Phosphorescent Ruthenium Complexes with a Nitroimidazole Unit that Image Oxygen Fluctuation in Tumor Tissue

Understanding oxygen fluctuation in a cancerous tumor is important for effective treatment, especially during radiotherapy. In this paper, ruthenium complexes bearing a nitroimidazole group are shown to report the oxygen status in tumor tissue directly. The nitroimidazole group was known to be accumulated in hypoxic tumor tissues. On the other hand, the ruthenium complex showed strong phosphorescence around 600 nm. The emission of ruthenium is quenched instantaneously by molecular oxygen due to energy transfer between triplet states of oxygen and ruthenium complex, but the emission is then recovered by the removal of oxygen. Thus, we could observe oxygen fluctuation in tumor tissue in a real‐time manner by monitoring the phosphorescence of the ruthenium complex. The versatility of the probe is demonstrated by monitoring oxygen fluctuation in living cells and tumor tissue planted in mice. The ruthenium complex promptly penetrated plasma membrane and accumulated in cells to emit its oxygen‐dependent phosphorescence. In vivo experiments revealed that the oxygen level in tumor tissue seems to fluctuate at the sub‐minute timescale.     

光响应超分子聚合物

超分子聚合物是超分子化学、高分子化学和材料化学领域的研究热点.将光响应的功能基团以非共价作用构筑到超分子聚合物体系中,得到光响应型超分子聚合物,从而能够将超分子聚合物的独特性质与光化学反应的优势有效地结合起来,从而构筑新型的光功能材料.本文总结了近年来本课题组有关光响应超分子聚合物方面的研究工作:介绍了主链型的光响应超分子聚合物的光调控组装和解离,超分子聚合物和共价聚合物的光控可逆切换和光调控组装形貌;另外还举例介绍了具有自修复和室温磷光发射等功能的侧链型光响应超分子聚合物,并对刺激-响应的超分子聚合物领域的发展做了展望.     

Palladium(II) Acetylide Complexes with Pincer‐Type Ligands: Photophysical Properties,Intermolecular Interactions,and Photo‐cytotoxicity

Two classes of cationic palladium(II) acetylide complexes containing pincer‐type ligands, 2,2′:6′,2′′‐terpyridine (terpy) and 2,6‐bis(1‐butylimidazol‐2‐ylidenyl)pyridine (C^N^C), were prepared and structurally characterized. Replacing terpy with the strongly σ‐donating C^N^C ligand with two N‐heterocyclic carbene (NHC) units results in the Pd^II acetylide complexes displaying phosphorescence at room temperature and stronger intermolecular interactions in the solid state. X‐ray crystal structures of [Pd(terpy)(C≡CPh)]PF₆ ( 1 ) and [Pd(C^N^C)(C≡CPh)]PF₆ ( 7 ) reveal that the complex cations are arranged in a one‐dimensional stacking structure with pair‐like Pd^II⋅⋅⋅Pd^II contacts of 3.349 Å for 1 and 3.292 Å for 7 . Density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) calculations were used to examine the electronic properties. Comparative studies of the [Pt(L)(C≡CPh)]⁺ analogs by ¹H NMR spectroscopy shed insight on the intermolecular interactions of these Pd^II acetylide complexes. The strong Pd−C_carbene bonds render 7 and its derivative sufficiently stable for investigation of photo‐cytotoxicity under cellular conditions.     

混合型间隔层对荧磷混合式白色有机电致发光器件性能的影响

制备了基于新型蓝绿色荧光MQAB与红色磷光Ir(MDQ)2acac的荧磷混合式白色有机电致发光器件,并探讨了TPBI或UGH3两种间隔层及二者的混合间隔层的器件的发光性能.研究发现,采用TPBI和UGH3的混合间隔层可以调控载流子注入与传输的平衡.当m(TPBI)∶ m(UGH3)=1∶1时,可有效地控制发光区域,使得器件性能得到优化,并获得发光亮度高达14 700 cd/m2的白色有机电致发光器件,最高电流效率可达11.60 cd/A,且器件具有较高的色稳定性.采用混合间隔层的器件比单用TPBI或UGH3作为间隔层的器件效率提高了200％ ～ 300％.     

ZnS:Mn/ZnS量子点在DNA定量分析中的应用

以巯基乙酸为稳定剂,采用成核掺杂的方法在水溶液中一步制备得到具有核壳结构的ZnS:Mn/ZnS量子点.研究了荧光、室温磷光产生的机理.基于DNA对量子点发光的增强效应,以ZnS:Mn/ZnS量子点作为标记探针建立了测定DNA的荧光、室温磷光的分析方法.考察了量子点浓度、EDC/NHS用量和反应时间等条件对DNA测定的影...     

Eu2+,Dy3+共掺杂硼铝锶长余辉玻璃陶瓷

首次介绍了一种新型长余辉材料:Eu^2 ,Dy^3 共掺杂硼铝锶长余辉玻璃陶瓷，该玻璃陶瓷用紫外灯、日光、荧光灯均可激发，发射黄绿色余辉，余辉的发射峰位于516nm，来自于Eu^2 的5d→^8S7/2跃迁。用12000 lx的荧光灯激发样品20分钟，停止激发后10秒时，该玻璃陶瓷的余辉亮度为3．53cd/m^2，色坐标为：x=0.2842,y=0.5772;停止激发后5小时55分钟，该玻璃陶瓷的余辉亮度为0．01cd/m^2；停止激发30小时后，余辉在黑暗中仍肉眼可见。文中对该玻璃陶瓷的相关性质进行了表征，并提出了可能的长余辉机理。     

磷光染料/宽禁带半导体聚合物高效率能量转移体系的电致发光

小分子磷光染料掺杂的聚合物发光器件具有发光效率高、制备工艺简单等优点，但是应该注意小分子染料的聚集与相分离问题，特别是在高掺杂浓度时更应注意防止相分离现象的发生。我们的思路是通过使用聚芴(Polyfluorene，PF)改性后的母体聚合物材料PC(poly[2，7-(9，9-dihexyl fluorene)-co-alt-2，10-(cyclohex—ane-1-spiro-6／-dibenzo[d，f][1，3]dioxepin)])，由于其发光峰位蓝移到紫外区，这就与作为掺杂分子的Ir(ppy)3配合物的吸收匹配得更好，进而达到提高能量转移效率的目的。在此条件下，可以实现较低掺杂浓度的发光，这对降低小分子染料的聚集以及相分离现象的发生是有帮助的。采用的器件结构为ITO／PEDOT：PSS/polymer:Ir(ppy)3／Ba／Al.当使用传统PF材料作为母体时，Ir(ppy)3需达到4％的掺杂比例才能实现能量的完全转移，而当采用改进后的PF作为母体时，Ir(ppy)3配合物只需达到0．5％的掺杂比例就能实现能量的完全转移，改进后的器件掺杂比例大幅度降低。     

Electronic excitation and singlet-triplet coupling in uracil tautomers and uracil-water complexes

Electronic spectra of uracil in its diketo (lactam) form and five enol (lactim) tautomeric forms have been investigated by means of combined density functional and configuration interaction methods. We have simulated the effects of hydrogen bonding with a protic solvent by recomputing the spectrum of uracil in the presence of two, four, or six water molecules. Geometries of the electronic ground state and several low-lying excited states have been optimized. Spin-orbit coupling has been determined for correlated wavefunctions employing a non-empirical spin-orbit mean-field approach. In accord with experiment, we find the diketo tautomer to be the most stable one. The calculations confirm that the first absorption band arises from the ¹( π↦π^*) S ₀↦S ₂ excitation. The experimentally observed vibrational structure in this band originates from a breathing mode of the six ring. Complexation with water molecules is seen to cause a significant blue shift of n↦π^* excitations while leaving π↦π^* excitations nearly uninfluenced. Computed radiative lifetimes are presented for the experimentally known weak phosphorescence from the π↦π^* excited T₁ state. Among the uracil lactim tautomers, one is particularly interesting from a spectroscopic point of view. In this tautomer, the π↦π^* excitation gives rise to the S₁ state. Received 18 February 2002 / Received in final form 5 June 2002 Published online 13 September 2002