyrazine‐2, 3, 5, 6‐tetracarboxylate (K₄pztc) or potassium pyridine‐2, 3, 5, 6‐tetracarboxylate (K₄pdtc), namely, {[KEu(pztc)(H₂O)₂] · H₂O}_n ( 1 ), {[KTb(pztc)(H₂O)₂] · 1.25H₂O}_n ( 2 ), {[KLn(pdtc)(H₂O)] · H₂O}_n [Ln = Gd ( 3 ), Ho ( 4 )], were synthesized by reaction of the corresponding lanthanide oxides with K₄pztc or K₄pdtc in presence of HCl under hydrothermal conditions, and characterized by elemental analysis, TGA, IR and fluorescence spectroscopy as well as X‐ray diffraction. In complexes 1 and 2 , the dodecadentate chelator pztc^4– links four Ln^III ions and four K^I ions. The coordination mode of the pztc^4– ligand is reported for the first time herein. Complexes 3 and 4 are isostructural with earlier reported Nd, Dy, Er complexes. Moreover, the Eu^III and Tb^III complexes exhibit the characteristic luminescence.     

Chloroacetate‐Promoted Selective Oxidation of Heterobenzylic Methylenes under Copper Catalysis

The efficient selective oxidation and functionalization of C? H bonds with molecular oxygen and a copper catalyst to prepare the corresponding ketones was achieved with ethyl chloroacetate as a promoter. In this transformation, various substituted N‐heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process. The N‐heterocyclic compounds and ethyl chloroacetate work synergistically to activate C? H bonds in the methylene group, which results in the easy generation of free radical intermediates, thus leading to the corresponding ketones in good yields.     

One‐pot Synthesis of CdS Nanocrystals Hybridized with Single‐Layer Transition‐Metal Dichalcogenide Nanosheets for Efficient Photocatalytic Hydrogen Evolution

Exploration of low‐cost and earth‐abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition‐metal dichalcogenides (TMDs) showed outstanding performance as co‐catalysts for the hydrogen evolution reaction (HER), designing TMD‐hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one‐pot wet‐chemical method is developed to prepare MS₂–CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single‐layer MS₂ nanosheets with lateral size of 4–10 nm selectively grow on the Cd‐rich (0001) surface of wurtzite CdS nanocrystals. These MS₂–CdS nanohybrids possess a large number of edge sites in the MS₂ layers, which are active sites for the HER. The photocatalytic performances of WS₂–CdS and MoS₂–CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS₂–CdS nanohybrids showed enhanced stability after a long‐time test (16 h), and 70 % of catalytic activity still remained.     

One step synthesis of Fe4.4Ni17.6Se16 coupled NiSe foam as self-supported,highly efficient and durable oxygen evolution electrode

The development of cost-effective, durable and high-efficient oxygen evolution reaction (OER) electrocatalysts is an extremely critical technology for the large-scale industrial water electrolysis. Here, a new strategy is proposed to significantly enhance the electrocatalytic activity by forming a hybrid electrode of NiSe and Fe_4.4Ni_17.6Se₁₆ through direct selenization of porous iron-nickel (FeNi) alloy foam via thermal selenization process. The obtained self-supported Fe_4.4Ni_17.6Se₁₆/NiSe hybrid (FNS/NiSe) foam displays outstanding durability and remarkable catalytic activity in 1.0 M KOH with low overpotentials of 242 and 282 mV to achieve the current densities of 100 and 500 mA cm^?2, respectively. To the best of our knowledge, it exceeds most of the reported OER electrocatalysts in alkaline electrolytes.     

常见光谱技术在植物油品质检测中的应用

植物油品质检测技术中,以光谱技术为代表的更为简单方便、快速而不失准确性的无损检测技术为市场所需要。该文从植物油组成成分、市场售卖植物油掺假现状两方面对植物油的品质相关指标进行了介绍,着重介绍了红外光谱技术、拉曼光谱技术、荧光光谱技术、紫外光谱技术等不同光谱技术在植物油品质检测中的研究进展和应用现状,最后提出了光谱技术在植物油品质检测发展中的瓶颈,并对光谱技术在植物油品质检测中应用前景进行了展望。     

现代教育技术在大学化学实验教学中的应用

多媒体教育技术结合视频录像、微格教学和应用软件等新型教学手段应用于本科实验课教学,不仅能形象地展现抽象的理论概念,揭示复杂的实验原理,而且能活跃课堂气氛,激发学习兴趣,提升创新意识和提高实验效率。这一理念对学生综合素质培养和实验教学方法改革具有重要意义。     

Relationship between grain boundary diffusion in nanocrystals and amorphous microstructure

The effects of microstructure on diffusion behaviors of Ni in Zr₄₈Cu₃₆Ag₈Al₈ alloy were investigated by transmission electron microscope and secondary ion mass spectrum. The temperature dependence of Ni diffusivities in Zr₄₈Cu₃₆Ag₈Al₈ alloy with different states (metallic glass, nanocrystals and coarse crystals) has been measured in the temperature range of 693–723 K. The results show that diffusion behavior is microstructure dependence, and the relations between the microstructure and diffusion are discussed. The activity energy of the grain boundary diffusion in nanocrystals calculated by the Suzuoka solution is about 1.433 eV/atom. It is equivalent with that of metallic glass, which is attributed to the similar microstructure between the two. Copyright © 2016 John Wiley & Sons, Ltd.     

离子色谱法-间接紫外检测离子液体中三种含氟酸根阴离子

建立了离子色谱-间接紫外检测法同时分析离子液体中的三氟乙酸根(CF3COO-)、四氟硼酸根(BF4-)和三氟甲烷磺酸根(CF3SO3-)的方法。用Shodex IC NI-424阴离子交换柱作为分离柱,探讨了影响上述三种离子保留和检测的因素及其保留规律。最终选用色谱条件为:以1.75 mmol·L-1邻苯二甲酸-1.68 mmol·L-1三(羟甲基)氨基甲烷为淋洗液,柱温45℃,流速1.0 m L·min-1,UV检测波长设定在265 nm。在此条件下,可实现上述三种阴离子的同时分析,且色谱峰形良好。所测阴离子的检出限(S/N=3)为0.39~1.57 mg·L-1,保留时间和峰面积的相对标准偏差(n=5)均在1%以下。将此方法应用于测定离子液体中的三氟乙酸根、四氟硼酸根及三氟甲烷磺酸根,加标回收率为99%~102%。该方法简单、准确、可靠,具有较好的实用性。