【作者】 贾丽华；

【导师】 钱旭红；

【作者基本信息】 大连理工大学 ， 应用化学， 2003， 博士

【摘要】 金属离子是化学、生命科学、环境科学和医学等许多科学领域研究的重要对象，对溶液中金属离子的识别和检测是分析化学的主要任务之一。荧光分子探针检测法不仅简便，而且在高灵敏度、选择性、时间分辨、实时原位检测方面均有突出优点。因此在传统的受体分子上按照荧光分子传感器设计原理连接荧光团构造的超分子荧光传感器用于识别金属离子的研究受到越来越广泛的关注。 设计并合成了3个仅连接一个氮原子受体作为识别基的简单结构的萘酰亚胺荧光分子探针，通过对其在不同溶剂体系中与金属离子作用时的荧光光谱变化的研究，提出了结构简单的“荧光发色团-连接基-受体”类型的荧光分子探针（如带有氨乙基受体）在有机溶剂中对过渡金属离子的开关作用，可能不是过渡金属离子与荧光分子探针直接作用的结果，是由于有机溶剂中存在的微量水或加入的过渡金属水合盐等带入的水使过渡金属离子水解，水解产生的氢质子与荧光分子探针的受体结合，阻断了光诱导电子转移（PET）过程，导致荧光增强。 基于PET原理，设计并合成了新型荧光分子开关4，5-二[2-（N’，N’-二甲氨基）乙氨基]-1，8-萘酰亚胺（H1）、4，5-二[3-（N’，N’-二甲氨基）丙氨基]-1，8-萘酰亚胺（H2）及4-氯-5-（N-甲基哌嗪基）-1，8-萘酰亚胺（H3）。在tris-HC1中性缓冲溶液中，H1与Ag⁺结合后，体系颜色由黄绿色变为红色，H1为Ag⁺的专一选择性变色识别探针；而且H1通过荧光淬灭选择性地识别金属离子Cu²⁺、Ag⁺，H1分别与Cu²⁺、Ag⁺形成了1：2和1：1的络合物。 设计并合成了新型类冠醚荧光分子开关4，5-二[2-（2-羟乙氨基）乙氨 大连理工大学博士学位论文基卜1，8一蔡酞亚胺（Cl）、4，5一二【2一（2一轻乙氧基）乙氨基卜1，8一蔡酸亚胺（C2）及4，5-二(2一轻乙氨基卜1，8一蔡酞亚胺（C3）。在tris-HCI中性缓冲溶液中，cl选择性地识别金属离子cu2+、co2+，在金属离子浓度为。一1 x 10一5 mol/l范围内，其荧光强度及吸光度分别与Cu2+、Co2+的浓度呈线性关系。设计并合成了冠醚类荧光分子开关C4一cs，在甲醇一四甲基氢氧化钱体系中cs选择性识别金属离子zn2+，Zn2+使CS荧光明显增强。 合成了蔡酞亚胺衍生物季钱盐阳离子表面活性剂一碘化4一(N’，N’一二甲基呱嚓基卜N-烷基一1，8一蔡酞亚胺（sl、52、53和54），该类化合物有明显的临界胶束浓度。利用共振光散射技术研究了51与DNA的相互作用，建立了利用51为光散射探针，测定纳克级核酸的新方法。在一定pH值的条件下，51能与小牛胸腺DNA相互作用，光散射强度较单一的51体系和DNA体系明显增强，无需加入表面活性剂和无机盐。对ct一DNA的检出限达到9 .5 ng/ml，线性范围为0一4林g/ml。 研究了卤代蔡醉的室温磷光性质。卤代蔡配在以NaZSO3作化学除氧剂环己烷作为起空间调节和空间匹配作用的第三组分，p一CD作为保护性介质在无外重原子存在的条件下，可以发射强而稳定的室温磷光。更多还原

【Abstract】 The analysis and detection of the transition metal ions is currently of significant importance for chemistry, as they are closed with biology, environment and clinic. The method of fluorescence is not only simple but also can realize real space, real time, high sensitive and selective. So the fluorescence supramolecular sensors, which are composed of traditional receptors connecting fluorophores, to metal ions are attracting many people’s attentions.Three naphthalimide fluorescent probes were designed based on PET principle and synthesized for studying the recognition mechanism of the fluorescent probes to transition metal ions in organic solvents, and the spectra of the probes in the absence or presence of metal ions in different solvents were studied. The results showed that the fluorescence enhancement corresponding to transition metal ions of the probes in fluorophore-spacer-receptor format in organic solvent, might be induced by protons, which originated from the hydrolysis of transition metal ions in the presence of trace water in solvents or in metal ions hydrate salts, the fluorescence enhancement might not be from the direct interaction between probes and metal ions in organic solvents.The novel fluorosensors of 4,5-disubstituted-N-alkyl-l,8-naphthalimides derivatives(Hl, H2, H3) with double ethylenediamino receptors, double propylenediamino receptors or one methylpiperazine receptor were designed and synthesized, respectively, their fluorescence and absorption spectra in the presence or absence of metal ions in tris-HCl buffer aqueous solution were studied. In the presence of Ag+, the H1’s absorption displayed color change from yellow-green to red, its quenching and red shift in fluorescence were also remarkable. Similarly, H1’s fluorescence was also strongly quenched in the presence of Cu2+.The novel fluorosensors of 4,5-di(2-hydroxylethyleneamino) ethyleneamino -N-dodycyl-1, 8-naphthalimides and its analogues(Cl, C2, C3), which can formedcrown ether-like receptors through the intramolecular hydrogen-bonding of hydroxyl groups at the end, were designed and synthesized. Their fluorescent spectra in tris-HCl buffer aqueous solution were recorded in the presence or absence of transition metal ions. Cl showed a strong quenching and a considerable blue shift response to Cu2+ and Co2+, and both of the fluorescence intensity and absorption of Cl were proportional to the concentration of Cu2+ or Co2+ in the range of 0-1 xl0"5 mol/l. The crown fluorosensors C4-C8 was designed and synthesized. And the fluorescence intensity of C8 was enhanced when zinc ions was added to its methanol-tetramethylhydroxylammonium solution.The naphthalimide cationic surfactants with piperazine were synthesized (SI, S2, S3, S4), and the cmc values of this kind of compounds were determined. The interaction of S1 with DNA was studied by resonance light scatting (RLS) in common fluorescent spectrameter, and the assay of determined DNA using S1 as RLS probe was built. In the absence of salt and surfactants, the RLS intensity of SI in DNA system was enhanced obviously compared with S1 or DNA single system with pH at 2.28. The increasing of RLS intensity is proportional to the concentration of DNA in the range of 0-4 u?ml for ct-DNA when the concentration of SI is l.0xl0-5 mol/l, and the detection limit (S/N = 5) is 9.5 ng/ml.Phosphorescence (RTP) of halogen naphthalic anhydride at room temperature was studied. The results showed that halogen naphthalic anhydride could emit strong and stable room temperature phosphorous when Na2SO3 as a chemical deoxygenator, P-CD as a protective medium and without heavy atom perturber, which imply that halogen naphthalic anhydride may be used as phosphor.更多还原