苝四羧酸二酰亚胺衍生物的合成及其性能研究

以苝四羧酸二酐为原料,设计并合成了3个苝四羧酸二酰亚胺类化合物[1,7-二溴-3,4,9,10-苝四酸酐(1), N,N′-二(十二烷基)-1,7-二溴-3,4,9,10-苝四羧酸二酰亚胺(2)和N,N′-二(十二烷基)-1,7-二对叔丁基苯氧基-3,4,9,10-苝四羧酸二酰亚胺(3)],其结构经1H NMR和MS表征.用循环伏安法和热分析法研究了2和3的电化学性质和热学性质.结果表明:2和3的氧化电位分别为931.6 mV, 170.1 mV,还原电位分别为-1 028 mV, -1 941 mV;2和3具有高的分解温度(>300 ℃),有良好的热稳定性.     

新型苝酰亚胺衍生物的合成及其光学性能

以3,4,9,10-苝四酸二酐为原料,设计并合成了三个新型的苝酰亚胺衍生物———N,N’-二(1-戊基己基)-3,4,9,10-苝四羧酸二酰亚胺,N,N’-二(1-戊基己基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺和N,N’-二(4-六氟异丙醇基苯基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺,其结构经1H NMR和MS表征。用UV-Vis和荧光光谱研究了他们的光学性质。     

取代基对苝酰亚胺衍生物气敏传感性能的影响

制备了两类酰胺位置含有吸电子基团的苝酰亚胺衍生物N,N′-双(三氟乙基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-3F)和N,N′-双(七氟丁基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-7F),并测定了其气敏传感性能.结果表明,两类苝酰亚胺衍生物在水合肼气氛中(10ppm)的灵敏度变化值基本相同、电阻均降低约4个数量级.其原因在于两者具有相同的最低空轨道能级.这表明酰胺位取代基对苝酰亚胺衍生物气敏传感性能的影响较小.     

不同pH环境中离子化水溶性染料分子的荧光性质

本文以3,4,9,10-苝四羧酸酐为原料合成了3,4,9,10-苝四羧酸和N,N′-二((3-二甲氨基)丙基)-3,4,9,10-苝二酰亚胺,这两个苝系衍生物在水溶液中的溶解度和荧光效率并不高,但是在不同的pH值条件下,两个衍生物形成了水溶性较强的PTCA阴离子和PMI阳离子,并且具有不同的荧光性质。实验结果显示:PTCA在pH 10.0的碱性环境中显示出较强的蓝色荧光,PMI在pH 5.0的弱酸性环境中显示出较强的黄色荧光,并且根据测试的荧光光谱推测了两种具有相同发色团、相似结构的衍生物在不同pH环境中可能存在分子或离子的堆积模式及发光模式。本文还探讨了PTCA阳离子在pH 6.0缓冲溶液中,作为离子型荧光探针对部分金属离子的识别。     

微波辐射合成N,N-二苯基-3,4,9,10-苝二酰亚胺

以3,4,9,10-苝四酸酐为原料,无水醋酸锌为催化剂,与苯胺利用微波辐射,合成N,N-二苯基-3,4,9,10-苝二酰亚胺.研究结果表明,在微波辐射下,无水醋酸锌对该反应有较好的催化活性,N,N-二苯基-3,4,9,10-苝二酰亚胺的产率可达60.02%.实验确定了该反应的最终优化条件为:无水醋酸锌的用量为0.5g,微波辐射功率为900 W,辐射时间为50min,反应温度为150℃.     

氟代位置对苝酰亚胺聚集态结构和电子传输性能的影响

合成了三种新型的有机电子受体: N,N'-二(2-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D2MFPP)、N,N'-二(3-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D3MFPP)和N,N'-二(4-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D4MFPP). 利用元素分析、傅立叶变换红外(FTIR)等方法表征了它们的分子结构, 用紫外-可见光吸收光谱(UV-Vis)、X射线衍射(XRD)和原子力显微镜(AFM)等手段研究了氟代位置对苝酰亚胺薄膜聚集态结构的影响, 发现氟代使苝酰亚胺的聚集态发生变化, 且不同位置的氟代对其影响也不一样. 除了分子结构的影响, 外场条件也会产生很大的作用. 通过制备场效应晶体管研究了其电子传输性能, 发现氟代后器件的空气稳定性有明显提高.     

新型有机电子受体氟代苝酰亚胺的合成与表征

设计和合成了一种新型有机电子受体N,N′-二(五氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(DFPP),利用傅里叶红外光谱和核磁共振谱等方法表征了DFPP的分子结构,用紫外-可见吸收光谱、循环伏安法和电子自旋共振谱等手段证明了DFPP中极低的最低未占有轨道(LUMO)能级为-4.37eV.另外,还发现了DFPP薄膜的独特聚集态结构,五氟代苯基正好处于相邻分子苝环的正上方或正下方.     

水溶性苝系衍生物荧光探针的合成及对金属离子的识别

用苝四酸酐为反应物,在酸酐位置上引入天冬氨酸,合成了水溶性的含4个羧基的荧光苝二酰亚胺衍生物:N,N'-二天冬氨酸铵盐-3,4,91,0-苝四羧酸二酰亚胺(PTCDA).在水溶液中与Fe3+、Al3+、Pb2+和Cu2+等金属离子反应,吸收光谱发生红移,荧光淬灭.当加入等量Hg2+、Zn2+、Ni2+、Co2+、Mn2+和Mg2+等金属离子后不干扰荧光反应,有选择性好、灵敏度高等特点.并探讨了衍生物的荧光反应机理,表明有好的应用价值和广阔发展前景。     

含三苯胺结构的非对称型苝酰亚胺的合成及性能

合成了2种含有三苯胺结构的非对称型苝酰亚胺N-(2-乙基己基)-N'-(4-三苯胺)-3,4,9,10-苝二酰亚胺(PDI-ATPA)和4,4',4″-三[N-(2-乙基己基)-3,4,9,10-苝二酰亚胺]-三苯胺(PDI-TATPA).利用核磁共振谱(NMR)、红外光谱(IR)和元素分析等方法表征了2种分子的结构,采用紫外-可见(UV-Vis)吸收光谱和荧光光谱研究了其分子光物理性能及在溶液中的聚集行为,并且对分子轨道、能级和偶极矩进行了分子模拟.研究结果表明,具有星形空间对称结构的苝酰亚胺分子PDI-TATPA在溶液中具有自组装行为;引入的三苯胺结构与苝核形成电子给体-受体结构,发生分子内电子转移(PET),进而导致荧光猝灭.     

一种新型苝类荧光开关的构建及对H2O2与Vc分子的识别

以苝四酸酐为原料合成了新型的水溶性荧光分子——N,N’-二谷氨酸铵盐-3,4,9,l0-苝四羧酸二酰亚胺(PTCDG),其结构经1 H NMR、IR证实.以顺磁性Fe3+和抗磁性Fe2+与PTCDG构建荧光开关,当以顺磁性的Fe3+存在时,荧光团和Fe3+之间发生PET效应,荧光猝灭,而当以抗磁性的Fe2+存在时,PE...     

苯乙烯嘧啶化合物的合成及其作为pH探针的光谱特点

合成并表征了化合物4,6-二[（4′-二乙基胺基）苯乙烯基]嘧啶-2-醇。 通过研究该化合物在不同pH值的磷酸盐缓冲溶液中紫外-可见吸收光谱和荧光光谱的变化,发现λmax约为500 nm的吸收峰在溶液pH=6.78中吸收强度最大。 荧光发射峰随着pH值的升高逐渐减弱,直至淬灭（pH=5.51）。     

2-(2-苯并咪唑)-6-甲基吡啶锌配合物的合成及发光性质

合成了2-(2-苯并咪唑)-6-甲基吡啶及其锌配合物,通过元素分析、摩尔电导率、红外光谱和紫外光谱对产物进行了表征,并运用荧光光谱对配合物的发光性质进行了研究。结果表明,锌配合物在DMF溶液中的荧光最大发射波长为428nm,在固态下的荧光最大发射波长为448nm,均属于蓝光发射,具有作为蓝色发光材料的潜能。     

2-糠醛缩N-乙基-3,6-二氨基咔唑双席夫碱的合成及其性能

以咔唑为起始原料经N-取代、硝化和还原反应制备中间体N-乙基-3,6-二氨基咔唑,然后以其与2-糠醛发生缩合反应制得新型双席夫碱化合物N-乙基-3,6-二(2-亚糠基亚氨基)咔唑,产率为72.36%。通过元素分析、FTIR、UV-Vis、1H NMR、溶液及固体荧光光谱、循环伏安(CV)和TG-DTA分析研究了标题化合物的分子结构、光物理特性、电化学特性和热稳定性。结果表明,化合物的DMF稀溶液在200~400 nm波段有较宽较强的紫外吸收;在365nm波长激发下,溶液发射深蓝色荧光,λem为446nm,固体荧光为λem=467nm的蓝色荧光,与溶液荧光相比固体荧光红移了21nm。由循环伏安测试得到产物的Eg=2.19e V,IP=4.99e V以及EA=2.80e V,说明其具有良好的空穴和电子传输材料性能。TG-DTA测试显示目标产物具有良好的热稳定性。该化合物在有机荧光、空穴注入传输材料以及电子传输材料方面具有潜在应用前景。     

Spectroscopic studies into the influence of UV radiation on elastin in the presence of collagen

An investigation into the influence of UV irradiation on elastin hydrolysates in the presence of collagen was carried out using UV-Vis spectroscopy and spectrofluorometry. It was found that the absorbance of elastin hydrolysates in solution increased during irradiation more than the absorbance of the elastin/collagen blend. The fluorescence of elastin hydrolysates was observed at 305nm and at 380nm after excitation at 270nm. For the elastin/collagen mixture in solution, fluorescence spectrum shows only one maximum at 305nm. UV irradiation caused fluorescence fading at 305nm. For irradiated elastin the fluorescence at 305nm decreased faster than for the irradiated elastin/collagen mixture. The maximum of the fluorescence peak was shifted for elastin by 4nm, whereas for the elastin/collagen blends the shift was only 1-2nm. All the obtained results point out the ability of mixing elastin and collagen, and suggest that the elastin/collagen mixture in solution is less sensitive to UV irradiation than elastin hydrolysates alone.     

Synthesis of positively charged CdTe quantum dots and detection for uric acid

The CdTe dots (QDs) coated with 2-Mercaptoethylamine was prepared in aqueous solution and characterized with fluorescence spectroscopy, UV-Vis absorption spectra, high-resolution transmission electron microscopy and infrared spectroscopy. When the λex=350 nm, the fluorescence peak of positively charged CdTe quantum dots is at 592 nm. The uric acid is able to quench their fluorescence. Under optimum conditions, the change of fluorescence intensity is linearly proportional to the concentration of uric acid in the range 0.4000-3.600 μmol L(-1), and the limit of detection calculated according to IUPAC definitions is 0.1030 μmol L(-1). Compared with routine method, the present method determines uric acid in human serum with satisfactory results. The mechanism of this strategy is due to the interaction of the tautomeric keto/hydroxyl group of uric acid and the amino group coated at the CdTe QDs.     

利用聚合物自组装实现绿色荧光蛋白生色团的荧光增强

根据绿色荧光蛋白的发光原理,采用聚乙二醇与聚甲基丙烯酸甲酯的两亲性两嵌段聚合物通过自组装包覆生色团的方式,模拟了绿色荧光蛋白发光,考察了组装行为对光学性能的影响,并将其用于细胞成像.通过核磁共振、高分辨质谱、傅里叶变换红外光谱、凝胶渗透色谱、紫外-可见吸收光谱及荧光光谱等表征了生色团分子和聚合物的结构及性能.生色团紫外最大吸收在371 nm,荧光最大发射峰在428 nm.聚合物和生色团进行组装后,其紫外吸收消失,而最大荧光发射峰强度大大增强,且发生了约70 nm的红移,这是因为组装使得生色团的自由旋转受到了限制,且生色团共平面性增加.动态光散射(DLS)和透射电镜(TEM)证明了纳米粒子的结构和尺寸.由于尺寸适合且具有较好的荧光性能,纳米粒子成功应用于细胞成像.这种绿色荧光蛋白生色团的简单自组装方式在生物成像领域具有良好应用前景.     

微波辐射合成含三苯基吡啶结构超支化聚酰亚胺及其光学性能的研究

利用自己合成的含三苯基吡啶结构的BB′2型芳香三胺TAPP与A2型的二酐3,3′,4,4′-二苯酮四羧酸二酐(BTDA)在微波辐射下经"两步法"分别合成了氨基封端和酐基封端的新型超支化聚酰亚胺(AM-HBPI和AD-HBPI).通过FTIR、1H-NMR、XRD、TGA、溶解性试验以及UV-Vis和荧光光谱等对产物进行了一系列的结构表征和性能测试.结果表明,两种新型的含三苯基吡啶结构超支化聚酰亚胺(HBPI)在强极性非质子溶剂中均显示出良好的溶解性,对无机稀酸也具有一定的抗腐蚀性;它们还体现出优异的耐高温性,在N2中的10%热失重温度(T10%)分别高达573℃和568℃.除此之外,AM-HBPI和AD-HBPI还分别在200～400nm和200～350nm具有良好的紫外光吸收性能,以及紫、蓝色荧光发射性能.而且它们被HCl质子化后的紫外光吸收谱带均扩宽至425nm,荧光发射峰的强度也大大增强.     

The influence of UV radiation on silk fibroin

An investigation into the influence of UV-irradiation on regenerated silk fibroin dissolved in water was carried out using UV-Vis and fluorescence spectroscopy. It was found that the absorption of regenerated silk fibroin in solution increased during UV-irradiation of the sample, most notably between 250 and 400 nm. Moreover, after UV-irradiation a wide peak emerged between 290 and 340 nm with maximum at about 305 nm. The new peak suggests that new photoproducts are formed during UV-irradiation of regenerated silk fibroin.The fluorescence of regenerated silk fibroin was observed at 305 nm, at 480 nm and at 601 nm after excitation at 275 nm. UV-irradiation caused fluorescence fading at 305 nm and at 601 nm. The increase of fluorescence was observed at 480 nm, probably due to formation of new photoproducts. After excitation at 305 nm the fluorescence of regenerated silk fibroin was observed at 340 nm and at 400 nm. UV-irradiation caused fluorescence fading at 340 nm. FTIR spectroscopy showed that primary structure of regenerated silk fibroin was not significantly affected by UV radiation. SDS-PAGE chromatography showed alterations of molecular weight of silk after UV exposure.     

四苯基卟啉镁的合成、表征及光化学性质

提出一种以乙酸镁和乙酸钠为原料合成四苯基卟啉镁(MgTPP)的新方法, 合成样品以柱层析法进行分离纯化. 分离产物经UV-Vis、1H-NMR、MALDI-TOF-MS(基质辅助激光解吸电离飞行时间质谱)等技术表征, 确定为MgTPP. UV-Vis光谱分析结果表明, 四苯基卟啉镁的Soret 吸收带为424 nm, Q 吸收带为563 nm 和602 nm. 此外, 光照对MgTPP的二氯甲烷溶液光谱性质的影响结果表明, 经光照射后MgTPP的UV-Vis光谱的Soret吸收带吸收强度明显降低, 同时, 经550 nm的光激发产生的荧光有明显的猝灭. 对光照后的MgTPP样品进行MALDI-TOF-MS分析, 发现有新的质核比(m/z)出现, 其为668, 这一结果表明, 在光照条件下, MgTPP分子可能与氧分子发生光化学作用, 形成MgTPP与氧的复合物MgTPP-O2.     

Spectroscopic studies into the influence of UV radiation on elastin hydrolysates in water solution

An investigation into the influence of UV irradiation on elastin hydrolysates dissolved in water was carried out using UV-Vis spectroscopy and spectrofluorometry. It was found that the absorption of elastin hydrolysates in solution increased during irradiation of the sample. For fluorescence of elastin hydrolysates we observed both, a decrease and increase of this value during irradiation of the sample. After UV irradiation of the elastin solution we observed a minor increase of overall absorption, most notably between 250 nm and 280 nm. Moreover, after UV irradiation a wide peak emerged between 290 nm and 310 nm with maximum at about 305 nm. The new peak suggests that new photoproducts are formed during UV irradiation of elastin hydrolysates. The fluorescence of elastin hydrolysates was observed at 305 nm and at 380 nm after excitation at 270 nm. UV irradiation caused fluorescence fading at 305 nm and 380 nm. After 30 min of irradiation a new broad weak band of fluorescence, attributable to new photoproducts, emerged in the UV wavelength region with emission maximum between 400 nm and 500 nm.