CN111808096A - 一种用于铜离子检测的新型配体及其制备、新型钌配合物和近红外长寿命荧光探针 - Google Patents
一种用于铜离子检测的新型配体及其制备、新型钌配合物和近红外长寿命荧光探针 Download PDFInfo
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Abstract
本发明提供了一种用于铜离子检测的新型配体及其制备、新型钌配合物和近红外长寿命荧光探针，结果表明，本发明提供的配体制备的配合物，发射波长在近红外区、激发态寿命长、生物相容性好，可以作为荧光探针或试纸应用于体外铜离子的检测，也可以作为荧光探针应用于体内铜离子的检测，进而应用于生命科学研究中的荧光生物成像领域，且检测限低；且该配合物的制备方法简单，适用于工业化生产，具有很好的工业应用前景。
Description
技术领域
本发明涉及配合物技术领域，尤其涉及一种用于铜离子检测的新型配体及其制备、新型钌配合物和近红外长寿命荧光探针。
背景技术
铜离子是人体高级器官必需的一种微量元素，在许多重要生理过程起着重要的作用。铜离子代谢异常与阿尔兹海默症、帕金森病等疾病的发生密切相关，铜离子检测试剂的研究对一些疾病的早期诊断有着重要意义。
目前铜离子的检测方法有原子吸收光谱、电感耦合原子发射光谱、电感耦合等离子体质谱、电化学方法、荧光光谱等。在众多方法中，荧光光谱作为一种灵敏、快速、高通量的方法被认为是最优的选择。目前已有多种铜离子荧光探针报道，如Hongping Zhou等报道了基于三苯胺骨架的荧光off-on探针(Sensors and Actuators B 206(2015)640)，C.Huang、T.Kaur,Org等报道了罗丹明类(Chem-Eur.J 14(2008)6892；Org Lett 14(2012)14 406),C.J.Fahrni等报道了冠醚类(Proc.Natl.Acad.Sci 102(2005)11179)。这些探针均可有效识别铜离子，但缺点是探针的合成步骤繁琐，检测限度低，发射波长短，荧光寿命一般只有几十个纳秒，无法实现深层组织的超分辨成像。因此研究出一种新型的可用于溶液及生物样本检测的近红外长寿命铜离子荧光探针是本领域技术人员亟待解决的技术问题。
发明内容
有鉴于此，本发明所要解决的技术问题在于提供一种配体及其配合物制备和应用，本发明提供的配合物作为铜离子检测的荧光探针荧光寿命长，生物相容性好，且制备工艺简单。
本发明提供了一种配体，具有式(I)所示结构，
本发明还提供了一种本发明所述的配体的制备方法，包括：
将2-咪唑甲醛和邻菲罗啉-5,6-二胺混合反应，得到式(I)所示结构的配体，
本发明还提供了一种配合物，由阴离子和阳离子构成，其特征在于，所述阳离子由主配体、辅助配体和过渡金属构成，
其中，所述主配体具有式(I)所示结构；
优选的，所述辅助配体为1,10-邻菲罗啉。
优选的，所述过渡金属为钌、锇、铑或铱。
优选的，所述阳离子的结构式如式(II)所示，
本发明还提供了一种本发明所述的配合物的制备方法，包括：
将式(I)结构的配体、含过渡金属的辅助配体和溶剂混合反应，得到配合物，
其中，所述主配体具有式(I)所示结构；
本发明还提供了一种本发明所述的配合物在制备检测铜离子用荧光探针中的应用。
本发明还提供了一种本发明所述的配合物在制备检测铜离子用试纸中的应用。
本发明还提供了一种本发明所述的配合物在制备检测细胞内铜离子用荧光探针中的应用。
与现有技术相比，本发明提供了一种配体及其配合物和应用，通过实验发现，本发明提供的配体制备的配合物，发射波长在近红外区、激发态寿命长，可达534纳秒、生物相容性好，可以作为荧光探针或试纸应用于体外铜离子的检测，也可以作为荧光探针应用于体内铜离子的检测，进而应用于生命科学研究中的荧光生物成像领域，且检测限低至24纳摩尔；且该配合物的制备方法简单，适用于工业化生产，具有很好的工业应用前景。
附图说明
图1为铜离子滴定Ru-2-pbm的缓冲液的荧光滴定结果；
图2为Ru-2-pbm在缓冲液中对金属离子的选择性实验的荧光曲线；
图3为Ru-2-pbm在缓冲液中对铜离子和其他金属离子的竞争性实验的荧光强度柱状图；
图4为Ru-2-pbm在缓冲液中与金属离子在365nm紫外灯下的荧光照片；
图5为Ru-2-pbm在缓冲液中的荧光寿命图。
具体实施方式
本发明提供了一种配体，具有式(I)所示结构，
本发明还提供了一种式(I)所示结构的配体的制备方法，包括：
将2-咪唑甲醛和邻菲罗啉-5,6-二胺混合反应，得到式(I)所示结构的配体，
按照本发明，本发明将2-咪唑甲醛和邻菲罗啉-5,6-二胺混合反应，得到式(I)所示结构的配体，其中，本发明对混合反应的溶剂没有特殊要求，如可以为乙醇；所述反应的温度60～90℃，更优选为70～80℃。
本发明还提供了一种配合物，由阴离子和阳离子构成，其中，所述阳离子由主配体、辅助配体和过渡金属构成，
其中，所述主配体具有式(I)所示结构；
本发明中，所述辅助配体优选为1,10-邻菲罗啉；所述过渡金属为钌、锇、铑或铱。
本发明中，所述阳离子的结构式如式(II)所示，
本发明中，本发明对阴离子的选择没有特殊要求，不影响配合物水溶型的离子均可，如可以为ClO4 -。
本发明还提供了一种本发明所述的配合物的制备方法，包括：
将式(I)结构的配体、含过渡金属的辅助配体、无机盐和溶剂混合反应，得到配合物，
其中，所述主配体具有式(I)所示结构；
按照本发明，本发明将式(I)结构的配体、含过渡金属的辅助配体、无机盐和溶剂混合反应，得到配合物，其中，所述含过渡金属的辅助配体优选为二(1,10-邻菲罗啉)-二氯-二水合钌，所述无机盐优选为NaClO4，所述溶剂优选为乙醇和水的混合溶液，其中，混合溶液中，乙醇和水的体积比为4:1。所述反应的温度优选为60～100℃，更优选为70～90℃，最优选为75～85℃；所述反应优选在氩气氛围下反应。
本发明还提供了一种本发明所述的配合物在制备检测铜离子用荧光探针中的应用。
本发明还提供了一种本发明所述的配合物在制备检测铜离子用试纸中的应用。
本发明还提供了一种本发明所述的配合物在制备检测细胞内铜离子用荧光探针中的应用。
本发明提供了一种配体的配体制备的配合物，发射波长在近红外区、激发态寿命长、生物相容性好，可以作为荧光探针或试纸应用于体外铜离子的检测，也可以作为荧光探针应用于体内铜离子的检测，进而应用于生命科学研究中的荧光生物成像领域。且该配合物的制备方法简单，适用于工业化生产，具有很好的工业应用前景。
下面将结合本发明实施例的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1配体2-pbm的合成
将1.2mmol(0.116g)的2-咪唑甲醛加热溶解于2.5mL的无水乙醇中，逐滴加入2.5mL溶有1.5mmol(0.314g)的邻菲罗啉-5,6-二胺的乙醇溶液，半个小时加完，混合液回流，反应6h，冷却、抽滤，得到的固体分别用无水乙醇，无水乙醚洗涤，真空干燥，得到配体2-pbm。
实施例2配合物(Ru-2-pbm)的制备
将0.142g(0.25mmol)cis-[Ru(phen)2Cl2]·2H2O和0.100g(0.25mmol)配体2-pbm在35mL乙醇-水(4:1)溶解，氩气氛围下回流6h，得红色反应液。冷却至室温，过滤，向滤液中滴加饱高氯酸钠溶液，得红色沉淀，静置、抽滤，水洗、乙醚洗，真空干燥，得到Ru-2-pbm配合物。
实施例3Ru-2-pbm2在缓冲液中的铜离子荧光滴定
配制浓度为1μmol/L的Ru-2-pbm的PBS溶液。向溶液中滴加氯化铜溶液(0.3mmol)，每次2μL，搅拌均匀，测试配合物Ru-2-pbm的荧光光谱，。重复滴加操作至连续滴加3次荧光强度不变为止。
结果如图1所示，图1为铜离子滴定Ru-2-pbm的缓冲液的荧光滴定结果；从图1可以看出，该配合物原溶液具有很强的荧光，随着铜离子的不断加入，荧光逐渐淬灭，当铜离子与配合物的浓度比达到4:1的时候，达到饱和此时荧光强度衰减近70％，通过铜离子荧光滴定，根据3δ/K可计算出其检测限为24nmol。
实施例4(Ru-2-pbm)在缓冲液中对各种金属离子的选择性
配制一系列Ru-2-pbm+M混合液(M＝Li+,Na+,K+,Ba2+,Ca2+,Mg2+,Co2+,Cd2+,Hg2+,Cr3 +,Mn2+,Zn2+,Fe3+,Pb2+，Cu2+,[Ru-2-pbm]＝2μmol,[Ru-2-pbm]:[M]＝1:4)，测试配合物Ru-2-pbm荧光光谱，并置于紫外灯下拍照。
结果如图2～图4所示，图2为Ru-2-pbm在缓冲液中对金属离子的选择性实验的荧光曲线；图3为Ru-2-pbm在缓冲液中对铜离子和其他金属离子的竞争性实验的荧光强度柱状图；图4为Ru-2-pbm在缓冲液中与金属离子在365nm紫外灯下的荧光照片；从图2～图4可以看出，Ru-2-pbm对铜离子的选择性明显高于其他金属离子，与铜离子作用后，荧光强度衰减明显。且在其他金属离子存在的情况下，该配合物也能特异性检测铜离子。
实施例5(Ru-2-pbm)在缓冲液中的荧光寿命
配制浓度为20mmol/L的Ru-2-pbm的DMSO母液，用PBS缓冲液稀释至5μmol/L,利用时间相关单光子记数法(Time-Correlated Single-Photon Counting，TCSPC)对探针进行荧光寿命检测，确定其激发态荧光寿命。结果如图5所示，图5为Ru-2-pbm在缓冲液中的荧光寿命图，经拟合可得出，其荧光寿命可达534纳秒，明显高于同类型其他铜离子荧光探针。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (10)
1.一种配体，具有式(I)所示结构，
2.一种权利要求1所述的配体的制备方法，包括：
将2-咪唑甲醛和邻菲罗啉-5,6-二胺混合反应，得到式(I)所示结构的配体，
3.一种配合物，由阴离子和阳离子构成，其特征在于，所述阳离子由主配体、辅助配体和过渡金属构成，
其中，所述主配体具有式(I)所示结构；
4.根据权利要求3所述的配合物，其特征在于，所述辅助配体为1,10-邻菲罗啉。
5.根据权利要求3所述的配合物，其特征在于，所述过渡金属为钌、锇、铑或铱。
6.根据权利要求3所述的配合物，其特征在于，所述阳离子的结构式如式(II)所示，
7.一种权利要求3所述的配合物的制备方法，包括：
将式(I)结构的配体、含过渡金属的辅助配体和溶剂混合反应，得到配合物，
其中，所述主配体具有式(I)所示结构；
8.一种权利要求3～6任意一项所述的配合物在制备检测铜离子用荧光探针中的应用。
9.一种权利要求3～6任意一项所述的配合物在制备检测铜离子用试纸中的应用。
10.一种权利要求3～6任意一项所述的配合物在制备检测细胞内铜离子用荧光探针中的应用。
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