【作者】 吕君；

【导师】 曾钫；

【作者基本信息】 华南理工大学 ， 材料学， 2015， 硕士

【摘要】 随着工业的迅速发展,一些化工原料和试剂造成的环境污染问题日显突出。肼及其衍生物是一类重要的化工原料,在防腐、纺织染料、感光化学品、制药和乳化剂等方面有着广泛的应用。但肼也是一种高毒性、可致癌的物质,过量吸收会刺激呼吸系统甚至影响到起肝、肺、肾脏和中枢神经系统的生理机能,因此对肼的检测具有重要的医学和生物学意义。与传统的检测方法相比,荧光检测技术因其灵敏度高、选择性好和低检测下限等优点被广泛应用在化学、材料、生物和医学等领域。2-(2-羟苯基)-苯并噻唑(2-(2-hydroxyphenyl)-benzothiazole,HBT)作为具有ESIPT(Excited-state Intramolecular Proton Transfer)效应的典型荧光材料,其独特的多重光谱性质使其具有很好的应用潜力,但环境敏感性又限制了它的应用。另一种常见的荧光生色团1,8-萘酰亚胺衍生物,具有荧光量子产率高、发射波长范围广、较大的stocks位移和光谱可调节性等优点,广泛应用于荧光分子探针的设计。首先,以2-(2-羟苯基)-苯并噻唑(HBT)为基体设计了一例基于ESIPT效应的探针HBTA-N2H4,但是该探针容易被水解,且其光谱容易受到极性溶剂和质子性溶剂的影响,在很大程度上会干扰HBTA-N2H4对肼的响应,因此,该探针不适用于实际应用中对肼的比率型检测。其次,我们以1,8-萘酰亚胺为基体设计并成功合成了另外一例具有ICT效应的肼检测比率型荧光探针,并对其结构、光谱性能和肼检测性能等方面进行了表征和研究。在385nm激发下,探针NA-N2H4在445 nm处有明显的荧光发射峰,与肼发生特异性反应后波长红移至545 nm处,能够实现比率型荧光检测。与肼反应前后,肉眼可观察到检测体系的颜色由无色变为浅黄色,证明NA-N2H4具有比色型检测的特点。另外,探针NA-N2H4具有良好的选择性和抗干扰性、灵敏度高、检测下限可达到3.47 n M(0.111 ppb),且响应时间短(5分钟内),有利于对肼的实时监测。p H稳定性试验表明,NA-N2H4在p H=5~10的范围内不易被水解,表现出较好的稳定性。更重要的是,NA-N2H4不仅可以对实际水样中的微量肼进行定量检测,还成功地应用于L929细胞和斑马鱼体内,实现了活细胞和活体内对肼的荧光成像。此外,探针还能定性地检测气态肼。因此,在水质和环境检测以及肼对细胞和生物体毒害作用的研究方面,探针NA-N2H4具有潜在的应用价值。更多还原

【Abstract】 With the rapid development of industry, the pollution problem caused by some chemical raw materials has become increasingly prominent. Hydrazine as well as its derivatives is not only an important industry raw material, but also a kind of highly toxic and possibly carcinogenic substance. Therefore, the detection of trace hydrazine will be of great importance to biological and medical sciences. In comparison with conventional detection methods, fluorescence detection techniques have been widely used in areas including chemistry, materials science and biology due to its simple, high sensitivity, specific selectivity and low detection limit. As a typical fluorescent material with ESIPT effect, the unique multiple spectra property of 2-(2-hydroxyphenyl)-benzothiazole(HBT) has made it a potential fluorescent material. However, it’s been limited by the environment-sensitivity character. 1,8- naphthalene imide, another common fluorescent chromophore with advantages of high fluorescence quantum yield, wide range of emission wavelength, large stocks shift and tunable wavelength, has been one of the most commonly used fluorescent chromophore for design of fluorescent molecular probe.In this paper, we firstly designed a probe based on 2-(2- hydroxyphenyl)- benzothiazole with ESIPT effect. However, to a great certain, property of being easily hydrolyzed and the environment-sensitivity to polar solvent and protic solvent had limited its practical application in hydrazine detection by affecting the fluorescence spectra. Therefore, it’s not applicable to realize the ratiometric fluorescent detection for hydrazine.Instead, a ratiometric fluorescent probe NA-N2H4 for hydrazine detection, which is based on 1,8-naphthalene imide with ICT effect had been designed and successfully synthesized. And the structure, property of spectra and detection for hydrazine had been tested and researched. Results show that, this probe can realize the colormetric and ratiometric detection for hydrazine with the color change from colorless to orange-yellow and with the emission peak transferring to 545 nm from 445 nm wavelength after specific reaction of probe with hydrazine. In addition, the sensitivity of probe NA-N2H4 is pretty high with a low detection limit of 3.47 n M(0.111 ppb) and the specific selectivity and anti-interference performance of probe is desirable. Besides, probe NA-N2H4 has a rapid response towards hydrazine within five minutes, which is benefit to the real-time detection. According to the p H stability test result, probe NA-N2H4 is not easy to be hydrolyzed, performing a desirable stability. What’s more, this probe not only can realize quantitative detection for hydrazine in real water sample, but also can fulfill the fluorescent imaging in cell(L929) and in vivo application(zebrafish). Also, as for qualitative detection for gaseous hydrazine, it works as well. Therefore, in aspects of monitor of water quality and environment and the research about toxic effect of hydrazine for cell and organism, probe NA-N2H4 is expected to be utilized in a variety of chemical and biological applications.更多还原