CN115058010A - 一种核壳型高发光聚集诱导发光纳米粒子及其制备方法 - Google Patents
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Abstract
本发明涉及一种高发光聚集诱导发光纳米粒子,特别是一种核壳型聚集诱导发光(AIE)二氧化硅纳米粒子及其制备方法。该方法具体包括前驱体溶液的制备等步骤,具体包括本发明将一种AIE分子与3‑氨基丙基三甲氧基硅烷(APTMS)反应制成前驱体,然后采用油包水微乳液法,获得一种新型聚集诱导发光分子掺杂的二氧化硅荧光纳米粒子。所制得的纳米颗粒呈球形,具有分散性好、光稳定性好、生物相容性好且不易发生染料泄漏等特点。
Description
技术领域
本发明属于荧光纳米材料合成领域,具体涉及一种核壳型高发光聚集诱导发光纳米粒子及其制备方法。
背景技术
染料掺杂型二氧化硅荧光纳米粒子可用作细胞染色、免疫检测、药物传输及DNA示踪等的纳米探针,在生命科学领域的应用越来越受到重视。由于在一个纳米粒子中可掺杂多个染料分子,这类纳米探针相对于已得到广泛应用的荧光分子探针如FITC等,但是传统的荧光分子存在聚集导致淬灭现象,会影响其发光强度,从而降低其灵敏度。
唐本忠院士团队发现的“聚集诱导发光”(AIE)材料由于分子内受限的机理,使得其在分散状态下不发光,但在特定的底物下可诱导形成聚集体,并且荧光效率显著增加,从而可实现对刺激源的定性和定量分析,使得高灵敏度的传感监测变得更加容易。此外,由于二氧化硅的亲水性以及生物相容性,使得染料为核二氧化硅为壳的结构将染料与检测液隔开,可有效抑制检测液极性对染料发光波长的漂移和对发光强度的猝灭效应,并降低染料的光漂白,并能用作细胞分析的探针,对细胞生物学行为进行监测。因此,聚集诱导发光分子掺杂的荧光纳米粒子用作细胞分析的探针具有良好的应用前景。
发明内容
本发明的目的之一是旨在提供一种核壳型聚集诱导发光二氧化硅纳米粒子。
本发明的目的之二是旨在提供该核壳型荧光纳米粒子的制备方法。
为实现以上目的,本发明采用的制备机理为:
根据以上原理,本发明采用以下技术方案:
本发明提供一种核壳型高发光聚集诱导发光纳米粒子,该纳米粒子是AIE分子通过其分子中的活性官能团羰基与3-氨基丙基三甲氧基硅烷分子的氨基发生反应生成Schiff碱,然后在氨水作用下,该Schiff碱与正硅酸乙酯共水解后发生聚合反应而形成的核壳性纳米粒子,其结构式为:
本发明还提供上述核壳型高发光聚集诱导发光纳米粒子的制备方法,该方法的具体步骤为:
(1)AIE分子与APTMS反应制得前驱体AIE-APTMS;
(2)将环己烷、Triton X-100、正己醇按5:1:1~10:1:1的体积比混合形成混合液,再将该混合液与去离子水按60:1~20:1的体积比混合,形成清澈透明的微乳液;
(3)将步骤(1)所得的前驱体AIE-APTMS加入上述微乳液中,充分搅拌混匀,并控制前驱体与微乳液的质量比为1:5~1:10,充分搅拌混匀,加入正硅酸乙酯,其与前驱体的用量体积比为1:5~5:10,然后加入氨水,其与正硅酸乙酯体积比为1:5~5:5,室温避光磁力搅拌反应24-72小时后加入丙酮破乳,再用无水乙醇和超纯水交替离心、洗涤,得到纯的AIE-APTMS/SiO2核壳型荧光纳米粒子,最后将该荧光纳米粒子烘干。
本发明的有益效果在于:
本发明将AIE分子与APTMS反应制成前驱体AIE-APTMS,采用油包水微乳液法,制得了一种新型的AIE分子掺杂的二氧化硅核壳纳米颗粒。由于APTMS与正硅酸乙酯的共水解与聚合作用,使AIE分子通过化学键与二氧化硅外壳相连接,有效地防止了AIE染料分子的泄漏,同时硅壳的保护作用,提高了染料的化学稳定性与光稳定性。
附图说明
图1为本发明合成的150nm AIE-APTMS/SiO2核壳型二氧化硅荧光纳米粒子的透射电镜图。
图2为本发明合成的300nm AIE-APTMS/SiO2核壳型二氧化硅荧光纳米粒子的透射电镜图。
具体实施方式
实施例1:150nm AIE-APTMS/SiO2核壳型二氧化硅荧光纳米粒子的合成
(1)AIE分子与APTMS反应制得前驱体AIE-APTMS;
(2)将环己烷、Triton X-100、正己醇按5:1:1的体积比混合形成混合液,再将该混合液与去离子水按60:1~50:1的体积比混合,形成清澈透明的微乳液;
(3)将步骤(1)所得的前驱体AIE-APTMS加入上述微乳液中,充分搅拌混匀,并控制前驱体与微乳液的质量比为1:10,充分搅拌混匀,加入正硅酸乙酯,其与前驱体的用量体积比为1:5,然后加入氨水,其与正硅酸乙酯体积比为2:5,室温避光磁力搅拌反应24小时后加入丙酮破乳,再用无水乙醇和超纯水交替离心、洗涤,得到AIE-APTMS/SiO2核壳型荧光纳米粒子,最后将该荧光纳米粒子烘干。
实施例2:300nm AIE-APTMS/SiO2核壳型二氧化硅荧光纳米粒子的合成
(1)AIE分子与APTMS反应制得前驱体AIE-APTMS;
(2)将环己烷、Triton X-100、正己醇按6:1:1的体积比混合形成混合液,再将该混合液与去离子水按60:1的体积比混合,形成清澈透明的微乳液;
(3)将步骤(1)所得的前驱体AIE-APTMS加入上述微乳液中,充分搅拌混匀,并控制前驱体与微乳液的质量比为1:8,充分搅拌混匀,加入正硅酸乙酯,其与前驱体的用量体积比为5:10,然后加入氨水,其与正硅酸乙酯体积比为4:5,室温避光磁力搅拌反应24小时后加入丙酮破乳,再用无水乙醇和超纯水交替离心、洗涤,得到AIE-APTMS/SiO2核壳型荧光纳米粒子,最后将该荧光纳米粒子烘干。
本发明的上述实施例是对本发明的说明而不能限制本发明,与本发明的权利要求书相当的含义和范围内的任何变化,都应认为是包括在权利要求书的范围内。
Claims (3)
3.一种如权利要求1-2任一项所述的核壳型高发光聚集诱导发光纳米粒子的制备方法,其特征在于:该方法的具体步骤为:
(1)AIE分子与APTMS反应制得前驱体AIE-APTMS;
(2)将环己烷、Triton X-100、正己醇按5:1:1~10:1:1的体积比混合形成混合液,再将该混合液与去离子水按60:1~20:1的体积比混合,形成清澈透明的微乳液;
(3)将步骤(1)所得的前驱体AIE-APTMS加入上述微乳液中,充分搅拌混匀,并控制前驱体与微乳液的质量比为1:5~1:10,充分搅拌混匀,加入正硅酸乙酯,其与前驱体的用量体积比为1:5~5:10,然后加入氨水,其与正硅酸乙酯体积比为1:5~5:5,室温避光磁力搅拌反应24-72小时后加入丙酮破乳,再用无水乙醇和超纯水交替离心、洗涤,得到纯的AIE-APTMS/SiO2核壳型荧光纳米粒子,最后将该荧光纳米粒子烘干。
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CN1392097A (zh) * | 2002-05-28 | 2003-01-22 | 湖南大学 | 氨基化硅壳类纳米颗粒材料及其制备工艺方法 |
CN101913611A (zh) * | 2010-03-17 | 2010-12-15 | 上海大学 | 一种简便的制备尺寸可控的单分散的纳米二氧化硅颗粒的方法 |
CN102120168A (zh) * | 2010-12-07 | 2011-07-13 | 复旦大学 | 多功能核壳结构荧光编码磁性微球及其制备方法 |
CN110143765A (zh) * | 2019-05-16 | 2019-08-20 | 辽宁师范大学 | 以两亲性aie分子制备的荧光二氧化硅膜及制备方法 |
US20210269707A1 (en) * | 2020-03-02 | 2021-09-02 | Hangzhou Shinedo Biotech Co., Ltd. | Method for preparing fluorescent-encoded microspheres coated with metal nanoshells |
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CN1392097A (zh) * | 2002-05-28 | 2003-01-22 | 湖南大学 | 氨基化硅壳类纳米颗粒材料及其制备工艺方法 |
CN101913611A (zh) * | 2010-03-17 | 2010-12-15 | 上海大学 | 一种简便的制备尺寸可控的单分散的纳米二氧化硅颗粒的方法 |
CN102120168A (zh) * | 2010-12-07 | 2011-07-13 | 复旦大学 | 多功能核壳结构荧光编码磁性微球及其制备方法 |
CN110143765A (zh) * | 2019-05-16 | 2019-08-20 | 辽宁师范大学 | 以两亲性aie分子制备的荧光二氧化硅膜及制备方法 |
US20210269707A1 (en) * | 2020-03-02 | 2021-09-02 | Hangzhou Shinedo Biotech Co., Ltd. | Method for preparing fluorescent-encoded microspheres coated with metal nanoshells |
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