以萘酰亚胺为母体的2种荧光分子探针及相关晶体的合成与性质研究

发布时间：2018-03-30 08:38

本文选题：1　切入点：8-萘酰亚胺　出处：《东南大学》2016年硕士论文

【摘要】：荧光分子探针是基于荧光分子与被检测物质之间的特异性作用,将识别信号转化为荧光信号,以此实现对分析物的靶向检测。与传统检测手段相比,荧光分子探针具有选择性好、灵敏度高、响应快、操作简便、以及实时检测等优点,在化学、生命科学、基础医学以及环境探测等领域逐渐成为重要的研究工具。1,8-萘酰亚胺类衍生物是一类特殊的荧光染料,因其具有较高的荧光量子产率,良好的光学及化学稳定性,较大的斯托克斯位移,优良的化学可修饰性,成为了荧光分析检测领域的研究热点。本文围绕1,8-萘酰亚胺类荧光分子探针的设计、合成及光谱性质进行了系统地研究,并得到以下结果：1.基于Claisen重排反应的钯离子荧光分子探针以4-溴-1,8-萘二甲酸酐为原料,通过多步反应合成了荧光分子探针P1,并通过元素分析、核磁共振谱、质谱等手段对结构进行了表征。在Na2_CO_3/NaHCO_3 (pH=10)溶液中,由于萘酰亚胺本身具有很好的平面性和较大的共轭体系,并且同时含有供电子基团和吸电子基团,因此该荧光分子发射强烈的蓝色荧光,荧光量子产率是66.72%,荧光寿命为4.78 ns,斯托克斯位移为82 nm。随着体系中靶向分析物Pd2+离子浓度的不断增加,荧光强度显著降低并伴随明显的颜色变化。经过多种数据论证,推测该检测基于Claisen重排反应。研究了pH、温度、反应时间、其他阳离子的影响,该探针实现了对Pd2+/4+的高选择性识别,可以完全排除Pd~0及Pt~(0/2+/4+)的干扰,在10-45 μM浓度范围内,钯离子浓度与探针荧光强度成线性关系,检测限达到1.4μM。2.用于检测有机溶剂中含水量的荧光分子探针为了进一步提高荧光分子探针的灵敏度,通过在萘环3、4位同时引入取代基,我们设计合成了对有机溶剂中含水量十分灵敏的荧光探针P2。研究了在不同溶剂(乙腈,DMF, DMSO)中的荧光光谱的变化,发现随着溶剂极性的增强,荧光最大发射波长发生红移,并伴随强度的减弱。随着有机溶剂中含水量的增加,形成分子内与分子间氢键,P2的荧光发射强度逐渐降低。当乙腈溶剂中含水量在0.00-4.25%(v:v)范围内,荧光强度与之存在相关关系,在0.00-1.50%(v:v)范围内成线性关系,检测限达到0.005%(v:v)。在DMF溶剂中在0.00-11.50%(v：v)范围内成线性关系,检测限达到0.08%(v:v)。在DMSO溶剂中在0.00-15.00%(v:v)范围内成线性关系,检测限达到0.11%(v:v)。荧光分子探针P2在乙腈中的灵敏性最高。探针P2的分子结构有待确认。3.晶体的合成及表征将中间产物溶于有机溶剂,得到了产物N3、N7的单晶,并通过X-射线单晶衍射进行了表征,进一步确定了产物结构。
[Abstract]:The fluorescent probe is based on the specific action between the fluorescent molecule and the detected substance, the recognition signal is transformed into the fluorescent signal, and the target detection of the analyte is realized. Fluorescent molecular probes have the advantages of good selectivity, high sensitivity, fast response, easy operation and real-time detection. The fields of basic medicine and environmental detection have gradually become important research tools. The derivatives of 8-naphthalimide are a kind of special fluorescent dyes, because of their high fluorescence quantum yield, good optical and chemical stability. The large Stokes shift and excellent chemically modifiable properties have become the research focus in the field of fluorescence analysis and detection. The design, synthesis and spectral properties of fluorescent molecular probes of 1-Naphthalimide have been systematically studied in this paper. Based on the Claisen rearrangement reaction, the palladium ion fluorescence probe was synthesized by multistep reaction using 4-bromo-1-butadiene-8-naphthalene dicarboxylic anhydride as the raw material, and the fluorescence molecular probe P1 was synthesized by elemental analysis and nuclear magnetic resonance spectroscopy. The structure was characterized by mass spectrometry. In the solution of Na2_CO_3/NaHCO_3 ~ (10), naphthalene imide has good flatness and large conjugate system, and it contains both electron donor and absorbent groups. Therefore, the fluorescence molecule emits strong blue fluorescence, the fluorescence quantum yield is 66.72, the fluorescence lifetime is 4.78 ns, and the Stokes shift is 82 nm. With the increasing of the concentration of the target analyte Pd2 ion in the system, the fluorescence quantum yield is 66.72 nm, the fluorescence lifetime is 4.78 ns, and the Stokes shift is 82 nm. The fluorescence intensity was significantly decreased and accompanied by obvious color changes. Based on various data, it was speculated that the detection was based on Claisen rearrangement reaction. The effects of pH, temperature, reaction time and other cations were studied. The probe realizes highly selective recognition of Pd2 / 4 and can completely eliminate the interference of Pd~0 and Pt~(0/2 / 4. In the range of 10-45 渭 M, the concentration of palladium ion has a linear relationship with the fluorescence intensity of the probe. The detection limit is 1.4 渭 M.2. in order to further improve the sensitivity of fluorescent molecular probes, the substituents are introduced simultaneously at the 4 position of naphthalene ring in order to improve the sensitivity of fluorescent molecular probes, which are used for the determination of water content in organic solvents. We have designed and synthesized a fluorescence probe P2which is sensitive to water content in organic solvents. We have studied the changes of fluorescence spectra in different solvents (acetonitrile DMF, DMSOs). It is found that the maximum emission wavelength shifts red with the increase of solvent polarity. With the increase of water content in organic solvents, the fluorescence emission intensity of intramolecular and intermolecular hydrogen bond P2 gradually decreased. When the water content in acetonitrile solvent was in the range of 0.00-4.25v: v, the fluorescence intensity was correlated with it. In the range of 0.00-1.50 v: v, the detection limit is 0.005v: v. In the DMF solvent, the linear relationship is established in the range of 0.00-11.50 v: v), the detection limit is 0.08% v: v, and the detection limit is 0.08% v: v. In the DMSO solvent, the linear relationship is within the range of 0.00-15.00 v: v). The detection limit is 0.11% v.The fluorescence probe P2 has the highest sensitivity in acetonitrile. The molecular structure of probe P2 needs to be confirmed .3.The crystal synthesis and characterization dissolve the intermediate product in organic solvent to obtain the single crystal of product N _ 3N _ 7. The structure of the product was further determined by X-ray single crystal diffraction.
【学位授予单位】：东南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3;O78

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