新型NIR氟离子荧光探针的合成及其光谱性能的研究与成像应用

发布时间：2018-03-29 04:11

本文选题：花菁染料　切入点：氟离子　出处：《海南大学》2017年硕士论文

【摘要】：氟离子属于人体必需的微量元素之一,它对人体健康起着至关重要的作用。在各种氟离子检测的分析方法中,荧光传感被认为是一种操作简单,专一性好和灵敏度高的理想技术。本文以具有近红外(Near-Infrared,简称NIR)光谱特征,光稳定性好以及水溶性好等优点的部花菁骨架1作为荧光发色团,以Si-O键为反应位点,设计合成了 OFF-ON型的具有NIR激发和发射波长的荧光探针CyR-Si(3a,3b和3c)。完成的主要工作包括:1、以环己酮为原料合成了部花菁骨架1,再通过与间苯二酚等发生消除、retro-Knoevenagel、环化及脱水反应得到一种带有羟基的荧光物质。随后在羟基邻位构建出含有H,C1和F取代基的探针3a,3b和3c,其结构通过HRMS,1HNMR和13CNMR等测试手段得到验证。此外,对探针的光物理数据的计算方法以及其他操作步骤做了简要说明,如荧光量子产率,pKa,检测限等。2、考察了探针 3a,3b 和 3c 在 DMSO/PBS=7:3(v/v,0.01M,pH = 7.4)体系中分别对氟离子的响应情况。其中荧光选择实验和竞争实验表明探针3a-c对氟离子都具有专一选择性和很好的抗干扰能力。荧光滴定实验表明探针的荧光强度和氟离子浓度在0～100mM(探针3a),0～70mM(探针3b)和0～70mM(探针3c)范围内具有很好的线性关系,由此计算出探针3a-c对F-的检测限分别为:0.116MM,0.061μM和0.152 μM,说明探针对氟离子的检测具有很高的灵敏度。探针对氟离子的响应机理通过高效液相色谱(HPLC)得到了验证。由MTT实验可知探针3a-c在20μM时都具有良好的生物相容性,且在HepG2细胞内对氟离子的成像检测均取得了显著的效果。另外,光谱数据表明探针3c具有更快的响应速率和更强的荧光信号等优点,因此被用在小鼠体内对氟离子进行成像检测,且在活体内检测到的最低氟离子的量为1 mgF/Kg。
[Abstract]:Fluorine ion is one of the essential trace elements in human body, and it plays an important role in human health. In all kinds of analytical methods of fluorine ion detection, fluorescence sensing is considered to be a simple operation. An ideal technique with good specificity and high sensitivity. In this paper, the part cyanine skeleton 1, which has the advantages of near infrared Near-Infrared (NIR) spectral characteristics, good light stability and good water solubility, is used as the fluorescence chromophore, and the Si-O bond is used as the reaction site. The fluorescence probes CyR-Si3aO3b with NIR excitation and emission wavelengths of OFF-ON type were designed and synthesized. The main work accomplished included: 1: 1, the cyclization, cyclization, cyclization and cyclization of cyclization and cyclization by using cyclohexanone as raw material to synthesize part cyanine skeleton 1, and to eliminate retro-Knoevenagel1 with resorcinol and so on. In the dehydration reaction, a fluorescent substance with hydroxyl group was obtained. The probes 3aF3b and 3ccontaining HNC1 and F substituents were constructed at the hydroxyl ortho site. The structures of the probes were confirmed by HRMS 1H NMR and 13CNMR. The calculation method and other operation steps of the photophysical data of the probe are briefly described. For example, fluorescence quantum yield and detection limit. 2. The response of probe 3ah3b and 3c to fluorine ions in DMSO / PBS7: 3 / V / V / V / V = 0.01Mg pH = 7.4) system was investigated. The fluorescence selection experiment and competitive experiment showed that the probe 3a-c had a special effect on fluorine ions. The fluorescence titration experiments show that the fluorescence intensity and the concentration of fluorine ion are linear in the range of 0 ~ 100mM (probe 3b) and 0 ~ 70mM (probe 3c). The detection limits of F- for probe 3a-c were calculated to be respectively 0. 116 and 0. 061 渭 M and 0.152 渭 M, respectively, indicating that the probe has a high sensitivity to fluorine ion detection. The response mechanism of probe to fluorine ion is verified by high performance liquid chromatography (HPLC). The results showed that the probe 3a-c had good biocompatibility at 20 渭 M. In addition, the spectral data show that the probe 3c has the advantages of faster response rate and stronger fluorescence signal. Therefore, fluorine ion was detected by imaging in mice, and the lowest fluorine ion was detected in vivo with a dose of 1 mg F / K g.
【学位授予单位】：海南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

【相似文献】