CN110143985A - 一种识别亚硫酸氢根的铱配合物探针及其制备方法 - Google Patents
一种识别亚硫酸氢根的铱配合物探针及其制备方法 Download PDFInfo
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000523 sample Substances 0.000 title claims abstract description 33
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 29
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Abstract
本发明公开了一种识别亚硫酸氢根的铱配合物探针及其制备方法。该配合物探针由一个金属铱中心、一个中性N^N辅助配体和两个环金属C^N配体组成,其中C^N配体上含有醛基,N^N配体的碳链上具有线粒体靶向的三苯基磷基团。本发明首先制备铱二氯桥化合物、环金属C^N配体,利用环金属C^N配体接枝三苯基膦,然后将铱二氯桥化合物与接枝三苯基膦的环金属C^N配体反应得到所述铱配合物探针。本发明的铱配合物的醛基能与亚硫酸氢根发生特异性加成反应,使铱配合物激发态和光物理性质的改变从而实现对亚硫酸氢根离子的检测。本发明的铱配合物材料在生物方面具有重要的应用前景。
Description
技术领域
本发明涉及一种配合物探针及其制备方法,尤其涉及一种识别亚硫酸氢根的铱配合物探针及其制备方法。
背景技术
亚硫酸氢盐已广泛用于纺织和食品工业,用于防止氧化和细菌生长,以及生产和储存过程中的酶促反应。在食品工业中,该阴离子用作抗微生物剂,饮料中的添加剂和各种食品的抗氧化剂。HSO3-通常被美国食品和药物管理局(FDA)认定为安全(GRAS)。在动物体内,低浓度(低于450μM)的HSO3被报道为心血管系统的新信使,在血管舒张,抗高血压和抗动脉粥样硬化起作用。尽管亚硫酸氢盐具有有价值的特性,但它对组织,细胞,和生物大分子。它可引起明显的损伤,如坏死,抑制细胞分裂,诱导微核,这往往导致细胞死亡。大量摄入亚硫酸氢根可导致细胞和组织的有害作用,引起某些人的哮喘发作和过敏反应,鉴于此,能够快速、灵敏和准确地检测生物样品中的亚硫酸氢根离子尤为重要。
荧光探针是一种小分子传感器,能够在暴露于特定刺激时发出明亮的荧光,是化学生物学的强大工具。荧光探针是一种潜在的荧光团,它能在环境变化、与分析物的相互作用或特定的化学反应时显示其信号。通过化学调节荧光团的荧光来制备荧光探针,使其非荧光直至通过特定的触发事件激活荧光传感成像技术由于灵敏度高,选择性好,数据采集简单,空间分辨率和时间分辨率高,从而被认为是一种独特的检测亚硫酸氢根的方法。
近年来已经有一些亚硫酸氢根荧光探针被合成出来,用于进行活细胞中亚硫酸氢根的监测,相比于荧光信号,铱(III)配合物分子由于其高三重态量子产率,小的非辐射能量损失和快速的辐射衰减率,其中以其优异的磷光发射性质而最为突出。通过设计与铱配位的各种共轭配体,可以使铱配合物达到检测、成像、靶向的作用,将其应用于细胞成像时,可以实现对细胞内目标物的成像和检测。
发明内容
发明目的:本发明的其中一个目的在于提供一种识别亚硫酸氢根的铱配合物探针,既能够具有线粒体靶向功能又能够识别亚硫酸氢根;
本发明的另一个目的是提供一种识别亚硫酸氢根的铱配合物探针的制备方法。
技术方案:针对上述第一个发明目的,本发明的识别亚硫酸氢根的铱配合物探针,在环金属配体上含有亚硫酸氢根识别基团醛基,辅助N^N配体上具有线粒体靶向基团三苯基膦;所述铱配合物探针结构通式如下:
其中,n为1-10的正整数;结构通式中为
针对上述第二个发明目的,本发明所述的制备方法,包括以下步骤:
(1)惰性氛围下,与三水合三氯化铱在2-乙氧基乙醇和水的混合液中在90℃~120℃条件下密闭反应,得到铱二氯桥化合物;
(2)将化合物a和三苯基磷在DMF中回流,后用石油醚和水萃取,得到色谱柱提纯得黄色油状液体b;
(3)将得到的铱二氯桥化合物与化合物b在二氯甲烷/甲醇2:1,混合液在惰性氛围下密闭反应,冷却至室温后加入六氟磷酸钾或六氟磷酸铵继续反应,分离提纯得到含有醛基的铱配合物。
具体的合成路线如下:
优选地,所述化合物a中的n为1~10的正整数。
优选地,所述合成铱的醛基二氯桥的反应温度为90℃~120℃,时间为12~48h。
优选地,所述合成化合物b的反应温度为100℃,时间为4~72h,继续反应的时间为1~8h。
优选地,所述合成铱配合物探针的反应温度为40℃~60℃,时间为4~72h,加入KPF6或NH4PF6后继续反应的时间为1~8h。
优选地,所述二氯甲烷和甲醇的体积比为2:1~3:1。
优选地,所述2-乙氧基乙醇和水的体积比为2:1~3:1。
有益效果:本发明与现有技术相比,能够取得下列有益效果:1、本发明的探针可以实现对亚硫酸氢根的基于磷光淬灭的检测,并且具有很好的响应性和选择性。2、该探针可以进入细胞中,实现对线粒体的靶向成像。3、该探针可以通过荧光法容易地检测细胞中的亚硫酸氢根水平。
附图说明
图1为本发明的Ir1的1H NMR谱图;
图2为本发明的Ir1的质谱图;
图3为本发明的Ir1加入过量亚硫酸氢根离子后的质谱图;
图4为本发明的Ir1对亚硫酸氢根离子的滴定图;
图5为本发明的Ir1对亚硫酸氢根离子的选择性光谱图;
图6为本发明的Ir1细胞成像实验图。
具体实施方式
以下结合说明书附图对本发明创造作进一步的详细说明。
实施例1
当n=2,为时,探针Ir1的制备:
合成路线如前述所示,具体制备步骤如下:
(1)铱的醛基二氯桥化合物的合成:在双口瓶中加入1.5mmol的水合三氯化铱IrCl3·3H2O与3.3mmol的4-(2-吡啶基)苯甲醛,加入磁子,装上冷凝管密封,抽真空除氧,鼓氮气三次。加入鼓泡除氧的水和乙二醇乙醚,体积比为2:1,反应温度为110℃,反应时长为12h。反应完成后,冷却至室温后用分液漏斗分液以除去无机盐与乙二醇乙醚。浓缩后用硅胶色谱柱提纯,得到黄色固体产物为二氯桥化合物。产率:80%。
(2)化合物a的合成:称取吡啶基苯并咪唑1mmol共195mg与氢氧化钾6mmol共336mg放入50mL茄形瓶中,用双排管密封抽真充氮气除氧三次后,注入3mL离子液体,反应体系用氮气保护,室温搅拌4h,注入0.8mL二溴己烷继续反应8h。反应结束后用水和二氯甲烷萃取,色谱柱提纯得到无色油状液体产物。产率:90%。1H NMR(400MHz,CDCl3,298K):d1/4 8.70(d,J1/4 4.80Hz,1H),8.41(d,J1/4 7.97Hz,1H),7.88–7.33(m,2H),7.46–7.44(m,1H),7.37–7.30(m,3H),4.84(t,J1/4 7.6Hz,2H),3.38(t,J1/4 6.8Hz,2H),1.95–1.88(m,2H),1.86–1.79(m,2H),1.53–1.44(m,2H),1.42–1.35(m,2H)。
(3)化合物b的合成:将0.2mmol化合物a和0.4mmol三苯基磷装入50mL茄形瓶中,用双排管密封抽真空充氮气除氧三次后,加DMF使其充分溶解,在氮气气氛中100℃回流72小时。反应结束后用石油醚和水萃取,色谱柱提纯的黄色油状液体。产率:90%。1H NMR(400MHz,CDCl3):δ8.62–8.56(m,1H),8.28(d,J=8.0Hz,1H),7.80–7.67(m,12H),7.67–7.56(m,7H),7.44–7.38(m,1H),7.30–7.14(m,3H),4.72(t,J=7.4Hz,2H),3.56(ddd,J=17.3,13.5,9.2Hz,3H),2.45(s,3H),1.82–1.71(m,2H),1.61(dd,J=14.5,7.0Hz,2H),1.51(dd,J=15.4,7.8Hz,2H),1.35–1.27(m,2H)。
(4)铱配合物Ir1的合成:在双口瓶中加入1mmol的铱的醛基二氯桥与2.4mmol的化合物b,加入磁子,装上冷凝管密封,抽真空除氧,鼓氮气三次。加入鼓泡除氧的二氯甲烷和甲醇,体积比为2:1,反应温度为40℃,反应时长为4h。反应完成后,冷却至室温后加入六氟磷酸钾继续反应3h,分离提纯得到含有醛基的铱配合物Ir1。产率:60%。如图1所示为本发明的Ir1的1H NMR谱图,其中:1H NMR(400MHz,CDCl3)δ9.74(d,J=8.2Hz,2H),8.53(d,J=8.3Hz,1H),8.37(t,J=7.3Hz,1H),8.06(d,J=8.2Hz,1H),7.95(dd,J=11.0,6.7Hz,2H),7.91–7.76(m,8H),7.74–7.63(m,17H),7.58(td,J=7.9,1.4Hz,2H),7.40(t,J=6.6Hz,2H),7.15(t,J=6.8Hz,1H),6.98(t,J=7.7Hz,1H),6.82(d,J=1.3Hz,1H),6.73(d,J=1.4Hz,1H),6.23(d,J=8.5Hz,1H),4.81(s,2H),3.39–3.11(m,3H),1.76(s,7H),1.58(s,9H),1.32–1.16(m,19H)。
铱配合物Ir1的质谱测试:分别测试了Ir1及其加入亚硫酸氢根的质谱图,结果如图2和3所示。从图2可以看出,其质谱中呈现了配合物的分子离子峰1241.062。向Ir1中加入过量亚硫酸氢根离子后的质谱结果,如图3所示,呈现的分子离子峰为1405.564,这与Ir1与亚硫酸氢根发生加成反应的分子量一致。
铱配合物Ir1的滴定发射光谱:将Ir1在THF溶液中用0-50equiv的亚硫酸氢根滴定2μM的Ir1的荧光光谱变化,结果如图4所示。
铱配合物Ir1的选择性光谱:铱配合物探针Ir1对其他ROS和其他氧化性阴离子不发生反应,发光颜色和发射光谱基本不变化,结果如图5所示。
铱配合物Ir1的细胞成像实验:当海拉细胞与10μM的Ir1一起孵育时,观察到黄色荧光,如图6所示。在亚硫酸氢根处理后,在520-620nm窗口中可以观察到细胞类材料的发光变化。
实施例2
与实施例1不同的是,n=1,为时,探针Ir2的制备:
在铱的醛基二氯桥化合物的合成中,水和乙二醇乙醚的体积比为3:1,反应温度为90℃,反应时长为48h。在化合物a的合成中,a为使用二溴丁烷为原料进行制备。在化合物b的合成中,在氮气气氛中100℃回流4小时。在铱配合物Ir2的合成中,反应温度为60℃,反应时长为72h;冷却至室温后加入六氟磷酸铵继续反应1h,分离提纯得到含有醛基的铱配合物Ir2。
实施例3
与实施例1不同的是,n=3,为时,探针Ir3的制备:
在铱的醛基二氯桥化合物的合成中,水和乙二醇乙醚的体积比为3:2,反应温度为100℃,反应时长为24h。在化合物a的合成中,a为使用二溴辛烷为原料进行制备。在化合物b的合成中,在氮气气氛中100℃回流20小时。在铱配合物Ir3的合成中,反应温度为50℃,反应时长为60h;冷却至室温后加入六氟磷酸铵继续反应8h,分离提纯得到含有醛基的铱配合物Ir3。
实施例4
与实施例1不同的是,n=3,为时,探针Ir4的制备:
在铱的醛基二氯桥化合物的合成中,水和乙二醇乙醚的体积比为3:2,反应温度为115℃,反应时长为30h。在化合物a的合成中,a为使用二溴辛烷为原料进行制备。在化合物b的合成中,在氮气气氛中100℃回流50小时。在铱配合物Ir3的合成中,反应温度为55℃,反应时长为10h;冷却至室温后加入六氟磷酸铵继续反应5.5h,分离提纯得到含有醛基的铱配合物Ir4。
Claims (9)
1.一种识别亚硫酸氢根的铱配合物探针,其特征在于,在环金属C^N配体上含有亚硫酸氢根识别基团醛基,辅助N^N配体上具有线粒体靶向基团三苯基膦;所述铱配合物探针结构通式如下:
其中,n为1-10的正整数。
2.根据权利要求1所述的识别亚硫酸氢根的铱配合物探针,其特征在于,所述结构通式中为
3.一种权利要求1所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,合成路线如下:
4.根据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述化合物a中的n为1~10的正整数。
5.根据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述合成铱的醛基二氯桥的反应温度为90℃~120℃,时间为12~48h。
6.据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述合成化合物b的反应温度为100℃,时间为4~72h。
7.据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述合成铱配合物探针的反应温度为40℃~60℃,时间为4~72h,加入KPF6或NH4PF6后继续反应的时间为1~8h。
8.据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述二氯甲烷和甲醇的体积比为2:1~3:1。
9.据权利要求3所述识别亚硫酸氢根的铱配合物探针的制备方法,其特征在于,所述2-乙氧基乙醇和水的体积比为2:1~3:1。
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CN107141318A (zh) * | 2017-05-11 | 2017-09-08 | 陕西师范大学 | 含有(醛基)菲罗啉配体的铱配合物以及用其定量检测亚硫酸氢根的方法 |
Non-Patent Citations (1)
Title |
---|
QING LI等: "A water-soluble iridium complex: Highly sensitive to bisulfite and sequential recognition to Cu2+ ions", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
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