CN111548445A - 一种旋光性aie荧光材料及其水性聚合物的制备方法 - Google Patents
一种旋光性aie荧光材料及其水性聚合物的制备方法 Download PDFInfo
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- CN111548445A CN111548445A CN202010464101.XA CN202010464101A CN111548445A CN 111548445 A CN111548445 A CN 111548445A CN 202010464101 A CN202010464101 A CN 202010464101A CN 111548445 A CN111548445 A CN 111548445A
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种旋光性AIE荧光材料水性聚合物的制备方法,包含以下步骤:A、利用苯硼酸和溴苯的Suzuki偶联反应合成醛基AIE荧光化合物;B、利用醛基和苯乙腈间的缩合反应合成甲氧基荧光化合物,进一步通过BBr3将甲氧基脱甲基化生成羟基;C、通过苯羟基与脂肪氯间的亲核取代反应,将叔羟基引入到荧光化合物上,生成相应的叔羟基AIE荧光化合物;D、通过在脂肪酶B催化下的选择性酯交换反应将丙烯酸基元引入到荧光化合物上从而得到具有旋光性的AIE荧光单体;E、通过RAFT活性聚合制备出具有旋光性的AIE荧光聚合物。该荧光染料和聚合物具有旋光性。
Description
技术领域
本发明涉及化工技术领域,具体是一种旋光性AIE荧光材料及其水性聚合物的制备方法。
背景技术
具有光学活性的高分子又称旋光性聚合物,近年来一直是聚合物化学领域中的研究热点之一。旋光性聚合物在众多领域扮演着重要的角色,例如在外消旋化合物的拆分、手性识别、不对称合成等方面得到广泛应用,并在手性催化剂、液晶、生物医药、光学开关和非线性光学等领域展现出良好的应用前景。
传统有机小分子荧光材料大多都具有聚集猝灭效应(ACQ),在稀溶液中具有较强的荧光,但在聚集状态时荧光较弱甚至不发光,这在很大程度上限制了其实际应用。近年来,基于聚集诱导发光(AIE)染料的荧光有机纳米粒子的发展也吸引了研究者的广泛关注。这类材料在溶液中荧光非常弱甚至没有荧光,但聚集状态下荧光急剧增强。这一有趣的现象使得AIE活性材料迅速成为研究者关注的焦点,并将其在许多领域进行了应用,如化学/生物传感器、生物成像、免疫标记等。众所周知,生物体所处的环境均为水溶性环境,而AIE活性分子本质是疏水的,这极大地限制了其在生物领域的应用,所以提高其水溶性成为解决问题关键所在。目前较为常用的将疏水AIE化合物转化为亲水材料的方法是制备水溶性纳米粒子,疏水的荧光分子集中在核心,亲水的聚合物包裹在其外围。并且由于AIE效应,荧光分子在纳米粒子核心发生聚集时,其荧光会逐渐增强,因此这类AIE纳米粒子同时具有水溶性和高荧光量子效率,是进行生物成像的理想材料。
本发明首次公开了一种兼具有旋光性和AIE特性的荧光染料及其聚合物纳米粒子的制备方法,将AIE性质与旋光性相结合,为新型多功能材料的设计开发提供一种新的思路。
发明内容
本发明的目的在于提供一种旋光性AIE荧光材料及其水性聚合物的制备方法,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:
一种旋光性AIE荧光材料水性聚合物的制备方法,本发明提供的旋光性AIE荧光单体及其水性荧光聚合物具有以下式(Ⅰ)和(Ⅱ)所示结构:
其中的R1包括含有四苯乙烯、吩噻嗪、苯并噻唑、六苯基噻咯、二苯蒽等其它荧光基元,R2为水性组分。包含以下步骤:
A、利用荧光化合物和活性亚甲基间的缩合反应合成醛基甲氧基AIE荧光化合物;
甲氧基荧光化合物的制备:将含有醛基的荧光化合物、对羟基苯乙腈、四丁基氢氧化铵、乙醇依次加入反应管中,加热回流反应3h;反应结束后冷却至室温,用乙醇洗涤数次得到式Ⅲ化合物,反应式如下:
其中的R为荧光基元,反应特征为荧光化合物与活性亚甲基间的缩合反应,生成相应的甲氧基荧光化合物。
B、利用BBr3将甲氧基脱甲基化生成羟基AIE荧光化合物;
羟基荧光化合物的制备:将化合物Ⅲ、二氯甲烷依次加入反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,脱去氧气,将三溴化硼(1.0M二氯甲烷溶液)注射到稳压漏斗中,缓慢滴加到反应管中,恢复到室温后搅拌反应20h;反应结束后用饱和碳酸氢钠溶液中和至中性,用二氯甲烷萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化,得到式(Ⅳ)化合物,反应式如下:
其反应特征为荧光化合物上的甲氧基和BBr3间的脱甲基反应,生成相应的羟基荧光化合物。
氯代叔醇的制备:将氯代-2-酮、四氢呋钠和甲醇混合液依次加入反应管中,反应管置于冰水浴中,缓慢少量多次向其中加入硼氢化钠,待硼氢化钠完全溶解后继续在冰水浴中反应6h;反应结束后用稀盐酸调节其pH值至4-5,用乙酸乙酯萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到产物氯代叔醇粗产品,进一步利用硅胶色谱柱分离纯化。
C、通过苯羟基与脂肪氯间的亲核取代反应,将叔羟基引入到荧光化合物上,生成相应的叔羟基AIE荧光化合物;
叔醇荧光化合物的制备:将式Ⅳ化合物、氯代叔醇、碳酸钾、碘化钠、N,N’-二甲基甲酰胺依次加入反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,脱去氧气;恢复到室温后在100℃油浴锅中搅拌反应24h;反应结束后用乙酸乙酯萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化,得到式Ⅴ化合物,反应式如下:
其反应特征为荧光化合物上的活性羟基和6-氯-2-叔醇间的亲核取代反应,生成相应的叔醇荧光化合物。
D、通过在脂肪酶B催化下的选择性酯交换反应将丙烯酸基元引入到荧光化合物上从而得到具有旋光性的AIE荧光单体。
旋光AIE荧光单体的制备:将脂肪酶B(Novozym 435)加入到反应管中,反应管进行真空-氮气循环5次,脱去氧气,化合物Ⅴ、甲基丙烯酸三氟乙酯、三乙胺溶解到甲苯中,混合液注射到反应管中,在55℃油浴锅中搅拌反应24h;反应结束后离心除去Novozym435,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化,得到式Ⅴ化合物,反应式如下:
其反应特征为荧光化合物上的叔羟基和甲基丙烯酸三氟乙酯(TFEMA)酯交换反应,脂肪酶B(Novozym 435)能够选择性催化外消旋醇和TFEMA酰基供体间的酯交换反应,从而生成相应的旋光性AIE荧光单体。
E、通过RAFT聚合制备两亲性具有旋光性的AIE荧光聚合物。
旋光性AIE荧光聚合物的制备:将旋光AIE荧光单体Ⅰ、亲水性单体、2,2-偶氮二异丁腈(AIBN)、链转移剂CTA、甲苯加入到反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,脱去氧气;待恢复到室温后在70℃油浴锅中搅拌反应24h;反应结束后反应液用丙酮透析三次,减压蒸馏,得到的粗产物用四氢呋喃溶解石油醚沉淀三次,得到最终产物聚合物Ⅱ,反应式如下:
其聚合反应特征为活性自由基聚合,防止聚合过程中发生交联,以便得到良好水溶性的荧光聚合物。
本发明的目的是提供一种结构新颖的兼具有旋光性AIE荧光单体及其水性荧光聚合物,该聚合物具有良好的水溶性、旋光性及AIE特性。
作为本发明所制备的水性的旋光的荧光聚合物应用于生物成像领域。也可用于手性识别、外消旋混合物分离、不对成合成等领域。
本发明所述的旋光AIE荧光单体及其水性聚合物的合成,除了异戊酸三硫酯作为链转移剂,还包括其它类型的链转移剂;引发剂除了AIBN,还包括其它自由基引发剂;在聚合方法上,除了RAFT聚合外,还包括以水性大分子化合物为催化剂的ATRP聚合。
作为本发明的进一步技术方案:所述荧光化合物是四苯乙烯、吩噻嗪、苯并噻唑的荧光分子。
与现有技术相比,本发明的有益效果是:1.通过亲核取代反应将叔羟基引入到AIE荧光化合物上,生成含有叔羟基的荧光分子;2.以脂肪酶B(Novozym 435)作催化剂,含有叔羟基的荧光分子与甲基丙烯酸三氟乙酯进行选择性酯交换得到具有旋光性的AIE荧光单体;3.最后通过RAFT活性聚合制备出具有旋光性的AIE荧光聚合物。
附图说明
图1为旋光性AIE荧光单体(Ⅰ-1)的合成路线图。
图2为水性旋光荧光聚合物的合成路线及细胞成像示意图。
图3为固态TPB和旋光性AIE荧光单体(Ⅰ-1)在相同条件下的荧光光谱图。
图4为化合物Ⅳ-1、Ⅴ-1、旋光性AIE荧光单体(Ⅰ-1)及其聚合物的1H NMR图谱示意图。
图5为水性的旋光的荧光聚合物(Ⅱ-1)在不同体积比的水/四氢呋喃混合溶液中的荧光光谱图。
图6为水性的旋光的荧光聚合物(Ⅱ-1)的细胞毒性和细胞成像效果图。
图6中,A为被不同浓度荧光聚合物(Ⅱ-1)培养后的细胞存活率;B为被培养细胞的明场成像;C为被培养细胞的405nm激光激发成像;D为B和C的复合成像。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的仅仅是本发明一部分实例,而不是全部的实例。基于本发明中的实例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实例,都属于本发明保护的范围。
下面结合附图和具体实例对本发明技术方案做进一步详细描述,所描述的具体实例仅对本发明进行解释说明,并不用以限制本发明。
实施例1:水性的旋光的荧光聚合物(Ⅱ-1)的制备,其合成路线图如图1和图2所示,包括:
步骤一:将三苯基溴基乙烯(7.04mmol,2.3581g)、4-甲酰苯硼酸(8.48mmol,1.2647g)、四丁基溴化铵(0.704mmol,0.2268g)、2mol/L碳酸钾水溶液(12.6mL)、甲苯(12.6mL)依次加入反应管中,室温下搅0.5h;加入四(三苯基膦)钯(0)(8.22×10-3mmol,9.5mg),反应管在氮气保护下放入90℃的油浴锅中反应48h;反应结束后加入去离子水,用乙酸乙酯萃取,取有机层用无水硫酸镁干燥,过滤,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化(洗脱剂:正己烷/二氯甲烷2:1体积比),得到4-(1,2,2-三苯基乙烯)苯甲醛。
步骤二:将4-(1,2,2-三苯基乙烯)苯甲醛(2.50mmol,0.9010g)、对甲基苯乙腈(2.75mmol,0.4048g)、乙醇(30mL)依次加入反应管中,滴加5-6滴0.8mol/L四丁基氢氧化铵;反应管放入78℃的油浴锅中加热回流反应3h;反应结束后冷却至室温,用乙醇洗涤数次得到式Ⅲ-1化合物。1H NMR(400MHz,CDCl3,δ):3.84(s,3H;-CH3),6.93-6.95(J=8.0Hz,d,2H;Ar H),7.01-7.06(J=20.0Hz,m,6H;Ar H),7.09-7.14(J=20.0Hz,m,11H;Ar H),7.29(s,1H;CH),7.55-7.57(J=8.0Hz,d,2H;Ar H),7.61-7.63(J=8.0Hz,d,2H;Ar H).
步骤三:将式Ⅲ-1化合物(1.65mmol,0.8078g)、无水二氯甲烷(20mL)加入反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,脱去氧气;三溴化硼(1.0M二氯甲烷溶液)(4.95mmol,4.95mL)注射到稳压漏斗中,在冷冻条件下缓慢滴加到反应管中,这个过程大约30分钟,然后恢复到室温反应20h;反应结束后用饱和碳酸氢钠溶液中和至中性,用二氯甲烷萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化(洗脱剂:正己烷/二氯甲烷2:1体积比),得到Ⅳ-1化合物。1H NMR(400MHz,CDCl3,δ):4.91(s,1H;-OH),6.73-6.75(J=8.0Hz,d,2H;Ar H),6.89-7.94(J=20.0Hz,m,6H;Ar H),7.06-7.11(J=20.0Hz,m,11H;Ar H),7.31(s,1H;CH),7.53-7.55(J=8.0Hz,d,2H;Ar H),7.63-7.65(J=8.0Hz,d,2H;Ar H).
步骤四:将6-氯-2-己酮(7.06mmol,0.9503g)、四氢呋喃(25mL)、甲醇(13mL)依次加入反应管中,反应管置于冰水浴中,缓慢少量多次向其中加入硼氢化钠(42.4mmol,1.6025g),待硼氢化钠完全溶解后继续在冰水浴中反应6h;反应结束后用稀盐酸调节其pH值至4-5,用乙酸乙酯萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到产物6-氯-2-己醇,进一步利用乙酸乙酯和石油醚的混合液过柱提纯。1H NMR(400MHz,CDCl3,δ):1.22(d,J=6.0Hz,3H;CH3),1.47-1.52(m,4H;-CH2-),1.60(s,1H,-OH),1.80-1.84(m,2H;-CH2-),3.56(t,J=6.8Hz,2H;-CH2-),3.84(m,1H;-CH-).
步骤五:将式Ⅳ-1化合物(3.05mmol,1.45g)、6-氯-2-己醇(3.90mmol,0.55g)、碳酸钾(7.5mmol,1.05g)、碘化钠(50mg)、N,N-二甲基甲酰胺(15mL)依次加入反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,以除去氧气。恢复到室温后在100℃油浴锅中搅拌反应24h。反应结束后加入去离子水用乙酸乙酯萃取,萃取液用无水硫酸镁干燥,过滤,减压蒸馏,得到的粗产物用硅胶色谱柱分离纯化(洗脱剂:石油醚/乙酸乙酯2:1体积比),得到式Ⅴ-1化合物。1H NMR(400MHz,CDCl3,δ):1.22(d,J=6.0Hz,3H;CH3),1.52-1.55(m,4H;-CH2-),1.57(s,1H,-OH),1.80-1.85(m,2H;-CH2-),3.83(m,1H;-CH-),4.00(t,J=6.4Hz,2H;-CH2-),6.91-6.93(J=8.0Hz,d,2H;Ar H),7.02-7.06(m,7H;Ar H),7.09-7.14(m,10H;Ar H),7.30(s,1H;CH),7.54-7.56(J=8.0Hz,d,2H;Ar H),7.61-7.63(J=8.0Hz,d,2H;ArH).
步骤六:将Novozym435(227mg)加入到反应管中,反应管进行真空-氮气循环5次,脱去氧气,Ⅴ-1化合物(2.7mmol,1.5552g)、甲基丙烯酸三氟乙酯(1.73mmol,0.29g)、三乙胺(1.35mmol,0.1366g)溶解到甲苯(8mL)中,混合液注射到反应管中,在55℃油浴锅中搅拌反应24h;反应结束后离心除去Novozym435,溶剂减压蒸馏除去,得到的粗产物用硅胶色谱柱分离纯化(洗脱剂:石油醚/乙酸乙酯4:1体积比),得到式Ⅰ-1化合物。1H NMR(400MHz,CDCl3,δ):1.29-1.31(d,J=8.0Hz,3H;CH3),1.54-1.64(m,4H;-CH2-),1.82-1.85(m,2H;-CH2-),1.96(s,3H,-CH3),4.00(t,J=6.4Hz,2H;-CH2-),5.02(m,1H;-CH-),5.56(s,1H;CH),6.11(s,1H;CH),6.92-6.94(J=8.0Hz,d,2H;Ar H),7.04-7.08(m,7H;Ar H),7.11-7.15(m,10H;Ar H),7.31(s,1H;CH),7.56-7.58(J=8.0Hz,d,2H;Ar H),7.64-7.66(J=8.0Hz,d,2H;Ar H).
步骤七:将式Ⅰ-1化合物(0.15mmol,96.5mg)、聚(乙二醇)甲基丙烯酸酯(PEGMA)(0.47mmol,225mg)、2,2-偶氮二异丁腈(AIBN)(0.006mmol,1mg)、链转移剂CTA(0.012mmol,3.1mg)、甲苯(2mL)加入到反应管中,反应管在液氮冷冻下进行真空-氮气循环5次,脱去氧气;待恢复到室温后在70℃油浴锅中搅拌反应24h;反应结束后反应液用丙酮透析三次,减压蒸馏,得到的粗产物用四氢呋喃/石油醚溶解-沉淀三次,得到最终产物聚合物Ⅱ-1。另外,将Ⅰ-1化合物与PEGMA的投料比由24.2%增加到32.3%,得到聚合物聚合物Ⅱ-2。
实施例2:水性旋光荧光聚合物的AIE特性:
测量旋光AIE荧光单体Ⅰ-1的固体荧光,与已经报道的TPB荧光染料相比,其荧光强度明显增强,且荧光发射波长从475nm增加到了496nm,发生了明显的红移(见图3)。以CDCl3为溶剂,所得化合物Ⅳ-1、Ⅴ-1、Ⅰ-1、Ⅱ-1和Ⅱ-2的1H NMR的谱图如图4所示,每个化合物均出现了自己的特征峰,表明个化合物均成功制备出。称取10mg水性旋光荧光聚合物Ⅱ-1分别溶于4mL的不同体积比的去离子水和四氢呋喃混合溶液中,测定其荧光发射强度(见图5)。在水溶液中,在495nm处有一个明显的荧光发射峰,而在四氢呋喃溶液中几乎没有荧光,并且随着混合溶剂中水体积比的增大,荧光强度逐渐增大,当水的体积比达到90%时,荧光强度有非常明显的增强,当水的体积比达到100%时,即完全的不良溶剂时,荧光强度达到最大值。说明荧光聚合物Ⅱ-1具有明显的AIE性质。荧光聚合物Ⅱ-1在水溶液中自组装成具有核壳结构的纳米颗粒,疏水性片段将在内部聚集,由于它们的分子内运动受到限制,非辐射衰变途径被阻断,激发态能量通过辐射途径衰减,从而增强了荧光强度。
实施例3:旋光AIE荧光单体Ⅰ-1及其两亲性聚合物的旋光特性:
称取一定量旋光AIE荧光单体Ⅰ-1及其水性聚合物溶于20mL丙酮(浓度为10.0mg/mL),配成均匀透明的溶液,加入到20cm长的旋光管中,测定荧光单体和聚合物的比旋光度。经计算旋光AIE荧光单体Ⅰ-1及其水性聚合物Ⅱ-2的比旋光度分别为[α]20 D=-9.67°和[α]20 D=-3.74°。
实施例4:水性的旋光的荧光聚合物的细胞成像应用:
使用细胞计数试剂盒-8(CCK-8)测定评估荧光聚合物对L929细胞的活性的影响。结果显示,L929细胞保持了较高的存活率。即使荧光聚合物Ⅱ-1浓度高达120μg/mL,细胞成活率仍然超过90%。将20μg/mL荧光聚合物Ⅱ-1溶液加入细胞培养介质中,以此作为培养基在37℃下对L929细胞孵化3小时,通过激光共聚焦扫描显微镜,以405nm作为激发波长可以在细胞质区域观察到强烈的绿色荧光信号,表明荧光聚合物Ⅱ-1可以被细胞很好吸收,具有优良的细胞成像效果(见图6)。
实施例5:在实施例1的基础上,荧光化合物是四苯乙烯、吩噻嗪、苯并噻唑等不同类型的荧光分子。
在实施例1的基础上,步骤E中的RAFT活性聚合方法还可以采用包括以水性大分子化合物为催化剂的ATRP聚合方法替代。
1.所制备的荧光单体(R)-THM在水和THF中表现出明显的AIE特性,其比旋光度[α]D 25℃=-9.67°;
2.当荧光单体(R)-THM投料比从24.2%增加到32.3%,聚合物中(R)-THM的摩尔分数从22.3%增加到30.2%,聚合物在水溶液中能够自组装成粒径约100nm的纳米粒子,且表现出优良的荧光效果,其比旋光度[α]D 25℃随着荧光分子含量的增加而增加;
3.以L929细胞作为评价对象,将得到的聚合物纳米粒子和细胞孵化一段8h和24h后加入CCK-8染料,通过样品在450nm处的吸收值进一步评价其细胞毒性,细胞成活率均在90%以上,并展示了良好的细胞成像效果。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (7)
1.一种旋光性AIE荧光材料及其聚合物的制备方法,其特征在于,包含以下步骤:
A、利用苯硼酸和溴苯的Suzuki偶联反应合成醛基AIE荧光化合物;
B、利用醛基和苯乙腈间的缩合反应合成甲氧基荧光化合物,进一步利用BBr3将甲氧基脱甲基化生成羟基;
C、通过苯羟基与脂肪氯间的亲核取代反应,将叔羟基引入到荧光化合物上,生成相应的叔羟基AIE荧光化合物;
D、通过在脂肪酶B催化下的选择性酯交换反应将丙烯酸基元引入到荧光化合物上从而得到具有旋光性的AIE荧光单体。
E、通过RAFT活性聚合制备出具有旋光性的AIE荧光聚合物。
2.根据权利要求1所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,步骤D和E得到的AIE荧光单体和荧光聚合物在水和THF中表现出明显的AIE特性。
3.根据权利要求1所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,步骤D和E得到的AIE荧光单体和荧光聚合物具有旋光性。
4.根据权利要求1所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,步骤E得到的AIE荧光聚合物的旋光度随着AIE旋光染料的增加而增加。
5.根据权利要求1所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,所述荧光化合物是四苯乙烯、吩噻嗪、苯并噻唑的荧光分子。
6.根据权利要求1所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,所述荧光化合物是四苯乙烯、吩噻嗪、苯并噻唑的荧光聚合物。
7.根据权利要求4所述的一种旋光性AIE荧光材料水性聚合物的制备方法,其特征在于,步骤E中的RAFT活性聚合方法可被包括以水性大分子化合物为催化剂的ATRP聚合方法替代。
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