A new method for inversion of hydroxyl group of carbocyclic nucleosides

The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN.     

铁催化剂在碳—氧反应中的热重研究

采用动态TG－DTG，研究了铁催化剂的制备方法、前驱化合物的 种类及 热处理对其在碳－氧反应中催化活性的影响。观察到在干混法制备催化剂时，所用铁盐分解温度越低活性越高。此外还发现，热处理可明显提高由分解温度高的含氧铁盐制备的 催化剂的活性，但对于不含氧铁盐和分解温度低的含氧铁盐无影响。     

碳点增强的Ru纳米颗粒复合材料用于碱性条件下高效电解水析氢

In the 21st century, hydrogen energy is a novel energy source. Its use is expected to mitigate the problems of environmental pollution and global warming caused by the excessive use of conventional fossil fuels. The hydrogen evolution reaction (HER) for water splitting has attracted considerable attention because of its environmental friendliness. To improve electrocatalyst performance and reduce operation cost, carbon-based metal hybrid materials exhibiting high efficiency and catalytic activity have been developed. Among them, carbon dots (CDs) have garnered significant research attention and have been widely applied in biosensing, bioimaging, and energy conversion/storage because of their facile synthesis, biocompatibility, tunable photoluminescence, excellent stability, and good electronic properties. CDs are widely used as carriers in the construction of electrocatalysts prepared from carbon-based metal hybrid materials. At present, it is believed that CDs exhibit excellent confinement effects, which can effectively inhibit the growth and agglomeration of metal nanoparticles, thereby preparing well-distributed carbon-based metal hybrid materials with a uniform and controllable size. However, the formation process of the small-molecule raw materials of CDs has not been elucidated. In this study, CDs and small-molecule raw materials from synthetic CDs were used as precursors to prepare nitrogen-doped CD-supported ruthenium nanoparticle (Ru@CDs) and small-molecule-supported ruthenium nanoparticle (Ru@Molecule) hybrid materials, respectively. The interaction between the small molecules and Ru in the process of CD formation and the effect on HER performance were explored. Moreover, we prepared different carriers such as metal organic frameworks(MOF), carbon nanotubes (CNTs), and graphene (GO)-supported ruthenium nanoparticle hybrid materials. Among them, Ru@CDs exhibited controllable size and excellent dispersibility and exhibited outstanding HER activity and good stability. Ru@CDs were found to require a low overpotential of 22 mV to reach a current density of 10 mA·cm⁻². Moreover, we observed the presence of an intermediate state between the molecules and CDs and demonstrated that the intermediate state exhibits no confinement effect. Furthermore, we found that with increasing calcination temperature, the intermediate state gradually changes to CDs. The unique spatial confinement between CDs and metal ions is key to the formation of monodisperse Ru nanoparticles. Our results confirmed that Ru@CDs serve as excellent HER catalyst supports. This work not only reveals the effect of the unique spatial confinement of CDs on the supported metals and their promoting effect on electrocatalytic activity but also provides guides the future development of CD-based metal hybrid electrocatalysts.     

碳六十内嵌复合物中钠及氯与碳六十之间的相互作用

本文用量化学及分子力学方法计算了（Ｎａ＠Ｃ６０）及（Ｃｌ＠Ｃ６０）中Ｎａ及Ｃｌ与Ｃ６０之间的相互作用，总的相互作用是吸引。在静电相互作用、色散相互作用及电子云重排斥相互作用三项中前一项占９０％以上，有着决定性的影响，色散相互作用约占５％。对电子云重叠排斥作用来说，由于Ｃｌ＾－的半径比Ｎａ＾＋的大很多，所以在（Ｃｌ＠Ｃ６０）中这种作用要比在（Ｎａ＠Ｃ６０）中大很多。     

基于氮化碳复合材料磁性固相萃取结合高效液相色谱法测定尿液中3种羟基多环芳烃

建立了测定尿液中3种羟基多环芳烃的氮化碳复合材料磁性固相萃取结合高效液相色谱-荧光检测法。所构筑的磁性氮化碳材料，经扫描电子显微镜、X射线衍射仪、振动样品磁强计和比表面积分析仪表征后，用于尿液中3种羟基多环芳烃的富集净化。考察了吸附剂用量、吸附时间、洗脱溶液和洗脱体积（单次洗脱体积×洗脱次数）对萃取效率的影响。结合高效液相色谱-荧光分析，在0.25~250 μg/L范围内线性关系良好（相关系数r=0.999），3种羟基多环芳烃的检出限和定量限分别为0.08和0.25 μg/L，回收率为90.1%~102%，日内和日间精密度分别为1.5%~7.7%和2.2%~8.7%。该本方法简单、快速、高效，可用于尿液中羟基多环芳烃的分析。     

气相色谱-微波等离子体发射光谱的研究 I. 化合物结构对经验式测定的影响

本文以烯烃、芳烃、多核芳烃、烯烃-烷烃混合物、烯烃-多核芳烃混合物、氯代烃和溴代烃等类型的化合物为代表, 考察了化合物结构对气相色谱-微波等离子体发射光谱联用测定化合物经验式结果的影响。对属于同系物的烃类选其中任一种为参比物, 测定准确度不受化合物结构的影响; 对含有非同系物的混合物, 如烯烃-多核芳烃, 参比物和被测物的结构对测定结果准确度有一定的影响, 选择其中的非同系物作参比物时, 所测得的经验式准确度相对较差; 含卤素原子的化合物结构对经验式测定影响较大, 必须选择结构相近(碳架结构和卤素原子数相近)的化合物作为经验式测定的参比物。     

富勒烯C60、C70的超分子化学

介绍了富勒烯Ｃ６０、Ｃ７０与环糊精、冠醚、杯芳烃等主体形成超分子的进展和一些潜在的应用前景。     

Ge—132与稀土离子的配合物及其对单核苷酸磷酯键的催化水解作用

Ｇｅ－１３２的羧酸阴离子与稀土离子螯合配位，生成３：１型配合物，在配合物中，Ｇｅ－１３２的ＧｅＯ３／２基团水解为Ｇｅ（ＯＨ）３，并且不参与稀土配位，系列稀土离子配合物的结构性质基本相同，在５０℃，ｐＨ值为６的水溶液中，该配合物选择性地催化５’－ＡＭＰ或５‘－ｄＡＭＰ的磷酯键水解断裂、生成相应的核苷和磷酸，而不影响碱基与戌糖之间的苷键。     

富勒烯化聚环氧丙基咔唑的合成与表征

通过Ｆｒｉｅｄｅｌ－Ｃｒｒａｆｔｓ反应制备了富勒烯化的聚环氧丙基咔唑，聚合物中Ｃ６０的含量最高可达７．６ｗｔ％。通过凝胶渗透色谱法测定了聚合物分子量，并采用＾上Ｈ和＾１３Ｃ－ＮＭＲ，ＩＲ，热分析及光谱等手段对其结构进行了分析与表征。