Cyclometallated iridium phosphors with amino acid ancillary ligand for intracellular imaging

Two new iridium complexes, (dfppy)₂Ir(L-alanine) (dfppy=2-(2,4-difluorophenyl)pyridine) and (piq)₂Ir(L-alanine) (piq=L-phenylisoquinoline) were prepared with L-alanine as ancillary ligand. The two complexes show bright greenish-blue and red emission respectively. Theoretic study demonstrated that the emission nature of these complexes is mainly determined by the main ligand. And their improved aqueous solubility and the retained quantum yield favor their application in cell imaging. Intracellular imaging suggested that these two complexes have fine cell membrane permeability and is mainly distributed in cytoplasm. This study displayed a new strategy to design aqueous soluble phosphorescent cyclometallated Ir(Ⅲ) complex via introducing amino acid as ancillary ligand.     

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 μmol g⁻¹ h⁻¹), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.     

Synthesis of quaternary 8-(1-acylethene-1-yl)-13-methylcoptisine chlorides and their selective growth inhibitory activity between human cancer cell lines and normal intestinal epithelial cell-6

Quaternary 8-(1-acylethene-1-yl)-13-methylcoptisine chlorides targeting TrxRs were designed and synthesized. An in vitro evaluation for the growth inhibitory activities against cancer cell lines and for the viability of the normal intestinal epithelial cell-6 cell line is reported.     

Fe掺杂与天然沸石载体对TiO2光催化活性的影响

以具有多孔结构的天然斜发沸石为载体, FeCl₃和TiCl₄为前驱物制备铁离子掺杂TiO₂光催化剂. 分别在紫外光和太阳光照射下, 研究了Fe-TiO₂, TiO₂/沸石和Fe-TiO₂/沸石对甲基橙溶液(MO)的光催化分解过程, 并通过XRD, AFM, FTIR和吸收光谱等手段, 探讨了Fe和沸石对TiO2的光催化活性的影响. 结果表明, 适当浓度的Fe不仅可以提高TiO₂的光催化效率, 而且能够拓展TiO₂的吸收波长范围至可见光区. 而沸石的引入不仅提高了光催化剂的效率, 而且也增强了光催化剂的抗失活性能.     

蒸汽冷凝过程的分子团聚模型及其对不凝性气体影响传热性能的解释

根据相变过程的微观物理机理和热力学特性,提出了冷凝传热过程中,近壁面蒸汽分子经由团聚阶段进而冷凝成宏观液滴的物理模型.并将团聚体分布与滴状冷凝传热性能相联系,从而研究不凝性气体对滴状冷凝传热过程的影响.在改进的Dillmann和Meier(DM)模型基础上,将分子团聚过程中的临界过饱和度与冷凝过程中的过冷度相联系,以及将团聚体的能量特性与液固界面物理化学特性相联系,将团聚模型与考虑固液界面效应的滴状冷凝传热模型相联系,建立了近壁面条件影响的分子团聚模型.利用模型计算了近壁面蒸汽中团簇体尺寸和分布,以及不凝性气体存在导致的蒸汽冷凝团聚体分布的变化,并结合滴状冷凝传热模型,定量解释了少量不凝性气体的存在,极大影响了冷凝传热性能的现象.模型计算结果与实验结果及文献中含不凝气的蒸汽冷凝传热实验数据进行了比较,两者符合较好,验证了所提出模型的合理性.     

利用吡啶衍生物主配体共轭效应调控铱配合物发光颜色(英文)

利用2-苯基吡啶及其衍生物为主配体、四苯基膦酰亚胺为辅助配体合成了3个铱配合物Ir(ppy)2tpip(Hppy:2-苯基吡啶,Htpip:四苯基膦酰亚胺)、Ir(npy)2tpip(Hnpy:2-(1-萘基)吡啶)和Ir(pnpy)2tpip(Hpnpy:2-(9-菲基)吡啶)。它们的结构通过1H NMR和MALDI-TOF质谱进行了表征,其中配合物Ir(ppy)2tpip还进一步通过晶体结构分析验证。主配体从苯环到萘环和菲环的改变增加了配合物的π共轭,减小了能级差,导致了3种配合物的磷光发射光谱从516 nm红移到600和633 nm(从绿光到红光),发光量子效率也从0.36增加到0.51和0.53。从量化计算的结果可以看出,这种共轭效应增加了主配体的电子密度,提高了配合物的LUMO能级。配合物结构和发射性质之间的关系规律为设计不同发光颜色的铱配合物提供了思路。     

Evaluation of membranes of copolypeptide of γ-benzyl -glutamate and -glutamic acid for the permeability of anticancer drugs

The membranes of poly(γ-benzyl -glutamate-co- -glutamic acid) [P(BLG-LGA)] were prepared by saponification of poly(γ-benzyl -glutamate) (PBLG) membranes. The permeation of two anticancer drugs, 5-fluoro-uracil (5-fu) and 2-hydroxyethyl-oxy-methyl-5-fluoro-uracil (2-HEOM-5-Fu), through these membranes was studied. The results showed a sharp increase in permeability of the copolymer membranes compared to the PBLG membranes.     

基于DE历表的岁差公式

本文论证了在编制DE200历表过程中,因转换坐标历元所产生的历表分点偏离,是由目前采用的岁差公式中的行星岁差部分不够准确引起的。利用Standish拟合DE102历表所得的黄道,推导了新的岁差公式。考虑到用天体测量方法只能直接测量日月岁差ψ,故认为在天文常数系统中采用ψ代替p作为基本常数更为合适。鉴于DE200历表已被天文年历所采用,为使天文年历中的天文常数相互自洽,建议对岁差基本常数作如下改交,取 J2000.0 每儒略世纪黄经总岁差 P=50291″.0966
J2000.0 黄赤交角 ε=23°26′21″.412
或用ψ取代pJ2000.0 每儒略世纪日月岁差 ψ=5038″.7803。     

A new metric for rotating charged Gaussben Bonnet black holes in AdS space

In this paper, we study a new metric for slowly rotating charged Gauss-Bonnet black holes in higher-dimensional anti-de Sitter space. Taking the angular momentum parameter a up to second order, the slowly rotating charged black hole solutions are obtained by working directly in the action.