邻菲罗啉-芴基聚合物的金属离子荧光淬灭研究

设计并合成了一种共轭主链含5%邻菲罗啉结构单元的无规聚合物——聚(9,9-二辛基芴-2,7-二基-co-邻菲罗啉-3,8-二基)(PFO-co-Phen)。研究了不同数量级浓度的Cd2+、Ca2+、Hg2+、Sn2+、In3+、Pd2+、Na+、Zn2+、Cu2+、Mg2+对PFO-co-Phen的荧光淬灭行为。结果表明:Cu2+对PFO-co-Phen的荧光淬灭较为明显且具有一定的选择性。     

苯丙烯酸邻菲罗啉铕钇配合物的合成及荧光特性

在乙醇介质中,合成了标题化合物,测定了其组成,红外光谱及荧光光谱,结果表明,羧酸的羟基氧及邻菲罗啉中的氮原子均与稀土离子配位,铕钇配合物的荧光强度值高于铕配合物。     

1,10-邻菲罗啉-5,6二酮的合成工艺研究

以1，10-邻菲罗啉为起始原料，经氧化合成1，10-邻菲罗啉-5，6二酮，并通过正交实验探索得到其合成的最佳条件为：反应温度130℃、反应时间2h、浓硫酸和浓硝酸的加入量为70：35,产率93.11%.     

2-羰基丙酸水杨酰腙锌(Ⅱ)配合物的合成及与DNA相互作用的研究

以2-羰基丙酸水杨酰腙作为配体与六水硝酸锌在无水乙醇中进行反应,制得2-羰基丙酸水杨酰腙锌(Ⅱ)配合物,经元素分析、红外光谱和乙二胺四乙酸(EDTA)滴定等技术进行了表征。在模拟人体生理条件下,采用荧光光谱和紫外光谱,结合盐效应实验研究了2-羰基丙酸水杨酰腙锌(Ⅱ)配合物与小牛胸腺DNA(ctDNA)的相互作用。研究结果表明2-羰基丙酸水杨酰腙锌(Ⅱ)配合物对溴化乙锭小牛胸腺DNA(EB-ctDNA)体系的猝灭属于静态猝灭;根据修正的SternVolmer方程计算了不同温度下两者的结合常数,并结合Van’t Hoff方程计算出相应的热力学参数,焓变值(ΔH=-34.07kJ/mol)和熵变值(ΔS=-50.91J·mol~(-1)·K~(-1))表明氢键和范德瓦尔斯力是维持2-羰基丙酸水杨酰腙锌(Ⅱ)配合物-EB-ctDNA复合物稳定的主要作用力;2-羰基丙酸水杨酰腙锌(Ⅱ)配合物与ctDNA主要作用方式为嵌插作用,而不是沟槽作用和静电作用。     

5-硝基-1,10-邻菲罗啉的合成工艺改进

改进了5 硝基 1,10 邻菲罗啉的合成工艺,对目标产物进行了表征。新合成工艺的产率超过90%,较原方法大为提高。     

邻菲罗啉分光光度法测定肉制品中铁的含量

本文着重介绍邻菲罗啉分光光度法测定肉与肉制品中的铁，其方法简易、灵敏，便于操作。经试验该法的重复性较为满意，其方法的平均回收率为98．82％(n=10)。本法与原子吸收分光光度法作了比较试验，结果两者无显著性差异，测定值在允许误差范围内。     

用共振Rayleigh散射光谱研究12-硅钼酸和邻菲罗啉的相互作用

在醋酸钠-盐酸缓冲溶液体系中,邻菲罗啉与12-硅钼酸结合能导致共振瑞利(Rayleigh)散射(RRS)的显著增强,其最大散射波长位于382.8nm处。实验考察了体系的光谱特点、影响因素及最佳条件。该方法呈现出的高灵敏性使邻菲罗啉的检测限达到0.077μg·mL-1。同时还考察了散射增强的原因,吸收光谱和RRS光谱的关系。提出了一种简单、灵敏、快速检测邻菲罗啉的新方法。     

2-氨基-1,10-邻菲罗啉的合成

文章以1,10-邻菲罗啉为起始原料,经成盐、氧化、溴化得2-溴-1,10-邻菲罗啉,最后氨化得到2-氨基-1,10-邻菲罗啉,总收率达58.4%。     

共存离子对八元瓜环与菲罗啉及其衍生物相互作用的影响

利用紫外光谱技术考察了一些离子对八元瓜环与1,10-菲罗啉及其衍生物作用的影响,结果显示:碱金属与碱土等金属离子及强酸根离子在一定的浓度范围内影响较小;H 和OH-影响较大,在pH=2～6时能生成包结比为1:2的包结物,在碱性条件下包结物分解;弱酸酸根离子对八元瓜环与菲罗啉及其衍生物的作用影响主要因为其水解产生的OH-的影响。可以通过调节溶液的酸度来控制瓜环对底物分子的包结作用。     

咪唑喹啉衍生物与小牛胸腺DNA作用机理研究

对于咪唑喹啉衍生物(IQDs)与小牛胸腺脱氧核糖核酸(CT-DNA)的相互作用机理,采用荧光光谱法、黏度法、热变性研究和琼脂糖凝胶电泳法等实验技术进行研究.实验结果显示,咪唑喹啉衍生物Ⅰ以嵌插模式与CT-DNA作用,衍生物Ⅱ以沟槽模式与CT-DNA作用,且衍生物Ⅰ与CT-DNA的作用强于衍生物Ⅱ,而衍生物Ⅲ几乎不与CT...     

Analysis of the Interaction of Dp44mT with Human Serum Albumin and Calf Thymus DNA Using Molecular Docking and Spectroscopic Techniques

Di-2-pyridylketone-4,4,-dimethyl-3-thiosemicarbazone (Dp44mT) exhibits significant antitumor activity. However, the mechanism of its pharmacological interaction with human serum albumin (HSA) and DNA remains poorly understood. Here, we aimed to elucidate the interactions of Dp44mT with HSA and DNA using MTT assays, spectroscopic methods, and molecular docking analysis. Our results indicated that addition of HSA at a ratio of 1:1 did not alter the cytotoxicity of Dp44mT, but did affect the cytotoxicity of the Dp44mT-Cu complex. Data from fluorescence quenching and UV-VIS absorbance measurements demonstrated that Dp44mT could bind to HSA with a moderate affinity (K_a = approximately 10⁴ M⁻¹). CD spectra revealed that Dp44mT could slightly disrupt the secondary structure of HSA. Dp44mT could also interact with Ct-DNA, but had a moderate binding constant (K_EB = approximately 10⁴ M⁻¹). Docking studies indicated that the IB site of HSA, but not the IIA and IIIA sites, could be favorable for Dp44mT and that binding of Dp44mT to HSA involved hydrogen bonds and hydrophobic force, consistent with thermodynamic results from spectral investigations. Thus, the moderate binding affinity of Dp44mT with HSA and DNA partially contributed to its antitumor activity and may be preferable in drug design approaches.     

Ru（phen）3^2＋-SDBS-KMnO4化学发光体系检测半胱氨酸的研究

在20 mmol·L-1硫酸-1.2 mmol·L-1十二烷基苯磺酸钠(SDBS)介质中,半胱氨酸可以增强三(1,10-菲咯啉)钌(Ⅱ)[Ru(phen)32+]-KMnO4化学发光体系的发光强度.基于此,建立了一种化学发光直接检测半胱氨酸的新方法.在优化的实验条件下,该方法的线性范围和检测限分别为2.5×10-2-2.0μg·mL-1和2.1×10-2μg·mL-1,对11份含半胱氨酸0.5μg·mL-1的溶液平行测定的相对标准偏差(R.S.D.)为5.3%.将其用于合成样品中半胱氨酸含量的测定,结果令人满意.并提出了可能的化学发光机理.     

FITC and Ru(phen)32+ co-doped silica particles as visualized ratiometric pH indicator

The performance of fluorescein isothiocyanate (FITC) and tris(1, 10-phenanathroline) ruthenium ion (Ru(phen)32+) co-doped silica particles as pH indicator was evaluated. The emission intensity ratios of the pH sensitive dye (FITC) and the reference dye (Ru(phen)32+) in the particles were dependent on pH of the environment. The changes in emission intensity ratios of the two dyes under different pH could be measured under single excitation wavelength and readily visualized by naked eye under a 365-nm UV lamp. In particular, such FITC and Ru(phen)32+ co-doped silica particles were identified to show high sensitivity to pH around the pKa of FITC (6.4), making them be potential useful as visualized pH indicator for detection of intracellular pH micro-circumstance.     

DNA与（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1，4-丁二酸相互作用的电化学和光谱学研究

以自组装制得的DNA修饰电极为工作电极,采用循环伏安研究了抗癌药物（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1,4-丁二酸（5FUASP）与DNA的相互作用,还结合紫外-可见光谱进一步研究了这种相互作用。循环伏安测试结果表明：5FUASP与DNA在pH=6．86的缓冲溶液中有强烈的相互作用,在电极表面反应的过程为准可逆电化学反应一化学反应偶合（Ec）过程。当扫描速度较低时,EC反应是扩散控制过程;紫外吸收光谱表明抗癌药物5FUASP与DNA通过插入作用相互结合。     

Synthesis of New Five Coordinated Copper(II) and Nickel(II) Complexes of L-Valine and Kinetic Study of Copper(II) with Calf Thymus DNA

Five coordinated novel complexes of CuII and NiII have been synthesized from benzil and 1,3- diaminopropane-CuII/NiII complex and characterized by elemental analysis, i.r., n.m.r., e.p.r, molar conductance and u.v-vis, spectroscopy. The complexes are ionic in nature and exhibit pentaeoordinated geometry around the metal ion. The reaction kinetics of C25H36N5O2CuCl with calf thymus DNA was studied by u.v-vis, spectroscopy in aqueous medium. The complex after interaction with calf thymus DNA shows shift in the absorption spectrum and hypochromicity indicating an intercalative binding mode. The Kobs values have been calculated under pseudo-first order conditions. The redox behaviour of complex C25H36N5O2CuCl in the presence and in the absence of calf thymus DNA in the aqueous solution has been investigated by cyclic voltammetry. The cyclic voitammogram exhibits one quasi-reversible redox wave corresponding to CuII/CuI redox couple with E1/2 values of -0.377 and -0.237 V respectively at a scan rate of 0.1Vs-1 .On interaction with calf thymus DNA, the complex C25H36N5O2CuCl exhibits shifts in both Ep as well as in E1/2 values, indicating strong binding of the complex to the calf thymus DNA.     

Spectroscopic and Thermal Studies on Pentaerythritol Tetranitrate (PETN)

Kinetics of the thermal decomposition of pentaerythritol tetranitrate (PETN) in condensed state has been investigated by high temperature infrared spectroscopy (IR) and thermogravimetry (TG) in conjunction with pyrolysis gas analysis, differential thermal analysis (DTA) and hot-stage microscopy. Kinetics of thermolysis has been followed by IR after suppressing volatilization by matrixing and by isothermal TG without suppressing volatilization to simulate actual user conditions. The best linearity was obtained for Avrami-Erofe'ev equation, n=1, in IR and isothermal TG. Activation energy was found to be 152 kJ mol⁻¹ and log A (in s⁻¹) 16.96 by IR. The effect of additives on the initial thermolysis of PETN has been studied. Evolved gas analysis by IR shows that NO₂, H₂CO are produced in the initial stage of decomposition followed by NO, N₂O, CO₂, HCN and H₂O. The decomposition in KBr matrix shows relative preferential loss in NO₂ band intensity which indicates that the rupture of O−NO₂ bond is the primary step in the thermolysis of PETN.     

DNA分子光开关钌配合物[Ru(phen)2(dppz)]2+的研究进展

综述了近20年来典型的DNA-分子光开关钌(Ⅱ)多吡啶类配合物[Ru(phen)2(dppz)]2+在实验和理论上的研究进展与应用.阐明了该配合物的结构特征及其与DNA的作用机理、作用模式以及在一些相关热点问题上的争议,同时还介绍了该配合物在DNA-结构识别及定量分析等方面的重要应用.基于此,还对DNA-分子光开关钌配合物的开发作了展望.     

甲草胺与牛血清白蛋白相互作用的光谱法研究

在模拟人体生理条件下,采用分子光谱法研究了甲草胺与牛血清白蛋白的相互作用.结果发现,甲草胺对牛血清白蛋白的内源荧光有一定的猝灭作用,由Stern-Volmet方程和Van't Hoff等压方程分析和处理实验数据,得到了结合作用的平衡常数、结合反应的热力学参数,确定甲草胺与牛血清白蛋白主要依靠疏水作用力进行结合,该结合反...