CN108047260B - 一种生物识别检测材料bodipy类化合物及其用途 - Google Patents

一种生物识别检测材料bodipy类化合物及其用途 Download PDF

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CN108047260B
CN108047260B CN201711482164.2A CN201711482164A CN108047260B CN 108047260 B CN108047260 B CN 108047260B CN 201711482164 A CN201711482164 A CN 201711482164A CN 108047260 B CN108047260 B CN 108047260B
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严润达
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Abstract

本申请公开了锰离子探针及其合成方法，该锰离子探针采用氟硼二吡咯荧光染料和4‑N,N‑二乙酰胺醇苯甲醛合成而成，由于4‑N,N‑二乙酰胺醇苯甲醛具有良好的水溶性，因此该锰离子探针在水溶液中对Mn2+表现出高度的选择性和敏感度。

Description

一种生物识别检测材料BODIPY类化合物及其用途
技术领域
本申请涉及一种新的近红光氟硼吡咯二甲川衍生物及其制备方法，属于荧光探针方面的内容，能够作为锰离子响应的荧光探针。
背景技术
近年来，在现代生物技术和生命科学研究的诸多检测识别方法中，荧光分析方法由于其灵敏度高，选择性好，检出限低等优点，在生物化学分析领域有着不可替代的作用。因此，使用人工设计合成的荧光探针选择性的检测和识别生态环境及生物系统中的重要离子，尤其是重金属离子受到诸多科学研究者的广泛关注。锰离子在工业上有着广泛的应用，同时，锰离子又是维持人体健康的必需微量元素。尽管锰离子在人体和其他生物系统中扮演着重要角色，但是锰离子的代谢异常同样会引起一系列的疾病。例如，锰离子代谢异常，会导致延迟凝血、高胆固醇血症、神经损伤等病症。因此，在生态环境和生物体系中快速简单且具有选择性的检测锰离子显得尤为重要。
用于锰离子检测的荧光探针，最近荧光素系列和罗丹明系列探针被报道用于生物体内的锰离子含量的检测(Adhikari S,Ghosh A,Sahana A,et al.Tailoring LigandEnvironment toward Development of Colorimetric and Fluorescence Indicator forBiological Mn(II)Imaging[J].Analytical Chemistry,2015,88(2).)。但是这些荧光探针具有较小的斯托克斯位移，光稳定性较差和NIR荧光团的低量子产率，荧光受环境影响较大，具有一定的低毒性，难以准确的检测细胞中锰离子。
发明内容
本申请所要求解决的技术问题是：提供一种水溶性好、高灵敏度、高选择性的锰离子探针，以克服现有技术的不足。
为了解决上述问题，本申请的技术方案如下：提供一种BODIPY锰离子荧光探针，其结构式如下：
Figure BDA0001534065270000021
为了解决上述BODIPY荧光探针，本申请要解决的技术问题是：提供上述锰离子探针的合成方法。该方法如下：
在室温条件下，将取氟硼二吡咯荧光染料和4-N，N-二乙酰胺醇苯甲醛溶解在甲苯和N，N-二甲基甲酰胺的混合溶液中，然后加入哌啶和冰醋酸，再加入少量Mg(ClO4)2，加热回流，TLC跟踪至原料反应完全后，减压蒸发溶剂后，柱层析，减压蒸馏除去溶剂后，得到红棕色产物。
采用上述技术方案，本发明采用氟硼二吡咯荧光染料和4-N，N-二乙酰胺醇苯甲醛合成而成，由于4-N，N-二乙酰胺醇苯甲醛具有良好的水溶性，因此该BODIPY探针在水溶液中对Mn2+表现出高度的选择性和敏感度。
附图说明
图1为BODIPY锰离子探针的合成示意图
图2为BODIPY锰离子探针在不同浓度的金属离子溶液中的荧光变化的统计图表，其中1代表空白，2代表Fe3+，3代表Zn2+，4代表Cu2+，5代表Mn2+
本申请取得的有益效果如下：
1、本申请所述的BODIPY荧光探针对Mn2+具有高选择性，可以专一检测Mn离子。
2、本申请所述的荧光探针其具有两个可以与金属离子结合的位点，灵敏度更高，可达1.0×10-6mol/L。
3、本申请采用少量的Mg(ClO4)2作为助催化剂，使得所述反应具有很好的化学选择性，其中一分子氟硼二吡咯可以与两分子的取代的苯甲醛反应，使得所述产物具有两分子的螯合位点，此外，所述反应取得高达95％的收率。
具体实施方式
实施例1
在室温条件下，分别称取氟硼二吡咯荧光染料(0.37mmol)和4-N,N-二乙酰胺醇苯甲醛(0.98mmol)溶解在30毫升的甲苯和30毫升的N，N-二甲基甲酰胺的混合溶液中，加入0.1ml哌啶和0.1ml冰醋酸做催化剂，再加入Mg(ClO4)2(0.1mmol)，加热回流，TLC跟踪至原料反应完全后，减压蒸发溶剂后，柱层析(CH2Cl2/CH3OH，100∶1，v/v)，减压蒸馏除去溶剂后，得到红棕色的产物，所述化合物通过核磁1H NMR谱图进行表征，1H NMR(d6-DMSO，400M)数据如下：δ1.71(s，3H),2.01(br,4H)，2.05(s，3H),3.39(t，8H)，3.73(s,3H),3.79(t,8H),4.24(s,8H),5.62(d,1H),6.54(d,4H),6.61(d,1H),6.72(d,2H)6.99(d,2H),7.12(d,4H)，7.19(d,2H)，8.01(t,4H)，产率95％，熔点：178-179.5℃。
应用实施例1
在pH＝7.5的缓冲溶液中，配制浓度为1.0×10-6mol/L BODIPY锰离子探针溶液，然后分别加入5.0×10-6mol/L的FeCl3、ZnCl2、CuCl2、MnCl2，测定荧光光谱的变化(见图2)。发现当分别加入相同当量的各种金属离子时，锰离子较明显地增强探针的荧光，其它重金属离子对探针的荧光强度有微弱的影响。从图2可以看出，相对与其他金属离子，Mn2+对BODIPY锰离子探针的荧光强度有更为显著的影响。当Mn2+与其他各种离子共存时，BODIPY锰离子探针仍显现出明显的荧光增强，说明其他离子对BODIPY锰离子探针识别镉离子的识别行为没有影响。可见BODIPY锰离子探针对Fe3+，Zn2+，Cu2+等离子不敏感，只对Mn2+表现出极好的选择性荧光增强识别。另实验也发现了BODIPY锰离子探针在混合溶剂中对镉离子的识别有较好的选择性。
BODIPY锰离子探针的灵敏度分析：
随着锰离子的加入，BODIPY锰离子探针在583nm的荧光发射强度明显增强，当加入1.5当量Mn2+(15μM)时，荧光强度增强了10倍。因为BODIPY锰离子与Mn离子络合后成为很好的电子受体，发生PET阻断，从而导致BODIPY锰离子探针的荧光增强。(该光谱测定的条件：在25℃，中性缓冲水溶液，化合物(1)的浓度为5μM，0，0.12，0.2，0.4，1.0，2.0，4.0，7.0，10.0，20.0，30.0and 50.0eq不同浓度的Mn2+)。
由此可见，对Mn离子的紫外和荧光识别具有较好的线性关系。锰离子对吸收光谱的波长的影响明显，随着锰离子加入浓度的增大，探针的吸光度增大。在锰离子的浓度为0～5.0×10-6mol·L-1范围内，随锰离子的浓度增加，1.0×10-6mol·L-1的探针在580nm处的吸光度也逐渐增加，最大吸收波长600nm后逐渐下降。与Mn2+的浓度达到1∶2以后，进一步增加Mn2+浓度溶液的吸收强度基本保持不变。这些光谱行为显示Mn2+与探针形成的是1∶2的络合物。

Claims (2)

1.一种锰离子响应的BODIPY化合物，其特征在于：结构式如下：
Figure FDA0002208229060000011
，
其中R为甲氧基。
2.一种权利要求1所述的BODIPY化合物的应用，其特征在于：所述化合物用于荧光探针，所述荧光探针用于锰离子的检测。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817838A (zh) * 2009-02-26 2010-09-01 上海市七宝中学 镉离子探针及其合成方法
WO2016133913A1 (en) * 2015-02-16 2016-08-25 Seed Research And Development Llc Fluorescently labeled molecules containing modified tryptophan

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817838A (zh) * 2009-02-26 2010-09-01 上海市七宝中学 镉离子探针及其合成方法
WO2016133913A1 (en) * 2015-02-16 2016-08-25 Seed Research And Development Llc Fluorescently labeled molecules containing modified tryptophan

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* Cited by examiner, † Cited by third party
Title
Red-Emission Fluorescent Probe Sensing Cadmium and Pyrophosphate Selectively in Aqueous Solution;Xuhong Qian et al.;《Org. Lett.》;20110620;第13卷(第14期);第3656-3659页 *

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