本文選題：熒光聚合物 + 聚集誘導(dǎo)發(fā)光��； 參考：《河北大學(xué)》2017年碩士論文

【摘要】：聚集誘導(dǎo)發(fā)光(AIE)材料在溶液狀態(tài)下有微弱的熒光信號,在聚集狀態(tài)下熒光顯著增強,這與傳統(tǒng)生色團的聚集誘導(dǎo)淬滅(ACQ)行為相反。近年來,這類具有AIE特點的發(fā)光有機分子已經(jīng)被引起廣泛關(guān)注。其中四苯乙烯及其衍生物因其發(fā)光性能優(yōu)良、合成簡便、易功能化、AIE效應(yīng)明顯等優(yōu)點而得到了研究者的青睞。本文合成了6個含四苯乙烯單元化合物、2個含四苯乙烯單元油溶性熒光聚合物和1個含四苯乙烯單元水溶性熒光聚合物,并對其結(jié)構(gòu)和光學(xué)性能等進行了表征和測試。以4-羥基二苯甲酮為起始原料合成了兩端帶有環(huán)氧丙氧基的四苯乙烯衍生物1,2-二[4'-(2'',3''-環(huán)氧丙氧基)苯基]-1,2-二苯基乙烯(M2)。再以叔丁醇鉀為引發(fā)劑,M2為單體,通過陰離子開環(huán)聚合制備了含四苯乙烯單元的超支化油溶性聚合物(P1)。利用NMR、MALDI-TOF-MS、FTIR、GPC、UV-Vis和PL等對M2和P1的化學(xué)結(jié)構(gòu)和光學(xué)性能進了表征與測試。結(jié)果表明:P1保持了四苯乙烯基的油溶性AIE特性,其溶液狀態(tài)與聚集狀態(tài)均發(fā)射出藍綠色熒光;P1在THF/H2O(1/99,V/V)中的熒光強度比其在THF中的增加了6.06倍。主要原因是由于P1的分子鏈結(jié)構(gòu)約束了苯環(huán)的自由旋轉(zhuǎn),從而成功地解決了AIE分子在溶液狀態(tài)熒光極低的局限。利用循環(huán)伏安法測得P1的HOMO值為-5.55 eV,LUMO值為-2.34 eV。通過MTT法對P1的細胞毒性進行了測試,結(jié)果表明:P1在濃度不大于100μg·mL-1情況下對細胞沒有毒性。通過TG測試表明P1在氮氣中的熱失重階段為340~600℃,表明P1具有較高的熱分解溫度,具有優(yōu)良的熱穩(wěn)定性。以4-羥基二苯甲酮和4-溴二苯甲酮為起始原料,通過McMurry偶聯(lián)反應(yīng)和Suzuki偶聯(lián)反應(yīng)合成兩端帶有硼酸酯和溴的四苯乙烯衍生物(M4),將M4引入到傒酰亞胺衍生物N,N'-二(3-戊基)-1,7-二溴傒-3,4,9,10-四羧酸二酰亞胺(C1)中,Suzuki偶聯(lián)反應(yīng)合成了含四苯乙烯-傒酰亞胺單元的ATRP引發(fā)劑(M6)。然后以M6為引發(fā)劑,2-(2',3',4',6'-四-O-乙�；�-α-D-吡喃甘露糖基氧基)甲基丙烯酸乙酯(C2)為單體進行ATRP反應(yīng)制備油溶性聚合物P2;脫除乙�；蟮玫胶谋揭蚁�-傒酰亞胺共軛單元水溶性熒光聚合物P3。利用NMR、MALDI-TOF-MS、GPC、UV-Vis和PL等對化合物M3、M4、M5、M6和聚合物P2、P3的化學(xué)結(jié)構(gòu)和光學(xué)性能進行表征與測試。其實驗結(jié)果表明:M3、M4保持了四苯乙烯基所具有的AIE特性,且M4成功地引入到傒酰亞胺衍生物C1中分子中,解決了C1分子的ACQ效應(yīng)使其具有AIE活性,得到的含四苯乙烯-傒酰亞胺共軛單元化合物M6同樣具有AIE效應(yīng);通過TTRP反應(yīng)得到的聚合物P2有較好的油溶性,其數(shù)均分子量(Mn)為18000 g/mol,具有AIE特性;P3具有較好的水溶性,其峰位分子量(Mp)為7200 g/mol,在光學(xué)細胞成像領(lǐng)域存在一定的潛在應(yīng)用價值。
[Abstract]:The agglomeration induced luminescence (AIEs) materials have weak fluorescence signals in the solution state and enhanced fluorescence in the aggregation state, which is contrary to the agglomeration induced quenching (ACQ) behavior of the traditional chromophore. In recent years, this kind of luminescent organic molecules with the characteristics of AIE have attracted wide attention. Among them, tetrastyrene and its derivatives have been favored by researchers because of their excellent luminescent properties, simple synthesis, easy functionalization of AIE effect and so on. In this paper, six tetrastyrene unit compounds, two oil-soluble fluorescent polymers containing tetrastyrene unit and one water-soluble fluorescent polymer containing tetrastyrene unit were synthesized, and their structures and optical properties were characterized and tested. A tetrastyrene derivative with epichloropropyl group at both ends was synthesized from 4-hydroxybenzophenone. The hyperbranched oil-soluble polymer (P1N) containing tetrastyrene unit was prepared by anion ring-opening polymerization with potassium tert-butanol as initiator M 2 as monomer. The chemical structures and optical properties of M2 and P1 were characterized and tested by NMR-MALDI-TOF-MST FTIRI GPC-Vis and PL et al. The results show that: P1 maintains the oil-soluble AIE property of tetrastyrene-group, and the luminescence intensity of the blue-green fluorescence P1 in THF / H _ 2O _ 1 / 9 / 9 V / V) is 6.06 times higher than that in THF, both in the solution state and in the aggregation state. The main reason is that the molecular chain structure of P1 restricts the free rotation of benzene ring, which successfully solves the limitation of extremely low fluorescence of AIE molecule in the solution state. By cyclic voltammetry, the HOMO value of P1 is -5.55 EV / L UMO = -2.34 EV. The cytotoxicity of P1 was tested by MTT method. The results showed that no cytotoxicity was found when the concentration of P1 was not more than 100 渭 g mL-1. The TG results show that the thermal weight loss of P1 in nitrogen is 340 鈩，

本文編號：1852979