【作者】 陈涛；

【导师】 崔京南； 徐兆超；

【作者基本信息】 大连理工大学 ， 精细化工， 2013， 硕士

【摘要】 很多信使气体在生物体内都发挥中重要的作用,而利用荧光探针技术可以对包括H2S、NO在内的众多生物信号气体进行专一性的检测,并且其响应浓度低,灵敏度高以及其对细胞的生物相容性好等优点,都使荧光探针技术在生物气体检测方面拥有广泛的应用。其中H2S气体作为一种重要的生物信使气体需要我们设计能够对其进行准确检测的荧光探针。本文就是基于H2S能够还原叠氮为氨基的机理,设计了利用三氰基二氢呋喃(DCDHF)为发色团,叠氮为H2S受体的荧光探针分子。DCDHF其作为一种D-π-A型分子,具有P-π共轭体系,它的激发波长和发射波长均在长波长区,因此这是一种红光发射的硫化氢荧光分子探针。由于在红光波长范围内可避免因紫外线引起的光毒性和自荧光的干扰,因此本探针可应用与生物体内H2S的检测,而且其与生物试样通光窗口是一致的,从而能够使光最佳渗透到各种生物介质中去。在向探针分子DCDHF-1溶液中引入H2S时,会在619nm处得到一个荧光强度显著增大的吸收峰,同时溶液由黄色变为红色,这个现象可以作为一个方便的比色测定来应用。相对于一些其它阴离子和其它含硫化合物,此探针对H2S具有很好的专一性和选择性。此外探针DCDHF-1还被应用于检测活细胞中的H2S,证明了该探针能够透过细胞膜检测细胞内的H2S。另外,4-氨基取代的1,8-萘酰亚胺是一个具有推-拉电子体系的荧光团,其通过分子内电荷转移机理(ICT),可以在4-位上连接供电子取代基,从而实现荧光波长的移动,因此设计并合成了探针分子2。同样利用叠氮被H2S还原为胺基的机理,实现对H2S的比率荧光检测。同样道理,我们又利用4-氨基取代的1,8-萘酰亚胺为荧光团,同时根据之前文献里报道的两个氨基在NO存在条件下转化为具有三唑结构的产物DAN-T,并在生理条件下能够进一步脱去一个质子,形成三唑盐结构的原理,设计并合成NO探针N-丁基-4-氨基-5-丁胺萘酰亚胺3,从而期望其实现荧光强度的变化,达到对NO的比率检测的效果。目标化合物2和3合成都进行到最后一步。更多还原

【Abstract】 Many kinds of messenger gas play an important role in organisms, fluorescence probes can be used to detect and sence biological signal gas such as H2S. NO, etc. Fluorescence probes have a wide range of applications in biological gas detection because of its high sensitivity, high response to the low concentration and its biocompatibility to cells.We should design fluorescence probes which can detect H2S accurately due to its significance as a biological signal gas. We ased on the mechanism of reduction reaction of azide by H2S to designe a new probe molecule for H2S detection, in this probe we used dicyanomethylenedihydrofuran (DCDHF)as fluorophore and azide group as H2S’s receptor.Because DCDHF is a molecule of D-π-A type and it has a P-πconjugate system, it’s excitation wavelength and emission wavelength are all in the long wavelength region. this is a kind of fluorescent molecular probes which has red light emission for hydrogen sulphide.We all know that within the scope of the red light wavelengths, the fluorescence probe can be avoided toxicity caused by uv light and also can be avaided the fluorescence interference by itself, and it has the asme optical window with the biological specimen, so that they can make best light penetration into various biological medium.With the addition of H2S to the solution of DCDHF-1, an emission centered at619nm was observed and increased in intensity significantly. Concomitantly, the solution color changes from yellow to red with the convenience and aesthetic appeal of a colorimetric assay. The probe has a high selectivity for H2S over competitive anions and sulfide-contining analytes. Finally, the probe was applied to sense H2S in living cells.4-amino or4-hydroxy-1,8-naphthalimide fluorophore with a pull-push electron system is characterized by the intramolecular charge transfer (ICT). When the electron-donating ability of4-amino or4-hydroxyl group in1,8-naphthalimide changes, a shift in the emission wavelength can be expected. In this thesis, a1,8-naphthalimide fluorescent probes based on the ICT mechanism were designed and synthesized. It is ased on the mechanism of reduction reaction of azide by H2S too.In the same way.we use4-amino-1,8-naphthalimide fluorophore as fluorophore, and double amino structure as a receptor to synthesized another fluorescent probe N-butyl-4-bromine-5-nitro-1,8-naphthalimide(3) for NO. According to a report in the literatures before that double amine under the condition of NO can be converted into triazole structure compound, and it will lose a proton under physiological conditions then form a triazole salt structure. We expect the probe3could detect NO with ratio fluorescence.更多还原