新型羟基苯基苯并咪唑类衍生物的合成及其光谱性质研究

合成了8个具有不同结构的羟基苯基苯并咪唑类荧光化合物,通过1 H NMR,IR对其进行了结构表征,并研究了它们在甲醇溶液中的光谱性质及取代基对光谱性质的影响。该类化合物的荧光量子产率在0.006～0.75之间,Stokes位移大(>117nm)。实验结果表明,化合物上所连取代基的性质对其光谱有显著影响,具有推电子基团的羟基苯基苯并咪唑类化合物在光激发下出现荧光双发射峰,而具有吸电子基团的化合物在光激发下仅出现激发态质子转移荧光发射峰,表现出Stokes位移大和荧光量子产率高的优点。     

一类蓝色有机发光材料的合成及荧光性能研究

以4,4-(二乙氧基膦酸)联苯苄酯和芳香醛(或肉桂醛)为原料,碱催化下,在DMF溶液中,经过Wittig-Horner反应,合成了7种含苯乙烯基联苯类化合物。利用MS,1H NMR或元素分析表征了化合物的结构,采用紫外光谱和荧光光谱研究了化合物的光谱性能。结果表明,所合成的化合物是一种较为理想的蓝光材料。     

荧光氧化石墨烯的合成与发光性能

通过将氧化石墨烯进行胺化反应,在其表面修饰上甘氨酸,合成出了具有很强蓝色荧光的荧光氧化石墨烯。通过荧光仪、紫外可见分光光谱仪、傅氏转换红外线光谱分析仪等表征手段对甘氨酸修饰的氧化石墨烯进行表征,结果表明,甘氨酸是以共价键的形式修饰在氧化石墨烯上的,1.0mg/m L的甘氨酸修饰的氧化石墨烯在紫外灯下就能表现出很强的蓝色荧光,当用360nm紫外激光激发甘氨酸修饰的氧化石墨烯时,可以检测到在450nm处有一个很强的发射峰。     

菲并咪唑类席夫碱双核卟啉的合成及性能

以9,10-菲醌、对苯二甲醛、对氟苯甲醛、对甲氧基苯甲醛、对硝基苯甲醛及吡咯等为主要原料,设计合成了双核卟啉(P2-PPI).通过FT-IR光谱、1HNMR和13CNMR表征了其结构,利用UV-Vis光谱、荧光光谱测试了其光谱特征.UV-Vis光谱测试表明,双核卟啉(P2-PPI)Soret带的摩尔消光系数是对应单核卟啉(P1)的2.85倍,光谱吸收范围显著变宽;在浓度测试范围内,双核卟啉(P2-PPI)的聚集形态未改变.同浓度下,荧光光谱测试表明,双核卟啉(P2-PPI)中菲并咪唑部分的荧光强度仅为菲并咪唑前驱体的1/3,卟啉单元的荧光强度是单体卟啉的2倍.通过循环伏安法测试并比较了P2-PPI和P1的电化学性质,并结合光化学带隙计算了ELUMO和EHOMO值,分别与TiO2和I-/I3-氧化还原电对能级匹配.     

热活化延迟荧光材料的研究与分析

现阶段用于照明的电力消耗约占全球电力消耗的20%左右,如果热活化延迟荧光材料能够得到广泛应用,那么可以显著缓解当前能源需求的压力。从2014年至今,热活化延迟荧光材料蓬勃发展,可见光范围内的热活化延迟荧光材料不断被研发出来,基于热活化延迟荧光材料制备的OLEDs产品已经超过400多种,但热活化延迟荧光材料的发展仍然有许多亟待解决的问题,例如红光热活化延迟荧光材料的EQE还无法超过20%(主要是由于红光材料所需的带隙比蓝绿光更窄,合成更加困难),需要研究者的进一步探索。     

两种三苯胺衍生物的合成及其光谱性质研究

以三苯胺为起始原料,经过甲酰化反应、Claisen-Schmidt反应和Knoevenagel反应,较高产率地合成了两种具有D-A-D型结构的三苯胺衍生物。光谱分析发现,两种化合物的最大吸收波长分别位于450 nm和506 nm,对应的最大发射波长分别位于558 nm和633 nm,二者都具有较大的斯托克斯位移,从而有利于荧光材料的应用。     

二苯基马来酰亚胺绿光材料的合成及性能研究

有机绿色荧光材料由于在分子识别、生物探针和电致发光领域具有广泛的应用而备受关注。本文以苯乙腈为原料,在甲醇钠的催化下,合成了3,4-二苯基马来酰亚胺中间体,并在在碱性条件下,将苄基引入到马来酰亚胺的N上,得到具有高量子产率的绿色荧光材料——N-苄基-3,4-二苯基马来酰亚胺(BDPM)。采用各种分析方法分别对BDPM的结构和性能进行了表征,研究发现苄基的引入对材料量子产率的提高有重要的影响。     

有机物ANT、PT、TPB溶液的极化共振同步光谱和斯托克斯位移荧光研究

荧光材料的光学特性,包括其紫外线吸收、散射和共振荧光活动。极化共振同步光谱(PRS2)实现了材料散射去极化光谱的定量。斯托克斯位移(SSF)是荧光现象的一般表现特征。各向异性和去极化是荧光和光散射光谱中的两个可转换参数,用于描述用线性极化激发光产生的发射光子和散射光子的极化分布。本文通过检测有机物的PRS2、SSF,理论计算得到相应的去极化及各向异性光谱。然后分析有机物的相关特征,得到浓度及溶液背景对荧光性质的初步影响结果。这项工作对后期溶液背景对荧光性质的具体影响有初步的依据及实验可能性,为后期PRS2、SSF等用于有机污染物的检测和处理有一定作用。     

咪唑类化合物的合成与应用研究

咪唑是一种含氮的五元杂环化合物,广泛应用于农业、医药等领域。综述了咪唑及其衍生物的应用前景,总结了含有单环、多环和含金属元素的咪唑类化合物的合成方法,有望为新型杀虫剂和医药的开发提供帮助。     

含咔唑基团芘类荧光材料的合成与发光性质

以1-溴芘、1,6-二溴芘和9-对乙炔苯基咔唑为原料,通过Sonogashira偶联反应合成了1-（4-（9-咔唑）苯乙炔基）芘和1,6-二（4-（9-咔唑）苯乙炔基）芘两种荧光分子。经熔点、核磁共振氢谱以及元素分析等结构表征,对中间体和目标产物的紫外-可见吸收、荧光发射以及结构与性质之间的构效关系进行了研究。通过结构修饰,可有效调节此类分子的吸收及发射性质。当芘单元作为中心电子受体,以4-苯乙炔基为桥连基,引入咔唑基团作为电子给体时,其分子共轭程度、结构刚性和分子内电荷转移能力显著提高。相对于D-π-A结构的单取代化合物,双取代D-π-A-π-D结构分子的最大发射峰由422 nm红移至446 nm,荧光量子效率由0.64提升至1.08。该类化合物可作为高效的蓝光荧光材料,应用于有机光致/电致发光材料以及有机发光二极管等领域。     

Preparation and photophysical properties of organic fluorescent polymers and their nanoparticles

New classes of stable organic florescent polymer nanoparticles were prepared from the corresponding tetrahydrofuran (THF) solutions, upon slow evaporation of solvent under a mild vacuum. Uniform spherical nanospheres having mean diameter of ? 500–700 nm, showed enhanced fluorescence emission in solution, but it diminished when it is destroyed using an organic base. These end‐capped fluorescent polymers are highly stabilized in the excited states at higher concentration in solution, leads no more intra‐ and intermolecular interactions among the excited molecules, because of the absence of free functional groups. The significant enhancement in fluorescence emission was attributed to the high level of molecular stacking in the fluorescent nanoparticles, when compared with micron‐sized isolated powder sample. In addition, these fluorescent polymers exhibited significant thermal properties, along with better solubility in most of common organic solvents for their future application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5344–5350, 2006     

Study the synthesis and the properties of self-crosslinking acrylic latex via a novel fluorescent labeling method

To make waterborne painting be applied into metal protection area, the mechanical, water resistant, and anti-corrosion properties of the dried coating based on it should be improved effectively. Among various methods, self-crosslinking the latex during its drying process is thought to be an effective way. For example, the latex with DAAM/ADH (diacetoneacrylamide/adipoyl hydrazide) as the self-crosslinker has attracted a lot of attention due to its excellent stability and coating performance. In this study, a kind of reactable AIEgen was used and taken part in synthesizing the self-crosslinkable acrylic latex. Based on Aggregation Induced Emission(AIE) phenomenon, it is easy to real-time trace the preparation and curing process of the obtained latexes. At the same time, the influence of DAAM/ADH on the properties of the cured coating was studied in detail. In addition, as AIEgen is knitted onto the polymer chains via chemical bonds, external stimulus might interfere the coating's fluorescent property. Based on this phenomenon, the cured coating was studied and explored the feasibility to be applied into gas sensing area via its fluorescent property.     

Simulation,synthesis, characterisation and dyeing properties of a fluorescent hemicyanine dye

In this study, a hemicyanine dye, trans‐4‐(4‐(diethylamino)styryl)‐1‐ethylpyridinium bromide (DYE‐BD), was synthesised and simulated. The maximum absorption wavelength of DYE‐BD was calculated with the same basis set by using the Gaussian 09 software based on different methods, while time‐dependent density functional theory was applied to simulate the maximum emission wavelength of the designed dye. The changes in enthalpy and Gibbs free energy were simulated at the b3lyp/6‐31G(d) level, and energy changes in the luminescence process were assessed using mathematical methods. Furthermore, DYE‐BD was used to colour acrylic fabric following the typical dyeing procedure for cationic dyes. The photostability of the synthesised dye was analysed using quantum theory and mathematical methods. The synthesised dye, analysed using the Ecological Structure Activity Relationships class program, had no toxicity to aquatic life, while the acrylic fabrics dyed with DYE‐BD met the fluorescent orange requirements for background and combined performance materials according to the EN ISO 20471:2013 standard.     

水性聚氨酯荧光增白材料的合成及其性能研究

荧光增白剂可吸收不可见的紫外光,并且将紫外光转变为可见的蓝色或蓝紫色光发射出来;由于蓝色和黄色互为补色,消除了物质中的黄色部分,从而达到了增白效果。因此,采用荧光增白剂合成的水性聚氨酯(WPU)增白材料,用于涂料和织物上,可初步解决芳香族WPU的耐黄变问题。研究了乳液pH值、荧光增白剂的用量及其添加方式对WPU增白效果的影响,并通过透射电镜(TEM)观察增白剂在WPU中的分散情况。实验结果表明,WPU乳液及其胶膜的蓝光效果随着荧光增白剂用量的增加呈先增后降的趋势,当w(荧光增白剂)=0.008%时为最佳;当pH=7～9时,荧光增白剂在WPU中的分散稳定性和增白效果都较好;荧光增白剂的两种添加方式对其在WPU乳液及其胶膜中的分散稳定性和增白效果的影响不明显。     

钙荧光试剂的合成及其性质的研究

激发波长位于可见区的钙荧光试剂 Fluo-l 的合成,探讨了其紫外及荧光性质。     

淀粉-阳离子接枝共聚荧光乳液的制备及性能

利用亲核取代法制备含有紫外线吸收基团的二苯乙烯型荧光单体（FBs）,然后采用接枝共聚技术将FBs、苯乙烯分别与二甲基二烯丙基氯化铵（DMDAAC）和甲基丙烯酰氧乙基三甲基氯化铵（DMC）接枝聚合在淀粉大分子上,制备两种阳离子荧光乳液（ST-DMDAAC-FBs / ST-DMC-FBs）。采用1H-NMR、FT-IR、UV-vis、荧光光谱对产物的结构及光学性能进行表征;通过抗张强度、接触角、紫外光老化试验、SEM等手段对施胶前后纸张的物理性能进行测试。结果表明,经ST-DMDAAC-FBs、ST-DMC-FBs施胶纸张的抗张强度相比空白纸张分别提高43.1%、39.7%,白度分别提高15.52 %ISO、15.28 %ISO,返黄值分别降低1.88、1.75。说明ST-DMDAAC-FBs、ST-DMC-FBs均可以提高纸张白度与强度、抑制纸张返黄,且ST-DMDAAC-FBs对纸张的作用效果更佳。     

淀粉-阳离子接枝共聚荧光乳液的制备及性能

以4,4'-二氨基二苯乙烯-2,2'-二磺酸为母体、三聚氯氰为桥联剂,利用亲核取代法制备了具有紫外吸收性能的二苯乙烯型荧光单体(FBs),然后采用接枝共聚技术将FBs、苯乙烯分别与二甲基二烯丙基氯化铵(DMDAAC)或甲基丙烯酰氧乙基三甲基氯化铵(DMC)接枝聚合在淀粉大分子上,制备两种阳离子荧光乳液(ST-DMDAAC-FBs,ST-DMC-FBs).采用1HNMR、FTIR、UV-Vis、荧光光谱对产物的结构及光学性能进行表征;通过抗张强度、接触角、紫外光老化实验、SEM等手段对施胶前后纸张的物理性能进行测试.结果表明,经ST-DMDAAC-FBs、ST-DMC-FBs施胶纸张的抗张强度相比空白纸张分别提高43.1％、39.7％,白度分别提高15.52％ISO、15.28％ISO,返黄值分别降低1.88、1.75.说明ST-DMDAAC-FBs、ST-DMC-FBs均可以提高纸张白度与强度、抑制纸张返黄,且ST-DMDAAC-FBs对纸张的作用效果更佳.     

Enzymatic synthesis of fluorescent oligomers assembled on a DNA backbone

A number of research laboratories have investigated the properties of multichromophore molecules and their applications in materials science and in biotechnology. Previous approaches for preparing such molecules have involved traditional organic synthesis. Here we describe the one-step enzymatic synthesis of such a multichromophore species by using a DNA-polymerizing enzyme (terminal deoxynucleotidyl transferase (TdT)). We find that a nucleotide-like molecule with pyrene replacing the DNA base (dPTP) can be accepted as a substrate for this enzyme to produce discrete chromophores that have 3 or 4 pyrenes consecutively, depending on which anomer (alpha or beta) is used. Products were characterized by gel electrophoresis, mass spectrometry, and fluorescence. The reaction was found to change the fluorescence emission of the chromophore from a maximum at 375 nm (the monomer nucleotide) to 490 nm in the oligomeric product. This new green-white emission is consistent with the formation of a pyrene excimer between adjacent pyrene glycosides, which exhibit a large Stokes shift of 130 nm. The enzymatic synthesis of the pyrene excimer might have applications in homogeneous biological assays for DNA fragments, such as those that arise during apoptosis.     

新型系列噻咯衍生物合成表征及光学性质研究

以二苯乙炔和不同取代基的硅烷为原料,通过1,1-位取代反应,合成噻咯衍生物,并对合成工艺条件进行优化。结果表明,原料摩尔比为1∶0.5和改变加料顺序,产物产率有较大提高,能达70%。硅烷取代基官能团越大,产物越易合成,产率越高,能达75%以上。对合成产物用氢核磁共振、红外光谱进行了表征,并通过紫外光谱和荧光光谱研究了其发光性能。     

荧光橡胶的制备及其性能

采用共混法制备了荧光橡胶,考察了原胶、硫黄、黄油、荧光粉对其性能的影响及光照时间对荧光时间的影响。结果表明,原胶采用顺丁橡胶,1．8～2．0份硫黄,2．5份荧光粉,不加入黄油的配方可制备力学性能、荧光效果较好的荧光橡胶;荧光橡胶受光照射时间越长,则其发光时间越长,但最长时间为5h。