【作者】 颜范勇；

【导师】 陈立功；

【作者基本信息】 天津大学 ， 应用化学， 2007， 博士

【摘要】 为提高罗丹明荧光染料的荧光强度、发射波长、增大斯托克斯位移、扩大荧光对pH值的敏感范围、增加对一些过渡或重金属离子的识别响应,本文设计并合成了一系列底环修饰,N端基固定,不对称,双发色团以及离子识别型罗丹明衍生物,并通过紫外-可见光谱和荧光光谱对所得罗丹明衍生物进行荧光性能检测,总结出其结构特点与其光学性能之间的关系。主要包括以下内容:合成了硝基和氨基罗丹明,并通过氨基的重氮化,桑德迈尔反应得到了一系列5(6)位卤代罗丹明衍生物;合成并分离出底环不同位置单氯代、全氟(或氯)代罗丹明衍生物以及底环上无羧基的“Rhosamine”类衍生物。光谱性能研究表明,与母体罗丹明B相比,硝基的罗丹明荧光强度明显减弱,氨基罗丹明荧光强度增强,λmax-ex和λmax-em红移;罗丹明B底环上引入不同的卤原子使λmax-ex和λmax-em有所增长,随着卤代基个数的增加,λmax-ex和λmax-em红移,斯托克斯位移降低;底环上的的羧基对荧光性能几乎没有影响。合成了氧杂蒽母环末端N固定的五个罗丹明衍生物,经紫外-可见光谱及荧光光谱检测,五个罗丹明衍生物的λmax-ex和λmax-em明显向长波偏移20nm以上,由所处的可见光区红移至近红外光区,斯托克斯位移明显增大,荧光量子产率增加,成为近红外荧光标记试剂,结果证明N端基固定可以增加分子共平面性和刚性,对荧光的产生有利,可使荧光增强。设计合成了氧杂蒽母环端基氨不对称的罗丹明衍生物bdc-1～bdc-11,与对称结构罗丹明相比较,不对称罗丹明衍生物的激发光谱和发射光谱的重叠变少,斯托克斯位移明显增大,顶环结构不对称性越明显,斯托克斯位移增大就越显著。其中bdc-4、bdc-5的λmax-em明显向长波发生迁移,是很好的近红外荧光染料试剂。bdc-10改变了对pH值的敏感范围,在酸性和碱性环境下具有不同的吸收、发射波长。通过桥链将在不同pH值条件下进行荧光检测的罗丹明、荧光素结构连接在一起,合成了具有双发色团的两种罗丹明衍生物,不同pH值时两种罗丹明衍生物荧光光谱有明显差别,拓宽了pH的适用范围,可以作为检测细胞内部的pH值的荧光探针。为增加对一些过渡或重金属离子的识别响应,本文将罗丹明衍生物键合到杯[4]芳烃骨架上,合成了两种罗丹明杯[4]芳烃衍生物,对产物结构、光谱性能和对一些金属离子的识别进行了研究,两个衍生物与Cu2+、Zn2+混合溶液的紫外吸收发生明显变化,最大吸收峰强度降低,λmax-ex红移,与铜离子、锌离子在甲醇溶液中存在明显的络合现象。更多还原

【Abstract】 In this thesis, 5 series of rhodamine derivatives were designed and synthesized including bottom ring modified, N-stabilized, asymmetrical, consisted of double fluorescence groups and ion binding rhodamine derivatives in order to improve the fluorescence intensity and quantum yield, longer-wavelengths, pH-sensitive range, the large Stokes shift and ion binding specificity. The fluorescence properities of the obtained compounds were investigated by UV-vis spectra and fluorescence spectra. The relationship between their structures and photophysical properties were summarized. The details were described below:Nitro-rhodamine and amino-rhodamine were synthesized. A series of 5 (6)-halo-rhodamine were obtain from amino-rhodamine through diazotization, Sandmeyer reaction. Synthesis and isolation of mono and full substituted chlororhodamines, full-fluoro substituted rhodamines and rhosamine without carboxyl group on the bottom ring were investigated in this paper. Comparing with rhodamine B, although the fluorescence intensity of aminorhodamine was improved, this property of nitrorhodamine had weakened,λex andλem were red shift. The introduction of halo element to rhodamine structure enlargedλmax-ex andλmax-em As the number of halo-atom increasing,λmax-ex andλmax-em were red shift, Stokes shift had decreased. Carboxyl group on the bottom ring had almost no influence to fluorescence properties.Five N stabilized rhodamine derivatives at xanthene were synthesized and their fluorescence properties were tested by UV-vis spectra and fluorescence spectra. It was found thatλmax-ex andλmax-em were red shift more than 20nm from visible light area to IR area. N-stablization increased in co-planar and rigidity which lead to the enlargement of Stokes shift and intensity of fluorescence intensity.Asymmetric rhodamines bdc-1～bdc-11 was designed and synthesized.the overlap betweenλmax-ex andλmax-em for these compounds decreased, at same time Stokes shift increased. The greater asymmetric degree, the larger of the Stokes shift. Theλmax-em of bdc-4 and bdc-5 were red shift. Bdc-10 showed different absorption and emission wavelengths in acid and base solution.Rhodamine and fluorescein were linked to obtain double fluorescence group by chemical bond. The fluorescence spectrum of the compounds showed obvious variety in different pH solution. Rhodamine-calix[4]arene was linked together by amide group. Its fluorescence and metal ion bind ability were tested. The UV-vis absorption changed when the addition of this compound into the methanolic solution containing Cu2+ and Zn2+.更多还原