本文選題：手性高分子　切入點(diǎn)：聚集誘導(dǎo)發(fā)光效應(yīng)　出處：《南京大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

【摘要】：手性是自然界普遍存在的現(xiàn)象。作為生命結(jié)構(gòu)基本單元的氨基酸和核酸中的核糖幾乎分別都是L-和D-構(gòu)型,在分子的水平上實(shí)現(xiàn)了對(duì)稱性的破缺。這種不對(duì)稱分子是生命的物質(zhì)基礎(chǔ),光學(xué)活性是生命有序化和組織化的基礎(chǔ)。圓偏振熒光(CPL)是源于手性發(fā)色團(tuán)體系的左手性和右手性圓偏振光的選擇性發(fā)射。手性高分子在溶液中呈孤立的單分子分布,在聚集態(tài)下則以聚集體的形式存在,手性高分子這種不同的存在形式會(huì)對(duì)其CPL產(chǎn)生影響。手性高分子中手性單元的存在會(huì)對(duì)高分子的堆積方式和電子分布方式產(chǎn)生影響,并且有利于分子內(nèi)相互纏繞和扭曲,有利于發(fā)生能量傳遞。本論文研究工作分為兩個(gè)部分,一是基于四苯乙烯的手性高分子的合成及其聚集誘導(dǎo)發(fā)光效應(yīng)和圓偏振熒光性能研究；二是手性稀土銪高分子合成及其在“通過鍵能”能量轉(zhuǎn)移和熒光量子產(chǎn)率調(diào)控方面的研究。第二章,通過單體1,2-二(4-乙炔基苯基)-1,2-二苯乙烯與單體3’,5’-二碘-N-a-叔丁氧羰基-O-辛基-L-酪氨酸甲酯的Sonogashira偶聯(lián)反應(yīng)合成了基于四苯乙烯(TPE)的手性高分子TPETyr。有趣地是,該手性高分子在其良溶劑THF中發(fā)射弱的熒光,但當(dāng)加入水之后,便形成了納米粒子懸浮物,能夠發(fā)射出較強(qiáng)的熒光,展示出一種新穎的聚集誘導(dǎo)發(fā)光現(xiàn)象(AIE)。無論是在THF溶液中還是在聚集態(tài)下手性高分子TPETyr均具有較大的CPL不對(duì)稱因子(glum)。更重要的是,glum表現(xiàn)出環(huán)境應(yīng)激性,其值可通過改變THF中水的含量來調(diào)控,從0.44到0.08。第三章,首次合成了以(R,R)-1,2-環(huán)G二胺為手性源的三種新穎的手性高分子,這三種手性高分子分別與Eu(TTA)3·2H2O反應(yīng)得到相應(yīng)的稀土高分子P-2、P-4和P-6,通過光譜分析發(fā)現(xiàn)稀土高分子P-2、P-4和P-6中手性高分子與Eu(TTA)3之間發(fā)生了鍵能傳遞。并且,稀土高分子P-2、P-4和P-6均具有較大的斯托克斯位移(△λmax=265nm)和發(fā)光光譜的紅移(△λmax=214nm)。此外,稀土高分子P-2、P-4和P-6的熒光量子產(chǎn)率是模板化合物Model的60-100倍,且熒光量子產(chǎn)率的值可通過稀土高分子中亞甲基連接單元的長短來調(diào)控,從3.01%到5.30%。
[Abstract]:Chirality is a common phenomenon in nature. The amino acids and ribosomes in nucleic acids, which are the basic units of life structure, are L- and D-, respectively. At the molecular level, symmetry is broken. This asymmetric molecule is the material foundation of life. Optical activity is the basis of life ordering and systematization. Circular polarization fluorescence (CPL) is derived from the selective emission of left-handed and right-handed circular polarized light from chiral chromophore systems. In the aggregate state, the chiral polymer exists in the form of aggregates, and the existence of chiral polymers has an effect on their CPL. The existence of chiral units in chiral polymers will have an effect on the stacking and electron distribution of the polymers. This paper is divided into two parts, which are conducive to intermolecular entanglement and distortion, and to the generation of energy transfer. The first is the synthesis of chiral polymers based on tetrastyrene and their aggregation induced luminescence and circularly polarized fluorescence properties. The second is the synthesis of chiral rare earth europium polymer and its study on the energy transfer through bond energy and the regulation of fluorescence quantum yield. The chiral macromolecule TPETyr based on tetrastyrene was synthesized by the Sonogashira coupling reaction of monomeric 1h2- dioxynylphenyl-1 ethynylphenyl-1-distyrene with the monomer 3H _ (5N) -diiodo-N-a- (tert-butylcarbonyl) -O _ (-octyl) -tyrosine methyl ester. Interestingly, the chiral macromolecule TPETyr based on tetrastyrene (TPE) was synthesized. The chiral polymer emits weak fluorescence in its good solvent THF, but when water is added, the suspensions of nanoparticles are formed, which can emit strong fluorescence. A novel phenomenon of agglomeration induced luminescence has been demonstrated. Both in THF solution and in aggregated TPETyr, TPETyr has a large CPL asymmetry factor, and more importantly, it shows environmental stress. Its value can be controlled by changing the content of water in THF, from 0.44 to 0.08. in Chapter 3, three novel chiral polymers were synthesized, which were chiral source. The three chiral polymers reacted with Eu(TTA)3 路2H2O to obtain the corresponding rare earth polymers P-2P4 and P-6.The bond energy transfer between the chiral polymers P-2P4 and P-6 and Eu(TTA)3 was found by spectroscopic analysis. Both P-2P4 and P-6 have a large Stokes shift (位 max-265nm) and a red shift of luminescence spectra (位 max-214nm). In addition, the fluorescence quantum yields of the rare earth polymers P-2P4 and P-6 are 60-100 times higher than those of the template compound Model. The fluorescence quantum yield can be controlled by the length of methylene bonding units in rare earth polymers, ranging from 3.01% to 5.30.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：O631
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本文編號(hào)：1581674