CN106496260A - 一种噁二唑三苯胺‑氟硼二吡咯红光化合物opa‑bodipy及其制备方法和应用 - Google Patents
一种噁二唑三苯胺‑氟硼二吡咯红光化合物opa‑bodipy及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种噁二唑三苯胺‑氟硼二吡咯红光化合物OPA‑BODIPY。本发明还公开了该噁二唑三苯胺‑氟硼二吡咯红光化合物OPA‑BODIPY的制备方法及其应用。本发明的新型化合物OPA‑BODIPY是包含2,5‑二苯基噁二唑、三苯胺及1,3,5,7‑四甲基氟硼二吡咯3种复合荧光基团的树形红光染料，固态及水溶液中发射红色荧光，具有优良的聚集诱导荧光增强性能。可作为性能优异的红光染料，在近红外荧光成像、荧光传感器、生物荧光分析、荧光标记等领域具有广泛应用。
Description
技术领域
本发明涉及荧光化合物及其制备方法和应用领域，具体涉及一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY及其制备方法和应用。
背景技术
氟硼二吡咯荧光分子的摩尔消光系数大，荧光量子产率高，稳定好，具有优良的光学性能，可用于荧光传感器及生物荧光分析领域，但现有技术中氟硼二吡咯衍生物发射波长大部分均小于600nm，且在聚集态荧光淬灭，限制了其应用范围。发展高效便捷的有机合成方法对氟硼二吡咯进行结构修饰，制备聚集诱导荧光增强，且发射波长位于红光或近红外区域的氟硼二吡咯类荧光化合物是近期的研究热点。
噁二唑三苯胺-氟硼二吡咯红光化合物在文献中鲜有报道，其荧光性能优异，荧光量子效率高，具有优良的聚集诱导荧光增强性能，发射很强的红色荧光，生物相容性好，可作为长波长的红光染料，在荧光传感器、生物荧光分析、荧光标记等领域具有广泛应用。
发明内容
发明目的：本发明所要解决的第一个技术问题是提供了一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY。
本发明所要解决的第二个技术问题是提供了一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备方法。
本发明所要解决的第三个技术问题是提供了一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的应用。
本发明制备得到一种新型噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY。该红光化合物在现有技术中未见报道，其荧光性能优异，荧光量子效率高，具有良好的聚集诱导荧光增强性质，发射很强的红色荧光，可作为长波长的红光染料用于制备染料负载的二氧化硅荧光纳米粒子，在细胞成像、荧光传感器、生物荧光分析、荧光标记等领域具有广泛应用。
技术方案：为了解决上述技术问题，本发明提供了一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY，由如下结构式构成：
上述噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备方法，所述噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY，由如下步骤实现：在无水无氧及氮气保护下，将碘代三苯胺-氟硼二吡咯IPA-BODIPY与2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑、醋酸钯、三(邻甲基苯基)膦、无水磷酸钾按摩尔比1：2.4～2.8：0.10～0.12：0.20～0.24：2.4～2.8加入到干燥N,N-二甲基甲酰胺中，搅拌加热，温度控制在110～120℃，反应时间48小时，结束反应，经萃取、干燥、柱色谱提纯，得到噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY。
具体反应式如下：
其中，化合物碘代三苯胺-氟硼二吡咯IPA-BODIPY以4-{N,N-二[4-碘代苯基]氨基}苯甲醛为原料，在氮气保护下与2,4-二甲基吡咯反应制备得到。
化合物2,4-二甲基吡咯按文献方法制备(Ge Meng,Mei-Lin Zheng,and MeiWang.An improved two-step preparationof 2,4-dimethylpyrrole.Organicprepararions and procedures international.2011,43,308～311)。
本发明的新型化合物是包含2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑共轭双臂、三苯胺及1,3,5,7-四甲基氟硼二吡咯3种荧光基团的树形红光化合物，其中荧光团构成比例氟硼二吡咯：三苯胺：噁二唑为1:1:2。
上述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在作为聚集诱导发光材料方面的应用。
上述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY作为长波长的红光染料在肿瘤细胞的非治疗和诊断目的的成像方面的应用。
上述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在作为染料负载荧光纳米粒子制备方面的应用。
有益效果：本发明具有以下优点：本发明的树形红光分子OPA-BODIPY的结构、合成、荧光性质及应用在现有技术中未见报道，其荧光性能优异，发射很强的红色荧光，荧光量子效率高，荧光发射波长大于600nm，并且具有良好的聚集诱导荧光增强性能。OPA-BODIPY固态时发射红光，最大发射波长为614nm；在四氢呋喃等纯有机溶剂中发射红色荧光，最大发射波长为647nm；在水/四氢呋喃混合溶剂中发射红色荧光，且随含水量增加荧光增强，在含水量90％混合溶剂中荧光最强，最大发射波长为630nm；负载BCPA-BODIPY染料的二氧化硅荧光纳米粒子发射很强的红色荧光。本发明的咔唑基三苯胺-氟硼二吡咯可作为红光染料用于制备染料负载的二氧化硅荧光纳米粒子，在非治疗和诊断目的的细胞成像、荧光传感器、生物荧光分析、荧光标记等领域具有广泛应用。
附图说明
图1为噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的固体荧光光谱；
图2为噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在水/四氢呋喃混合溶液中不同含水量时荧光发射强度变化图(其中OPA-BODIPY浓度为10-5mol/L，I0为OPA-BODIPY在四氢呋喃中的荧光强度，I为OPA-BODIPY在不同含水量混合溶剂中的荧光强度。)
图3为噁二唑三苯胺-氟硼二吡咯红光染料OPA-BODIPY与乳腺癌细胞MDA-MB-231共同孵化后的激光共聚焦荧光显微照片(红光成像)。
具体实施方式：
以下通过具体实施例对本发明作进一步详细说明。
实施例1噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备
在无水无氧及氮气保护下，将碘代三苯胺-氟硼二吡咯IPA-BODIPY(0.372g,0.50mmol)与2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑(0.37g,1.20mmol)、醋酸钯(0.011g,0.050mmol)、三(邻甲基苯基)膦(0.030g,0.10mmol)、无水磷酸钾(0.25g,1.20mmol)按摩尔比1：2.4：0.1：0.2：2.4反应，加入到干燥N,N-二甲基甲酰胺中，搅拌加热，温度控制在110℃，反应时间48小时。结束反应，经萃取，干燥，柱色谱提纯，得到噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY。
化合物OPA-BODIPY的合成路线如下：
其中，化合物碘代三苯胺-氟硼二吡咯IPA-BODIPY以4-{N,N-二[4-碘代苯基]氨基}苯甲醛为原料，在氮气保护下与2,4-二甲基吡咯反应制备得到。氮气保护及磁力搅拌下，将N,N-二(4-碘苯基)氨基苯甲醛(0.5g,1.0mmol,)，2,4-二甲基吡咯(0.21g,2.2mmol,)均匀溶于100mL二氯甲烷中，滴加一滴三氟乙酸溶液，常温反应8h，接着将四氯苯醌(0.27g,1.1mmol)加入到反应体系中继续反应5h，然后依次滴加3mL三乙胺以及4mL三氟化硼乙醚，反应12h。萃取，干燥，柱色谱提纯得到碘代三苯胺-氟硼二吡咯IPA-BODIPY(carbazol-N-yl)-triphenylamine-BODIPY)。
化合物2,4-二甲基吡咯按文献方法制备(Ge Meng,Mei-Lin Zheng,and MeiWang.An improved two-step preparationof 2,4-dimethylpyrrole.Organicprepararions and procedures international.2011,43,308～311)。
分析所得化合物OPA-BODIPY：
核磁共振氢谱1H NMR(CDCl3,ppm):δ8.14～8.06(m,8H),7.56(d,J＝9.00Hz,4H),7.57(d,J＝9.00Hz,4H),7.51(d,J＝9.00Hz,4H),7.26(s,2H),7.21～7.06(m,10H),6.03(s,2H),2.57(s,6H),1.62(s,6H),1.38(s,18H)。
核磁共振碳谱13C NMR(CDCl3,ppm):δ164.59,164.27,155.46,155.35,147.79,146.92,142.80,140.71,132.08,130.08,129.52,129.25,127.97,127.26,126.84,126.78,126.54,126.05,124.53,124.36,122.53,121.28,121.15,35.09,31.12,14.5。
所获得红光化合物OPA-BODIPY的结构式为：
实施例2噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备
与实施例1基本一样，所不同的在于，本实施例中的碘代三苯胺-氟硼二吡咯IPA-BODIPY与2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑、醋酸钯、三(邻甲基苯基)膦、无水磷酸钾按摩尔比1：2.8：0.12：0.24：2.8；反应温度控制在120℃。
实施例3噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备
与实施例1基本一样，所不同的在于，本实施例中的碘代三苯胺-氟硼二吡咯IPA-BODIPY与2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑、醋酸钯、三(邻甲基苯基)膦、无水磷酸钾按摩尔比1：2.6：0.11：0.22：2.6；反应温度控制在115℃。
实施例4噁二唑三苯胺-氟硼二吡咯OPA-BODIPY的红色固体荧光
噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY固态时发射红光，最大发射波长为614nm。在暗室中紫外灯下BCPA-BODIPY固体态发出很强的红色荧光。附图1为本发明实施例1制备的噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY的固体荧光光谱。
实施例5噁二唑三苯胺-氟硼二吡咯OPA-BODIPY的聚集诱导荧光增强
噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY在四氢呋喃等纯有机溶剂中发射红色荧光，最大发射波长为647nm；在水/四氢呋喃混合溶剂中发射红色荧光，且随含水量增加荧光增强，混合溶剂中含水量达到90％时荧光最强，最大发射波长为630nm。附图2为噁二唑三苯胺-氟硼二吡咯荧光染料OPA-BODIPY在水/四氢呋喃混合溶液中不同含水量时荧光发射强度变化图(其中OPA-BODIPY浓度为10-5mol/L，I0为OPA-BODIPY在四氢呋喃中的荧光强度，I为OPA-BODIPY在不同含水量混合溶剂中的荧光强度。)本发明的实例化合物噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY，荧光性能优良，发射红色荧光，具有聚集诱导发光增强性能，可作为性能优异的近红外荧光染料。
实施例6噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY用于非治疗和诊断目的的细胞成像
将噁二唑三苯胺-氟硼二吡咯荧光染料OPA-BODIPY与乳腺癌细胞MDA-MB-231共同孵化后在激光共聚焦荧光显微镜下观察MDA-MB-231细胞成像照片。附图3为MDA-MB-231细胞与近红外荧光染料OPA-BODIPY共同孵化后的激光共聚焦荧光成像照片。在MDA-MB-231细胞中加入荧光分子OPA-BODIPY共同孵化后，红光染料进入MDA-MB-231细胞内部，在红光区域清晰成像。噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY可作为性能优良的经红外荧光染料用于非治疗和诊断目的的肿瘤细胞成像。
实施例7 OPA-BODIPY红光染料负载荧光纳米微球的制备方法
保持0℃，在超声反应器中将0.44g二(2-乙基己基)琥珀酸磺酸钠溶于20mL去离子水中，搅拌下加入0.8mL正丁醇，缓慢滴加溶有0.5mg噁二唑三苯胺-氟硼二吡咯荧光染料OPA-BODIPY的60μL DMF溶液。滴加完毕后继续超声3min，加入0.2mL乙烯基三乙氧基硅烷，室温下搅拌8h，接着滴加20μL 3-氨基丙基三乙氧基硅烷后室温下搅拌24h。反应结束后透析72h得到噁二唑三苯胺-氟硼二吡咯OPA-BODIPY红光染料负载的荧光纳米微球，在5℃保存使用。
负载OPA-BODIPY染料的二氧化硅荧光纳米粒子发射很强的红色荧光，负载OPA-BODIPY染料的二氧化硅荧光纳米粒子易溶于水中，表面富含大量活性氨基，易于修饰，生物相容性好，荧光性质优良，可作为生物分子近红外荧光探针用于生物荧光分析、药物高通量筛选等生命科学领域。
本发明的实例化合物噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY，荧光性能优良，发射很强的红色荧光，具有聚集诱导发光增强性能，可用于制备染料负载的二氧化硅荧光纳米粒子，可作为长波长红光染料用于非治疗和诊断目的的肿瘤细胞荧光成像，在细胞成像、荧光传感器、生物荧光分析、荧光标记、药物高通量筛选等领域具有广泛应用。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY，其特征在于，由如下结构式构成：
2.权利要求1所述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY的制备方法，其特征在于，由如下步骤实现：在无水无氧及氮气保护下，将碘代三苯胺-氟硼二吡咯IPA-BODIPY与2-(4-叔丁基苯基)-5-(4-乙烯基苯基)-[1,3,4]-噁二唑、醋酸钯、三(邻甲基苯基)膦、无水磷酸钾按摩尔比1：2.4～2.8：0.10～0.12：0.20～0.24：2.4～2.8加入到干燥N,N-二甲基甲酰胺中，搅拌加热，温度控制在110～120℃，反应时间48小时，结束反应，经萃取、干燥、柱色谱提纯，得到噁二唑三苯胺-氟硼二吡咯荧光分子OPA-BODIPY；该过程的反应式如下：
3.权利要求1所述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在作为聚集诱导发光材料方面的应用。
4.权利要求1所述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在作为红光染料在肿瘤细胞的非治疗和诊断目的的成像方面的应用。
5.权利要求1所述的噁二唑三苯胺-氟硼二吡咯红光化合物OPA-BODIPY在作为染料负载荧光纳米粒子制备方面的应用。
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