含萘酰亚胺光功能基元的吡唑啉酮席夫碱的合成及其光谱性质

以4-溴-1,8-萘酐为原料,经亚胺化、取代和还原反应合成了中间体N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(4),4与1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩合得到一种含萘酰亚胺光功能基元的的新型吡唑啉酮席夫碱——1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5缩N-对氨基苯基-4-哌啶-1,8-萘酰亚胺(6)。4和6的结构经1H NMR和IR确证。研究了6在不同溶剂中的光谱性质,发现其吸收光谱和荧光光谱随溶剂的极性不同而表现出不同的光谱特性。进一步研究表明6在不同溶剂中可能以不同的互变异构体存在。     

Electroluminescence of Belophores in a Wide Spectral Region

The results of spectral investigations of the electroluminescence of triazinestilbene derivatives in the amorphous state and in a polymeric matrix are presented. These compounds also possess transport properties. The use of two layers that contain belophores, i.e., triazinestilbene and naphthalimide, led to radiation in the blue and green spectral regions.     

Aromatic nitro substitution reaction between 4‐nitro‐N‐n‐butyl‐1,8‐naphthalimide and n‐heptanethiol in water–methanol binary mixtures

The second‐order rate constants of thiolysis by n‐heptanethiol on 4‐nitro‐N‐n‐butyl‐1,8‐naphthalimide (4NBN) are strongly affected by the water–methanol binary mixture composition reaching its maximum at around 50% mole fraction. In parallel solvent effects on 4NBN absorption molar extinction coefficient also shows a maximum at this composition region. From the spectroscopic study of reactant and product and the known H‐bond capacity of the mixture a rationalization that involves specific solvent H‐donor interaction with the nitro group is proposed to explain the kinetic data. Present findings also show a convenient methodology to obtain strongly fluorescent imides, valuable for peptide and analogs labeling as well as for thio‐naphthalimide derivatives preparations. Copyright © 2008 John Wiley & Sons, Ltd.     

含有萘酰亚胺单元的铕配合物合成及其发光性能研究

通过在邻菲啉中性配体上引入萘酰亚胺发色团,合成了新型含有萘酰亚胺单元的铕配合物Eu(DBM)3(PNI-phen).通过控制激发,可以得到具有萘酰亚胺和Eu³⁺特征发射的荧光光谱.通过荧光光谱和激发光谱研究了铕配合物的能量传递及发光机制.     

两种萘酰亚胺类化合物及其聚合物荧光性质的研究

本文以1,8萘酰亚胺为原料,合成了两种萘酰亚胺类型的化合物,系统地研究了它们在不同溶剂中的吸收光谱和荧光光谱.并以这两种化合物单体为基础,通过共聚合成了它们与甲基丙烯酸甲酯和N 乙烯基咔唑的嵌段共聚物.研究了聚合物在溶液和薄膜中的荧光性质.研究结果证明,所得共聚物不但保持了单体的基本荧光特性,其溶解性、成膜性、热稳定性等都得到了大大改善,是一种有应用前景的有机发光半导体材料.此外,本文还利用荧光猝灭的手段研究了萘酰亚胺类化合物与C₆₀之间的相互作用.     

萘酰亚胺类电荷转移化合物能隙的理论研究

采用TD-DFT的最优Hartree-Fock(HF)交换方法, 计算以1,8-萘酰亚胺为受体(A), 9,9-二甲基-9,10-二氢吖啶、吩噁嗪等为给体(D)构建的12种分子内电荷转移化合物的最低激发单重态和最低激发三重态的能级差(ΔE_ST), 并探寻降低ΔE_ST的方法. 结果表明: D-A型分子比相应的D-苯桥-A型分子具有更低的ΔE_ST. 增加D与A间的扭曲二面角(空间位阻)和提高D的给电子能力能够有效地降低D-A型分子的ΔE_ST. 计算发现4-(9,9-二甲基-9,10-二氢吖啶)-N-苯基-1,8-萘酰亚胺(4b)和4-(吩噁嗪)-N-苯基-1,8-萘酰亚胺(5b)的ΔE_ST分别为0.01和0.02 eV, 它们的起始荧光波长分别为575 nm和621 nm, 垂直激发的振子强度分别是0.0002和0.0025. 这两种化合物有望成为发橙红光和红光的热激活延迟荧光材料.     

Discovery of a more potent anticancer agent than C4-benzazole 1,8-naphthalimide derivatives against murine melanoma

Three novel naphthalimide-based derivatives were synthesized and tested in vitro as anticancer agents. Our previous report of the C4-benzazole 1,8-naphthalimide derivatives showed good inhibition against murine melanoma. We aimed to synthesize more potent agents and found that compound 5 reported in this article behaved 5- to 10-fold potency than our previous best results. The unique structure of compound 5 consisted of a naphthalimide framework in which C4 position was linked with an ethylenediamine group where the amino group was coupled with a 2-piconic acid moiety. Compound 5 exhibited the most potent inhibitory activity toward human DNA topoisomerase II proteins with IC₅₀ value (2.6 ± 0.1 μM) against murine B16F10 melanoma cells among the three target compounds synthesized in this study. In accordance with this finding, the results of molecular docking also revealed that compound 5 has the highest affinity with human DNA topoisomerase II among the selected compounds. Compound 5 , therefore, has high potential for becoming a lead compound.     

萘酰亚胺衍生物的合成及对苦味酸的检测

设计并合成了萘酰亚胺衍生物N-正己基-4-[2-(3-苯基硫脲)-乙氨基]-1,8-萘酰亚胺(HTN),通过NMR和MS表征了其结构。利用荧光光谱法研究了HTN对苦味酸(PA)的识别作用。研究发现,在C₂H₅OH/H₂O (2:1)体系中,HTN荧光强度随PA浓度的增加而大幅度下降。PA浓度在1×10^-6~5×10^-4 mol·L^-1范围内时,猝灭率(I₀-I)/I₀与[PA]^0.5呈线性关系,R²=0.995 5。常见苯系物,如苯胺、苯甲醛、三硝基甲苯、苯酚、苯乙烯、吡啶、对甲苯磺酸、甲苯、硝基苯及氯苯等均不干扰HTN对PA的识别。结果表明,HTN对PA具有较好的选择性和灵敏度。     

双核钌-DMBA双芳香炔化合物的合成和电化学性质

在弱碱性条件下,双核钌(III)配合物Ru₂（DMBA）₄（NO₃）₂（DMBA=tetrakis-N,N''-dimethylbenzamidinate）与不同芳香炔反应（其中芳香基团包括：NAP^me,N-甲基-1,8-萘二甲酰亚胺;NAP^iso,N-异丙基-1,8-萘二甲酰亚胺;Naphth,萘;Ant,蒽）,制备了相应的端基炔取代配合物trans-Ru₂（DMBA）₄（C₂Ar）₂（Ar=NAP^me,1;NAP^iso,2;Naphth,3;Ant,4）。利用X射线晶体衍射测定了它们的结构。所有化合物的Ru-Ru键长处于单键范围（0.2450~0.2491 nm）,它们均是抗磁性物质。进一步通过¹H NMR和UV-Vis-NIR光谱进行了表征。电化学研究表明,所有化合物显示出与芳香基团有关的2个可逆的单电子氧化还原过程（包括一个氧化过程和一个还原过程）。