CN112708417A - 一种聚集诱导发光聚合物纳米粒子及其制备方法与应用 - Google Patents
一种聚集诱导发光聚合物纳米粒子及其制备方法与应用 Download PDFInfo
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- CN112708417A CN112708417A CN202011640840.6A CN202011640840A CN112708417A CN 112708417 A CN112708417 A CN 112708417A CN 202011640840 A CN202011640840 A CN 202011640840A CN 112708417 A CN112708417 A CN 112708417A
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Abstract
本发明公开了一种聚集诱导发光聚合物纳米粒子及其制备方法与应用,所述制备方法包括:(1)将乳化剂溶于去离子水中,得到水相溶液;(2)将AIE分子、助稳定剂和聚合物溶于与水不互溶的溶剂中,得到油相溶液;(3)将步骤(1)所制的水溶液加至步骤(2)所制的油相溶液中,混合搅拌进行预乳化,得到粗乳液;超声处理,制得细乳液液滴;挥发性的溶剂在减压条件下除去,制得AIE聚合物纳米粒子乳液;纯化处理后得到AIE聚合物纳米粒子。本发明可以通过改变表面活性剂类型及含量调控AIE聚合物纳米粒子的粒径;同时AIE聚合物纳米粒子的发光颜色和荧光强度可以简便通过AIE分子类型和用量来调控。
Description
技术领域
本发明涉及聚集诱导发光材料,具体涉及一种聚集诱导发光聚合物纳米粒子及其制备方法与应用。
背景技术
荧光聚合物纳米粒子是指将荧光分子通过共价或者包埋方式引入聚合物纳米粒中,是一类重要的功能纳米材料,其具有稳定性好、光稳定性高、粒径可调控和表面可修饰等特点,在防伪材料、体外诊断和细胞成像等众多领域有重要的实际应用价值。传统的ACQ分子在稀溶液状态下发强荧光,在高浓度或聚集状态下的荧光减弱,使得传统的荧光聚合物纳米粒子,往往存在荧光量子产率低、荧光分子合成复杂等缺陷。2001年,唐本忠课题组首次发现聚集诱导发光(AIE)现象,AIE分子刚好可以克服上述缺点,将AIE分子引入荧光纳米粒子后,由于分子内运动受限,纳米粒子荧光强度和量子产率大幅度增加【Chem Soc Rev2011,40,5361–5388.】。
目前,已制备出多种AIE聚合物纳米粒子的方法,比如有学者开发了乳化溶剂蒸发法、纳米沉淀法、自组装与RAFT聚合、点击反应相结合的方法来制备不同的AIE聚合物纳米粒子【Chem.Soc.Rev.,2014,43,6570--6597】。自组装法【Chem.Commun 2010,46,1377–1393.】和纳米沉淀法【J Mater Chem,2009,19,3838–3840.】制备的AIE聚合物纳米粒子需要在较低浓度下进行,合成效率不高。乳化溶剂蒸发法【ACS Nano,2012,6,6843–6851.】是由不溶于水的聚合物油相和含乳化剂的水相组成,通过升高温度或减压蒸发有机溶剂,形成稳定的纳米颗粒,这种方法制备的粒径往往不可调控并且固含量较低。
因此,开发出量子产率高、重复性好并且微球尺寸可调控的AIE荧光微球,推动AIE荧光微球在防伪材料、体外诊断试剂和细胞成像领域的应用具有重要的实际价值。
发明内容
本发明旨在提供一种基于细乳化溶剂蒸发技术制备AIE聚合物纳米粒子及其制备方法与应用,所制的AIE聚合物纳米粒子具有量子产率高、重复性好、粒径可调控、可规模化生产等优点。
本发明采用的技术方案是:
一种AIE聚合物纳米粒子的制备方法,所述方法包括以下步骤:
(1)将乳化剂溶于去离子水中,得到水相溶液;
(2)将AIE分子、助稳定剂和聚合物溶于与水不互溶的挥发性的有机溶剂中,得到油相溶液;
(3)将步骤(1)所制的水溶液加至步骤(2)所制的油相溶液中,混合搅拌进行预乳化,得到粗乳液;超声处理,制得细乳液液滴;挥发性的溶剂在减压条件下除去,制得AIE聚合物纳米粒子乳液;纯化处理后得到AIE聚合物纳米粒子。
优选的,所述的AIE分子选自下列AIE-1至AIE-28分子中的至少一种:
优选的,本发明步骤(1)中,所述乳化剂,选自下列至少一种:阴离子乳化剂、阳离子乳化剂、两性乳化剂和非离子乳化剂。
进一步优选的,所述阴离子乳化剂,可选自下列至少一种:烷基苯磺酸盐乳化剂、烷基磺酸盐乳化剂和烷基硫酸盐乳化剂。所述阳离子乳化剂,可选自下列至少一种:烷基二甲基苄基卤化铵乳化剂、烷基三甲基卤化铵乳化剂。所述两性乳化剂,可选自下列至少一种:十二烷基氨基丙酸、十八烷基二羟乙基氧化胺、羧酸基甜菜碱、磺酸基甜菜碱。所述非离子型乳化剂,可选自下列至少一种:OP-系列乳化剂、O系列乳化剂、聚乙二醇、吐温系列乳化剂和聚乙烯醇系列。
更优选的,本发明步骤(1)中,考虑到乳液液滴的胶体稳定性以及AIE聚合物纳米粒子的粒径可控性,所述的乳化剂优选非离子型乳化剂、阴离子乳化剂和阳离子乳化剂,更优选聚乙烯醇、吐温20、十二烷基硫酸钠、十六烷基三甲基溴化铵中的至少一种。
优选的,本发明步骤(1)中,所述乳化剂的质量用量为水质量用量的0.1%~10%;进一步优选的,所述的水溶性乳化剂质量用量优选为水质量用量的0.2%~8%;更优选为0.3%~4%。
优选的,步骤(2)所述助稳定剂选自下列至少一种:C14~C22的脂肪烃、C14~C22的脂肪醇;
优选的,步骤(2)所述聚合物选自下列至少一种:聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯、聚乙烯基甲醚、聚乙烯醇、聚醋酸乙烯酯、聚氯乙烯、聚丙烯、聚丙烯酸、聚丙烯酸乙酯、聚丙烯酰胺、聚丙烯腈、聚乳酸-羟基乙酸共聚物、聚己内酰胺、聚(L-丙交酯)、聚己内酯、磷脂聚乙二醇、磷脂聚乙二醇氨基、磷脂聚乙二醇羧基、磷脂聚乙二醇马来酰亚胺。
进一步优选的,本发明步骤(2)中,考虑到制备的AIE聚合物纳米粒子在防伪、体外诊断和细胞成像等多个领域的应用,聚合物优选为聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚甲基丙烯酸、聚苯乙烯、聚乳酸-羟基乙酸共聚物和磷脂聚乙二醇马来酰亚胺。更优选为聚甲基丙烯酸甲酯、聚苯乙烯和聚乳酸-羟基乙酸共聚物。
优选的,步骤(2)所述溶剂选自下列至少一种:辛烷、石油醚、二硫化碳、四氯化碳、乙烷、环乙烷、乙醚、乙酸乙脂、正己烷、二硫化碳、甲苯、三氯甲烷和二氯甲烷。
进一步优选的,本发明步骤(2)中,考虑制备AIE聚合物纳米粒子溶剂蒸发实效性和环保性,溶剂优选为乙醚、乙酸乙脂、苯、三氯甲烷和二氯甲烷,更优选为乙酸乙脂、三氯甲烷和二氯甲烷。
优选的,所述AIE分子质量用量为聚合物总质量的0.1%~10%;
进一步优选的,本发明步骤(2)中,考虑到制备不同发射波长的AIE聚合物纳米粒子在不同领域的应用,优选红色、绿色和蓝色的AIE分子为荧光组分,AIE分子的质量用量优选为聚合物质量用量的0.2%~5%。
优选的,所述助稳定剂质量用量为聚合物总质量的1%~10%。
进一步优选的,本发明步骤(2)中,考虑到细乳液液滴的稳定性,助稳定剂优选正十六烷;助稳定剂的质量用量优选为聚合物质量用量的4%~8%。
优选的,聚合物的质量用量为水总质量0.1%~20%;溶剂的质量用量为水总质量5%~40%。
优选的,本发明步骤(3)中,所述超声处理为将装有粗乳液的容器置于冰水浴中,在30W~900W的功率下超声处理0.5min~30min制得细乳液液滴;
进一步优选的,为防止超声过程中细乳液温度升高,将装乳液的玻璃瓶置于冰水浴中进行超声处理,超声功率优选100W~500W,超声时间优选3min~20min。
优选的,本发明步骤(3)中,为了让产品中溶剂降低至安全含量以下,使用旋转蒸发仪在低压下有效去除溶剂。
优选的,本发明步骤(3)中,所述纯化处理为将乳液离心,再重新分散在水中,按照此方法循环三次到五次,得到纯化后的AIE聚合物纳米粒子。
进一步优选的,所述的离心优选按照如下操作:离心转速优选10000-12000rpm,离心时间优选10min~40min。
上述任一制备方法制得的聚集诱导发光聚合物纳米粒子。
上述聚集诱导发光聚合物纳米粒子在制备防伪材料、体外诊断试剂和细胞成像试剂的应用。
关于本发明,经过发明深入研究,表面活性剂类型及其用量对AIE聚合物纳米粒子的粒径和稳定性起着重要作用。因此,在一系列实验中,我们研究了不同离子型和非离子型表面活性剂对AIE PNPs体系的影响。相比较非离子表面活性剂,随着表面活性剂浓度的增加,水油两相的界面张力下降,并且离子型的基团为液滴之间提供静电排斥,大大提高液滴的稳定性,制备出的AIE聚合物纳米粒子粒径最小为50nm。在使用非离子表面活性剂时,可以制备出高达500nm且均一性好的AIE聚合物纳米粒子。综上,应根据AIE聚合物纳米粒子的胶体稳定性、应用领域以及后续修饰修饰程度的要求来确定合适的表面活性剂类型和用量。
本发明的有益效果主要体现在:
提出一种简便的制备AIE聚合物纳米粒子方法,把商用聚合物和AIE分子溶解于溶剂中,加入含表面活性剂的水溶液,通过超声和溶剂挥发,就可以得到稳定的AIE聚合物纳米粒子。该方法的优点在于:(1)可以通过改变表面活性剂类型及含量调控AIE聚合物纳米粒子的粒径;(2)AIE聚合物纳米粒子的发光颜色和荧光强度可以简便通过AIE分子类型和用量来调控;(3)本制备方法操作简便,重复性好,容易工业放大,有望在防伪材料、体外诊断和细胞成像等领域大规模商用。
附图说明
图1为实施例1所制的AIE聚合物纳米粒子的扫描电镜图。
图2为实施例1所的AIE聚合物纳米粒子乳液荧光发射光谱图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不限于此。
实施例1
称取十二烷基硫酸钠0.05g,溶于12.5g水中,用作连续相的乳化剂水溶液。
将0.001g AIE-14分子、0.06g正十六烷和0.1g聚甲基丙烯酸甲酯溶解在4mL二氯甲烷溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声10min,超声功率为400W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌(图1),结果显示AIE聚合物纳米粒子为球形结构,粒径约为70nm。AIE聚合物纳米粒子的最大发射波长在550nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的橙黄色荧光(图2)。
实施例2
称取十六烷基三甲基氯化铵0.2g,溶于50g水中,用作连续相的乳化剂水溶液。
将0.004g AIE-18分子、0.04g正十六烷和0.4g聚乳酸-羟基乙酸共聚物溶解在16mL乙酸乙酯溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声8min,超声功率为450W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为60nm。AIE聚合物纳米粒子的最大发射波长在697nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的红色荧光。
实施例3
称取聚乙烯醇2g,溶于100g水中,用作连续相的乳化剂水溶液。
将0.008g AIE-6分子、0.08g正十六烷和0.8g磷脂聚乙二醇马来酰亚胺溶解在30mL三氯甲烷溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声6min,超声功率为500W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为160nm。AIE聚合物纳米粒子的最大发射波长在590nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的橙红色荧光。
实施例4
称取吐温-20表面活性剂2g,溶于250g水中,用作连续相的乳化剂水溶液。
将0.020g AIE-26分子、0.2g正十六烷和2g聚醋酸乙烯酯溶解在50mL甲苯溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声12min,超声功率为550W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为180nm。AIE聚合物纳米粒子的最大发射波长在705nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的红色荧光。
实施例5
称取O-50表面活性剂10g,溶于500g水中,用作连续相的乳化剂水溶液。
将0.050g AIE-8分子、0.5g正十六烷和5g聚醋酸乙烯酯溶解在80mL甲苯溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声12min,超声功率为600W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为240nm。AIE聚合物纳米粒子的最大发射波长在603nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的红色荧光。
实施例6
称取十二烷基硫酸钠表面活性剂0.02g,溶于12.5g水中,用作连续相的乳化剂水溶液。
将0.050g AIE-7分子、0.5g正十六烷和5g聚醋酸乙烯酯溶解在3mL二氯甲烷溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声10min,超声功率为380W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为90nm。AIE聚合物纳米粒子的最大发射波长在460nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的蓝色荧光。
实施例7
称取十六烷基三甲基氯化铵表面活性剂0.005g,溶于12.5g水中,用作连续相的乳化剂水溶液。
将0.004g AIE-13分子、0.04g正十六烷和0.3g聚醋酸乙烯酯溶解在2mL二氯甲烷溶剂中,用作分散相的油性溶液。将两种溶液混合并在700rpm磁力搅拌下,在水浴锅中预乳化15min,得到粗乳液。粗乳液在冰水浴中超声10min,超声功率为425W,脉冲序列为工作12s、间隙6s,获得稳定的细乳液液滴。把AIE聚合物纳米粒子乳液放入旋转蒸发仪中,在低压环境下除掉溶剂溶剂,得到AIE聚合物纳米粒子乳液。将乳液离心,再重新分散在水中,按照此方法循环三次,得到纯化后的AIE聚合物纳米粒子。
通过扫描电子显微镜观察AIE聚合物纳米粒子的形貌,结果显示AIE聚合物纳米粒子为球形结构,粒径约为150nm。AIE聚合物纳米粒子的最大发射波长在550nm,并且在365nm紫外灯激发下,AIE聚合物纳米粒子显示出明亮的黄色荧光。
以上实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种聚集诱导发光聚合物纳米粒子的制备方法,其特征在于,包括以下步骤,
(1)将乳化剂溶于去离子水中,得到水相溶液;
(2)将AIE分子、助稳定剂和聚合物溶于与水不互溶的挥发性的溶剂中,得到油相溶液;
(3)将步骤(1)所制的水溶液加至步骤(2)所制的油相溶液中,混合搅拌进行预乳化,得到粗乳液;超声处理,制得细乳液液滴;挥发性的溶剂在减压条件下除去,制得AIE聚合物纳米粒子乳液;纯化处理后得到AIE聚合物纳米粒子。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述乳化剂为阴离子乳化剂、阳离子乳化剂、两性乳化剂和非离子乳化剂中的至少一种;所述乳化剂的质量用量为水质量用量的0.1%~10%。
4.根据权利要求3所述的制备方法,其特征在于,所述阴离子乳化剂选自下列至少一种:烷基苯磺酸盐乳化剂、烷基磺酸盐乳化剂和烷基硫酸盐乳化剂;所述阳离子乳化剂选自下列至少一种:烷基二甲基苄基卤化铵乳化剂、烷基三甲基卤化铵乳化剂;所述两性乳化剂选自下列至少一种:十二烷基氨基丙酸、十八烷基二羟乙基氧化胺、羧酸基甜菜碱、磺酸基甜菜碱;所述非离子型乳化剂选自下列至少一种:OP-系列乳化剂、O系列乳化剂、聚乙二醇、吐温系列乳化剂和聚乙烯醇系列;所述的乳化剂质量用量为水质量用量的0.2%~8%。
5.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述助稳定剂选自下列至少一种:C14~C22的脂肪烃、C14~C22的脂肪醇;步骤(2)所述聚合物选自下列至少一种:聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯、聚乙烯基甲醚、聚乙烯醇、聚醋酸乙烯酯、聚氯乙烯、聚丙烯、聚丙烯酸、聚丙烯酸乙酯、聚丙烯酰胺、聚丙烯腈、聚乳酸-羟基乙酸共聚物、聚己内酰胺、聚(L-丙交酯)、聚己内酯、磷脂聚乙二醇、磷脂聚乙二醇氨基、磷脂聚乙二醇羧基、磷脂聚乙二醇马来酰亚胺;步骤(2)所述溶剂选自下列至少一种:辛烷、石油醚、二硫化碳、四氯化碳、乙烷、环乙烷、乙醚、乙酸乙脂、正己烷、二硫化碳、甲苯、三氯甲烷和二氯甲烷。
6.根据权利要求1所述的制备方法,其特征在于,步骤(2)所述AIE分子质量用量为聚合物总质量的0.1%~10%;助稳定剂质量用量为聚合物总质量的1%~10%;聚合物的质量用量为水总质量0.1%~20%;溶剂的质量用量为水总质量5%~40%。
7.根据权利要求6所述的制备方法,其特征在于,所述AIE分子的质量用量为聚合物质量用量的0.2%~5%;助稳定剂的质量用量为聚合物质量用量的4%~8%。
8.根据权利要求1所述的制备方法,其特征在于,步骤(3)中所述超声处理为将装乳液的容器置于冰水浴进行,超声功率为30W~900W,超声时间为0.5min~30min;步骤(3)中所述除去溶剂使用旋转蒸发仪在低压下除去;所述纯化处理为将乳液离心,再重新分散在水中,按照此方法循环三次到五次,得到纯化后的AIE聚合物纳米粒子。
9.权利要求1-8任一项所述的制备方法制得的聚集诱导发光聚合物纳米粒子。
10.权利要求9所述的聚集诱导发光聚合物纳米粒子在制备防伪材料、体外诊断试剂和细胞成像试剂的应用。
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