【摘要】：聚集誘導(dǎo)熒光是一種特殊的發(fā)光現(xiàn)象,即分子在溶解狀態(tài)時(shí)熒光很弱,而在聚集態(tài)時(shí)則表現(xiàn)出強(qiáng)熒光。與傳統(tǒng)熒光染料相比,聚集誘導(dǎo)熒光分子可以有效避免由聚集所引起的熒光淬滅作用。經(jīng)由水楊醛和氨基之間的簡單縮合反應(yīng)得到的西弗堿衍生物,正是一類擁有此種獨(dú)特發(fā)光性質(zhì)的分子。在西弗堿結(jié)構(gòu)中,西弗堿與鄰位羥基通過分子內(nèi)氫鍵形成了穩(wěn)定的六元環(huán),該結(jié)構(gòu)使整個(gè)分子自由旋轉(zhuǎn)受阻,由此帶來了聚集誘導(dǎo)熒光的發(fā)光特征。結(jié)合螺雙芴的三維正交結(jié)構(gòu)及摩爾吸光系數(shù)大、熒光量子產(chǎn)率高等性質(zhì),本論文在螺雙芴的結(jié)構(gòu)基礎(chǔ)上,引入水楊醛西弗堿結(jié)構(gòu)以構(gòu)筑一類新的聚集誘導(dǎo)發(fā)光體系,將在開發(fā)新型熒光探針及固體發(fā)光材料領(lǐng)域有較大的前景。此外,探索了手性螺二胺化合物的小分子催化性能。本文工作分為以下兩個(gè)部分:第一部分:合成了兩種具有聚集誘導(dǎo)發(fā)光性質(zhì)的西弗堿類熒光探針SPF-T1和SPF-T2。首先,以含螺雙芴結(jié)構(gòu)的西弗堿SPF-T1為探針,研究其對(duì)金屬離子的識(shí)別。實(shí)驗(yàn)結(jié)果表明,探針對(duì)銅離子、鈷離子和鋅離子有識(shí)別作用。其中銅離子和鈷離子對(duì)探針的吸收光譜有很大影響,溶液顏色由無色變?yōu)辄S色,檢測(cè)極限分別為為0.15μM和0.12μM。對(duì)鋅離子表現(xiàn)出聚集誘導(dǎo)熒光增強(qiáng)現(xiàn)象,檢測(cè)極限為0.3μM。而且SPF-T1作為鋅離子探針用于細(xì)胞成像。其次,將三芳胺單元引入SPF-T1結(jié)構(gòu)中,得到了具有發(fā)黃色固體熒光的材料SPF-T2,同樣能用作熒光增強(qiáng)型鋅離子探針,檢測(cè)極限為0.063μM。通過紫外檢測(cè)鈷離子和銅離子,檢測(cè)極限分別為0.084μM和0.073μM。SPF-T2的聚集誘導(dǎo)性能更加明顯且具有雙光子吸收性能。第二分:將軸手性的螺二胺應(yīng)用于小分子不對(duì)稱催化反應(yīng),用于開發(fā)新型手性催化劑。成功的催化了Michael加成反應(yīng)及Friedel Crafts反應(yīng)。得到了較好的收率,分別為75%和86%,但在不對(duì)稱催化方面沒有較好的表現(xiàn)。
[Abstract]:Agglomeration induced fluorescence is a special luminescence phenomenon, that is, the fluorescence of molecules is very weak in the dissolved state and strong fluorescence in the aggregation state. Compared with traditional fluorescent dyes, agglomeration induced fluorescence molecules can effectively avoid fluorescence quenching caused by aggregation. Sieverine derivatives obtained by simple condensation reaction between salicylaldehyde and amino are a class of molecules with this unique luminescent property. In the sieverbase structure, sieverine and o-hydroxyl group form a stable six-member ring through intramolecular hydrogen bonding, which hinders the free rotation of the whole molecule, resulting in the luminescence of aggregation induced fluorescence. Combined with the three dimensional orthogonal structure of spirobifluorene and its high molar absorptivity and high fluorescence quantum yield, a new aggregation induced luminescence system was constructed by introducing the structure of salicylaldehyde-sieverine on the basis of the structure of spirobifluorene. It will have a great prospect in the field of developing new fluorescent probes and solid state luminescent materials. In addition, the catalytic properties of chiral spirodiamine compounds were investigated. The work of this paper is divided into two parts as follows: in the first part, two kinds of fluorescence probes SPF-T1 and SPF-T2 with aggregation induced luminescence have been synthesized. Firstly, the recognition of metal ions was studied by using sieverine SPF-T1 with spirobifluorene structure as a probe. The results show that the probe can recognize copper, cobalt and zinc ions. Copper ion and cobalt ion have great influence on the absorption spectrum of the probe. The color of the solution changes from colorless to yellow. The detection limits are 0.15 渭 M and 0.12 渭 M, respectively. The concentration induced fluorescence enhancement of zinc ion was observed, and the detection limit was 0.3 渭 M. And SPF-T1 is used as a zinc ion probe for cell imaging. Secondly, the triarylamine unit was introduced into the SPF-T1 structure to obtain a yellow solid fluorescence material SPF-T2, which can also be used as a fluorescence enhanced zinc ion probe with a detection limit of 0.063 渭 M. By UV detection of cobalt ion and copper ion, the aggregation inductive performance of the detection limit of 0.084 渭 M and 0.073 渭 M.SPF-T2 is more obvious and the two-photon absorption property is more obvious. Second, the axial chiral spirodiamine was applied to the asymmetric catalytic reaction of small molecules to develop new chiral catalysts. Michael addition reaction and Friedel Crafts reaction were successfully catalyzed. The yield was 75% and 86%, respectively, but there was no good performance in asymmetric catalysis.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.3

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相關(guān)期刊論文 前1條

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本文編號(hào)：2181172