K7[P2Mo4W13M(H2O)O61]及其有机复合材料的合成及光谱研究

用降解法制得了Dawson结构铬、铁取代的磷钼钨酸钾,并将其与溴化(E)-N-丁基-4-(2-(4-二甲氨基苯基)乙烯基)吡啶反应制备了有机复合材料.通过元素分析和TG-DTA确定了配合物的组成分别为K7[P2Mo4W13M(H2O)O61](M=Cr(1),Fe(2))和(C19H25N2)6K3[P2Mo4W13MO62](M=Cr(3),Fe(4)).利用红外光谱、紫外-可见光谱、固体漫反射紫外-可见-近红外光谱、X射线光电子能谱以及荧光光谱对上述化合物进行了表征,并研究了复合材料中无机与有机组分间的相互作用及其荧光性质.     

应用于生物医疗领域的碳纳米点及其复合物

碳纳米点作为新兴的碳纳米材料,具备制备成本低、尺寸小、低毒、生物相容性高、水溶性好、易修饰、光物理性质独特等诸多优点,在生物医疗领域展现了独有的优势和应用前景。由于具有丰富的表面官能团,碳纳米点可以与靶向配体、医学影像造影剂、核酸、化学药物、光敏剂、光热转换试剂等功能性诊断治疗试剂相互作用形成复合物。目前,碳纳米点及其复合物在医学影像、基因治疗、化学药物治疗、光热、光动力治疗等生物医学诊断治疗领域的应用正在被广泛的开发和报道。这些工作对开发基于碳纳米点的医学诊断治疗试剂及其临床推进具有重要意义,为推进人类重大疾病的个体化、可视化、非入侵式、小损伤的诊断治疗提供一种新的药物体系。本文将关注应用于诊断治疗领域的碳纳米点及其复合物的设计、构建及性能研究,对已报道的基于碳纳米点的诊断治疗试剂在生物医疗领域的研究进展进行总结和讨论。     

不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的 理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质. 结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构. 通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率. 通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

Spectroscopic studies of lanthanide(III) ion complexes with diethyl(phthalimidomethyl) phosphonate

Complexation and photophysical properties of complexes of lanthanide ions, Ln(III), with diethyl(phthalimidomethyl)phosphonate ligand, DPIP, were studied. Interactions between Ln(III) and DPIP were investigated using Nd(III) absorption and Eu(III) and Tb(III) luminescence (emission and excitation) spectra, recorded in acetonitrile solution containing different counter ions (NO₃^-, Cl^- and ClO₄^-). Results of the absorption spectroscopy have shown that counter ions play a significant role in the complexation of Ln(III)/DPIP complexes. Studies of luminescence spectra of Eu(III) and Tb(III) ions proved that the formation of Ln(III)/DPIP complexes of stoichiometry Ln:L=1:3 is preferred in solution. Based on the results of elemental analysis, Nd(III) absorption spectra and IR and NMR data, it was shown that the DPIP ligand binds Ln(III) ions via oxygen from phosphoryl group, forming complexes of a general formula Ln(DPIP)₃(NO₃)₃·H₂O, in which the NO₃^- ions are coordinated with the metal ion as bidentate ligands. Luminescent properties and energy transfer, from the ligand to Ln(III) ions in the complexes formed, were studied based on the emission and excitation spectra of Eu(III) and Tb(III). Their luminescent lifetimes and emission quantum yields were also measured.     

具有生物活性钼钨仿生配合物与ATP作用的NMR研究

在常温下合成了以邻苯二酚为配体,分别以乙二胺、1,2-丙二胺、1,3-丙二胺为抗衡离子的7种手性钼钨八面体配合物(NH2CH2CH2NH3)3[Mo(V)O2(OC6H4O)2](1),(NH2CH2CH2NH3)2[W(VI)O2(OC6H4O)2](2),(NH2CH2CH2NH3)2.5[Mo(V)0.5W(VI)0.5O2(O2C6H4)]2](3),(NH3CH2CHNH2CH3)3[Mo(V)O2(OC6H4O)2](4),(NH3CH2CHNH2CH3)2[W(VI)O2(OC6H4O)2](5),(NH3CH2CHNH2CH3)2.5[Mo(V)0.5W(VI)0.5O2(OC6H4O)2](6),(NH3CH2CH2CH3NH2)2.5[Mo(V)0.5W(VI)0.5O2(OC6H4O)2](7),并在生理条件下对其与ATP的相互作用进行了液体NMR研究,发现标题配合物的中心金属离子在纯D2O溶剂中大多数以+5价形式存在,W(VI)被还原为W(V),但与ATP混合后又转化为+6价,配合物原有的顺磁性特征完全消失.研究还发现ATP可以促进中心离子与原配体发生解离.     

Correlation between adsorption and thermal properties of lanthanide(III) dinicotinates

Structural and thermal properties of the two isostructural lanthanide metal-organic frameworks: [Er₂(pdc)₃(dmf)₂]·dmf (1) and [Tm₂(pdc)₃(dmf)₂]·dmf (2) where pdc = C₅H₃N(COO)₂²⁻ and dmf = N,N′-dimethylformamide, have been investigated. They are characterized by the BET surface area of 302 and 101 m²/g for 1 and 2, respectively. This paper deals with the influence of activation conditions on sorption properties of the investigated complexes. Thermal investigations of as-made and activated complexes point to their entirely different thermal decompositions.     

新型苯基吡唑铱(Ⅲ)配合物的合成及光物理性能研究

合成了4种新型铱配合物(ppz)₂Ir(LX)(ppz＝1-苯基吡唑,LX＝2-(2’-羟基苯基)苯并噻唑(BTZ),2-(3’-甲基-2’-羟基苯基)苯并噻唑(3-MeBTZ),2-(4’-甲基-2’-羟基苯基)苯并噻唑(4-MeBTZ),2-(4’-三氟甲基-2’-羟基苯基)苯并噻唑(4-TfmBTZ)),并对其分子结构和光物理性能进行了表征。结果表明,4种配合物的最大发光峰分布在583～615 nm,并都在400 nm左右出现一个弱发射带。400 nm的弱发射被认为是金属离子微扰的辅助配体BTZ的单重态激子的辐射跃迁,长波段的光发射被认为是Ir(BTZ)的3MLCT三重态激子的辐射跃迁。而Ir(ppz)₂的3MLCT的三重态激子在室温下被猝灭。最强激发带位于250～310 nm,表明这些配合物的发射主要源于ppz和BTZ配体的跃迁,而不是3MLCT跃迁。与Ir(ppz)₃相比,不仅实现了室温磷光,也通过第二配体的修饰实现了对发光颜色的调制。     

钕、钐-邻苯二甲酸-1,10-邻菲咯啉配合物的合成及谱学性质

合成了稀土钕、钐的邻苯二甲酸 1,10 邻菲咯啉二元、三元配合物 ,通过元素分析、1HNMR、中红外光谱、差热 热重分析 ,确定了配合物的组成为RE2 L3 ·2H2 O ,RE2 L3 phen·2H2 O(RE :稀土离子 ,L :邻苯二甲酸根 ,phen :1,10 邻菲咯啉 ) ,讨论了配合物的谱学性质 ,并对配合物的远红外光谱、拉曼光谱进行了归属研究。     

镧、镨及钐与氨基酸配合物的滴定量热研究

用滴定量热法测定了298.15K下稀土镧(Ⅲ)、镨(Ⅲ)及钐(Ⅲ)离子与8种氨基酸配合物的稳定常数及反应焓变,并由此推出反应的吉布斯自由能变化和熵变.实验结果表明焓变是配合反应的主要驱动力;氨基酸侧链R基极性的增加对配合反应有阻碍作用,而氨基酸中环参与配合反应则有助于提高配合物的稳定性.     

Structure of zinc-borate low-melting glasses derived from IR spectroscopy data

The IR spectra of glasses of the ZnO—SrO—B₂O₃ system with constant additions of PbO, Al₂O₃, and Li₂O (20 mol. % in sum) were studied. It is established that on replacement of B₂O₃ by ZnO, the structure of the glasses is characterized by the presence of groupings with the bridge bonds B^III— O—B^III, B^III—O—B^IV, B^IV—O—B^IV and end groups B^III— O⁻; ZnO practically exerts no influence on the coordination transition [BO₃] → [BO₄]. At a high content of ZnO, zinc ions are present in both a six-and a four-coordinated state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 778–781, November–December, 2005.