CN112029094A - 离子型芴基三聚氰胺超支化共轭聚合物及其制备方法和应用 - Google Patents
离子型芴基三聚氰胺超支化共轭聚合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于水溶液体系中I‑的检测技术领域,具体涉及一种离子型芴基三聚氰胺超支化共轭聚合物及其制备方法和应用。本发明提供的一种离子型芴基三聚氰胺超支化共轭聚合物及其制备方法,合成方法简单,合成条件易达到,制备成本低。本发明提供的一种离子型芴基三聚氰胺超支化共轭聚合物可用于制作识别I‑的离子型超支化聚合物荧光探针,该荧光探针在不同pH、不同极性的溶剂中光学活性很高,对I‑的鉴别检出选择性好,可同时实现定量与定性检测。该荧光探针在重原子效应机制作用下是一种高灵敏度、高选择性的检测I‑的荧光探针,该荧光探针对I‑具有较高的特异性识别能力。
Description
技术领域
本发明属于水溶液体系中I-的检测技术领域,具体涉及一种离子型芴基三聚氰胺超支化共轭聚合物及其制备方法和应用。
背景技术
碘是人体内基础代谢必需的微量元素之一,它不仅是合成甲状腺激素的必要元素,同时也在人类发育和基础代谢等过程中起着关键作用。人体内缺乏I-会导致工作效率低下,体内的生理功能紊乱,精神发育迟缓,同时还会引起各种疾病,如新生儿发育异常、甲状腺肿、克汀病等。现在有许多检测I-的分析方法,如毛细管电泳法、离子色谱法、电化学法、气相色谱-质谱法和电感耦合等。但是这几种方法存在检测时间长、操作复杂、检测范围相对窄、对设备要求高等局限性。
荧光传感检测法由于灵敏度高、数据采集方便快捷、时间空间分辨率高的特点在许多领域备受关注。共轭聚合物是一种具有π-π*电子共轭结构的线性高分子聚合物,具有很强的光捕获以及显著的光信号放大能力,可以被用来放大荧光传感信号,也可作为高敏感性生物和化学检测的平台,是一类新型生物成像荧光探针。其中,离子型共轭聚合物具有良好的电子传导能力和溶解性,使其在很多领域有广泛的应用,如生物医学、环境监测以及光电器件开发等。因此,开发选择性强、准确度高、检测成本低等优点的检测识别方法成为一直以来研究的热门课题。
发明内容
本发明的目的在于提供一种离子型芴基三聚氰胺超支化共轭聚合物。
本发明的目的通过如下技术方案来实现:化学式为:
本发明的目的还在于提供一种离子型芴基三聚氰胺超支化共轭聚合物的制备方法。
本发明的目的通过如下技术方案来实现:包括以下步骤:
步骤1:将2,7-二溴芴、四丁基碘化铵和1,6-二溴己烷置于50%NaOH溶液中,在氮气保护下,升温至60℃进行反应12h;待反应结束后,将反应装置温度降至室温;
步骤2:对反应后的产物用三氯甲烷萃取,用饱和氯化钠水溶液洗涤,重复三次,收集有机相,加入适量无水硫酸钠干燥;利用柱层析分离,石油醚为洗脱剂,之后减压蒸馏得到白色晶体,真空干燥,得到提纯后的产物9,9-二(溴己基)-2,7-二溴芴;
步骤3:将9,9-二(溴己基)-2,7-二溴芴加入到四氢呋喃溶液中,滴入正丁基锂及DMF,在-78℃的环境下反应2h,然后升到室温中反应14h;
步骤4:待反应结束后用三氯甲烷萃取,饱和氯化钠水溶液洗涤有机相,无水硫酸钠干燥,收集滤液,旋干溶剂,得到浅黄色粗产物;
步骤5:对浅黄色粗产物用二氯甲烷与正己烷2∶3比例混合溶剂作洗脱剂,利用层析柱提纯收集纯馏分测核磁,得到最终浅黄色油状产物9,9-二(溴己基)-2,7-二芴醛;
步骤6:将9,9-二(溴己基)-2,7-二芴醛、三聚氰胺和除水的DMSO置于反应茄瓶中,氮气保护下将反应茄瓶置于油浴锅中加热至100-110℃反应12h;反应结束后将反应茄瓶中产物倒入冰水中沉淀;
步骤7:将沉淀物离心去离子水洗涤2-3次,真空干燥机除水,得到浅黄色产物芴基三聚氰胺超支化共轭聚合物;
步骤8:将芴基三聚氰胺超支化共轭聚合物和DMAc置于三甲胺水溶液中,放置于室温环境中反应3天;反应结束后,将产物真空干燥24h,得到浅棕色粉末状的固体离子型芴基三聚氰胺超支化共轭聚合物。
本发明的目的还在于提供一种离子型芴基三聚氰胺超支化共轭聚合物的应用。
本发明的目的通过如下技术方案来实现:用于制作识别I-的离子型超支化聚合物荧光探针。
本发明的有益效果在于:
本发明提供了一种离子型芴基三聚氰胺超支化共轭聚合物及其制备方法,该制备方法的合成方法简单,合成条件易达到,制备成本低。本发明提供的一种离子型芴基三聚氰胺超支化共轭聚合物可用于制作识别I-的离子型超支化聚合物荧光探针,该荧光探针在不同pH、不同极性的溶剂中光学活性很高,对I-的鉴别检出选择性好,可同时实现定量与定性检测。
在250-400nm以及350-542nm,该荧光探针在不同pH以及不同极性的溶剂中,均表现出良好稳定的紫外和荧光光学活性,同时其较大的斯托克斯位移值(39-110nm)也说明它在不同环境中作为荧光检测试剂的可能和广泛适用性。I-的加入使该探针产生显著的荧光响应,猝灭效率高达76%,而其他潜在干扰阴离子仅仅在6.94%-19.32%之间,而混合阴离子的干扰也仅为8%。这表明该荧光探针对I-具有较高的特异性识别能力。此外,在40-300μmol L-1的浓度范围内该荧光探针与I-具有良好的线性定量关系,I-的检出限可低至295.4μmol L-1。经分析,该荧光探针在重原子效应机制作用下是一种高灵敏度、高选择性的检测I-的荧光探针。
附图说明
图1为产物1(1)、产物2(2)、产物3(3)、离子型芴基三聚氰胺超支化共轭聚合物(4)的红外光谱图。
图2为产物1的1H NMR谱图(CDCl3,20℃,500MHz)。
图3为产物2的1H NMR谱图(CDCl3,20℃,500MHz)。
图4为产物3的1H NMR谱图(DMSO-d6,20℃,500MHz)。
图5为离子型芴基三聚氰胺超支化共轭聚合物的1H NMR谱图(D2O,80℃,500MHz)。
图6为在PBS缓冲溶液(5mmol L-1)中不同pH对离子型芴基三聚氰胺超支化共轭聚合物的紫外-可见吸收光谱(左,实线)-荧光发射光谱(右,虚线)的影响。
图7为离子型芴基三聚氰胺超支化共轭聚合物在不同溶剂中的归一化紫外-可见吸收光谱(左,黑线)和荧光发射光谱(右,红线)(λex=332nm)。
图8为在PBS缓冲溶液(5mmol L-1,pH=7)中不同阴离子(1000μmol L-1)对离子型芴基三聚氰胺超支化共轭聚合物(10μmol L-1)的荧光发射光谱的影响(λex=332nm)。
图9为在PBS缓冲溶液(5mmol L-1,pH=7)中离子型芴基三聚氰胺超支化共轭聚合物(10μmol L-1)对不同阴离子(1000μmol L-1)的荧光响应(λex=332nm)。
图10(a)为在PBS缓冲溶液(5mmol L-1,pH=7)中离子型芴基三聚氰胺超支化共轭聚合物的荧光发射光谱随I-浓度的变化(λex=332nm)。
图10(b)为离子型芴基三聚氰胺超支化共轭聚合物在424nm处荧光猝灭效率与I-浓度关系图(λex=332nm)。
图11为离子型芴基三聚氰胺超支化共轭聚合物在不同溶剂中的光学性质表。
图12为离子型芴基三聚氰胺超支化共轭聚合物的合成路线图。
具体实施方式
下面结合附图对本发明做进一步描述。
为了达到在水溶液体系中检测I-的目的,本发明合成了一种离子型芴基三聚氰胺超支化共轭聚合物荧光探针,该荧光探针的合成方法简单,合成条件易达到,制备成本低。同时该荧光探针在不同pH、不同极性的溶剂中光学活性很高,对I-的鉴别检出选择性好,可同时实现定量与定性检测。
以简单的方法和温和的反应条件,以2,7-二溴芴、1,6-二溴己烷为原料首先合成了主链含有荧光芴环和侧链含有十二烷基的二醛化合物,之后将其与三聚氰胺经醛胺缩聚和侧链季铵化反应后获得了一种成本低,产率高的可用于检测I-的离子型芴基超支化共轭聚合物荧光探针。
采用瑞士Bruker公司AvanceⅢ-500核磁共振波谱仪在室温的条件下,以氘代氯仿、氘代二甲基亚砜以及氘代重水为溶剂对合成产物的结构进行核磁共振氢谱表征。采用美国PE公司Spectrum 100型FT-IR傅里叶红外光谱仪在室温条件下,波数范围为4000-450cm-1,扫描次数为8次,采用溴化钾压片法对合成产物的结构进行红外光谱表征。
为了研究该荧光探针的光学活性,在pH分别为5,7,12,浓度为5mmol L-1的PBS缓冲溶液以及EA,Ethanol,Methanol,DMF,EG,AN,DMSO,DMAc,H2O溶剂体系中,分别加入10μmolL-1的离子型超支化聚合物,采用上海美普达仪器有限公司UV-6100型号紫外-可见分光光度计,在室温,波长范围为200-800nm的条件下,将2000μl样品放置在10×10mm的石英比色皿中来测其紫外-可见吸收光谱。采用美国PE公司LS55型号荧光光度计,在波长范围为200-800nm,激发波长为332nm,狭缝宽度为15nm的室温条件下,将2000μl样品放置在10×10mm的石英比色皿中来测其荧光发射光谱。
将该荧光探针溶解在pH=7的PBS缓冲溶液中,稀释至10μmol L-1,然后分别加入1000μmol L-1浓度的F-,Cl-,Br-,I-,OH-,PO4 3-,HPO4 2-,ClO-,NO3 -,H2PO4 -,SO4 2-,HCO3 -,CO3 2-,在激发波长为332nm的条件下进行荧光光谱的测定,进行离子型超支化聚合物对I-特异性识别的研究。之后,对离子型超支化聚合物加入I-进行荧光滴定实验(I-浓度梯度为0,20,40,100,200,300,1000μmol L-1),通过不同浓度I-与离子型超支化聚合物在424nm处的荧光猝灭效率的关系获得检测I-的线性范围,建立标准曲线方程并计算离子型超支化聚合物对I-的检出限。最后,采用Job-plot荧光滴定方法,在离子型超支化聚合物与I-的浓度之和为10μmol L-1的条件下确定了二者相互作用的化学计量比。
在250-400nm以及350-542nm,该荧光探针在不同pH以及不同极性的溶剂中,均表现出良好稳定的紫外和荧光光学活性,同时其较大的斯托克斯位移值(39-110nm)也说明它在不同环境中作为荧光检测试剂的可能和广泛适用性。I-的加入使该探针产生显著的荧光响应,猝灭效率高达76%,而其他潜在干扰阴离子仅仅在6.94%-19.32%之间,而混合阴离子的干扰也仅为8%。这表明该荧光探针对I-具有较高的特异性识别能力。此外,在40-300μmol L-1的浓度范围内该荧光探针与I-具有良好的线性定量关系,I-的检出限可低至295.4μmol L-1。经分析,该荧光探针在重原子效应机制作用下是一种高灵敏度、高选择性的检测I-的荧光探针。
产物1,2,3,4的红外光谱图如图1所示,反应原料2,7-二溴芴中(-CH2-)的面外变角振动峰在685cm-1处。在产物1的FT-IR谱图中,该处的吸收峰消失,并在2930cm-1和2852cm-1处出现特征吸收峰,应归属为9位上饱和烷烃链上的亚甲基,在具有-(CH2)n-结构的链中,当n>4时,CH2的面内摇摆出现在722cm-1处。1060cm-1处2,7-二溴芴中2位和7位上苯环和Br(Ar-Br)的伸缩振动峰以及在1603cm-1处苯环上C-C的骨架振动峰依旧存在,都证明2,7-二溴芴的9号位上成功的连接了两个溴己基。
产物2与产物1的光谱图相比,1605cm-1处苯环上C-C的骨架振动峰、2929cm-1和2855cm-1处9位上饱和烷烃链上的亚甲基特征吸收峰、722cm-1处CH2的面内摇摆仍旧存在。在2740-2720cm-1之间出现醛基的C-H特征吸收峰以及1710-1695cm-1处芳香醛的C=O伸缩振动特征峰,1060cm-1处产物1芴环上2和7位上Br(Ar-Br)的伸缩振动峰的消失,这都说明溴原子被醛基取代。
产物3与产物2的光谱图相比,1603cm-1处苯环上C-C的骨架振动峰以及2933cm-1和2862cm-1处的亚甲基的特征吸收峰依旧存在,同时2740-2720cm-1之间处醛基C-H的中强吸收峰以及1710-1695cm-1处芳香醛的C=O伸缩振动特征峰消失。在1603cm-1处出现亚胺的吸收峰,1547cm-1处为三嗪环C=N的伸缩振动峰,815cm-1为三嗪环变形振动特征吸收峰,由此证明产物3的合成。
离子型超支化聚合物与产物3的光谱图相比,支链结构相同,唯一的差别就是支链末端的溴原子被叔胺基取代,因此只要红外谱图中出现叔胺基的特征峰就证明第四步离子型超支化聚合物的成功合成。由于叔胺中C-N是连在脂肪链上,因此伸缩振动峰通常出现在1250cm-1-1020cm-1区间,且峰强为中等强度。离子型超支化聚合物的红外谱线中在1088cm-1处出现一个中等强度的红外峰,此峰应为叔胺中C-N的伸缩振动峰,由此证明成功合成了离子型超支化聚合物。
图2为产物1的核磁共振氢谱图,从低场到高场,7.54-7.43ppm处出现多重峰,各谱峰分别对应的是芴基上三种位置的氢(Ha,Hb,Hc),以溴原子相连的亚甲基上的4个氢(Hd)为基准进行积分,得到其氢个数为1.98,1.97,1.99。3.35ppm处三重峰为溴原子相连的4个氢(Hd),由于诱导效应的影响,溴原子的电负性较大,成键电子云偏离氢原子,去屏蔽作用增强,导致与溴相连的亚甲基上的氢电子云向低场移动。1.93-1.89ppm(三重峰),1.68-1.55ppm(多重峰),1.20-1.17ppm(多重峰),1.09-1.06ppm(多重峰),0.57ppm(多重峰),溴己基上其余亚甲基上的氢(He,Hf,Hg,Hh,Hi)。其积分个数分别为3.98,4.03,4.07,4.05,4.01。与结构式基本相同,因此可以证明我们成功制备了产物1。此外,谱图上没有杂峰,可以看出合成产物的纯度较高。
图3为产物2的核磁共振氢谱图。从高场到低场,并以溴原子相连的亚甲基上的氢个数为4进行积分,各谱峰对应的氢核的化学位移δ为0.53-0.61ppm(多重峰),1.06-1.09ppm(多重峰),1.09-1.18ppm(多重峰),1.58-1.67ppm(多重峰),2.05-2.11ppm(三重峰),其对应溴己基亚甲基上的氢(He,Hf,Hg,Hh,Hi),3.23-3.27ppm(三重峰),对应溴原子相连的亚甲基上的4个氢(Hd)。7.91-7.96ppm(多重峰)对应芴环上6个氢(Ha,Hb,Hc),10.2ppm(单峰)对应2-和7-位上的2个醛基氢(Hj)。与结构式基本相同,证明醛基已经成功取代了2位和7位上的溴原子,即产物2制备成功。
图4为产物3的核磁氢谱图。8.4ppm处亚胺峰的出现证明在第三步反应中发生了醛胺缩合反应,由此证明产物3制备成功,此步反应产率为60%。
图5为离子型超支化聚合物的核磁氢谱图。3.4ppm处的峰为季胺基团甲基氢的峰,它的出现证明离子型超支化聚合物制备成功,此步反应产率为87%。
一、离子型芴基超支化共轭聚合物荧光探针的合成:
1.1、产物1(9,9-二(溴己基)-2,7-二溴芴)的合成
将4.9g 2,7-二溴芴、0.1g四丁基碘化铵、8ml 1,6-二溴己烷、8ml 50%NaOH混合。氮气保护下,升温至60℃,反应12h。待反应结束后,将反应装置温度降至室温。反应后用三氯甲烷(氯仿)萃取,用饱和氯化钠水溶液洗涤,重复三次,收集有机相。加入适量无水硫酸钠干燥。利用柱层析分离,石油醚为洗脱剂,之后减压蒸馏得到白色晶体,真空干燥,即得到提纯后的第一步产物1。
1.2、产物2(9,9-二(溴己基)-2,7-二芴醛)的合成
称取3.9g产物1、150ml四氢呋喃,加入三口烧瓶中,滴入20ml正丁基锂及2ml DMF,在-78℃的环境下继续反应2h,然后升到室温中反应14h。反应结束后用三氯甲烷(氯仿)萃取,饱和氯化钠水溶液洗涤有机相,无水硫酸钠干燥,收集滤液,旋干溶剂,得到浅黄色粗产物。用二氯甲烷与正己烷2∶3比例混合溶剂作洗脱剂,利用层析柱提纯收集纯馏分测核磁,得到最终浅黄色油状产物2。
1.3、产物3(芴基三聚氰胺超支化共轭聚合物)的合成
取少量0.3909g产物2与过量一倍的三聚氰胺0.1796g、量取15ml DMSO(除水)于反应茄瓶中,氮气保护下置于油浴锅中加热至100-110℃反应12h。反应结束后倒入冰水中沉淀,后将沉淀物离心去离子水洗涤2-3次,真空干燥机除水,得到浅黄色0.2275g产物3(芴基三聚氰胺超支化共轭聚合物),产率54%。
1.4、离子型超支化聚合物4(离子型芴基三聚氰胺超支化共轭聚合物)的合成
称取0.02g的产物3,15ml DMAc,15ml三甲胺水溶液,把反应装置放在室温环境中反应3天。反应结束后,将产物真空干燥24h,得到浅棕色粉末状的固体离子型芴基三聚氰胺超支化共轭聚合物(后文简称为离子型超支化聚合物),产率为80%。
二、pH值对离子型超支化聚合物光学性质的影响:
图6(左,实线)是离子型超支化聚合物在pH为5,7,12的PBS缓冲溶液中的紫外-可见吸收光谱,在不同的pH值条件下离子型超支化聚合物的紫外波谱的峰形基本相同,在250-400nm的波长范围内,最大吸收波长均出现在332nm处,在最大吸收峰左右两侧各伴随一个吸收肩峰,分别在320nm和340nm处。在酸性条件下紫外-可见吸收强度稍大。图6(右,虚线)是离子型超支化聚合物在不同pH缓冲溶液中,以332nm为激发波长得到的荧光发射光谱,波长范围是350-542nm,它在不同pH下的荧光光谱形状基本相同。在三种不同的酸、中和碱性环境中,最大荧光发射峰出现在422nm,产生的荧光来源于聚合物主链中的芴基荧光发色团。因此,在不同的酸碱环境中离子型超支化聚合物均表现出了良好的光学活性。
三、溶剂对离子型超支化聚合物光学性质的影响:
图7为离子型超支化聚合物在不同溶剂中的归一化紫外-可见吸收光谱(左,黑线)和荧光发射光谱(右,红线)。可以看出,离子型超支化聚合物只在Methanol中的紫外-可见吸收光谱中出现了两个吸收峰,而在其他几种溶剂中均出现三个吸收峰。其中,在EA,Ethanol中有最大吸收峰波长为336nm,在Methanol中吸收峰波长最小为326nm。在图11中总结了不同极性溶剂对离子型超支化聚合物的光学性质的影响。由于离子型超支化聚合物是含有疏水主链和亲水阳离子侧链的两亲性化合物,它与不同极性的溶剂会产生不同的相互作用,致使聚合物的伸展状态和排列方式发生变化从而影响其光学性质。在Ethanol中离子型超支化聚合物有最大斯托克斯位移值110nm,在DMAc中最小,为39nm,在其余溶剂中斯托克斯位移在50-90nm之间。离子型超支化聚合物在不同溶剂中较大的斯托克斯位移值说明,其荧光发射光谱与紫外-可见吸收光谱的重叠越少,自吸收现象越小,是一种在酸碱介质以及大部分有机介质中非常适宜做荧光传感和检测试剂的材料。
四、离子型超支化聚合物对I-的识别:
图8是在pH为7的PBS缓冲溶液中13种不同阴离子对离子型超支化聚合物的荧光发射光谱的影响。加入I-后,离子型超支化聚合物的荧光发射光谱的最大发射波长由424nm蓝移了2nm至422nm。加入F-,Cl-,Br-,OH-,PO4 3-,HPO4 2-,ClO-,NO3 -,H2PO4 -,SO4 2-,HCO3 -,CO3 2-这些常见的阴离子后离子型超支化聚合物的荧光光谱的最大发射波长出现在421nm-425nm之间。从离子型超支化聚合物不同的荧光响应程度可以看出,I-对它的荧光光谱影响最为明显,光谱下降程度最大,而其他阴离子的影响并不显著。
离子型超支化聚合物与I-作用后,其荧光发生了猝灭。首先,离子型超支化聚合物结构中含有芴基荧光发色团,芴基中含有π-π*离域电子,并且,聚合物疏水主链中的亚胺键有-C=N-结构,结构中的N原子含有一对孤对电子,由亚胺键连接的三聚氰胺也是共轭结构,所以离子型超支化聚合物中主链是一个单双键交替的大共轭体系,这样的结构特点十分有利于电子在三维方向上的离域运动和转移。同时,离子型超支化聚合物由332nm激发作用下产生的激发态分子与I-之间的相互作用后使荧光发色团中的电子自旋–轨道耦合作用增强,系间窜跃显著增加,发生了由重原子效应导致的荧光猝灭。此外,离子型超支化聚合物离子化侧链的季铵阳离子带正电荷,可以与带负电荷的碘离子发生静电结合作用,在静电吸引力作用下二者的距离被拉近了,有利于二者之间的相互作用,进而促进了荧光猝灭现象的发生。
图9是在pH为7的PBS缓冲溶液中通过公式(1)计算出的不同阴离子对离子型超支化聚合物的荧光猝灭效率,它反映了离子型超支化聚合物对不同阴离子荧光信号响应程度的不同,加入F-,Cl-,Br-,OH-,PO4 3-,HPO4 2-,ClO-,NO3 -,H2PO4 -,SO4 2-,HCO3 -,CO3 2-后,荧光猝灭效率分别为16.24%,15.63%,11.37%,19.32%,16.25%,17.96%,16.76%,15.93%,10.06%,6.94%,8.34%,9.09%,而加入I-后,荧光猝灭效率可高达76%,而加入包含了I-在内的13种混合阴离子后出现了和I-类似的猝灭行为,84%的荧光猝灭效率仅比I-单独存在时高了8%,由此可以看出离子型超支化聚合物对I-具有很明显的特异性识别能力,而且其它常见阴离子的存在,并不会对离子型超支化聚合物识别I-产生干扰和影响。
式中,E—荧光猝灭效率
F0—离子型超支化聚合物的荧光强度
F—离子型超支化聚合物加入I-之后的荧光强度
如图10(a)所示,随I-浓度增大,离子型超支化聚合物的荧光发射光谱呈现逐渐下降的趋势。并且,荧光发射光谱逐渐发生蓝移,在I-浓度由20μmol L-1增加到1000μmol L-1的时候,最高峰位置也由最初的424nm蓝移2nm至422nm。图10(b)为离子型超支化聚合物的荧光猝灭效率与I-浓度关系图,可以看出,在I-浓度为40-300μmol L-1时,猝灭效率与I-浓度呈现良好的线性关系,线性方程为y=0.0012+0.3208x,相关系数R2=0.96209。
LOD=3σ/K (2)
式中LOD—检出限
K—绘制标准曲线的斜率
σ—离子型超支化聚合物空白样品的13次测量结果的标准偏差
随后,将K=0.0012,σ=0.1182带入公式(2)计算出了在pH=7环境下离子型超支化聚合物对I-的最低检出限为295.5μmol L-1。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
2.一种离子型芴基三聚氰胺超支化共轭聚合物的制备方法,其特征在于,包括以下步骤:
步骤1:将2,7-二溴芴、四丁基碘化铵和1,6-二溴己烷置于50%NaOH溶液中,在氮气保护下,升温至60℃进行反应12h;待反应结束后,将反应装置温度降至室温;
步骤2:对反应后的产物用三氯甲烷萃取,用饱和氯化钠水溶液洗涤,重复三次,收集有机相,加入适量无水硫酸钠干燥;利用柱层析分离,石油醚为洗脱剂,之后减压蒸馏得到白色晶体,真空干燥,得到提纯后的产物9,9-二(溴己基)-2,7-二溴芴;
步骤3:将9,9-二(溴己基)-2,7-二溴芴加入到四氢呋喃溶液中,滴入正丁基锂及DMF,在-78℃的环境下反应2h,然后升到室温中反应14h;
步骤4:待反应结束后用三氯甲烷萃取,饱和氯化钠水溶液洗涤有机相,无水硫酸钠干燥,收集滤液,旋干溶剂,得到浅黄色粗产物;
步骤5:对浅黄色粗产物用二氯甲烷与正己烷2∶3比例混合溶剂作洗脱剂,利用层析柱提纯收集纯馏分测核磁,得到最终浅黄色油状产物9,9-二(溴己基)-2,7-二芴醛;
步骤6:将9,9-二(溴己基)-2,7-二芴醛、三聚氰胺和除水的DMSO置于反应茄瓶中,氮气保护下将反应茄瓶置于油浴锅中加热至100-110℃反应12h;反应结束后将反应茄瓶中产物倒入冰水中沉淀;
步骤7:将沉淀物离心去离子水洗涤2-3次,真空干燥机除水,得到浅黄色产物芴基三聚氰胺超支化共轭聚合物;
步骤8:将芴基三聚氰胺超支化共轭聚合物和DMAc置于三甲胺水溶液中,放置于室温环境中反应3天;反应结束后,将产物真空干燥24h,得到浅棕色粉末状的固体离子型芴基三聚氰胺超支化共轭聚合物。
3.一种离子型芴基三聚氰胺超支化共轭聚合物的应用,其特征在于:用于制作识别I-的离子型超支化聚合物荧光探针。
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