热活化延迟荧光聚合物及其电致发光器件

热活化延迟荧光(TADF)聚合物,不仅具有小分子TADF材料高的激子利用效率特性,而且还具备分子多样性好、可溶液加工、低成本、以及易实现大面积柔性器件等诸多优势,在近几年受到广泛的关注并展现了良好的应用前景。本文从TADF聚合物分子设计原理、器件结构及发光机理出发,依据TADF聚合物的构筑方法不同,概括了其结构设计策略,详述了各种类型TADF聚合物的分子结构和光电性能及其在有机电致发光器件领域应用的研究进展,最后探讨了TADF聚合物存在的问题,并展望了其发展前景。     

铁羰基络合物制备的一氧化碳加氢催化剂的研究

本文采用Ｆｅ＿３（ＣＯ）＿（１２）制备担载型络合物催化剂。采用程序升温反应技术考察了这类催化剂（ＣＯ＋Ｈ＿２）的反应性能，井使用紫外漫反射光谱和穆斯堡尔谱对催化剂进行了表征。经２５０℃和１５０℃还原的Ｆｅ／γ－Ａｌ＿２Ｏ＿３催化剂不仅活性远远高于４５０℃还原的Ｆｅ／γ－Ａｌ＿２Ｏ＿３，而且前者在反应过程中有乙烯和乙烷生成，后者则只有甲烷生成。经２５０℃还原的Ｆｅ／分子筛催化剂的活性高于４５０℃还原的Ｆｅ／分子筛催化剂，而且前者在反应过程中有乙烯、乙烷和丙烯生成，后者则只有甲烷生成。紫外漫反射谱和穆斯堡尔谱结果表明：较温和条件下活化的催化剂上有金属于属键骨架的存在。     

椭圆法用于阳极溶出伏安法测定微量银

用新物理量Ｖｏｐ的椭圆法对阳极溶出伏安法分析的含银离子浓度为１０＾５－１０＾－９ｍｏｌ／Ｌ的一系列溶液进行了研究。结果表明：光学方法与电化学方法所得分析结果相同；椭圆法可检测的浓度下限比电化学方法低一个数量级以上。而且测量的相对平均偏差也小于电化学方法。     

Interaction between Ti-gel and silver, copper, as well as nickel compounds under ultrasound irradiation

Ag-TiO₂, Cu-TiO₂ and Ni-TiO₂ were prepared by sonication. The interactions of Ti-gel with silver, copper and nickel ions under ultrasound irradiation are very different, although these ions can be dispersed very well in titania. The results of EDXA and XRD analysis indicate that Ti-gel does not react with AgCl and crystallizes unaffectedly to form rutile. M(OH)₂ (M = Cu and Ni), on the other hand, favors polycondensation with Ti-gel and affects the crystallization of Ti-gel. CuO favors stabilization of the anatase phase. Ni²⁺ ions tend to incorporate more easily into titania than Cu²⁺ ions do when the samples are calcined. TEM, and BET were also used to characterize the samples.     

N—BOC—8—氨甲基—2—萘甲酸的改进合成法

以２－萘甲酸为原料，经硝化，酯化，重氮化，选择性催化氢化，ＢＯＣ酸酐保护等六步反应，完成了Ｎ－ＢＯＣ－８氨甲基－２－萘甲酸（１ａ）的合成，为化合物１的合成提供了新的合成途径。     

Thermal behaviour and firing characteristics of Zr/KClO4 primer mixture containing CuO

The effect of CuO on the thermal behaviour of Zr/KClO₄ primer mixtures was studied by thermoanalytical techniques, and the Bruceton method and its related calculation. It was found that the CuO catalytically promoted the decomposition of Zr/KClO₄ primer mixtures and shifted the exothermic peak of DSC curves to lower temperatures. In addition, the Zr/KClO₄ primer mixture containing CuO had a significant effect on the firing characteristics of electro-explosive devices.     

Spectroscopic evidence for triplet excitation energy transfer among carotenoids in the LH2 complex from photosynthetic bacterium <Emphasis Type="Italic">Rhodopseudomonas palustris</Emphasis>

The LH2 complex from Rhodopsudomonas (Rps.) palustris is unique in the heterogeneous carotenoid compositions. The dynamics of triplet excited state Carotenoids (³Car* has been investigated by means of sub-microsecond time-resolved absorption spectroscopy both at physiological temperature (295 K) and at cryogenic temperature (77K). Broad and asymmetric T _n ←T ₁ transient absorption was observed at room temperature following the photo-excitation of Car at 532 nm, which suggests the contribution from various carotenoid compositions having different numbers of conjugated C=C double bonds (N_c=c). The triplet absorption bands of different carotenoids, which superimposed at room temperature, could be clearly distinguished upon decreasing the temperature down to 77 K. At room temperature the shorter-wavelength side of the main T_n04T₁ absorption band decayed rapidly to reach a spectral equilibration with a characteristic time constant of ∽1 μs, the same spectral dynamics, however, was not observed at 77 K. The aforementioned spectral dynamics can be explained in terms of the triplet-excitation transfer among heterogeneous carotenoid compositions. Global spectral analysis was applied to the time-resolved spectra at room temperature, which revealed two spectral components peaked at 545 and 565 nm, and assignable to the T_n04 T₁ absorption of Cars with Nc=c=11 and Nc=c=13, respectively. Surprisingly, the decay time constant of a shorter-conjugated Car, i.e. 0.72 ώs (aerobic) and 1.36 ώs (anaerobic), is smaller than that of a longer-conjugated Car, i.e. 2.12 us (aerobic) and 3.75 ώs (anaerobic), which is contradictory to the general rule of carotenoids and relative polyenes. The results are explained in terms of triplet-excitation transfer among different types of Cars. It is postulated that two Cars with different conjugation lengths coexist in an α, β-subunit in the LH2 complex.     

Synthesis,crystal structure and property of a novel azide-bridged one-dimensional chain copper(II) complex with a dinucleating macrocyclic polyamine

An azide-bridged polymeric cationic chain complex, [LCu₂(N₃)₂]n(ClO₄)_2n ·n(H₂O)**, where L=the dinucleating macrocyclic ligand bis-p-xylylBISDIEN, has been prepared and characterized by x-ray crystallography, u.v.-vis and i.r. spectra, and by magnetic measurements. The structure consists of cationic azide-bridged [LCu₂(N₃)₂]²⁺ (unit) chains, non-coordinated perchlorate anions and crystallized water molecules. The azide anion is bound to two copper atoms in neighboring units with an end-to-end bridging mode. In each unit, the copper atoms have a different coordination geometry; Cu(1) is a four-coordinated, distorted square-planar geometry, whereas Cu(2) is a five-coordinated, distorted square-pyramid. The electronic spectra of the title complex differ in anhydrous and in aqueous MeCN solutions, indicating that dissociation and solvation occur in aqueous solutions. The characteristic i.r. absorptions of azides and perchlorates are described. Magnetic moments vary from 2.05 (B.M.) at 300K to2.01 (B.M.) at 80K, which suggests that very weak interactions exist between the metals.     

抗肿瘤药物氮三乙酰肼和金属离子配位能力的研究

本文研究了抗癌药物氮三乙酰肼(Nitrilotriacetic hydrizide,NTH)和生命必需元素以及Al~(3 ),Ga~(3 ),In~(3 )的配位能力并用pH电位法测定了它们在生理条件下(37℃,Ⅰ=150mM dm~(-3)NaCl)的配合物生成常数。电位滴定数据是用ZPLOT,MINIQUAD,ESTA等计算机程序处理的。实验结果表明NTH与它的非生理活性的母体化合物氮三乙酸相比较,对Zn~(2 ),Mn~(2 )等过渡元素的配位能力表现较大的差异性。这种情况在Revercan,ICRF-198,ICRF-236和5-烯去甲基斑蝥酸等其他抗肿瘤活性化合物中也曾观察到。 NTH与三价金属Fe~(3 ),Ga~(3 ),Al(3 )和In~(3 )等有较大的配位能力,这与它的烯醇式结构有关。由于这些配合物在广泛的pH范围内生成,以及它的高稳定性,因此有可能被用作为肿瘤定位试剂或生物体营养元素铁传输的有效载体。