丝裂霉素C酸活化机理研究

丝裂霉素C(MMC)是一种广谱抗肿瘤药物,它在体内活化后可以与DNA以共价结合或交联反应等模式相互作用,从而抑制肿瘤细胞DNA的合成。文中首次采用光谱学方法,结合紫外 可见光谱、圆二色光谱手段,提出了MMC的酸活化机理。证明它是一个质子化水解过程,同时推导了酸活化第一步基元反应的反应级数和反应速率常数的计算公式,并计算得该基元反应的速率常数k为3.083×10-4s-1。     

荧光光谱法研究橙皮苷与牛血清白蛋白相互作用特征

研究了不同温度下,橙皮苷与牛血清白蛋白作用的荧光猝灭光谱、三维荧光光谱和同步荧光光谱特征。证实了橙皮苷与牛血清白蛋白间的相互作用为单一的动态猝灭过程,求出了不同温度下的猝灭常数。根据Frster非辐射能量转移理论,计算出橙皮苷在蛋白质中的结合位置与212位色氨酸残基间的距离为3.29 nm。由求得的热力学参数,证明了橙皮苷与牛血清白蛋白之间主要靠疏水作用力结合。用三维荧光光谱及同步荧光光谱技术探讨了橙皮苷对牛血清白蛋白构象的影响。     

核黄素与牛血清白蛋白相互作用的荧光光谱研究

采用荧光猝灭光谱、同步荧光光谱研究了核黄素与牛血清白蛋白(BSA)相互作用的光谱行为。结果发现,在温度为293 K和310 K时核黄素与BSA的结合常数(Kb)分别为4.879×105L.mol-1和1.880×105L.mol-1,结合热力学方程计算得到了对应温度下的热力学参数。结果表明核黄素对BSA有较强的荧光猝灭作用,其荧光猝灭过程属于动态猝灭机制,二者主要靠疏水作用力结合。采用同步荧光光谱探讨了核黄素对BSA构象的影响。     

甘草酸二铵与牛血清白蛋白相互作用的光谱

在模拟人体生理条件下,用常规荧光光谱和紫外－可见吸收光谱研究甘草酸二铵和牛血清白蛋白的相互作用机制,并利用同步荧光光谱和三维荧光光谱研究了药物对牛血清白蛋白构象的影响。研究表明,甘草酸二铵对牛血清白蛋白具有荧光猝灭作用,且为单一的动态猝灭过程。根据Stern-Volmer方程求出了两者相互作用的动态猝灭常数,并根据Förster非辐射能量转移理论确定了药物与蛋白的结合距离。     

头孢美唑钠与BSA及纳米银-BSA体系相互作用的研究

纳米银与牛血清白蛋白(BSA)均匀混合形成纳米银-BSA体系,运用荧光光谱,紫外吸收光谱,同步荧光光谱研究了注射用头孢美唑钠(Cefmetazole Sodium for Injection,CS)与BSA及纳米银-BSA体系的相互作用.头孢美唑钠对BSA具有荧光猝灭作用,其猝灭方式为静态猝灭,求出了猝灭常数,结合常数...     

反白藜芦醇与牛血清白蛋白相互作用的多光谱法研究

利用荧光技术研究了抗癌药物反白藜芦醇与牛血清白蛋白的相互作用,结果证实,反白藜芦醇对牛血清白蛋白有很强的荧光猝灭作用,猝灭类型为静态猝灭.计算了反白藜芦醇与牛血清白蛋白在300、310和320 K时的结合常数、结合位点、结合距离和热力学常数等参数.由热力学参数推断两者结合过程中,起主导作用的是范德华力或氢键.同步荧光光谱和红外光谱同时说明两者结合前后蛋白质的结构发生了变化.研究还表明,金属离子Fe3 、Cu2 和Zn2 的加入使反白藜芦醇与牛血清白蛋白之间的结合常数和结合位点减小.     

竹红菌甲素与血红蛋白相互作用光谱

竹红菌甲素与血红蛋白相互作用光谱;马心血红蛋白;竹红菌甲素;相互作用;UV-Vis吸收光谱;荧光光谱;荧光猝灭动力学常数     

敏化光解 盐的研究——蒽、芘、 电子转移荧光猝灭

本文采用稳态和瞬态光谱方法研究了四种二苯基碘 盐(Ph~2I^+X^-)对蒽、芘、 的激发态的猝灭作用, 通过Stern-Volmer方程确定了它们的光致电子转移速度常数。结果表明Ph~2I^+AsF^-~6对荧光猝灭是最有效的, 猝灭过程是扩散控制的。比较荧光强度和荧光寿命测定得到的猝灭常数, 表明猝灭是动态过程, 敏化剂与 盐间没有基态复合物生成。     

敏化光解螉盐的研究——蒽、芘、苝电子转移荧光猝灭

本文采用稳态和瞬态光谱方法研究了四种二苯基碘鎓盐(Ph_2I~+X~-)对蒽、芘、苝的激发态的猝灭作用,通过Stern-Volmer方程确定了它们的光致电子转移速度常数,结果表明Ph_2I~+AsF_6~-对荧光猝灭是最有效的,猝灭过程是扩散控制的。比较荧光强度和荧光寿命测定得到的猝灭常数,表明猝灭是动态过程,敏化剂与鎓盐间没有基态复合物生成。     

敏化光解 盐的研究——蒽、芘、 电子转移荧光猝灭

本文采用稳态和瞬态光谱方法研究了四种二苯基碘 盐(Ph~2I^+X^-)对蒽、芘、 的激发态的猝灭作用, 通过Stern-Volmer方程确定了它们的光致电子转移速度常数。结果表明Ph~2I^+AsF^-~6对荧光猝灭是最有效的, 猝灭过程是扩散控制的。比较荧光强度和荧光寿命测定得到的猝灭常数, 表明猝灭是动态过程, 敏化剂与 盐间没有基态复合物生成。     

STUDY ON THE PROTONATION MECHANISM OF 2,6-DIMETHYL NAPHTHALENE DICARBOXYLATE

By the study of absorption and fluorescence spectra and the lifetime of fluorescence at room and low temperatures of 2,6-dimethyl naphthalene dicarboxylate (DMN) in different concentrations of sulfuric acid, different interactions between molecules of DMN and sulfuric acid have been observed. These interactions have been revealed by the absorption spectra of charge transfer complex in the ground state, emission of exciplex, absorption spectra of hydrogen bonding interaction, absorption and emission spectra after proton transfer and different lifetimes before and after protonation. The interaction mechanism of DMN and sulfuric acid through first the CT complex and exciplex then hydrogen bonding and finally proton transfer is proposed.     

ENERGY TRANSFER FROM MICELLAR SODIUM PHENYLUNDECANOATE TO SOLUBILIZED NAPHTHALENE

Abstract— Excitation energy transfer from the phenyl groups of surface active phenylundecanoate ions to naphthalene molecules has been studied under conditions such that the naphthalene molecules have been solubilized by micelles of phenylundecanoate. From measurements of the naphthalene fluorescence intensity in solutions of varying surfactant concentration the critical micelle concentration has been determined as 0·0091 M. The product of the micellar aggregation number and the efficiency of energy transfer has been obtained as 75 from measurements of both the sensitized naphthalene fluorescence and the quenching of the phenylgroup fluorescence. In the evaluation of the experimental data it has been assumed that the partition of naphthalene between the micelles and the aqueous phase may be treated as a distribution equilibrium, and that the solubilized naphthalene molecules are partitioned among the micelles according to a Poisson distribution. With this model, the naphthalene fluorescence intensities may be accounted for over the whole range of surfactant concentrations.
At high naphthalene concentrations, emission from naphthalene excimers has been observed. The possibility of self-quenching via excimer formation is considered.
The experimental results point to a quantum efficiency near unity for the transfer of excitation energy from the phenyl groups of the surfactant ions that form a micelle to a single solubilized naphthalene molecule. The high efficiency suggests that the naphthalene molecule and the phenyl groups are present inside the micelles.     

ENERGY TRANSFER IN PHENANTHRENE-DOPED NAPHTHALENE CRYSTALS

Abstract— Measurements at 77°K and room temperature are described on naphthalene crystals containing varying concentrations of phenanthrene. The lowest excited singlet and triplet states of phenanthrene iie between the singlet and triplet exciton bands of the host crystal. Triplet-triplet annihilation in the host was studied by absorbing radiation purely into the guest molecules; the absence of any phosphorescence or delayed naphthalene fluorescence allowed the radiationless processes out of the naphthalene triplet to be discussed. Singlet-singlet energy transfer was studied using radiation absorbed by the naphthalene. Two separate mechanisms of transfer were observed: (A) free exciton motion in the naphthalene band till encounter with a phenanthrene trap, the last step having an activation energy of 65 cm^-1, and (B) defect traps in the naphthalene transferring energy by a resonance mechanism to the phenanthrene; the average depth of the defect traps was calculated at 200 cm^-1.     

2,6-萘二甲酸二甲酯与一些二甲基萘所形成的激基复合物

2,6-萘二甲酸二甲酯与一些二甲基萘可以形成激基复合物。本文通过稳态和动态荧光光谱研究了这类激基复合物的形成与分子结构的关系。结果表明,尽管这些二甲基萘的电离能基本相同,但因取代基位置不同使分子中电荷分布不同,从而影响了激基复合物的形成能力。     

用乳化液膜法从萘油直接制取精萘的研究

本研究依据乳化液膜分离技术的原理，采用阴离子表面活性形成的乳化液膜从萘油直接制取精萘，考察了各种工艺条件对精萘产品质量和收率的影响。实验结果表明，以阴离子表面活性剂形成的乳化液膜结合精馏可有效地将萘油制成精萘，萘含量大于９９％，符合国家精萘标准，萘收率大于８８％。     

SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE BLOCK COPOLYMERS WITH AN END-TAGGED NAPHTHALENE PROBE

Water-soluble A-B block copolymers of 2-perfluoroethyl-2-oxazoline or 2-pentyl-2-oxazoline as hydrophobic monomers and 2-methyl-2-oxazoline as hydrophilic monomer were prepared by means of the living cationic ring-opening polymerization. The polymerization was initiated with N-methyl-2-(1-naphthyl)-2-oxazolinium trifluoromethanesulfonate as fluorescence label followed by sequential addition of the hydrophobic and the hydrophilic monomer. The polymerization was monitored by ¹H NMR spectroscopy and gel permeation chromatography (GPC) measurements. The results revealed that fluorophilic block copolymers can be prepared by this method while lipohilic block copolymers are not accessible by this monomer sequence. Micelle formation of the fluorophilic block copolymers in aqueous solution was studied by means of steady-state fluorescence spectroscopy which confirmed strong intermolecular excimer formation of the terminal bounded naphthalene moiety. In chloroform as a good solvent for both blocks, only monomer fluorescence could be observed.     

Benzindoles

A large amount of structural similarity between 4,5-benzindole and naphthalene and between 6,7-benzindole and indole was detected on a basis of a comparison of the absorption, fluorescence, and phosphorescence spectra of isomeric benzindoles with the spectra of indole and naphthalene. A great analogy between indole and 6,7-benzindole as compared with 4,5-benzindole is also observed during the formation of hydrogen bonds, as indicated by the shift in the absorption band of the NH group in the IR spectra of the investigated compounds in the presence of various proton acceptors.     

苯、萘、蒽及其衍生物的荧光光谱及激发态性能的计算研究

根据Franck-Condon原理,用PPP-SC(β,γ)-CI方法在IBM-PC微机上,对苯、萘、蒽的衍生物的荧光性质以及基态和第一激发单重态在键级、偶极矩、π电子总能量上的差异进行了研究。发现最大荧光波数V~(F.L.)与荧光辐射能△F~(V.L.)、荧光量子产率φ与基态、第一激发单重态间的π电子能量差(E_g~π—E_e~π)存在着以下的关系:上述F.L.表示荧光,g表示基态,e表示激发态。由此得出的理论计算值与实验值有着良好的一致性。     

以工业萘和粗甲基萘为主要原料合成萘系高效减水剂

工业萘、粗萘、甲基萘或萘残油等均可作为制取萘高效减水剂的原料。目前 ,其主要原料工业萘出现全球性紧缺 ,价格不断上扬[1] 。而攀枝花粗甲基萘比工业萘便宜许多 ,如果能用粗甲基萘代替工业萘生产萘系高效减水剂 ,可降低成本 ,使之具有更大的市场竞争力。前期实验表明单独使用粗甲基萘制备的减水剂 ,其减水率虽然较高 ,但产品含气量较大且引气不均匀 ,使混凝土抗压强度达不到要求。为了将工业萘和粗甲基萘混合物作为原料制备高效减水剂 ,并尽量用粗甲基萘替代工业萘 ,我们做了大量的实验 ,寻求到了工业萘和粗甲基萘混合物作为原料制备高效…     

Singlet-singlet intermolecular optical energy transfer from naphthalene to benzophenone in the vapor phase

By using the exothermic energy transfer as a function of pressure, the rate constant for diffusion was evaluated for benzophenone/naphthalene and naphthalene/benzophenone systems. In principle the optical energy absorbed by a complex molecule raises that molecule to one of its excited states, and afterwards this excitation energy decays through the different relaxation channels. Initially, electronically excited naphthalene "S1" state emits photons in the fluorescence band of naphthalene and these emitted photons, as a stream of particles, are absorbed by the acceptor molecule benzophenone, then excited benzophenone fluoresces. In this investigation, sensitized fluorescence decay times in different conditions were measured for naphthalene-benzophenone system in the vapor phase, and found to be 12+/-1 ns. The ultraviolet-visible spectra of the system in the vapor phase at room temperature conditions were broad and structureless.