发光铱(Ⅲ)配合物抗肿瘤活性研究及应用

铱(Ⅲ)配合物因其发光量子产率高且波长易调控、发光寿命长和光稳定性好的特点,在发光材料领域备受关注。铱(Ⅲ)配合物细胞渗透能力强,能靶向多种细胞组织并影响其结构和功能,表现出独特的抗肿瘤活性,是目前金属抗肿瘤药物特别是PDT光敏剂方向的研究热点。本文重点关注铱(Ⅲ)配合物的结构对其发光性能与抗肿瘤性能的影响,综述了近期铱(Ⅲ)配合物在生物成像、探针与传感、抗肿瘤诊疗等领域的研究进展,并对目前研究中存在的问题及其应用前景进行探讨和展望。     

四苯乙烯及其衍生物超声辅助合成与光电性能研究

四苯乙烯及其衍生物被广泛报道具有典型的聚集诱导发光(AIE)性能，在有机发光二极管、荧光离子探针、生物化学成像等诸多领域有着广阔的应用前景。以此为背景，可以将相关前沿议题转化为本科综合实验教学方案。本文针对现有的实验教学方案设计进行了探究和改进，在原有使用McMurry偶联反应制备四苯乙烯的实验方案基础上，利用生色团上不同取代基的推拉电子效应设计平行对照试验，合成溴代、甲氧基取代的四苯乙烯衍生物，实现了荧光发射光谱最大峰波长的显著移动，使得在紫外灯下即可观察到荧光从蓝色到黄绿色的变化。利用超声辅助合成的方法，成功将反应时间从原有的6–8 h压缩至2 h，使之更适应本科教学实验所需的时间空间。除光学性能表征外，本实验还综合了循环伏安法表征产物的能带结构。本实验针对原有方案进行了诸多改进，引入平行实验锻炼科学思维、别出心裁地引入超声辅助合成法，极大地缩短了反应时间，展现出较强的前沿性、绿色性和高效性。     

微波法制备CaMoO4:Tb3+,Eu3+白色荧光粉及其发光性能研究

通过微波法制备了CaMoO4:Tb3+,Eu3+白色荧光粉.采用X射线粉末衍射仪、扫描电子显微镜和荧光光谱仪对样品材料的结构、形貌和发光性能进行了表征.分别讨论了在不同助剂、不同反应浓度、不同反应温度及稀土离子Eu3+和Tb3+共掺比例变化对荧光粉的发光性能的影响.结果表明:不加活性剂所得CaMoO4:Tb3+,Eu3+样品在反应浓度为0.06 mol/L、反应温度为120℃时发光性能最好;通过调节CaMoO4:Tb3+,Eu3+荧光粉中稀土离子Eu3+和Tb3+共掺比例荧光粉的发光颜色可以很容易地从冷白光变为暖白光.     

复合电极La-Ni-B的制备及电催化偏硼酸钠的性能

为进一步提高对偏硼酸钠电催化还原的效率,采用化学镀的方法,以铜片为基体,PdCl2乙醇胶体溶液为活化剂,乙醇为化学镀溶剂,制备了稀土复合电极La-Ni-B.并采用XRD、SEM、EDS方法对催化剂进行表征分析,结果表明稀土合金以纳米颗粒的形式附着在基体表面,所得合金膜是非晶态的.通过循环伏安法研究了复合电极La-Ni-B用于电解偏硼酸钠制备硼氢化钠的可行性.以硼氢化钠实际生产量为指标,探讨了直流、脉冲两种不同供电方式、脉冲电流频率、电解时间对电解行为的影响.结果表明稀土镧对电解偏硼酸钠有催化作用,以20 mL镀液制备的复合电极,在脉冲频率阳极时间T1=1 s,阴极时间T2=1 s时,最佳电解时间为4h.复合电极在重复使用3次的情况下,硼氢化钠产量降低15;,催化剂的重复使用性能良好.     

基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

基于电化学发光和阻抗技术研究DNA单碱基错配

单碱基错配的识别和稳定性差异在核酸多态性研究中至关重要。在同一电化学传感器平台上，采用电化学发光（ECL）和电化学阻抗（EIS）2种技术，协同研究DNA链中不同类型和不同位点的单碱基错配识别和稳定性差异。电极表面具有茎环构象的探针DNA与完全互补DNA、不同类型或不同位点单碱基错配DNA杂交前后的ECL和EIS信号强度变化有显著差异。信号强度变化可揭示单碱基错配识别的稳定性。结果表明，DNA链中心位点的C-A单碱基错配稳定性低于链两端的，靠近键合电极表面双链链端的C-A单碱基错配稳定性低于非键合电极表面双链链端的，同一中心位点C-X碱基对的稳定性顺序为C-G?C-T>C-A≥C-C。研究结果可为核酸多态性研究提供参考。     

基于苯基喹啉配体修饰的铱磷光配合物及其高效纯红光有机电致发光器件EI北大核心CSCD

通过对2,4⁃2R⁃苯基⁃4⁃甲基喹啉主配体进行修饰,在苯基空间位阻较小的2位和4位引入供或吸电子能力的取代基(甲基,Me或甲氧基,MeO),分别合成了2种铱磷光配合物(2,4⁃2Me⁃mpq)_(2)Ir(acac)和(2,4⁃2MeO⁃mpq)_(2) Ir(acac),采用元素分析、核磁共振谱和单晶X射线衍射对其组成和化学结构进行了表征与确认。它们的光致发光光谱发射波长分别为610 nm和580 nm,光致发光量子产率分别为75%和80%,HOMO/LUMO能级差分别为2.04 eV和2.19 eV。以纯红光发射的磷光配合物(2,4⁃2Me⁃mpq)_(2)Ir(acac)为客体材料,制备了结构为ITO/TAPC(30 nm)/CBP∶(2,4⁃2Me⁃mpq)_(2)Ir(acac)(30 nm)∶x%/TPBi(30 nm)/Liq(2 nm)/Al的OLED器件,并优化了掺杂浓度,在10%的优化浓度下实现了高效红光OLED发光。器件的发射波长为607 nm,CIE坐标为(0.63,0.37),最大亮度为25980 cd/m^(2),电流效率为23.11 cd/A,外量子效率(EQE)高达20.28%。