CN111349067B - 一类聚集诱导发光型荧光材料及其制备方法 - Google Patents

一类聚集诱导发光型荧光材料及其制备方法 Download PDF

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CN111349067B
CN111349067B CN201811567762.4A CN201811567762A CN111349067B CN 111349067 B CN111349067 B CN 111349067B CN 201811567762 A CN201811567762 A CN 201811567762A CN 111349067 B CN111349067 B CN 111349067B
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李楠
赵娜
尹伟
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Abstract

本发明公开了一类聚集诱导发光型荧光材料及其制备方法，该荧光材料的结构通式为
Figure DDA0001914695270000011
式中R代表H、C1～C4烷基、C1～C3烷氧基、卤素中任意一种，其是将N,N‑二芳基香豆素与三氯氧磷反应制备得到。本发明基于N,N‑二芳基香豆素的简单骨架，通过与三氯氧磷反应，合成了一系列具有聚集诱导发光性的荧光材料。该类荧光材料发射波长可从550nm到578nm，在有机溶剂中具有良好的溶解性，而在水中几乎不溶解，在水相中可形成聚集体，具有显著的聚集诱导发光特性，可实现对细胞、组织以及细菌进行成像，对蛋白进行糖基化分析，以及对离子进行检测等。

Description

一类聚集诱导发光型荧光材料及其制备方法
技术领域
本发明属于生物医学用荧光材料技术领域，具体涉及一类具有聚集诱导发光性质的荧光材料，以及该荧光材料的制备方法。
背景技术
荧光材料由于在光电器件、环境传感器、生物科学等领域具有重大的应用价值，近年来引起了科学家们的极大关注。荧光检测不仅具有很高的灵敏度，而且克服了在生物化学试验上需要昂贵和操作难的放射性追踪试剂的一系列问题。随着荧光在细胞和分子成像方面的应用研究增加，荧光成像揭示了对细胞内分子的定位和测量，并且有时会实现单个分子水平的检测。目前，有很多关于线粒体生物成像的文献报道，生物成像的研究也吸引了科研工作者的兴趣，但是传统的荧光材料在高浓度时易荧光猝灭且固体量子产率低。随着高发射效率、强的耐光性、良好生物相容性的聚集诱导发光(AIE)荧光材料的发展，大量的AIE荧光材料被用于生物成像。
发明内容
本发明的目的是提供一类具有聚集诱导发光性能的荧光材料，并为该荧光材料提供一种制备方法。
针对上述目的，本发明所采用的荧光材料的结构通式如下所示：
Figure BDA0001914695250000011
式中R代表H、C1～C4烷基、C1～C3烷氧基、卤素中任意一种，优选R代表H、CH3、OCH3、I、Br中任意一种。
本发明荧光材料的制备方法为：以N,N-二甲基甲酰胺为溶剂，在氮气保护下，将式I所示的N,N-二芳基香豆素与三氯氧磷在50～70℃下反应至完全，分离纯化产物，得到II所示的聚集诱导发光型荧光材料。
Figure BDA0001914695250000021
上述制备方法中，优选所述N,N二芳基水杨醛与三氯氧磷的摩尔比为1:8～10。
本发明的有益效果如下：
本发明基于N,N-二芳基香豆素的简单骨架，通过与三氯氧磷反应，合成了一系列具有聚集诱导发光性的荧光材料。该类荧光材料发射波长可从550nm到578nm，在有机溶剂中具有良好的溶解性，而在水中几乎不溶解，在水相中可形成聚集体，具有显著的聚集诱导发光特性，可实现对细胞、组织以及细菌进行成像，对蛋白进行糖基化分析，以及对离子进行检测等。
附图说明
图1是实施例1制备的荧光材料在乙腈与水混合体系中的荧光发射光谱图。
图2是实施例1制备的荧光材料在乙腈与水混合体系中的相对荧光强度图。
图3是实施例2制备的荧光材料在乙腈与水混合体系中的荧光发射光谱图。
图4是实施例2制备的荧光材料在乙腈与水混合体系中的相对荧光强度图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
在氮气保护下，将668μL N,N-二甲基甲酰胺滴加到690μL(8.5mmol)POCl3中，室温搅拌30min，得红色溶液，然后将所得红色溶液加入到3mL含341mg(1mmol)N,N-二苯基香豆素(化合物I-1)的N,N-二甲基甲酰胺溶液中，在60℃下搅拌反应24h，然后加入冰水淬灭反应，用NaOH调pH＝5.2，减压浓缩、柱层析(洗脱剂为石油醚与乙酸乙酯体积比为40:1混合液)，得到式II-1所示的荧光材料，其产率为52％。
Figure BDA0001914695250000031
所得荧光材料的结构表征数据为：1H NMR(300MHz,CDCl3)δ10.16(s,1H),8.28(s,1H),7.39(dd,J＝12.6,4.9Hz,5H),7.29(s,1H),7.25-7.17(m,5H),6.84(dd,J＝8.8,2.2Hz,1H),6.73(d,J＝2.1Hz,1H).
实施例2
本实施例中，用等摩尔量的N,N-二甲苯基香豆素(化合物I-2)替换实施例1中的N,N-二苯基香豆素，其他步骤与实施例1相同，得到式II-2所示的荧光材料，其产率为47％。
Figure BDA0001914695250000032
所得荧光材料的结构表征数据为：1H NMR(300MHz,CDCl3)δ10.14(s,1H),8.26(s,1H),7.34(d,J＝8.8Hz,1H),7.15(dd,J＝28.4,8.3Hz,8H),6.78(dd,J＝8.8,2.1Hz,1H),6.67(d,J＝2.1Hz,1H),2.37(s,6H).
发明人对上述实施例1～2制备的荧光材料进行了聚集诱导发光性能测试，具体测试方法为：配制含水量分别为0％、10％、30％、50％、70％、90％、95％、99％的乙腈水溶液，将荧光材料加入所得溶液中，得到浓度为1×10-5mol/L的荧光材料溶液，采用日立F-7000荧光分光光度计测试荧光材料的聚集诱导发光性质，结果见图1～4。由图可见，本发明实施例1～2得到的荧光材料均具有聚集诱导发光性质。

Claims (4)

1.一类聚集诱导发光型荧光材料，其特征在于该荧光材料的结构通式如下所示：
Figure DEST_PATH_IMAGE002
式中R代表H、C1～C4烷基、C1～C3烷氧基、卤素中任意一种。
2.根据权利要求1所述的聚集诱导发光型荧光材料，其特征在于：所述的R代表H、CH3、OCH3、I、Br中任意一种。
3.一种权利要求1所述的聚集诱导发光型荧光材料的制备方法，其特征在于：以N,N-二甲基甲酰胺为溶剂，在氮气保护下，将式I所示的N,N-二芳基香豆素与三氯氧磷在50～70℃下反应至完全，分离纯化产物，得到II所示的聚集诱导发光型荧光材料；
Figure DEST_PATH_IMAGE004
式Ⅰ和Ⅱ中，R代表H、C1～C4烷基、C1～C3烷氧基、卤素中任意一种。
4.根据权利要求3所述的聚集诱导发光型荧光材料的制备方法，其特征在于：所述N,N-二芳基香豆素与三氯氧磷的摩尔比为1:8～10。
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