CN106967038B - 一种双通道检测硫化氢的荧光探针的合成及应用 - Google Patents

一种双通道检测硫化氢的荧光探针的合成及应用 Download PDF

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CN106967038B
CN106967038B CN201710228051.3A CN201710228051A CN106967038B CN 106967038 B CN106967038 B CN 106967038B CN 201710228051 A CN201710228051 A CN 201710228051A CN 106967038 B CN106967038 B CN 106967038B
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hydrogen sulfide
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厉凯彬
韩得满
陈逢灶
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Taizhou University
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    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Abstract

本发明属于分析化学的荧光探针领域，涉及一种新型的双通道检测硫化氢的长波长荧光探针的合成方法及应用。所述合成方法包括：在碱性催化剂存在条件下，类罗丹明衍生物与醛基香豆素通过羟醛缩合反应得到目标探针化合物。该探针制备方法简单，稳定性好，背景荧光极弱，可选择性的、灵敏的与硫化氢响应，表现为紫外光谱发生比率型变化并伴随约130nm的红移，荧光光谱在662nm与818nm发生双通道增强，对生物机体损伤小，因而在生物成像等方面具有很好的应用前景。

Description

一种双通道检测硫化氢的荧光探针的合成及应用
技术领域
本发明涉及一种新型的双通道检测硫化氢的长波长荧光探针的合成方法及应用。
背景技术
多年以来，硫化氢(H2S)这种具有特殊气味的气体作为一种环境污染气体已得到了人们深入的研究。然而最近的研究发现，硫化氢(H2S)还是继一氧化氮(NO)和一氧化碳(CO)之后的第三种内源性气体信号分子。内源性H2S主要来自于L-半胱氨酸的酶解作用。在正常生理浓度水平下，H2S参与调节心肌收缩、血管张力、神经传导和胰岛素分泌等一系列生理过程。然而，细胞内一旦不能维持正常的H2S浓度，便会引起动脉和肺动脉高压、阿尔茨海默氏症、胃粘膜损伤和肝硬化等疾病。因而，对于H2S浓度的灵敏检测尤为重要。
传统的硫化氢测定方法主要依赖比色法、电化学分析法、金属硫化物沉淀法等，但这些方法存在选择性差，测定操作复杂，成本较贵，不易普及应用等确定。因此，开发一种新型的检测硫化氢的方法具有重要意义。
发明内容
本发明涉及一种新型的双通道检测硫化氢的长波长荧光探针的合成方法及应用。所述合成方法包括：在碱性催化剂存在条件下，类罗丹明衍生物与醛基香豆素通过羟醛缩合反应得到目标化合物。该探针稳定性好，制备方法简单，背景荧光极弱，可选择性的、灵敏的与硫化氢响应，表现为紫外光谱发生比率型变化并伴随约130nm的红移，荧光光谱在662nm与818nm发生双通道增强。此外，动力学实验结果表明，该化合物与硫化氢反应时间不足60s，其它他活性小分子以及阴离子的存在对该检测体系均不产生干扰。因此，本发明所述化合物可作为检测硫化氢的荧光探针的应用。
本发明的一个目的在于提供一种罗丹明-香豆素衍生化合物，其为式I所述化合物(简记为化合物I，下同)：
化合物I的合成路线如下：
其中，化合物II的合成步骤参见J.Mater.Chem.B,2014,2,4500-4508；化合物III的合成步骤参见Chemistry-A European Journal,2015,21(15),5704-5708。
本发明的另一个目的在于揭示上述罗丹明-香豆素衍生化合物(式I所述化合物)的一种用途，即式I所述化合物作为检测硫化氢的荧光探针的应用。
附图说明
图1化合物I的紫外吸收光谱随硫化氢浓度变化曲线；
图2在560nm激发波长下，化合物I的荧光发射光谱随硫化氢浓度变化曲线；
图3在770nm激发波长下，化合物I的荧光发射光谱随硫化氢浓度变化曲线；
图4化合物I对系列干扰化合物的选择性图；
图5化合物I与硫化氢反应的动力学曲线；
具体实施方式
以下将结合实施例对本发明做进一步说明，本发明的实施例仅用于说明本发明的技术方案，并非限定本发明。
实施例1
在氮气保护下，准确称取罗丹明化合物II(780mg,1.64mmol)，对羟基苯甲醛(500mg,1.64mmol)，溶解在20mL乙醇中，再向混合液中滴加1滴哌啶，80℃回流搅拌反应10小时。TLC检测反应完全，停止反应，减压蒸馏除去溶剂，并用柱层析分离提纯得到墨绿色产物(化合物I)1.03g，产率82.5％。1H NMR(400MHz,DMSO-d6)δ8.34(s,1H),8.10(d,J＝4.0Hz,2H),7.94(d,J＝8.0Hz,1H),7.79(t,J＝8.0Hz,1H),7.68(t,J＝8.0Hz,2H),7.34(t,J＝12.0Hz,2H),6.76(d,J＝8.0Hz,1H),6.47-6.38(m,3H),3.60(q,4H),3.37(q,4H),1.78-1.54(m,6H),1.21(t,J＝8.0Hz,6H),1.10(t,J＝6.0Hz,6H)；HR-ESI-MS m/z:[M]+calcd.for 663.2620found 663.2618.
实施例2
在氮气保护下，准确称取罗丹明化合物II(780mg,1.64mmol)，对羟基苯甲醛(500mg,1.64mmol)，溶解在20mL乙醇中，再向混合液中滴加3滴哌啶，80℃回流搅拌反应6小时。TLC检测反应完全，停止反应，减压蒸馏除去溶剂，并用柱层析分离提纯得到墨绿色产物(化合物I)1.18g，产率94.5％。
将实施例中制备的化合物I应用于硫化氢的检测，其具体操作方法及结果如下应用实例：
应用实例1
向1cm×1cm×4cm的比色皿中依次加入3mL PBS缓冲溶液，3μL 5mM化合物Ⅰ的DMSO溶液，制备浓度为5μM的化合物Ⅰ溶液。依次向上述溶液中加入0-20μM的硫化氢溶液，并测定其紫外吸收光谱变化曲线(图1)。从图1可以看出，随着体系中硫化氢浓度的增加，640nm处的紫外吸收峰逐渐减弱，同时伴随着735，795nm处紫外吸收峰的增强，在705nm处出现等吸收点，说明硫化氢能够使探针的紫外光谱发生红移，并伴随比率型变化。
应用实例2
向1cm×1cm×4cm的比色皿中依次加入3mL PBS缓冲溶液，3μL 5mM化合物Ⅰ的DMSO溶液，制备浓度为5μM的化合物Ⅰ溶液。依次向上述溶液中加入0-20μM的硫化氢溶液。在560nm激发波长下，测定其荧光发射光谱变化曲线(图2)。从图2可以看出，随着体系中硫化氢浓度的增加，662nm处的荧光发射峰逐渐增强，并具备较好的浓度依赖关系，说明662nm处的荧光变化可以作为特征发射峰实现硫化氢的定量检测。
应用实例3
向1cm×1cm×4cm的比色皿中依次加入3mL PBS缓冲溶液，3μL 5mM化合物Ⅰ的DMSO溶液，制备浓度为5μM的化合物Ⅰ溶液。依次向上述溶液中加入0-20μM的硫化氢溶液。在770nm激发波长下，测定其荧光发射光谱变化曲线(图3)。从图3可以看出，随着体系中硫化氢浓度的增加，818nm处的荧光发射峰逐渐增强，并具备较好的浓度依赖关系，说明818nm处的荧光变化可以也可作为特征发射峰实现硫化氢的定量检测。
应用实例4
分别向浓度为5μM的化合物Ⅰ溶液中加入20μM的F-、Cl-、Br-、I-、OAc-、NO2 -、CO3 2-、CN-、N3 -、ClO4 -、SO4 2-、SO3 2-、ClO-、H2O2、GSH、Cys、Hcy、H2S，并测定其荧光光谱曲线。图4所示为系列活性小分子及阴离子的选择性图，探针化合物只与硫化氢响应，其他化合物均不产生干扰，说明探针对硫化氢具备高选择性。
应用实例5
向浓度为5μM的化合物Ⅰ溶液中，加入20μM的硫化氢溶液，分别测定反应在0，15，30，45，60，120，240秒时荧光光谱曲线，以662nm处荧光强度值为纵坐标，时间(s)为横坐标，做点图5。由图5可见当加入硫化氢60s后，662nm处荧光强度值即达到最大值，而随着时间的延长，荧光强度值不再改变，说明化合物Ⅰ可对硫化氢快速、灵敏响应。

Claims (4)

1.一种双通道检测硫化氢的长波长荧光探针的合成方法，其特征在于，具体包括以下步骤：
1eq的化合物Ⅱ和1.0eq化合物Ⅲ溶解在乙醇中，再向混合液中滴加1-3滴碱性催化剂，70-90℃反应6-10小时；TLC检测反应完全，停止反应，减压蒸馏除去溶剂，并用柱层析分离提纯得到墨绿色产物，即荧光探针，产率为82-95％；所述化合物Ⅱ和化合物Ⅲ结构式分别为：
2.如权利要求1所述的一种双通道检测硫化氢的长波长荧光探针的合成方法，其特征在于，步骤中所述反应过程中所用的碱性催化剂为哌啶，其滴加量为1-3滴。
3.如权利要求1所述的一种双通道检测硫化氢的长波长荧光探针的合成方法制备的荧光探针，其为式I所述化合物：
4.如权利要求3所述的荧光探针在检测硫化氢方面的应用。
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