含芘荧光化学敏感器及其与核苷磷酸盐的相互作用

设计合成3种含芘荧光化学敏感器--化合物(Ⅰ),(Ⅱ),(Ⅲ). 研究了芘丁酸,化合物(Ⅰ),(Ⅱ),(Ⅲ)等与腺嘌呤,5-腺苷单磷酸二钠盐(AMP),5-腺苷二磷酸二钠盐(ADP),5-腺苷三磷酸四钠盐(ATP),5-脱氧胸腺嘧啶三磷酸四钠盐(dTTP)等生物活性分子相互作用时的荧光猝灭光谱,运用Stern-Volmer猝灭等方程分别求出它们相互作用时的猝灭常数及稳定常数. 结合化合物荧光寿命的测定,对含芘荧光化学敏感器在不同波长激发下所得的荧光光谱以及基态下自由分子的CPK模型等对上述含芘荧光化学敏感器同核苷磷酸盐的作用机制进行了讨论.     

芘标记有机硅聚合物的合成和荧光氧猝灭特性

合成了丙烯酸芘甲酯、二甲基乙烯基芘甲氧基硅烷、10-十一碳烯酸芘甲酯三种含芘单体,用硅氢加成方法制备了一系列含芘封端侧链的聚二甲基硅氧烷光-氧敏感高分子,并分别用四乙氧基硅烷和甲基含氢硅油A交联.对基于上述高分子的压力敏感涂料(PSP)的荧光氧猝灭和光物理行为进行了研究.结果表明,芘封端的侧基结构和交联剂对此类PSP的性能,包括激基缔合物荧光强度和氧猝灭灵敏度、Stern-Volmer关系的线性和贮存稳定性等都有明显的影响.含长碳链芘甲酯侧链的聚合物显示较高激基缔合物荧光强度和氧灵敏度;以甲基含氢硅油A作为交联剂,既能提高PSP的储存稳定性,又能提高氧猝灭灵敏度.     

阳离子荧光敏感器的器件化问题研究

通过对石英玻片表面修饰, 制作了联有多氨基链萘基的超薄膜荧光敏感器件, 研究了它在镍、铜等金属离子水溶液及有机溶剂中的荧光猝灭现象. 发现其荧光光谱无论在水或其他有机溶剂中都存在着单体和激基缔合物(ex-cimer)的发射峰, 当处于镍离子水溶液中时, 其单体峰随离子浓度的增大出现了先增强后减弱的现象, 而激基缔合物的发光峰则仅略有减弱但变化不大. 在铜离子水溶液中其荧光的变化情况和镍离子有所不同, 对单体荧光只能观察到强度减弱的趋势, 而激基缔合物则变化不大. 比较了未联结的敏感器化合物分子在有机溶剂中荧光被铜离子猝灭的行为, 发现与其在器件表面时有很大的差别, 表明其分子结构和构象也有很大的不同.     

核苷磷酸盐对含双芘侧链荧光敏感器化合物的荧光猝灭与分子识别

合成了一种在水溶液中对核苷磷酸盐ATP,ADP,AMP阴离子具有识别能力的荧光化学敏感器分子---化合物1。通过检测化合物1在水溶液中芘激基缔合物荧光发射强度随核苷磷酸盐、腺嘌呤等的加入而引起的变化,求出不同核苷磷酸盐及腺嘌呤对芘激基缔合物荧光发射的猝灭常数,并进行了比较研究。利用荧光发射强度随不同核苷磷酸盐引入而发生的变化计算出化合物1对不同核苷磷酸盐进行配位的配位稳定常数。结果表明所合成的化合物1对ATP有着良好的识别力选择功能。此外,还利用分子力学的计算方法对化合物1及其与核苷磷酸盐形成配合物后的分子构象及几何尺寸作了计算,并结合实验结果进行了初步讨论。     

多足化合物的分子内激基缔合物形成及pH对其荧光的影响

研究了含萘脲基多足化合物溶液的稳态和瞬态光物理行为.由于分子内不同足间脲基的相互作用干扰了萘基的π-π叠合,使分子内萘基的激基缔合物生成受到影响.实验表明:由于三足化合物存在着给电子叔胺基团,因此当萘基被激发时、可因分子内的光诱导电子转移而导致荧光猝灭.正因如此,在三足化合物归一化后的稳态光谱中激基缔合物的发光强度很弱.用皮秒级单光子记数技术测得该化合物的瞬态荧光为三指数衰变过程.其中最长寿命的物种,即属于生成激基缔合物后再分解为萘激发态的部分仅占总量的4%,与稳态的结果相一致.工作表明对这类可用作荧光化学敏感器的三足化合物,如利用其激基缔合物的强度变化为其识别外来物种的敏感部位并不适合.相反,如引入的外来物种能影响化合物的分子内光诱导电子转移,进而影响萘基的发光强度,则是一较好的判别外来物种是否已进入主体的标志.     

离子型表面活性剂在水溶液中的分子构型

本文利用表面活性剂分子中内在的荧光探针及外加荧光探针,研究了离子型表面活性剂分子在水溶液中的构型,烷基三苯基鱗盐及N-烷基吡啶盐对芘的单体荧光猝灭服从Stern-Volmer方程,是扩散控制的碰撞猝灭,但不同链长的猝灭剂的荧光猝灭行为呈反常状态,即链越长,猝灭速率常数越大,在十六烷基三甲基铵(CTMAB)水溶液中观察到了芘的激基缔合物荧光,同时观察到了CTMAB对芘的荧光猝灭的阻碍(阳离子猝灭剂)和促进(阴离子猝灭剂)作用,提出离子型表面活性剂在水溶液中呈绕曲状的分子构型,且是一种动态构型。     

芘荧光探针法研究C60-胶束水溶液体系的微环境性质

首次运用芘荧光探针法考察了Ｃ６０－胶束水溶液体系的微环境性质,发现Ｃ６０的介入可以改变非离子表面活性剂所形成胶束的结构而破坏胶束的有序情,从而使胶束的体积变大。Ｃ６０能显著猝灭芘单分子的荧光,而几乎不会破坏芘单体与其激基二聚体的平衡,表明Ｃ６０主要是同芘单分子之间发生ＣＴ作用。同时Ｃ６０对芘单分子荧光的猝灭在有机体系中主要呈现静态猝灭而在胶束体系中则主要呈现动态猝灭。     

基于芘的离子荧光化学传感器

芘是一种简单的芳香化合物,在溶液中可形成动态的和静态的激基缔合物,在长波长处出现荧光发射峰。利用单体和激基缔合物荧光波长的不同,芘常被用作荧光团来合成各种荧光化学传感器。本文对基于芘的荧光化学传感器的研究进展进行综述,主要包括其在单一阳离子、双阳离子和阴离子识别检测中的分子设计、作用机理和应用,并对该类荧光化学传感器的发展前景进行了展望。     

疏水作用对光化学和光物理过程的影响 Ⅶ.芘基烷基酮的荧光光谱及其在不良溶剂中的簇集

溶剂的极性对芘基烷基酮的单体荧光和激基缔合物荧光有很大影响,在非极性溶剂中单体荧光很弱,随着溶剂极性增大,单体荧光增强,单体荧光和激基缔合物荧光明显红移。利用芘基烷基酮荧光的这些性质研究了长链分子在二甲基亚砜-水(DMSO-H₂O)中的簇集现象。在浓度非常低的情况下,长链芘基烷基酮发射激基缔合物荧光,单体荧光也明显蓝移,表明芘基烷基酮形成了簇集体。长链饱和烷烃和芘基烷基酮发生共簇集,簇集体内的极性比环己烷的极性稍大。     

聚甲基苯乙基硅烷的荧光光谱

本文研究了聚甲基苯乙基硅烷(PMPES)的荧光光谱。从浓度效应和猝灭规律证明了PMPES溶液中既有分子间激基缔合物又有分子内的激基缔合物。低温荧光光谱说明在基态时有部分生色团呈激基缔合物构象。     

Synthesis of bispyrenyl sugar-aza-crown ethers as new fluorescent molecular sensors for Cu(II)

Two N-pyrenylacetamide-substituted sugar-aza-crown ethers have been synthesized as new fluorescent chemosensors. The designed ligands 1 and 2 exhibit fluorescence characteristics of a pyrene monomer and a dynamic excimer emission when compared to N-pyrenylacetamide as a model compound. Both ligands displayed a Cu2+-sensitive fluorescence quenching with a 1:1 stoichiometry and high stability constants (log K = 6.7 for 1 and 7.8 for 2). The quenching effect was rationalized on the basis of photoinduced electron transfer from the excited pyrene to the complexed Cu2+ cation, while the changes in excimer-to-monomer ratio were explained by a conformational analysis through DFT calculations. The predicted structure suggests that the Cu2+ cation is coordinated with the two carbonyl groups and the sugar-aza-crown ethers which rigidified the complex structure and placed the two pyrene moieties far apart.     

Fluorescence quenching of pyrene monomer and excimer by CH3I

The fluorescence quenching rate constants of pyrene monomer and excimer by CH₃I were obtained at several temperatures in methylcyclohexane. Both quenching processes are kinetically controlled, allowing insight on the mechanism of quenching. The rate constants have both temperature-independent and temperature-dependent components. The temperature-independent component for both monomer and excimer fluorescence is consistent with quenching due to enhanced intersystem crossing to a lower energy triplet state. The monomer temperature-dependent component comes from the enhancement of the intersystem crossing to a higher energy triplet state. The thermally activated excimer quenching is associated with the excimer dissociation step to give a pyrene in a second triplet state plus a ground state pyrene molecule.     

抗癌药物4'-O-(α-L-夹竹桃糖基)柔红霉素与小牛胸腺DNA相互作用的荧光光谱法

在pH=7.4的Tris-HCl介质中,利用荧光光谱和紫外吸收光谱法,研究了一种新型蒽环类抗癌药物柔红霉素衍生物(4′-O-(α-L-夹竹桃糖基)柔红霉素,ODNR)与小牛胸腺DNA(ctDNA)的相互作用。 通过离子强度的影响、KI荧光猝灭实验和单双链ctDNA作用的比较实验,分析了ODNR与ctDNA的相互作用模式。 结果表明,ODNR通过嵌插方式与ctDNA发生作用。 ctDNA对ODNR的荧光有明显的猝灭作用,其机理属于静态猝灭。 通过Scatchard方程求得不同温度下的结合常数和结合位点数,由热力学参数确定分子间作用力为疏水作用,也可能存在静电作用。     

Study of the diffusion of pyrene in silicone polymer coatings by steady state fluorescence technique: effects of pyrene concentration

The concentration dependence of the diffusion coefficient of pyrene in single component and two-component room temperature curing silicone polymer coatings is investigated by the steady state fluorescence technique by measuring the pyrene excimer fluorescence intensity. At pyrene concentrations lower than 10 mM, the intensity of excimer fluorescence is proportional to the concentration and at higher concentrations it deviates from this trend due to concentration quenching. Thermal aging studies show that this concentration quenching can be removed by thermal annealing and the excimer emission intensity approaches the value expected from the trend at lower concentrations. The diffusion coefficient of pyrene at low concentrations in silicone polymer coatings is obtained using the approximate solution of one-dimensional diffusion equation. A modified approach is employed to estimate the diffusion coefficient at higher pyrene concentrations. In this method, the excimer intensity and time scale are shifted, respectively to I_max the maximum value of excimer intensity attained during annealing and t_max, the time taken to reach this. The estimated diffusion coefficients at different pyrene concentrations show a negligible dependence on pyrene concentration in both types of polymers. These results are attributed to the high structural mobility of silicone polymer chains due to their molecular structure.     

Intramolecular excimer formation and delayed fluorescence in sterically constrained pyrene dimers

The synthesis is described for a series of five molecular dyads comprising pyrene-based terminals covalently linked through a 1,3-disubstituted phenylene spacer. The extent of through-space communication between the pyrene units is modulated by steric interactions imposed by bulky moieties attached at the 6,8-positions of each pyrene unit. For the control compound, only hydrogen atoms occupy the 6,8 positions (DP1), whereas the remaining compounds incorporate ethynylene groups terminated with either triisopropylsilyl (DP2), 1-tert-butylbenzene (DP3), 2,6-di-tert-butylbenzene (DP4) or 1-tert-butyl-3,5-dimethylbenzene (DP5) units. Each compound shows a mixture of monomer and excimer fluorescence in fluid solution at room temperature, but only monomer emission in a glassy matrix at 77 K. The ratio of monomer to excimer fluorescence depends markedly on the molecular structure; DP1 is heavily biased in favour of the excimer and DP4 is enriched with monomer fluorescence. Photophysical properties, including laser induced and delayed fluorescence data, are reported for each compound. Delayed fluorescence occurs by both intramolecular and bimolecular steps, but these events take place on different timescales. The possibility is raised for using intramolecular triplet-triplet annihilation as a means of molecular imaging.     

MOLECULAR CONFORMATION OF IONIC SURFACTANTS IN AQUEOUS SOLUTION

The molecular conformation of ionic surfactant in aqueous solution is investigated withfluorescent probes which are intrinsic insurfactant molecules or externally introduced. Quench-lng or pyrene monomer fluorescence by alkyltriphenylphosphonium or N-alkylpyridiniumobeys Stern-Voimer equation, being diffusi6n-controlled dynamic quenching, but the behaviorof quenching with different lengths of alkyl chain is "abnormal", i.e. the longer the chain,the greater the quenching rate constant. The pyrene excimer fluorescence is observed in theaqueous solution of cetyltrimethylammonium bromide (CTMAB), and the inhibition (for cationicquenchers) and promotion (for anionic quenchers) effects of CTMAB on the quenching ofpyrene fluorescence are also observed. The self-coiling conformation of ionic surfactantmolecules in aqueous solution is proposed to be responsible for these observations and theconformation to be dynamic.     

S-异丙甲草胺与小牛胸腺DNA的相互作用

应用紫外光谱、荧光光谱、DNA热变性法以及黏度法研究了S-异丙甲草胺与小牛胸腺DNA(ctDNA)的相互作用. 结果表明, S-异丙甲草胺使ctDNA在200 nm处的吸收峰发生明显改变, 表现出红移和减色效应, 而对260 nm处的吸收峰产生影响较小, 排除了嵌插作用的可能; ctDNA对S-异丙甲草胺内源性荧光表现出很强的猝灭作用, 且随温度的升高, 其猝灭程度有所下降, 表明S-异丙甲草胺是以形成加合物的方式与ctDNA结合的, 并求得了它们在不同温度下的结合常数; 将不同离子强度条件下S-异丙甲草胺与ctDNA作用以及不同S-异丙甲草胺浓度下ctDNA的热变性温度和黏度变化的研究结果与紫外光谱和荧光光谱相结合, 可以判断S-异丙甲草胺是以沟槽作用的方式与ctDNA结合的.     

A calixarene based fluorescent Sr2+ and Ca2+ probe

A fluorescent probe, PyCalix, which has two pyrene moieties at the lower rim of a calix[4]arene fixed in the cone conformation was synthesized and its complexation behavior with alkali and alkaline earth cations was studied by fluorescence spectrometry. The compound showed intramolecular excimer emission at approximately 480 nm in the fluorescence spectra. Upon complexation with alkaline earth metal cations, a decrease of excimer emission was observed. The decrease of excimer emission was accompanied by an increase of monomer emission of pyrenes at 397 nm. The order of complexation constants of PyCalix with metal ions was Sr(+ approximately Ca2+ > Ba2+ > Mg2+ > K+ > Na+ > Cs+ for all reagents. PyCalix doped polyvinyl chloride (PVC) membrane was fabricated and our results showed that this membrane can be used for selective detection of Sr2+.     

Supramolecular Chemical Sensors Based on Pyrene Monomer–Excimer Dual Luminescence

The past ten years have seen a spectacular development of chemical sensors based on the monomer–excimer dual luminescence of aromatic systems, such as pyrene. Either in the form of integrated or multicomponent molecular devices these chemosensors have been attracting a high interest above all because of their unique ratiometric properties. This review will focus on the latter systems, which can be classified into two classes: Firstly, the assembly of receptor–effector conjugates is triggerred by the analyte of interest. As a result, the sensor shows monomer to excimer fluorescence switching upon substrate binding. Secondly, the supramolecular assembly that constitutes the sensor is perturbed by interaction with the analyte. This induces a conformational change or the exchange of a component of the system, which is the cause of the luminescence switch effect.