光谱法研究2-(4-二甲氨基苯基)-5-氟-6-吗啉-1-氢-苯并咪唑与小牛胸腺DNA的相互作用

研究了2-(4-二甲氨基苯基)-5-氟-6-吗啉-1-氢-苯并咪唑(1)在不同pH条件下的紫外-可见吸收光谱,采用非线性最小二乘法得出分子1的三级加质子常数lgβ₁, lgβ₂, lgβ₃分别为4.96±0.03, 5.72±0.07和7.95±0.10。当pH 3.40时,分子1主要以一价离子状态存在,紫外-可见吸收光谱及荧光光谱表明该条件下分子与小牛胸腺DNA存在明显的相互作用,并得出分子1与DNA的结合常数K_b为(2.30±0.10)×104 mol-1·L。当分子浓度为10-8～1.2×10-6 mol·L-1时,荧光强度随DNA含量的增加而线性增强,分子1是一种潜在的测定DNA的定量试剂。     

[Cu(DPPZ)(L-Ser)]+与DNA的相互作用及其分析应用研究

研究了DNA与铜(Ⅱ)-L丝氨酸-二吡啶并[3,2-a:2',3'-c]吩嗪配合物[Cu(DPPZ)(L-Ser)-]+相互作用的共振光散射光谱和紫外可见吸收光谱,通过研究体系与溴化乙啶相互作用的荧光光谱特征,证明其作用方式为插入作用.在pH 7.2的缓冲溶液中,[Cu(DPPZ)(L-Ser)]+由于插入作用而在DNA表面聚集,使体系的共振光散射强度增强,最大敞射峰在400 nm处.在最佳实验条件下,共振光散射增强的强度与浓度在0.42～4.20 ng·mL1范围的DNA具有良好的线性关系.方法的检出限为0.29 ng·mL-1.该法用于DNA样品的测定,回收率在97.8%～106.0%之间.     

阿霉素与DNA作用的共振光散射研究及在DNA分析中的应用

研究了抗癌药物阿霉素与DNA相互作用的吸收光谱、荧光光谱和共振光散射光谱,发现阿霉素与DNA相互作用产生强烈增强的共振光散射信号,共振光散射技术在研究DNA与阿霉素的相互作用时,其灵敏度远远高于吸收光谱和荧光光谱。DNA与阿霉素作用在322与564 nm处产生两个共振散射峰,在弱酸性条件下(pH 5.72),DNA的浓度在0～8.0 μg·mL-1范围内与散射强度呈良好的线性关系,对小牛胸腺DNA和鱼精子DNA的检出限分别为36.8和40.1 ng·mL-1。由此建立了一种选择性好,灵敏度高的DNA共振光散射分析方法。     

光谱法研究EGCG-Cu(Ⅱ)与ctDNA的相互作用

研究了EGCG-Cu(Ⅱ)-ctDNA系统的荧光光谱,电子吸收光谱和共振光散射光谱(RLS)。与EGCG-Cu(Ⅱ)二元配合物比较,EGCG-Cu(Ⅱ)-ctDNA三元体系光谱显示以下特征：(1)荧光光谱的发射位置没有变,荧光强度显著增强,并且三元体系的荧光强度随着DNA浓度增大而增大。在适宜的条件下,Cu(Ⅱ)-EGCG 配合物有望成为检测ctDNA的荧光探针;(2)电子吸收光谱有明显的增色效应;(3)共振光散射强度也增强。三种光谱的特征显示,EGCG-Cu(Ⅱ)配合物与核酸之间主要依靠插入作用和静电引力结合。由于配合物的插入,使系统的荧光强度增强,而静电作用使其电子吸收光谱和共振光散射光谱产生增色效应。酸度和离子强度对三元系统荧光强度的影响也进行了实验和讨论。     

荷叶中紫云英苷和DNA相互作用的光谱学研究

在pH 7.4 的Tris-HCl的缓冲溶液中,采用紫外及荧光光谱法研究了荷叶中紫云英苷(AST)与DNA之间的相互作用,探讨了离子强度和阴离子猝灭剂KI对紫云英苷及紫云英苷-DNA体系荧光强度的影响,同时考察了紫云英苷和中性红与DNA结合的竞争性。结果表明DNA通过静态猝灭作用机制猝灭紫云英苷的荧光,并测得其在298及308 K时的猝灭速率常数(K_q)分别为3.120 ×1012和2.630×1012 L·mol-1·s-1,结合常数(K_d)分别为3.412×104和1.762×104 L·mol-1,结合位点数(n)分别为1.007和0.962;DNA的存在使紫云英苷的紫外吸收光谱发生减色效应且吸收波长产生红移;发现离子强度的改变对紫云英苷及紫云英苷-DNA体系的荧光强度影响不大;KI对结合形式存在的紫云英苷的荧光猝灭效率明显小于自由形式存在的紫云英苷的荧光猝灭效率;紫云英苷可插入DNA中置换出与DNA结合的中性红。这些结果说明荷叶中紫云英苷以嵌插模式与DNA进行结合。     

不同电子取代基卟啉化合物的光谱和DFT研究

采用实验与密度泛函理论计算(DFT)相结合,研究了不同电子取代基修饰的5-邻羟基苯基-10,15,20-三苯基卟啉(TPPOH)和5-邻羟基苯基-10,15,20-三(对甲氧基)苯基卟啉[(p-OCH₃)TPPOH]化合物的吸收光谱及其电化学性质。结果表明,相对于TPPOH,由于对位甲氧基(-OCH₃)给电子能力强致使(p-OCH₃)TPPOH的卟啉环电子云密度增加,从而引起吸收光谱红移(3 nm)、氧化还原电位发生明显的负移,最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差降低0.06 eV。DFT理论分析分子前线轨道电子分布结果显示(p-OCH₃)TPPOH的HOMO和LUMO轨道能量均增加,而能级差却比TPPOH能级差小0.05 eV。理论结果与电化学和光谱实验结论一致,并进一步阐明了光谱和电化学性质变化机理,为揭示不同取代基卟啉化合物的设计与应用提供重要依据。     

共振光散射法研究硫酸粘杆菌素与牛血清白蛋白间的反应机理

在pH 7.40缓冲溶液条件下,以牛血清白蛋白(BSA)为检测对象,利用共振光散射法分别研究了298,310,318 K三个温度下BSA和硫酸粘杆菌素(CS)之间的相互作用机理。结果证明：该体系在反应过程中,主要的猝灭方式为生成新物质的静态猝灭;n值约为1,表明CS与BSA发生作用时只有一个结合位点;由热力学参数得知该体系的反应过程是自发进行的,药物与蛋白质主要是通过静电力结合;Hill系数约等于1,表现为零协同作用。将所得实验数据与荧光猝灭法所得数据进行比较,比较显示：利用共振光散射法所计算的猝灭参数(K_sv,K_q,n,K_a)与荧光猝灭法所得猝灭参数数值相似,猝灭结论一致,验证了该方法的正确性,说明共振光散射法用于研究蛋白质与药物的相互作用是可行的。共振光散射法与检测物质本身有无内源荧光无关,因此也可以用于没有内源荧光物质的研究,这使小分子与蛋白质相互作用的研究方法得到拓宽。     

共振光散射及荧光光谱法研究冰片对DNA的抑病机制

首次在分子水平上研究了冰片与DNA的相互作用,以期发现冰片的抗病机理.通过共振光散射技术、荧光光谱法以及粘度法,确定了冰片与DNA的作用方式为部分嵌入式.在pH7.40,温度37 ℃,离子强度低于0.01 mol/L条件下,冰片与DNA发生反应,导致410nm和470nm处的共振光散射增强,且反应体系至少在12h内保持稳定.通过改变反应体系的离子强度和pH值,发现二者的反应对离子强度及反应体系的pH值具有较强的敏感性.同时通过粘度实验和EB(溴化乙锭)荧光探针竞争实验发现:冰片的加入使DNA双螺旋发生扭结,导致DNA的粘度减少;冰片使EB-DNA体系的荧光强度降低.     

荧光猝灭光谱法测定DNA

利用荧光光谱法对5-邻氯乙酰氧基苯基-10,15,20-三苯基卟啉与脱氧核糖核酸（DNA）在不同条件下的荧光光谱特征进行了研究。实验表明,在低离子强度下,小牛胸腺DNA导致卟啉的荧光强度猝灭。在pH4.4的B-R缓冲介质中,荧光猝灭程度与小牛胸腺DNA的浓度呈线性关系,线性方程为ΔF=29.8C（μg/mL）-1.17,线性范围为0—10μg/mL,检出限为1.22μg/mL,相关系数为0.9949。对提取的植物基因组总DNA进行测试,由线性方程求得样品中的DNA含量。     

铜(Ⅱ)配合物与DNA作用的光谱法研究

采用紫外光谱和荧光光谱研究了配离子[Cu(A)₂]2＋(其中A=邻菲络啉(phen),联吡啶(bpy),乙二胺(en))与小牛胸腺DNA的相互作用。实验发现配合物的存在使DNA碱变性的pH增大,变性后增色效应减小。EB-DNA体系的荧光强度随[Cu(phen)₂]2＋的加入迅速减弱。在DNA存在下,配离子被猝灭剂[Fe(CN)₆]4-的发光猝灭程度减小。进一步研究了配体分子平面的大小对配合物与DNA作用的影响。结果表明,铜配合物与DNA之间发生了插入作用,且该作用随配体芳环平面的减小而减弱, 即[Cu(phen)₂]2＋＞[Cu(bpy)₂]2＋＞[Cu(en)₂]2＋。     

An investigation on fluorescence quenching of certain porphyrins by colloidal CdS

Certain porphyrin derivatives namely meso-tetraphenylporphyrin (TPP), meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP), meso-tetrakis(4-sulfonatophenyl)porphyrin (TSPP) were examined as sensitizers for colloidal CdS. The interaction of these porphyrins and colloidal CdS were studied by absorption, infrared, steady state and time resolved fluorescence spectroscopy and transient absorption techniques. The apparent association constants (K_app) resulting from adsorption of porphyrins on CdS surface were calculated from both absorption and fluorescence studies and they agree well. Using all the spectroscopic measurements we confirmed that the interaction between porphyrins and colloidal CdS occurs through ground state complex formation and the quenching follows static mechanism.     

The ‘size matching rule’ in di-, tri-, and tetra-cationic charged porphyrin/synthetic clay complexes: effect of the inter-charge distance and the number of charged sites

Novel inorganic/organic hybrids formed from cationic porphyrins and synthetic clay were investigated. Di-, tri- and tetra-cationic charged porphyrins with different distances between adjacent cationic sites within the molecules were incorporated into the hybrids with synthetic clay. When tetra-cationic porphyrins were used, in which distances between adjacent cation sites were 1.05 and 1.31 nm, the porphyrin molecules adsorb on the clay surfaces with high density, neutralizing all of the negative charges of the clay surface, i.e. 100% adsorption vs. the cation exchange capacity (CEC), without aggregation, even though it is generally difficult to control or suppress the aggregation of organic molecules on inorganic surfaces. The mean center-to-center distance between porphyrin molecules in the hybrids was estimated to be 2.4 nm. When Δl (the difference between the inter-cationic charge distance in the porphyrin molecule and the inter-anionic charge distance on the clay surface) was larger than ca. 0.2 nm, the porphyrin molecules adsorbed in amounts smaller than 100% vs. CEC. In the cases of di- and tri-cationic charged porphyrins, similar adsorption behavior was observed. The formation of these unique hybrids was rationalized by a size-matching of distances between the charged sites in the porphyrin molecule and on the clay surface (‘size-matching rule’).     

Zinc Oxide–Porphyrin Hybrid Rhombuses: Catalytically Active Microstructures via Self‐Assembly

A novel self‐assembled organic–inorganic hybrid structure consisting of zinc oxide and two oppositely charged porphyrins, showing significantly enhanced photocatalytic activity, is presented. Electrostatic self‐assembly of the cationic tetra‐(N‐methyl‐4‐pyridyl)porphyrin (TMPyP) with preformed assemblies of ZnO nanorods and the anionic tetra‐(4‐sulfonatophenyl)porphyrin (TPPS) in ethanol results in porphyrin microrhombuses decorated with ZnO nanorods. The structure formation is followed spectroscopically. The shape of the microrhombuses and the number of attached ZnO nanoparticles can be tuned through the porphyrin ratio TMPyP/TPPS. An enhanced and selective catalytic activity is found, giving insight into the degradation mechanism. Due to the tool‐box principle and its versatility, the concept may have great impact in fields such as solar‐energy conversion and optoelectronics.     

Charge and substituent effects on the stability of porphyrin/G-quadruplex adducts

The adduct ions of two tetramolecular G-quadruplexes formed from the d(TGGGGT) and d(TTGGGGGT) single strands with a group of cationic porphyrins, with different charges and substituents, and one neutral porphyrin, were investigated by ESI-MS and ESI-MS/MS in the negative ion mode. Formation of [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions (where Q = quadruplex, n = number of quartets minus 1, P = porphyrin and p(+) = 0,1,2,3,4) indicates that the porphyrins are bound outside the quadruplexes providing an additional stabilization to those structures. The fragmentation pathways of the [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions depend on the number of positive charges (p(+)) of the porphyrins and on the overall complex charge (z(-)), but do not show a significant dependence on the type of the substituent groups in the porphyrins. Formation of the 'unfilled' ions [Q + P(p+)-(z + p)H(+)](z-) predominates for porphyrins with a higher number of positive charges. Strand separation with the formation of [T + P(p+)-(z-2 + p)H(+)]((z-2)-) and (SS-2H(+))(2-) ions, where T = [d(TG(4)T)](3) and [d(T(2)G(5)T)](3) and SS = d(TG(4)T) and d(T(2)G(5)T) is only observed for the complexes with a higher overall negative charge. Porphyrin loss with the formation of [Q + nNH(4)(+)-(z + n)H(+)](z-) ions occurs predominantly for the neutral and monocharged porphyrins. The predominant formation of the 'unfilled' ions, [Q + P(p+)-(z + n)H(+)](z-), for porphyrins with a higher number of charges shows that these porphyrins can prevent strand separation and preserve, at least partially, the quadruplex structure.     

绿色植被红边特征的研究

通过系统分析绿色植被在紫外可见波段光谱的产生机理,得出绿峰和红边是由叶绿素产生的。从叶绿素的结构上看,它属于卟啉类化合物,为了进一步探究红边产生的机理,合成了四苯基卟啉、四(4-甲氧基苯基)卟啉、四(4-磺酸钠苯基)卟啉、四吡啶基卟啉、四甲基卟啉、四(4-甲氧基苯基)卟啉合锌和四(4-甲氧基苯基)卟啉合铜,并采用紫外可见光谱、红外及核磁进行表征。通过对其紫外可见光谱的系统分析,提出“红边”不仅限于叶绿素,而是卟啉类化合物特有的光谱特征,红边是由卟啉环a_2u(π)-e_g(π*) 跃迁产生的Q带所致。其位置不仅与卟啉的浓度相关,与卟啉化合物外侧取代基类型也有关系,金属卟啉对红边的位置影响较大。     

Enhanced photoactivity of CuPp-TiO2 photocatalysts under visible light irradiation

Three novel porphyrins, 5,10,15-tri-phenyl-20-[4-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-phenyl-10,20-di-[4-(3-phenoxy)-propoxy]phenyl porphyrin and 5-phenyl-10,15,20-tri- [4-(3-phenoxy)-propoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and characterized spectroscopically. The photocatalytic effects of TiO₂ samples impregnated with copper(II) porphyrins was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution under visible light. The photocatalysts were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectra and FT-IR spectra. The results indicated that CuPps were successfully loaded and interacted with the surface of TiO₂ microsphere, which is crucial to enhance the activity of the catalytic composite under visible light.     

Clay induced aggregation of a tetra-cationic metalloporphyrin in Layer by Layer self assembled film

Porphyrins have a general tendency to form aggregates in ultrathin films. Also electrostatic adsorption of cationic porphyrins onto anionic nano clay platelets results in the flattening of porphyrin moieties. The flattening is evidenced by the red-shifting of Soret band with respect to the aqueous solution. In the present communication, we have studied the clay induced aggregation behaviour of a tetra-cationic metalloporphyrin Manganese (III) 5, 10, 15, 20-tetra (4 pyridyl)-21 H, 23 H-porphine chloride tetrakis (methochloride) (MnTMPyP) in Layer-by-Layer (LbL) self assembled film. The adsorption of dye molecules onto nano clay platelets resulted in the flattening of the meso substituent groups of the dye chromophore. In Layer-by-Layer ultrathin film, the flattened porphyrin molecules tagged nano clay platelets were further associated to form porphyrin aggregates. This has been clearly demonstrated from the UV–vis absorption spectroscopic studies. Atomic Force Microscopic (AFM) studies gave visual evidence of the association of organo-clay hybrid molecules in the LbL film.     

无长链天然卟啉的LB膜制备与光谱研究

本工作对无长链天然血卟啉(HP),原叶啉(PP)和卟啉C行进了LB膜的成膜探索,制备了单层、多层以及与硬脂酸、卵磷脂混合后的复合LB膜.对它们进行了紫外——可见吸收光谱、荧光光谱和时间分辨荧光光谱的研究,发现在LB膜中荧光寿命是一个很好的表征手段.     

两种新型对称卟啉的合成及紫外可见光谱特性研究

本文采用一种新型的合成方法合成了两种新型对称卟啉meso-四（对苯甲酰胺基苯基）卟啉和meso－四（邻苯甲酰胺基苯基）卟啉,用元素分析,红外光谱,核磁共振谱对两种卟啉进行了表征,并对其紫外可见光谱特性进行了研究。     

DNA Binding and Photocleavage Study of Cationic Metalloporphyrins by Spectral Methods

The DNA binding and photocleavage specificities of the Zn(II), Cu(II), Co(III), Mn(III) complexes of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(4-propionoxyphenyl)porphyrin have been studied by using a combination of absorption, fluorescence titration, surface-enhanced Raman spectroscopy (SERS), induced circular dichroism (ICD) spectroscopy, thermal DNA denaturation as well as gel electrophoresis experiment. It is found that Cu(II) porphyrin has comparable binding ability with the free base porphyrin while the axial-coordinated Zn(II), Co(III), and Mn(III) porphyrins have lower K_b because of the molecular steric hindrance. However, those metalloporphyrins with lower K_b have similar DNA cleavage efficiencies with the free base porphyrin. This could be best understood by the enhancement of the ¹O₂ productivity which may also result from the steric hindrance of the axial-coordinated metalloporphyrins.