CN113527353B - 一种检测活性氧分子的荧光探针及其制备方法与应用 - Google Patents
一种检测活性氧分子的荧光探针及其制备方法与应用 Download PDFInfo
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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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"
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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"
- G01N2021/6432—Quenching
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Abstract
本发明公开一种检测活性氧分子的荧光探针及其制备方法与应用,其中荧光探针包括喹啉鎓离子骨架、通过碳硅单键与所述喹啉鎓离子骨架结构键合的三甲基硅基、通过碳碳单键与所述喹啉鎓离子骨架结构相连的对硼酸频哪醇酯苯基、以及抗衡离子。利用该类分子上的硼酸频哪醇酯基团与活性氧发生反应,实现对活性氧分子的高选择性检测。
Description
技术领域
本发明涉及荧光探针技术领域,尤其涉及一种检测活性氧分子的荧光探针及其制备方法与应用。
背景技术
荧光分子成像是一个快速发展的交叉学科,涉及分子生物学,化学以及药学等多个学科领域。它可以实现无创和实时可视化,在细胞或分子水平对生物体内的生理或病理过程进行检测,对生命过程的研究及药物在人体中作用过程及代谢研究具有重要价值。通过设计小分子荧光探针,在体外、细胞层次或体内对小分子进行检测和追踪是化学生物学研究的重要领域之一。而其中一个热门方向则是将检测从细胞层面拓展至亚细胞层次,即选择性地追踪小分子在不同细胞器、细胞核内或细胞膜上的作用过程。即便同一种活性小分子,其在不同细胞器中的作用机制也会不同。举例而言,在线粒体中,过氧化氢(H2O2)是涉及多种转导过程的重要信号分子。然而,在溶酶体中,过量的H2O2会引起功能障碍,导致细胞自噬和死亡。因此,利用荧光探针在亚细胞层次测量小分子的浓度和追踪其作用机理是急需突破的研究方向。
因此,现有技术仍有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种检测活性氧分子的荧光探针及其制备方法与应用,旨在解决现有技术中缺乏在亚细胞层次检测活性小分子的荧光探针的问题。
本发明的技术方案如下:
本发明的第一方面,提供一种检测活性氧分子的荧光探针,包括喹啉鎓离子骨架、通过碳硅单键与所述喹啉鎓离子骨架结构键合的三甲基硅基、通过碳碳单键与所述喹啉鎓离子骨架结构相连的对硼酸频哪醇酯苯基、以及抗衡离子(即BF4 -),所述荧光探针的结构式如式I所示:
本发明第一方面提供的荧光探针(属于有机荧光分子),利用荧光探针上的硼酸频哪醇酯对活性氧分子(如H2O2)的反应,实现了荧光分子对活性氧分子的选择性检测。
本发明的第二方面,提供一种本发明所述的检测活性氧分子的荧光探针的制备方法,其中,包括步骤:
将化合物II(三甲基硅基炔衍生物)、化合物III(重氮盐)和一价金催化剂溶于有机溶剂中,在光照射和室温(指的是16℃-25℃)条件下进行反应,得到目标化合物I,即所述荧光探针;
上述反应路线如下所示:
本发明第二方面提供的荧光探针的制备方法,该制备方法以两种小分子化合物为反应物,在一价金催化剂的作用下进行催化加成反应,该制备方法反应过程简单方便,操作步骤简单,反应速率高,可以有效、快速得到荧光探针,有效提高生产效率,降低生产成本。
优选地,所述化合物II、化合物III和一价金催化剂的摩尔比为 (1.2-1.5):1:(0.05-0.1)。
优选地,所述反应的时间为16-24小时,其可根据TLC板分析原料是否反应完确定得到。
优选地,所述光照射为16瓦或者60瓦的蓝色LED灯照射。
本发明中,所述一价金催化剂为一价金配合物。优选地,所述一价金催化剂为三(4-三氟甲基苯基)氯化金((4-CF3C6H4)3AuCl)或三苯基膦氯化金((C6H5)3PAuCl)。
优选地,所述有机溶剂为乙腈。
优选地,所述荧光探针的制备方法,包括如下步骤:在惰性气体氮气保护下,将化合物II﹑化合物III和一价金催化剂((4-CF3C6H4)3AuCl)按摩尔比1.2:1:0.1用5mL乙腈溶于30mL的反应管中,在16瓦的蓝色 LED灯和室温条件下进行催化环加成反应,反应16个小时后,旋蒸除去有机溶剂,所得残余物,过硅胶柱,用二氯甲烷和甲醇的混合溶液进行梯度洗脱,合并旋蒸除去溶剂,加入二氯甲烷后用水多次萃取,合并水相,最后旋蒸除去水,得到化合物I(即所述荧光探针)。上述反应路线如下所示:
优选地,所述化合物II的制备方法,包括以下步骤:
(1)在氮气保护下,在***(25mL)中加入4-碘苯硼酸(1.2g,5.0 mmol),频哪醇(0.59g,5.0mmol)和硫酸镁(10g)。反应搅拌2小时后,通过硅藻土过滤所得混合物,并在减压下除去挥发性物质。通过硅胶柱色谱法(正己烷∶***=10∶1,体积比计)获得4-碘苯硼酸频哪酯(1.5g, 89%);
(2)在装有磁力搅拌棒的50mL两口圆底烧瓶中装入Pd(PPh3)2Cl2(28 mg,0.040mmol)和碘化亚铜(15mg,0.080mmol)。将烧瓶抽空并用氮气回填。将四氢呋喃(6mL)加入到烧瓶中。通过冰/水浴将烧瓶冷却至0℃,依次添加三乙胺(0.30g,3.0mmol),4-碘苯硼酸频哪酯(0.70g,2.1mmol) 和三甲基乙炔基硅(0.26g,2.0mmol)。除去冷却浴,并使反应后混合物温热至室温。搅拌1小时后,将水(5mL)和***(30mL)加入到烧瓶中。通过使用分液漏斗分离所得溶液。有机层用水(10mL×3)洗涤,用无水 MgSO4干燥,并通过使用旋转蒸发仪浓缩。所得粗产物通过硅胶柱色谱法纯化(己烷∶***=10∶1,体积比计)得到化合物II(0.27g,产率为 45%)。
本发明的第三方面,提供一种如上所述荧光探针或者由如上所述的制备方法制得的荧光探针在活性氧分子的荧光检测中的应用。
本发明第三方面提供的荧光探针或者由所述的制备方法制备的荧光探针在活性氧分子(如H2O2)的荧光检测中的应用。结合如上反应式,由于该荧光探针上的硼酸频哪醇酯基团与活性氧分子可以发生反应,从而实现荧光探针对活性氧分子的高选择性检测。
本发明荧光探针对活性氧分子检测的操作步骤如下:将活性氧分子溶液、荧光探针溶液、缓冲液和有机溶剂混合,并置于室温反应0-2小时。反应结束后对产物进行表征。具体主要是通过UV-VIS和荧光分析,并在荧光分析前以ESI-MS质谱初步确认荧光探针I和H2O2有反应。
其中,所述荧光探针溶液浓度可以为2-200mmol/L。
其中,所述荧光探针溶液中的溶剂可以为甲醇、乙醇、2-异丙醇、N,N-二甲基甲酰胺、乙腈、丙酮、二甲基亚砜等中的一种或多种。
其中,所述活性氧分子溶液浓度为0-9800mmol/L,以水或缓冲液为溶剂。
其中,所述缓冲液可以是pH为4-10的磷酸盐缓冲液,Tris盐酸盐缓冲液,硼酸钠缓冲液等中的一种。
其中,所述缓冲液浓度为0-100mmol/L。
具体地,本发明荧光探针对活性氧分子检测的操作步骤如下:将1L 荧光探针溶液(乙腈为溶剂,浓度为10mmol/L)、80L的磷酸盐缓冲液(浓度为50mmol/L)和9L的乙腈混合在1.5mL离心管中,并加入H2O2溶液,置于25℃室温反应,反应时间为0-2小时。反应结束后对产物进行表征。
本发明成功地利用荧光探针I检测了H2O2。首先,研究探针的紫外吸收光谱,探针在285、355和420nm处有吸收峰。接着,研究该探针的荧光光谱性质。加入H2O2之前,荧光探针在490nm处有很强的荧光发射峰;加入H2O2之后,荧光减弱。并且随着H2O2浓度的增大,探针的荧光强度不断减弱。然后,研究了pH值对荧光探针测定H2O2的影响,当pH值在大于8时,不影响荧光探针对H2O2的测定。最后,研究探针的选择性,考察了探针与各种离子(Na+,K+,Ca2+,Zn2+,Cu2+,Fe3+)、生物硫醇(Cys,GSH)、抗坏血酸钠以及检测物(H2O2)的荧光响应情况。结果发现,只有H2O2能引起荧光光谱的明显改变,其他检测物对探针的荧光光谱没有明显的影响。
附图说明
图1为荧光探针I与H2O2作用前后的ESI-MS分析测试,其中(a)为加双氧水之前ESI-MS,(b)为加双氧水10分钟后ESI-MS。
图2为在不同有机溶剂中,荧光探针I与H2O2作用前后的荧光反应。
图3为荧光探针I分别在甲醇和乙醇中的紫外可见吸收光谱图。
图4为荧光探针I在乙醇中的荧光光谱图。
图5为荧光探针I在甲醇中的荧光光谱图。
图6为用不同体积比的甲醇/硼酸盐缓冲溶液配制的H2O2对荧光探针I 测定H2O2的响应时间的影响。
图7为溶液pH值对荧光探针I测定H2O2的荧光性质的影响。
图8为滴定实验-荧光探针I对H2O2测定的选择性。
图9为荧光探针I对不同H2O2浓度的荧光线性响应图。
图10为荧光探针I对H2O2测定的选择性和竞争性实验。
具体实施方式
本发明提供一种检测活性氧分子的荧光探针及其制备方法与应用,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:荧光探针I的合成
荧光探针I的合成路线如下:
荧光探针I的制备方法,包括如下步骤:
(1)在氮气保护下,在***(25mL)中加入4-碘苯硼酸(1.2g,5.0mmol),频哪醇(0.59g,5.0mmol)和硫酸镁(10g),反应搅拌2小时后,通过硅藻土过滤所得混合物,并在减压下除去挥发性物质。通过硅胶柱色谱法(正己烷∶***=10∶1,体积比计)获得4-碘苯硼酸频哪酯(1.5g,89%);
(2)在装有磁力搅拌棒的50mL两口圆底烧瓶中装入Pd(PPh3)2Cl2(28 mg,0.040mmol)和碘化亚铜(15mg,0.080mmol)。将烧瓶抽空并用氮气回填。将四氢呋喃(6mL)加入到烧瓶中。通过冰水浴将烧瓶冷却至0℃。依次添加三乙胺(0.30g,3.0mmol),4-碘苯硼酸频哪酯(0.70g,2.1mmol) 和三甲基乙炔基硅(0.26g,2.0mmol)。除去冷却浴,并使混合物温热至室温。搅拌1小时后,将水(5mL)和***(30mL)加入到烧瓶中。通过使用分液漏斗分离所得溶液。有机层用水(10mL×3)洗涤,用无水硫酸镁干燥,并通过使用旋转蒸发仪浓缩。所得粗产物通过硅胶柱色谱法纯化(己烷∶***=10∶1)得到化合物II(0.27g,45%);
(3)在惰性气体氮气保护下,将化合物II和化合物III,还有一价金配合物(4-CF3C6H4)3AuCl按摩尔比1.2:1:0.1,用5mL溶剂乙腈溶于30mL 的反应管中,在16瓦的蓝色LED灯和室温条件下进行催化环加成反应。反应16个小时后,旋蒸除去有机溶剂,所得残余物,过硅胶柱,用二氯甲烷和甲醇的混合溶液进行梯度洗脱,合并旋蒸除去溶剂,加入二氯甲烷后用水多次萃取,合并水相,最后旋蒸除去水,得到化合物I。
化合物I的表征分析数据:黄色固体,产率为47%。
1H NMR(400MHz,CDCl3)δ9.28(d,J=8.9Hz,1H),9.03(d,J=8.9Hz, 2H),8.24(d,J=7.7Hz,1H),8.18(d,J=8.0Hz,1H),8.04(dd,J=11.7,8.0 Hz,2H),7.89(d,J=7.9Hz,2H),7.63(t,J=7.4Hz,1H),7.50(d,J=8.9Hz,2H),7.39(d,J=7.9Hz,2H),1.40(s,12H),0.09(s,9H);
13C NMR(100MHz,CDCl3)δ149.48,145.99,143.47,140.24,136.05, 134.40,130.91,129.79,128.81,124.73,119.68,84.71,25.11,2.33;
HRMS(ESI)C32H35BNO2Si+,理论计算值504.2525,实测值504.2552。
实施例2:荧光探针I的光学性质
依上述实验步骤合成的荧光探针I在紫色可见光波段被激发,发射出蓝色的荧光。量子产率Φ计算如下列算式:
以荧光素为标准(Φ=0.95in 0.1N NaOH溶液)。
具体光学参数,包括最大吸收波长、最大发射波长、斯托克斯位移及量子产率如下表1所示。
表1、荧光探针I的光学性质
实施例3:荧光探针I与H2O2作用前后的ESI-MS分析
空白实验:1.5mL的离心管中,加入20μL的荧光探针I溶液(5mmol/L,溶剂为甲醇),和20μL的Milli-Q的超纯水,十分钟后,对反应液进行正离子ESI-MS测试分析,其测试结果见图1中A。
1.5mL的离心管中,加入20μL的荧光探针I溶液(5mmol/L,溶剂为甲醇),和20μL的市售体积分数为30%的H2O2溶液,十分钟后,对反应液进行正离子ESI-MS测试分析,其测试结果见图1中B。
实施例4:在不同有机溶剂中,荧光探针I与H2O2作用前后的荧光反应
本实施例研究了不同溶剂对荧光探针I测定H2O2的影响,其结果如图2。浓度为0.5M的H2O2溶液(溶剂为水)加入到浓度为10μM的荧光探针溶液中,溶剂分别为2-异丙醇、甲醇、乙醇、N,N-二甲基甲酰胺、乙腈、丙酮、二甲基亚砜。在255nm的紫外灯下,2-异丙醇、甲醇、乙醇三种溶剂中荧光探针I的荧光,在加入H2O2溶液后显著被淬灭;而在N,N-二甲基甲酰胺和乙腈中没有明显的淬灭效果;使用丙酮和二甲基亚砜的荧光探针I并没有淬灭效果。因此,甲醇和乙醇是比较好的溶剂。为了研究溶剂对 H2O2检测的影响,将H2O2溶液(0.5M)添加到荧光探针I(10μM)在不同溶剂(如2-PrOH、MeOH、EtOH、DMF、ACN、丙酮和DMSO)中的溶液中。在255nm的紫外灯下,结果表明,以2-PrOH、MeOH和EtOH为溶剂,加入H2O2后,荧光探针I的荧光信号被显著淬灭。
实施例5:荧光探针I在乙醇和甲醇中的紫外可见吸收光谱图
本实施例测定了荧光探针I分别在甲醇和乙醇中的紫外可见吸收光谱,荧光探针I的浓度为50μM,紫外可见吸收光谱测定用的仪器为Agilent Cary 8454紫外可见分光光度计,结果如图3。从图中可以看出,荧光探针I在甲醇和乙醇溶剂中的最大吸收峰分别在285、355nm。
实施例6:荧光探针I在乙醇和甲醇中的荧光光谱图
图4-图5分别为荧光探针I在乙醇和甲醇中的荧光光谱图,荧光探针I 的浓度为50μM,实验所用激发波长为285、355、410、425nm,发射波长范围为290~690nm。狭缝宽度为5.0nm/5.0nm,所用的荧光测定仪器为 Agilent Cary Eclipse荧光分光光度计。从图中可以看出,在甲醇和乙醇中,当激发波长285nm时,荧光强度最强,而且荧光探针I的荧光发射峰都在 490nm。
实施例6:用不同体积比的甲醇/缓冲溶液配制的H2O2对荧光探针I测定H2O2的影响
图6为用不同体积比的甲醇/硼酸盐缓冲溶液配制的H2O2对荧光探针I 测定H2O2的响应时间的影响。荧光探针I的浓度为1μM。浓度为10mM 的H2O2,是体积比为3:7和5:5的甲醇/pH=8的硼酸盐缓冲溶液配制的。图中可以看出用体积比5:5的甲醇/硼酸盐缓冲溶液配制的H2O2,荧光探针荧光强度下降的更快,更明显。响应时间为90min。
实施例7:溶液pH值对荧光探针I测定H2O2的荧光性质的影响
图7为溶液pH值对荧光探针I测定H2O2的荧光性质的影响。我们研究的pH范围为4~9,荧光探针的浓度为5μM,20当量的H2O2(溶剂为体积比为1:1的MeOH/50mM pH=9磷酸盐缓冲溶液)。从图中可以看出,荧光探针I随着pH的变化,荧光强度基本不变,说明pH对探针本身没有很大的影响。然而,加入H2O2之后,当pH<8时,荧光强度也基本不变,这是因为在酸性条件下,H2O2无法稳定存在;在pH大于8,荧光强度有显著减弱。因此,在弱碱性的条件下,荧光探针I可以测定H2O2。
实施例8:滴定实验-荧光探针I对H2O2测定的选择性
图8为荧光探针I与H2O2作用的荧光光谱,500μL荧光探针I甲醇溶液(浓度为10μM),pH=9的PBS缓存液浓度为50mM,H2O2的浓度依次为0-250μM。实验所用激发波长为420nm,发射波长范围为430~700nm。狭缝宽度为5.0nm/5.0nm,所用的荧光测定仪器为Agilent CaryEclipse荧光分光光度计。从图可以看出,加入H2O2之前,在490nm处出现了很强荧光发射峰。加入H2O2之后,荧光强度减弱,这是因为探针分子上硼酸频哪醇酯被H2O2氧化,导致硼酸酯键的断裂,从而发生荧光淬灭。并且随着 H2O2浓度的增大,探针分子的荧光强度不断减小,直至加入30当量的H2O2加入后,荧光完全淬灭。
实施例9:荧光探针I对不同H2O2浓度的荧光线性响应图
图9为荧光探针I对不同H2O2浓度的荧光线性响应图。荧光探针的荧光强度与H2O2的浓度(浓度范围0to 50μM)呈现很好的线性关系。基于信噪比,荧光探针的检测限是0.07μM,这说明该探针可以高灵敏的检测 H2O2。
实施例10:荧光探针I对H2O2测定的选择性和竞争性实验
图10为荧光探针I对H2O2测定的选择性和竞争性实验图。首先在选择性实验中,考察在490nm激发波长下,浓度为5μM的荧光探针溶液中加入各种其他干扰因素:离子(Na+,K+,Ca2+,Zn2+,Cu2+,Fe3+),生物硫醇(Cys, GSH),抗坏血酸钠和H2O2(100μM)的荧光响应情况。其他干扰因素的浓度也为100μM(溶剂为体积比为1:1的MeOH和50mM pH=9的磷酸盐缓冲溶液)。从图10中可以看出,只有H2O2能引起荧光强度的明显减弱,其他检测物对探针的荧光强度没有明显的影响。
其次在竞争性实验中,在本来已加入干扰分子的荧光探针I中,加入额外的H2O2(100μM)份量,然后出现了荧光强度的明显减弱。这些结果表明,荧光探针对H2O2有较好的选择性。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (4)
1.一种荧光探针在非疾病诊断和/或治疗为目的的活性氧分子的荧光检测中的应用,所述荧光探针包括喹啉鎓离子骨架、通过碳硅单键与所述喹啉鎓离子骨架结构键合的三甲基硅基、通过碳碳单键与所述喹啉鎓离子骨架结构相连的对硼酸频哪醇酯苯基、以及抗衡离子,所述抗衡离子为BF4 - ,所述荧光探针的结构式如式I所示:
;
所述活性氧分子为H2O2;
所述检测的操作步骤如下:将活性氧分子溶液、荧光探针溶液、缓冲液和有机溶剂混合,混合后溶液的pH为9,并置于室温反应0-2小时;
所述荧光探针溶液中的溶剂为甲醇、乙醇、2-异丙醇中的一种或多种。
2.根据权利要求1所述的应用,其特征在于,包括步骤:
将化合物II、化合物III和一价金催化剂溶于有机溶剂中,在光照射和室温条件下进行反应,得到目标化合物I,即所述荧光探针;
上述反应路线如下所示:
;
所述光照射为16瓦或60瓦的蓝色LED灯照射;
所述一价金催化剂为三(4-三氟甲基苯基)氯化金或三苯基膦氯化金;
所述有机溶剂为乙腈。
3.根据权利要求2所述的应用,其特征在于,所述化合物II、化合物III和一价金催化剂的摩尔比为(1 .2-1 .5):1:(0 .05-0 .1)。
4.根据权利要求2所述的应用,其特征在于,所述反应的时间为16-24小时。
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