香豆素噻唑烷二酮类化合物的合成

运用拼合原理并根据构效关系研究结果,设计了香豆素噻唑烷二酮类化合物,合成方法是以甲基取代的香豆素为原料,经NBS溴化后,再与5-(4-羟基苄叉)-噻唑烷-2,4-二酮在NaH作用下缩合得到,其中中间体5-(4-羟基苄叉)-噻唑烷-2,4-二酮是由噻唑烷二酮与对羟基苯甲醛在哌啶催化下缩合得到,共合成了5-[4-(香豆素-7-亚甲氧基)苄叉]-噻唑烷-2,4-二酮、5-[4-(4-甲基香豆素-7-亚甲氧基)苄叉]-噻唑烷-2,4-二酮、5-[4-(香豆素-6-亚甲氧基)苄叉]-噻唑烷-2,4-二酮、5-[4-(7-甲氧基香豆素-4-亚甲氧基)苄叉]-噻唑烷-2,4-二酮、5-[4-(3-溴香豆素-7-亚甲氧基)苄叉]-噻唑烷-2,4-二酮、5-[4-(3-溴-4-甲基香豆素-7-亚甲氧基)苄叉]-噻唑烷-2,4-二酮6个香豆素噻唑烷二酮类化合物,结构均经IR1、HNMR、MS确定,两步反应合成目标化合物总产率分别为10.4%、13.1%、7.1%、16.0%、22.0%、18.0%。     

两个D-π-A型双氰基二苯乙烯双光子荧光染料的合成

该文合成了两个以双氰基二苯乙烯为母体的D-π-A型双光子荧光染料,并以其作为模型化合物对双氰基与末端取代基对双光子吸收的影响进行了系统研究。两个化合物(DMO和DMA)具有大的双光子吸收截面(δ)。含有末端氨基的DMA较末端甲氧基的DMO具有更长的发射波长〔λem(DMA)=554 nm>λem(DMO)=459 nm〕、更大的双光子吸收截面〔δ(DMA)=3 650 GM>δ(DMO)=830 GM〕和更高的荧光量子产率〔η(DMA)=0.456>η(DMO)=0.294〕。理想的末端取代基不是烷氧基而是取代氨基。这类双氰基二苯乙烯染料拥有小的分子尺寸、大的δ(830～3 650 GM)、长的发射波长(459～554 nm)和大的斯托克斯位移(St)(131～150 nm),是比较理想的用于双光子荧光标记和探针的发色团。     

一种双波长激发型香豆素pH荧光探针及其识别机理研究

本项工作以7-羟基香豆素荧光团为原料,构建了一种双波长激发型pH值荧光探针CpH.该探针的pKa值为6.06,其线性检测范围为4.0～7.4,而且还具有光稳定性强、灵敏度高、选择性高和可逆性好等优点.     

不对称型噁二唑香豆素荧光色素的合成

对2-香豆素基-5-R-1,3,4-噁二唑的合成条件和工艺进行了探索和优化。实验结果为:3-香豆素羧酸:酰肼的摩尔比为1,反应温度为135℃,反应时间4~5 h。合成的12个化合物中有10个化合物未见文献报导。该方法操作简单,一步完成,有望在收率方面进一步提高。     

新型香豆素类荧光染料的合成研究

以７－二乙氨基－４－氯－３－甲醛基香豆素为基础合成了７只新型香豆素类的荧光染料。本类染料具有强烈的荧光,随着分子内π－共轭体系的增大,染料的色光从黄色增至红色。     

新型双香豆素化合物的合成

通过Pechmann反应、溴化反应和氨基化反应合成了2个新的双香豆素类化合物,利用核磁共振波谱、红外光谱和熔点测定等手段对化合物的结构进行了表征。     

香豆素及取代香豆素的合成

香豆素应用广泛,合成了香豆素、7-甲基香豆素、4,7-二甲基香豆素和6-甲基香豆素4个化合物,并对合成香豆素和6-甲基香豆素的后处理方法作了改进。     

香豆素类化合物的合成及其光谱性质的研究

本文分别用Wittig反应、Perkin反应和Pechmanmn反应合成了邻甲氧基取代二苯乙烯及其由内酯键固环为3-位苯环或4-位苯环取代的香豆素化合物，固环为3-位苯环取代的香豆素化合物的最大吸收波长稍有红移约2nm，而发射波长产生了约20nm的较大红移，Stokes位移增大了18nm，荧光量子效率也稍有提高。香豆素化合物在7-位由供电基甲氧基取代后，最大吸收波长红移16nm，发射波长红移21nm，Stokes位移增大5nm，荧光量子效率却提高了近四倍，荧光量子效率接近1．0。7-位同为甲免基取代，由3-位对溴苯基变为4-位对溴苯基取代时，吸收波长蓝移16nnn，荧光发射波长亦蓝移20nm，Scokes位移降低4nm，荧光量子效率大幅度降低。     

新型香豆素系荧光染料的研究

以7-二乙氨基-4-氯-3-甲醛基香豆素为基础,合成了7只新型香豆素系的荧光染料,在不同浓度下测定了它们的吸收光谱和发射光谱,在稀溶液中用PPP－MO方法预测的结果证明,其组成与光谱性质相符。     

高聚物双光子吸收材料研究进展

高聚物双光子吸收材料具有强度高与韧性好的特征，可以在膜状态下使用，因而具有潜在应用前景。介绍了双光子材料的应用，综述了高聚物双光子吸收材料的研究进展情况。     

含噁二唑四枝分子的合成与非线性吸收

选择噁二唑基团作为多枝化合物的“枝”，以苯甲腈基和咔唑基团为分子的“核”，合成了两个四枝化合物（BO-G2和NO-G2），进行了核磁共振和质谱的表征．从结构上看，BO-G2和NO-G2分别具有“D-A-A’-A-D”和“D＇-A-D-A-D’”电荷转移特征，后者具有pn结．吸收光谱和荧光光谱证实，NO-G2具有较大的激发态和基态偶极矩差值，存在着明显的分子内电荷转移和非线性吸收．     

Absorption and fluorescence of soluble polar diketo-pyrrolo-pyrroles

Six soluble derivatives of 3,6-diphenyl-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione N-alkylated on pyrrolinone ring with polar substituents in para positions of pendant phenyl rings were synthesized; five of them are reported for the first time. Absorption and fluorescence spectra were studied in solvents of different polarity. The compounds show small solvatochromism of absorption and a moderate positive solvatochromism of fluorescence, especially when substituted by strong electron-donating piperidino substituent. A significant decrease of fluorescence quantum yields and its biexponential decay for dipolar derivatives in polar solvents was tentatively ascribed to the formation of twisted intramolecular charge transfer (TICT) excited state. All six compounds show fluorescence in polycrystalline solid-state with the maxima covering a range over 200 nm in visible and near infrared region.     

一种新型含咔唑基的ICT化合物的合成及光谱研究

以芴、咔唑为起始原料,经硝化、还原、烷基化、酰化、缩合六步反应,合成了一种新型ICT化合物9-乙基-3-咔唑亚甲基-芴腙(简称ECzFH)。产物及中间体的结构经IR、1H NMR等测试得到证实,并对其荧光性质进行了初步研究。结果表明,该化合物具有优良的电荷转移效果,且在二甲基亚砜溶剂中发出浅蓝色的荧光(Exmax=295 nm,Emmax1=358 nm,Emmax2=370 nm)。该化合物有望在生物分子探测、光电子集成、光动力学、医学诊断和双光子上转换激射等领域得到应用。     

没食子酸取代酞菁锌的合成及其碱敏感荧光特性

以4-硝基邻苯二甲腈为主要原料,3,4,5-三甲氧基苯甲酰氯为酰胺化试剂,合成了没食子酸取代酞菁锌(GA-Zn PC)。通过FTIR、~1HNMR、MALDI-TOF-MS、UV-Vis、荧光光谱等对其结构及光谱性能进行了表征与测试。结果表明,GA-Zn PC可溶于多种有机溶剂。在GA-Zn PC浓度为2.0×10~(–6)～1.0×10~(–5)mol/L的N,N-二甲基甲酰胺(DMF)溶液中,GA-ZnPC以单体形式存在,其Q带最大吸收峰在692nm。用四丁基氢氧化铵水溶液对浓度2μmol/L的GA-Zn PC DMF溶液进行光谱滴定,结果证实,GA-Zn PC在溶液中保持单体形式,酚到酚盐转变增强分子内电荷转移使其表现出明显的碱敏感荧光特性。     

Synthesis and Photophysical Properties of Azomethynes-Bifluorophores

Abstract

The method of the synthesis of unsymmetrical azomethynes-bifluorophores where one of the fluorescent fragments is a donor of electron excitation energy and the second one is an acceptor was worked out. Photophysical properties of azomethynes-bifluorophores were investigated. It was shown that in these compounds non-radiation energy transfer takes place. It was established that quantum-chemical semiempirical method AMI may be used for the calculation of spatial structure of amines-fluorophores.     

新型旋转填料床的气相传质特性

以CO2-NaOH体系化学吸收测定不同超重力因子、液量和气液比(体积流量比)条件下的有效传质比表面积a,在相同操作条件下,以氨-空气-水体系进行空气吹脱含氨富液测定不同超重力因子、液量和气液比条件下的气相体积传质系数kya,从而得到气相传质系数ky,对其气相传质特性进行了研究. 结果表明,a随超重力因子、液量和气液比增大而增大,kya和ky均随超重力因子和气液比增大而增大,随液量增大而减小. 通过对比可知,在相近操作条件下新型旋转填料床的气相体积传质系数比文献折流旋转填料床的提高36%. 对实验数据进行回归,拟合出a, kya和ky分别与气相雷诺数ReG、液相韦伯数WeL和伽利略数Ga之间的关联式.     

Effect of Membrane Structural Characteristics on Mass Transfer in a Membrane Absorption Process

Carbon dioxide is absorbed by de-ionized water or NaOH aqueous solution in the unsteady-state membrane absorption process. A theoretical model has been developed to describe the mass transfer behavior in the liquid phase, in which the effects of membrane structural characteristics are investigated. The concentration profiles in the liquid phase are calculated as a function of time. When the membrane porosity is relatively high or the pore size is relatively small, the solute concentration profile near the membrane surface can get homogeneous instantly due to the short distance between adjacent pores. In this case, the existence of the porous membrane has less effect on the mass transfer process. However, when the membrane porosity is relatively low or the pore size is relatively large, the distance between the adjacent pores is large, so the concentration profile near the membrane surface is hard to get homogeneous during the absorption process. Therefore, the concentration profile can be influenced significantly by the membrane structural characteristics, which means that the membrane structure has a significant effect on the mass transfer in liquid phase. Moreover, the chemical reaction in the liquid phase makes it difficult for the concentration profile near the membrane surface to get homogeneous. The disturbance in the liquid phase caused by the gas flow and pressure fluctuation is also taken into account in the model, and the model results agree well with the experimental data.     

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Two donor-σ-acceptor molecules containing tetrathiafulvalene (TTF) and carbazole moieties were synthesized by the reaction of 9-(4-bromo-butyl)-carbazole (1) with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7- (methylthio)-tetrathiafulvalene (2) or 2,6-bis(2-cyanoethylthio)-3, 7-bis(methylthio)tetrathiafulvalene (3) in the presence of CsOH·H2O, respectively. The structures of the molecules were characterized by ¹H NMR, ¹³C NMR, MS, and elemental analyses. They showed negligible intramolecular charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results. Compared with carbazole, their fluorescence was strongly quenched, which implied that a photo induced electron transfer (PET) interaction between TTF and carbazole moieties occurred.     

Novel poly(phenylene ethynylene)‐type conjugated polymers containing diketopyrrolopyrrole or triphenylpyrazoline units in the main chain: synthesis,characterization and photophysical properties

BACKGROUND: Polymer‐based light emitting diodes (PLEDs) have received considerable attention as they combine the good mechanical and processing properties of polymers with semiconducting behavior, and can be easily fabricated as flexible devices. To obtain high‐performance PLED materials by balancing the carrier injection of poly(phenylene ethynylene)s (PPEs), polymers containing two aryl‐heterocyclic rings, namely diketopyrrolopyrrole (DPP) or triphenylpyrazoline (TPP), have been synthesized and investigated. RESULTS: PPE‐type polymers containing DPP or TPP units were synthesized using Heck–Sonogashira coupling methodology and characterized by ¹H NMR, Fourier transform infrared and UV‐visible spectroscopies, elemental analysis, gel permeation chromatography, photoluminescence (PL), X‐ray diffraction, thermogravimetic analysis and cyclic voltammetry. The polymers obtained are easily soluble in common solvents and form smooth and uniform films. They are yellow or red emitters as revealed by PL. In addition, they show large Stokes shifts, which is in agreement with their twisted molecular structures determined via quantum chemical calculations. CONCLUSION: PPE‐type polymers containing DPP or TPP units were successfully synthesized by coupling polymerization. They exhibit band gaps of 1.73 and 2.37 eV, respectively, and show potential as PLED materials. In addition, DPP‐containing polymers with a very low band gap could be applied as potential photovoltaic materials. Copyright © 2009 Society of Chemical Industry