吖啶类衍生物的荧光性质

用比较法测得23种啶类衍生物的荧光量子效率（Φf)，以评估这些化合物的荧光性质，结果表明，N－烃基吖啶酮类化合物的荧光量子效率要比9－取代苯基吖啶类和9－取代苯亚甲基－10－甲基－9，10－二氢吖啶类化合物的荧光量子效率大，在非极性溶剂中，9－聚代苯亚甲基－9，10二氢吖啶分子内的强吸电子基NO2增强荧光量子效率，强推电子基OCH3降低荧光量子效率，这些测量结果与取代基的电子作用经验规律不相符，这种现象可以用分子内电荷转移理论进行解释。     

二苯胺取代吖啶衍生物发光材料的合成、表征及电致发光性能

设计合成了2个苯胺取代吖啶衍生物N3,N3,N6,N6-四苯基吖啶基-3,6-二胺(1)和N3,N3,N6,N6-四对甲苯基吖啶基-3,6-二胺(2),通过化学修饰在吖啶核的两端引入二苯胺取代基可以调节化合物的能级和堆积结构等性质,从而使这些吖啶衍生物具有良好的发光性能,可用于制备电致发光器件.基于吖啶衍生物为掺杂发光材料制备的电致发光器件均呈现绿光发射,器件开启电压较低(2.4 V),以化合物1和2制备的器件最高功率效率分别为4.9和8.2 lm/W.考察了其光物理、电化学、热学和荧光量子效率等性能.结果表明,化合物1和2具有较高的量子效率及匹配的能级结构,这是获得较高电致发光效率的基础.     

3-和4-苯基香豆素化合物的电子结构及光谱性质的理论研究

采用从头算、密度泛函和单激发组态相互作用理论方法研究3-和4-苯基香豆素化合物的电子结构和光谱性质,并用极化连续模型考虑了溶剂对光谱性质的影响.结果发现,在3-苯基香豆素的7-位引入给电子基团甲氧基或吸电子基团氰基均使它们的吸收光谱和荧光光谱产生红移,4-苯基香豆素的衍生物的吸收光谱和荧光光谱均产生蓝移.3-苯基香豆素衍生物与4-苯基香豆素的衍生物的基态和激发态的电子转移方向相反.计算的结果与实验结果吻合的很好.     

苯基荧光酮类显色剂在光度分析中的应用进展

综述了1995～2010年苯基荧光酮类试剂在分光光度法测定金属离子方面的进展。分别评述了苯基荧光酮(PF)、4,5-二溴苯基荧光酮、9-取代苯基荧光酮和2,3,7-三羟基-9-[(取代基)偶氮]苯基荧光酮在光度分析中的应用,并从反应体系、最大吸收波长、灵敏度、线性范围等方面归纳了苯基荧光酮类试剂在实际样品中的应用情况,引用文献108篇。     

反-1,2-双[2′-(5′-苯基噁二唑-1′,3′,4′-基)]乙烯及其5′-取代苯基衍生物的合成及光性能研究

合成了反式-1,2-双[2′-(5′-苯基(口恶)二唑-1′,3′,4′-基)]乙烯及其二十种5′-取代苯基的衍生物,测定了它们的熔点、红外光谱、紫外光谱、荧光谱光及激光转换效率,并用相对法测定了它们的荧光量子产率。     

5-苯基-2-(2’-苯基(口恶)唑基-5’)1,3,4-(口恶)二唑及其5-对位取代苯基衍生物的研究

合成了十二个未见报道的5-苯基-2-(2’-苯基(口恶)唑基-5’)1,3,4-(口恶)二唑及其5-对位取代苯基衍生物。测试了它们的紫外光谱、荧光光谱、荧光量于产率和激光转换效率,发现化合物的(?)和(?)与 Hammett 取代基常数|σ_p~+|有线性关系,化合物分子受激发后结构的平面性增加。     

5-苯基-2-(2'-苯基啉基-5')1,3,4-二唑及其5-对位取代苯基衍生物的研究

合成了十三个未见报道的5-苯基-2-(2'-苯基唑基-5')1,3,4-二唑及其5-对位取代苯基衍生物. 测试了它们的紫外光谱、荧光光谱、荧光量子产率和激光转换效率, 发现化合物的γmax^u^v和νmax^u^v与Hammett取代基常数|σρ^+|有线性关系, 化合物分子受激发后结构的平面性增加.     

1,4—双（苯基乙炔基）苯及其双取代苯基衍生物的研究

合成了1,4-双(苯基乙炔基)苯及其双取代苯基衍生物。测定了它们的荧光量子产率、激光转换效率、红外光谱、拉曼光谱,指派了主要官能团的特征频率,讨论了化合物结构和取代基效应。     

化学发光免疫分析试剂吖啶酯的合成新路线

设计了一种化学发光免疫分析试剂吖啶酯的合成新路线,以二苯胺为原料合成吖啶-9-羧酸,经酰氯化后与3-(4-羟基苯基)-丙酸-N-羟基琥珀酰亚胺酯反应得4-(2-琥珀酰亚胺基氧羰基乙基)苯基-9-吖啶羧酸酯,最后与氟磺酸甲酯反应即得4-(2-琥珀酰亚胺基氧羰基)苯基-10-甲基吖啶-9-羧酸酯氟磺酸盐(俗称吖啶酯).     

水介质中9,10-二芳基吖啶的洁净合成

水介质中在十二烷基磺酸钠(SDS)催化下, 席夫碱与双甲酮反应合成了一系列9,10-二芳基吖啶衍生物, 同时分离得到一种中间产物. 所有产物的结构通过红外光谱和1H NMR光谱确定, 产物10-(4-氯苯基)-9-(4-甲氧基苯基)-3,3,6,6-四甲基-3,4,6,7,9,10-六氢化吖啶-1,8(2H,5H)-二酮(3i)和中间产物2-{4-氯苯基-[2-(4-甲氧基苯基氨基)-4,4-二甲基-6-氧代环已-1-烯基]甲基}-3-羟基-5,5-二甲基环已-2-烯酮(4h)的结构还通过单晶X射线衍射分析确证.     

Synthesis and evaluation of 10-(3,5-dimethoxy)benzyl-9(10H)-acridone derivatives as selective telomeric G-quadruplex DNA ligands

A class of 9(10H)-acridone derivatives with terminal ammonium substituents at C2 (and C7) position(s) on the acridone ring were successfully synthesized. The relative affinities of the acridone compounds to G-quadruplex DNA have been investigated and the results showed that these compounds had a binding specificity for G-quadruplex over duplex sequences. The acridones with two terminal ammonium substituents had much more effects on the human telomeric G-quadruplex DNA than the corresponding acridone derivatives with one terminal ammonium substituent, and more positive charges introduced to the side chains can improve the formation and stabilization of the G-quadruplex.     

Study on the second-order non-linear optical properties of 10-hydrocarbylacridones

Twenty 10-hydrocarbylacridones and 2-methylacridone, 1-hydroxyacridone were synthesized from acridone and characterized by mp, IR, UV, 1H NMR and MS. Using Nd:YAG as a laser source, the second-order harmonic generation (SHG) values of the acridone derivatives were measured in powder state as compared with urea powder. The results showed that the SHG values of some of 10-hydrocarbylacridones were higher than that of urea, while others were lower. Although the hydrocarbyl substituents (R) attached to nitrogen atom of acridone were different in size and electronegativity, they had a little effect on the SHG values of 10-hydrocarbylacridones. Substituents, such as methyl or hydroxy group connected to the phenyl ring, caused a little effect on the SHG values, too, compared with acridone. The ability of R to push electron toward the nitrogen atom or to pull electron from the nitrogen atom play an important role on the maximum wavelengthes of UV-visible absorption of acridone derivatives.     

萤火虫氧化荧光素及其衍生物的电子结构和光物理性质

通过密度泛函理论(DFT)的MPW3PBE泛函, 对萤火虫生物发光底物氧化荧光素及其衍生物进行了结构全优化. 计算了其电离能、 电子亲和势、 空穴抽取能、 电子抽取能、 空穴和电子重组能, 并评估了其空穴和电子传输能力. 采用含时密度泛函理论(TD-DFT)//MPW3PBE/6-31+G(d)方法计算了吸收光谱, 优化了最低单重态S₁, 研究了其荧光光谱, 进而考察了具有较高发光效率的氧化荧光素作为有机发光二极管(OLED)材料的可能性. 计算结果表明, 氧化荧光素及其衍生物可以同时作为电子传输层和发光层材料.     

Ortho effects in organic molecules on electron impact. 12—Mechanism of the H2O loss from the molecular ion of 2-(phenylamino)benzoic acid

The mass spectrum of 2-(phenylamino)benzoic acid is characterized by the presence of the base peak at m/z 195, formed by the expulsion of H₂O from the molecular ion. A mechanism for the water loss, involving the ? COOH and ? NH functions followed by cyclization leading to the molecular ion of acridone, is proposed based on the study of the substituted derivatives and MIKE spectra.     

吖啶酮衍生物的质谱研究

报道了8个吖啶酮衍生物的MS-EI谱,并就MS—EI谱碎片的断裂方式进行了探讨,说明了取代基位置和取代基类型对吖啶酮衍生物稳定性的影响。     

2,5-二取代噁唑的研究(Ⅵ)-2-联苯基-5-苯基噁唑和其5-对位取代苯基衍生物光谱的溶剂效应

本文报导了14种2-联苯基-5苯基噁唑和其5-对位取代苯基衍生物在环己烷、无水乙醇和1,4-二氧六环三种溶剂中测得的紫外吸收光谱和荧光发射光谱。并从21种溶剂的宏观物理性质(n,ε),Z值、E_T值和取代基常数σ_p三个方面研究2-联苯基-5-对乙苯基噁唑光谱的溶剂效应。     

Temporary anion states of pyrimidine and halopyrimidines

The empty-level electronic structures of pyrimidine and its 2-chloro, 2-bromo, and 5-bromo derivatives have been studied with electron transmission spectroscopy (ETS) and dissociative electron attachment spectroscopy (DEAS) in the 0-5 eV energy range. The spectral features were assigned to the corresponding anion states with the support of theoretical calculations at the ab initio and density functional theory levels. The empty orbital energies obtained by simple Koopmans' theorem calculations, scaled with empirical equations, quantitatively reproduced the energies of vertical electron attachment to π* and σ* empty orbitals measured in the ET spectra and predicted vertical electron affinities close to zero for the three halo derivatives. The total anion currents of the halo derivatives, measured at the walls of the collision chamber as a function of the impact electron energy, presented intense maxima below 0.5 eV. The mass-selected spectra showed that, in this energy, range the total anion current is essentially due to halide fragment anions. The DEA cross sections of the bromo derivatives were found to be about six times larger than that of the chloro derivative. The absolute cross sections at incident electron energies close to zero were evaluated to be 10(-16)-10(-15) cm(2).     

Photophysical properties of carborane-containing derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin

Absorption, fluorescence emission, fluorescence excitation spectra and fluorescence decay kinetics of carborane derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin have been investigated. Carborane derivatives are prepared by acylation of the amino groups of 5,10,15,20-tetra(p-aminophenyl)porphyrin by 9-carboranyl acetyl chloride. From the analysis of the absorption and fluorescence spectra, it is concluded that covalent linking of carborane molecules to the tetraphenylporphyrin molecule significantly changes the self-conjugated pi-system of the porphyrin macrocycle: positions of maxima of absorption and fluorescence spectra shift to the red region by 3-8 nm; the halfwidths of these bands are broadened by 2.5-5.0 nm; the relative intensity of the bands I-IV also changes. The fluorescence decay kinetics of the carborane derivatives are biexponential. According to the experimental data and model simulation, it is concluded that the intramolecular electron transfer proceeds from the porphyrin excited part of the molecule to carboranyls with a rate constant of 415 ps(-1) and efficiency of 0.16-0.8. Recombination of separated charges occurs within 1.4 ns.     

Laser-induced fluorescence, dispersed fluorescence and lifetime measurements of jet-cooled chloro-substituted benzyl radicals

We measured the laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled -, o- and m-chlorobenzyl radicals after they were generated by the 193 nm photolysis of the corresponding parent molecules. The vibronically resolved spectra were obtained to analyze their D₁–D₀ transitions. The fluorescence lifetimes of -, o-, m- and p-chlorobenzyls in the zeroth vibrational levels of the D₁ states were measured to estimate the oscillator strengths of a series of benzyl derivatives. It was found that the -substitution is inefficient to break the ‘accidental forbiddenness' of the D₁–D₀ transition of benzyl, while the ring-substitution enhances the oscillator strength by 50%.     

Synthesis and Antibacterial Activity of 9-Oxo-9,10-dihydroacridinecarboxylic Acids Esters Bearing a Triazole Fragment

An effective method for the synthesis of new acridine-9(10H)-one (acridone) derivatives containing 1,2,3-triazole fragment was developed. A number of new triazole-containing compounds were synthesized from propargyl acridone acetate and their antimicrobial activity was studied.