Formation of Metallophthalocyanine Trimers in Liquid Solutions

For solutions of the complexes of phthalocyanine (PhC) with magnesium (Mg-PhC) and of tetrachloromethyl-PhC with zinc (Zn-PhCCh) in mixtures of glycerin with dimethyl formamide (DMF) and for Zn-PhCCh in toluene and DMF it has been found that the electron absorption spectra substantially depend on the substance concentration. It is shown that these changes are attributable to the association of the molecules of pigments. The number of molecules in the associates and the equilibrium constants for this association are determined. The formation of the trimers of Mg-PhC in binary solutions and the dimers of Zn-PhCCh in toluene, DNF, and binary solutions has been established. It has been found that on association the Q absorption bands of the pigments shift to shorter wavelengths as compared to the bands of the monomers. For the Mg-PhC trimers, the shift is = 1410 cm^–1, while for the Zn-PhCCh dimers it is 990 cm^–1 in toluene, 930 cm^–1 in DMF, and 925 cm^–1 in the mixture of DMF with glycerin. It is concluded that the structure of the trimers and dimers is of the type of a stack in which molecules are arranged in parallel one above the other at a distance of 3.5 to 4.0 Å between the planes of the molecules. In association, the fluorescence intensity of the pigments decreases substantially (the decrease corresponds to the decrease in the concentration of the monomer molecules of phthalocyanines), with the fluorescence spectra remaining unchanged. Consequently, the associates of the pigments do not display pronounced fluorescence.     

Calculating Helix-to-Coil Transitions of Duplexes Formed by Phenazine-Conjugated Oligonucleotide, Using Flourescence Melting Data

A novel intercalating phenazine derivative (Pzn) was covalently linked to the 3-end of decathymidylate via a ribose residue of the dye. A fluorescence technique was used to study double helix formation by this conjugate with poly(rA) in aqueous solutions of neutral pH, at the presence of 0.1 and 1 M sodium ions. Proportionality between thermally induced changes in the fluorescence intensity of the free conjugate and bound one was revealed, that made it possible to calculate the helix-to-coil transition from fluorescence melting data using a simple equation. The transition curves were found to be in well conformity with those constructed from absorption measurements. It was shown that the attachment of Pzn significantly enhanced the stability of poly(rA) · (dT)₁₀ duplex due to intercalation of the dye chromophore into the adenine strand. The temperature of half-dissociation was increased by 12°C, and the stabilizing increment of standard free energy was 3.2–3.6 kcal/mol at 37°C.     

Solvation and Solvent Relaxation in Swellable Copolymers as Studied by Time-Resolved Fluorescence Spectroscopy

The fluorescent probe dimethylaminonaphthylsulfonamide is covalently bound to the ends of the pol(ethylene glycol) chains of the swellable block copolymers poly(ethylene glycol)–polystyrene (PEG-PS) and poly(ethylene glycol)–poly(ethylene imine) (PEG-PEI) to investigate the molecular mobility inside the polymers, swollen by different liquids. Steady-state and time-resolved studies of the Stokes shift between absorption and fluorescence spectra reveal that the probe is solvated by both the polymer matrix and the liquid phase. The extent of solvation by the liquid and the mobility of the microenvironment of the probe depend on both the swelling volume of the polymer and the solubility of the probe in this liquid. Steady-state and time-resolved fluorescence depolarisation measurements show that the polymer matrix forms a very rigid solvent cage, which almost completely immobilizes the probe. Upon solvation of the probe by the liquid, the mobility of the probe increases. In PEG-PEI swollen by polar solvents, the mobilities of the probe itself and of its microenvironment, although not reaching the values observed in homogeneous solution, are significantly higher than in PEG-PS, due to the hydrophilic nature of the polymeric backbone in PEG-PEI.     

单个心肌细胞内钙波的微观动力学研究

利用基于近场光学原理构建的全内反射荧光显微镜研究了大鼠单个心肌细胞中的钙信号. 利用这种显微镜的快速成像和高信噪比的特点，观察到单个细胞中复杂的二维钙波斑图. 分析了单个钙信号释放事件在钙波形成、运动过程中的作用. 建立在fire-diffuse-fire模型基础上的模拟显示，由基本钙释放事件组成的钙波可以在心肌细胞中稳定存在. 此研究对进一步认识活体可激发系统的微观动力学行为有指导意义. 关键词： 近场光学 全内反射荧光显微镜 心肌细胞 钙波     

固体材料反斯托克斯荧光制冷的理论研究及其最新进展

本文首先回顾了反斯托克斯荧光制冷的历史发展,简单讨论了激光制冷的循环过程及其制冷条件;其次,概述了反斯托克斯Raman散射、反斯托克斯荧光制冷的热力学理论和热力学限制,重点介绍了适用于各种制冷材料(如稀土离子掺杂玻璃、半导体和晶体等)反斯托克斯荧光制冷研究的理论模型,并简单讨论了激光制冷实验中各种测量温度变化的实验方法及其基本原理。最后,就反斯托克斯荧光制冷的一种最新应用及其前景进行了简单介绍与展望。     

液芯光纤中溶液吸收和荧光的性质对CS2受激拉曼散射阈值的影响

利用液芯光纤技术研究了不同浓度的β-Carotene的CS₂溶液的吸收与荧光的特性对CS₂的一、二阶Stokes谱线阈值的影响.实验发现随溶液浓度(10^-8—10^-6 mol/L)增加，CS₂的一阶Stokes谱线的激发阈值相对变高；并且与纯CS₂芯液的受激拉曼散射相比较，在低抽运能量激发下，就观察到CS₂的二阶Stokes谱线.这主要是由于在CS₂的受激拉曼谱线产生的过程中，β-Carotene的CS₂溶液的吸收和荧光共同影响了CS₂的一、二阶Stokes谱线的阈值.我们进行了理论上的拟合与分析，其结果与实验符合很好. 关键词： 2受激拉曼散射阈值')" href="#">CS₂受激拉曼散射阈值 液芯光纤 吸收与荧光     

乙醚的荧光光谱及其特性

用UV-240紫外分光光度计和SP-2558多功能光谱测量系统,通过测量紫外吸收光谱和荧光光谱,对乙醚在紫外光激励下的光谱特性进行了实验研究.发现,乙醚能吸收波长小于304 nm的紫外光,产生强的荧光;乙醚的荧光峰是波长306 nm至345 nm范围的宽谱峰,峰值波长在317 nm左右.分析得出,乙醚吸收紫外光、产生荧光光谱是其分子中氧原子上的孤对电子跃迁所为.由此对乙醚荧光光谱的产生机理和特性作出了解释,并计算出了乙醚分子相应能级差.这些结果可为乙醚这种重要溶剂和麻醉剂的应用提供帮助.     

ZnSe/SiO2半导体量子点玻璃的光谱特性

对采用溶胶凝胶法制备的ZnSe/SiO2半导体量子点玻璃的光谱性质进行了测试分析.UV-Vis透射光谱中观察到光吸收边相对于体相半导体有明显蓝移.稳态发射光谱(PL)中观察到ZnSe纳米晶体的位于蓝区的基本呈高斯分布的弱的最低激子发射峰、强而宽的表面态发光带以及对应杂质能级的三个锐峰发光.时间分辨荧光光谱(TRPL)中观察到发光效率高的最低激子发射峰,并测量其荧光衰减寿命,经尾部拟合为28.5 ps.同时,结合有效质量近似(EMA)模型,估计ZnSe纳米晶体的平均粒径介于2.45~3.60 nm之间,尺寸分布基本呈高斯型.     

极化子荧光及其断层扫描对Ti:LiNbO3光波导表征研究

小极化子(Nb⁴⁺_Li)荧光处于700—950 nm谱段，对不同化学还原程度同组分的纯铌酸锂晶体的研究表明荧光的强度反映了化学还原程度的强弱.从小极化子浅层能级出发，提出以“1中心3级态跃迁”来描述小极化子的受激荧光过程.钛扩散铌酸锂光波导(Ti：LiNbO₃)表面还原程度的均匀性可能在波导制造的热扩散过程中被破坏.在对铌酸锂波导表面、深部的扫描结果中，荧光的强度呈现出表面与深部、波导内与外的差异，表面的强度是深部的6—8倍.研究表明，利用非损伤性的极化子荧光谱，对加工过程热处理进行检控是非常有效的.同时，波导内与外的荧光强度差异间接反映了波导的横切面的外形.