本文選題：多酰胺基　切入點(diǎn)：熒光小分子　出處：《濟(jì)南大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：一般認(rèn)為,典型的有機(jī)熒光分子都具有剛性結(jié)構(gòu)和離域電子雙鍵共軛體系,芳環(huán)或具有共軛不飽和基團(tuán)的存在有利于提高熒光效率,從而產(chǎn)生強(qiáng)烈的熒光。但是近些年來,研究者發(fā)現(xiàn)一些只含有伯胺、仲胺、叔胺和酰胺等簡(jiǎn)單官能團(tuán)的含氮類枝狀聚合物具有熒光。含氮枝狀聚合物具有非典型性熒光生色團(tuán),其熒光性質(zhì)和生物學(xué)應(yīng)用很快得到了廣泛關(guān)注,但是由于含氮類聚合物的體系相對(duì)復(fù)雜,熒光中心結(jié)構(gòu)及其相互位置、相互作用難以確定,進(jìn)而造成影響熒光性質(zhì)的結(jié)構(gòu)因素較多,因此對(duì)含氮類枝狀聚合物發(fā)光機(jī)理的研究相對(duì)困難。與含氮類聚合物相比,含氮類小分子化合物的體系相對(duì)簡(jiǎn)單,制備方法多樣、分子結(jié)構(gòu)簡(jiǎn)單,便于系統(tǒng)研究多元羧酸和氨基試劑的結(jié)構(gòu)與產(chǎn)物發(fā)光機(jī)理、發(fā)光性能等之間的對(duì)應(yīng)關(guān)系,有利于明確熒光發(fā)光中心,進(jìn)而深入研究含氮小分子的熒光發(fā)光機(jī)理。由于含氮小分子的結(jié)構(gòu)簡(jiǎn)單,影響因素較少。具有明確的簡(jiǎn)單結(jié)構(gòu)的熒光含氮小分子的發(fā)現(xiàn),無論從理論計(jì)算還是實(shí)驗(yàn)方面都為最終探索含氮有機(jī)分子的發(fā)光機(jī)理提供了有效的途徑。本文具體研究工作如下:1、采用酰氯法制備了熒光多元酰胺,探索了適合的反應(yīng)條件;先用二氯亞砜活化有機(jī)酸中的羧基,再與有機(jī)胺反應(yīng)的反應(yīng)路線,使羧基和氨基通過簡(jiǎn)單的官能團(tuán)反應(yīng)生成酰胺小分子。2、改變羧酸的結(jié)構(gòu),探索羧酸結(jié)構(gòu)對(duì)多元酰胺熒光量子產(chǎn)率的影響;3、改變有機(jī)胺的結(jié)構(gòu),探索有機(jī)胺結(jié)構(gòu)對(duì)多元酰胺熒光量子產(chǎn)率的影響;4、改變多酰胺基熒光小分子外部條件,探索溫度、溶劑、紫外光照時(shí)間、離子等對(duì)多元酰胺基熒光量子產(chǎn)率的影響。某些多酰胺鍵熒光分子(如檸檬酸酰胺)的QY可高達(dá)70.2%(硫酸奎寧為參比),分子體積小,在熒光示蹤、呈像方面具有潛在的用途。另外如與多元酸反應(yīng)的氨基試劑中含有其他官能團(tuán)(如烷氧基),則有利于進(jìn)一步構(gòu)建多用途的復(fù)合材料。綜上所述,初步研究結(jié)果表明,該類分子有望成為是一類新型的發(fā)光材料,也將為新型發(fā)光機(jī)理研究提供有效支撐。
[Abstract]:It is generally believed that typical organic fluorescent molecules have rigid structures and delocalized electron double bond conjugation systems. The existence of aromatic rings or conjugated unsaturated groups is conducive to improving the fluorescence efficiency and thus producing strong fluorescence. The researchers found that some nitrogen-containing dendritic polymers containing only simple functional groups such as primary amine, secondary amine, tertiary amine and amides have fluorescence, while nitrogen-containing dendritic polymers have atypical fluorescent chromophore. Its fluorescence properties and biological applications have been paid more and more attention. However, due to the relatively complex system of nitrogen-containing polymers, the fluorescence center structure and its mutual position are difficult to determine. Therefore, it is difficult to study the luminescence mechanism of nitrogen-containing dendritic polymers. Compared with nitrogen-containing polymers, the system of nitrogen-containing small molecular compounds is relatively simple, and the preparation methods are various. The molecular structure is simple, and it is convenient to systematically study the corresponding relationship between the structure of polycarboxylic acid and amino reagent and the luminescence mechanism of the product, the luminescent property, etc. The fluorescence luminescence mechanism of nitrogen-containing small molecules is further studied. Because the structure of nitrogen-containing small molecules is simple, there are few influencing factors, and the discovery of fluorescent nitrogen-containing small molecules with clear and simple structure, Both theoretical and experimental results provide an effective way to explore the luminescence mechanism of nitrogen-containing organic molecules. In this paper, the specific research work is as follows: 1. Fluorescence polyamides were prepared by acyl chloride method, and suitable reaction conditions were explored. The carboxyl group in organic acid was activated by dichloro sulfoxide and then reacted with organic amine. The carboxyl group and amino group reacted with simple functional groups to form small amide molecule. 2, which changed the structure of carboxylic acid. To explore the effect of carboxylic acid structure on the fluorescence quantum yield of polyamides, to change the structure of organic amines, to explore the effects of the structure of organic amines on the fluorescence quantum yields of polyamides, to change the external conditions of polyamide-based fluorescent small molecules, to explore the temperature and solvent, The effects of UV irradiation time, ions and so on on the quantum yield of polyamide-based fluorescence. The QY of some polyamide bond fluorescent molecules (such as citric acid amide) can be as high as 70.2%. In addition, the amino reagents that react with polyacids contain other functional groups (such as alkoxy), which are conducive to the further construction of multipurpose composite materials. This kind of molecule is expected to be a new kind of luminescent material, and it will provide an effective support for the study of new luminescence mechanism.
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.22

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