本文選題：1　切入點(diǎn)：8-萘酰亞胺　出處：《東南大學(xué)》2016年碩士論文

【摘要】：熒光分子探針是基于熒光分子與被檢測(cè)物質(zhì)之間的特異性作用,將識(shí)別信號(hào)轉(zhuǎn)化為熒光信號(hào),以此實(shí)現(xiàn)對(duì)分析物的靶向檢測(cè)。與傳統(tǒng)檢測(cè)手段相比,熒光分子探針具有選擇性好、靈敏度高、響應(yīng)快、操作簡(jiǎn)便、以及實(shí)時(shí)檢測(cè)等優(yōu)點(diǎn),在化學(xué)、生命科學(xué)、基礎(chǔ)醫(yī)學(xué)以及環(huán)境探測(cè)等領(lǐng)域逐漸成為重要的研究工具。1,8-萘酰亞胺類(lèi)衍生物是一類(lèi)特殊的熒光染料,因其具有較高的熒光量子產(chǎn)率,良好的光學(xué)及化學(xué)穩(wěn)定性,較大的斯托克斯位移,優(yōu)良的化學(xué)可修飾性,成為了熒光分析檢測(cè)領(lǐng)域的研究熱點(diǎn)。本文圍繞1,8-萘酰亞胺類(lèi)熒光分子探針的設(shè)計(jì)、合成及光譜性質(zhì)進(jìn)行了系統(tǒng)地研究,并得到以下結(jié)果：1.基于Claisen重排反應(yīng)的鈀離子熒光分子探針以4-溴-1,8-萘二甲酸酐為原料,通過(guò)多步反應(yīng)合成了熒光分子探針P1,并通過(guò)元素分析、核磁共振譜、質(zhì)譜等手段對(duì)結(jié)構(gòu)進(jìn)行了表征。在Na2_CO_3/NaHCO_3 (pH=10)溶液中,由于萘酰亞胺本身具有很好的平面性和較大的共軛體系,并且同時(shí)含有供電子基團(tuán)和吸電子基團(tuán),因此該熒光分子發(fā)射強(qiáng)烈的藍(lán)色熒光,熒光量子產(chǎn)率是66.72%,熒光壽命為4.78 ns,斯托克斯位移為82 nm。隨著體系中靶向分析物Pd2+離子濃度的不斷增加,熒光強(qiáng)度顯著降低并伴隨明顯的顏色變化。經(jīng)過(guò)多種數(shù)據(jù)論證,推測(cè)該檢測(cè)基于Claisen重排反應(yīng)。研究了pH、溫度、反應(yīng)時(shí)間、其他陽(yáng)離子的影響,該探針實(shí)現(xiàn)了對(duì)Pd2+/4+的高選擇性識(shí)別,可以完全排除Pd~0及Pt~(0/2+/4+)的干擾,在10-45 μM濃度范圍內(nèi),鈀離子濃度與探針熒光強(qiáng)度成線性關(guān)系,檢測(cè)限達(dá)到1.4μM。2.用于檢測(cè)有機(jī)溶劑中含水量的熒光分子探針為了進(jìn)一步提高熒光分子探針的靈敏度,通過(guò)在萘環(huán)3、4位同時(shí)引入取代基,我們?cè)O(shè)計(jì)合成了對(duì)有機(jī)溶劑中含水量十分靈敏的熒光探針P2。研究了在不同溶劑(乙腈,DMF, DMSO)中的熒光光譜的變化,發(fā)現(xiàn)隨著溶劑極性的增強(qiáng),熒光最大發(fā)射波長(zhǎng)發(fā)生紅移,并伴隨強(qiáng)度的減弱。隨著有機(jī)溶劑中含水量的增加,形成分子內(nèi)與分子間氫鍵,P2的熒光發(fā)射強(qiáng)度逐漸降低。當(dāng)乙腈溶劑中含水量在0.00-4.25%(v:v)范圍內(nèi),熒光強(qiáng)度與之存在相關(guān)關(guān)系,在0.00-1.50%(v:v)范圍內(nèi)成線性關(guān)系,檢測(cè)限達(dá)到0.005%(v:v)。在DMF溶劑中在0.00-11.50%(v：v)范圍內(nèi)成線性關(guān)系,檢測(cè)限達(dá)到0.08%(v:v)。在DMSO溶劑中在0.00-15.00%(v:v)范圍內(nèi)成線性關(guān)系,檢測(cè)限達(dá)到0.11%(v:v)。熒光分子探針P2在乙腈中的靈敏性最高。探針P2的分子結(jié)構(gòu)有待確認(rèn)。3.晶體的合成及表征將中間產(chǎn)物溶于有機(jī)溶劑,得到了產(chǎn)物N3、N7的單晶,并通過(guò)X-射線單晶衍射進(jìn)行了表征,進(jìn)一步確定了產(chǎn)物結(jié)構(gòu)。
[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.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O657.3;O78

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