CN108863911B - 一种turn-on型汞离子荧光探针的制备方法及应用 - Google Patents

一种turn-on型汞离子荧光探针的制备方法及应用 Download PDF

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CN108863911B
CN108863911B CN201810788791.7A CN201810788791A CN108863911B CN 108863911 B CN108863911 B CN 108863911B CN 201810788791 A CN201810788791 A CN 201810788791A CN 108863911 B CN108863911 B CN 108863911B
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张彩红
李苗
张红红
姚庆佳
张国梅
董川
双少敏
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Abstract

本发明公开了一种turn‑on型汞离子荧光探针的制备方法及应用。所述的汞离子荧光探针，分子式为C21H18INO2S，其制备方法为：(1)通过4‑羟基苯甲醛和4‑甲基吡啶反应得到4‑(4‑羟基苯乙烯基)吡啶，即化合物3；(2)将化合物3和2‑(2‑二硫吡啶)苯甲酸反应得到4‑[4‑(2‑二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2；(3)化合物2通过CH3I进行离子化，得到4‑[4‑(2‑巯基)苯甲酸酯]苯乙烯基‑1‑甲基吡啶碘盐，即探针分子1。在纯PBS缓冲溶液中将探针分子与汞离子进行反应，利用荧光强度的变化可检测汞离子的浓度。本发明探针制备简单，对汞离子响应快、选择性好、灵敏度高。

Description

一种turn-on型汞离子荧光探针的制备方法及应用
技术领域
本发明涉及一种turn-on型汞离子荧光探针的制备方法及应用，属于金属离子检测的荧光探针技术领域。
背景技术
汞离子是目前全球最引人关注的环境污染物之一，汞离子被细菌吸收代谢后,会从无机汞转化为毒性更大的有机甲基汞。有机汞具有亲脂性、易吸收和难排泄等性能，它易穿过血脑屏障，在大脑中累积，导致大脑和其它器官严重的不可逆神经损伤，引发如前脑损伤、严重的认知或运动功能紊乱等疾病。因此，发展高效、准确、快速检测汞离子的方法是非常重要的。
分子荧光探针是目前检测汞离子的重要方法之一，已报道的汞离子分子荧光探针大多数存在着水溶性差、抗干扰能力弱、响应时间长、灵敏度差等问题。
发明内容
本发明旨在提供一种能在纯PBS缓冲溶液中检测汞离子并具有高选择性、高灵敏度和响应快的“turn-on”型汞离子荧光探针。
本发明是基于汞离子独特的化学反应设计荧光探针分子的结构，合成了探针分子，4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，它利用巯基和汞离子的相互作用触发反应，再借助吡啶碘盐强的拉电子效应加速酯键的断裂，释放出荧光团点亮荧光，实现对汞离子的检测。本发明制备的荧光探针水溶性好，对汞离子响应快、选择性好、灵敏度高，能用于实际水样中汞离子的检测。
本发明提供了一种turn-on型汞离子荧光探针，它的化学名称为：4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，分子式为C21H18INO2S，结构式如下：
Figure GDA0002436438960000011
本发明提供了上述turn-on型汞离子荧光探针的制备方法，包括以下步骤：
(1)将4-羟基苯甲醛和4-甲基吡啶在乙酸酐中回流10～12小时，反应完后倒入冰水中搅拌0.8～1.2小时，产生沉淀，将沉淀水洗并用乙醇重结晶，在醇钾(氢氧化钾/乙醇)溶液中回流1.4～1.6小时，加醋酸至沉淀产生，水洗干燥，得到化合物4-(4-羟基苯乙烯基)吡啶；反应过程如下：
Figure GDA0002436438960000021
(2)4-(4-羟基苯乙烯基)吡啶和2-(2-二硫吡啶)苯甲酸溶于二氯甲烷和二甲基亚砜的混合溶液中，加入1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC)和4－N,N-二甲氨基吡啶(DMAP)，在室温下进行酯化反应6～8小时，得到4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2；反应过程如下：
Figure GDA0002436438960000022
(3)将化合物2和碘甲烷在乙腈和二氯甲烷的混合溶剂中回流8～10小时，溶液中有沉淀产生，过滤，用二氯甲烷洗涤，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针化合物1。
Figure GDA0002436438960000023
步骤(1)中4-羟基苯甲醛和4-甲基吡啶的摩尔比为1：1.20～1.30；醇钾溶液是是指氢氧化钾的乙醇溶液，其中氢氧化钾的浓度为0.70～0.80M。
步骤(2)中4-(4-羟基苯乙烯基)吡啶、2-(2-二硫吡啶)苯甲酸、EDC和DMAP的摩尔比为1：1～1.2：1：0.05。
步骤(3)中化合物2和碘甲烷的摩尔比为1：1～1.2。最佳摩尔比为1：1.1。
步骤(3)中乙腈和二氯甲烷的体积比为5：1～2。最佳体积比为5：1。
本发明还提供了上述“turn-on”型汞离子荧光探针在纯PBS缓冲溶液中检测汞离子的应用。
所述的应用是在纯PBS缓冲溶液中将荧光探针与汞离子进行如下反应，利用520nm处的荧光强度变化来检测汞离子是否存在。在未加入汞离子前，探针溶液没有荧光信号，当加入汞离子后，反应溶液在520nm出现较强的荧光信号，所述检测汞离子的线性范围为2-18μM，检出限为6.5nM。
Figure GDA0002436438960000031
本发明的有益效果：
1、本发明探针合成简便，只需三步就可以完成，且后续处理过程便捷。
2、本发明荧光探针分子在汞离子检测时，响应快。
3、本发明荧光探针分子在汞离子与其他阳离子共存体系中，表现出较高的选择性和灵敏度。
附图说明
图1为实施例十一中探针分子与Hg2+反应前后荧光强度示意图。
图2为实施例十二中探针分子的荧光强度随Hg2+浓度变化示意图。
图3为实施例十三中探针分子与Hg2+反应荧光强度随时间变化示意图。
图4为实施例十四中探针分子与不同金属离子反应前后的荧光强度变化示意图。
具体实施方式
下面通过实施例来进一步说明本发明，但不局限于以下实施例。
实施例一：化合物3的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(5.821g,0.0625mol)4-甲基吡啶，(6.100g，0.05mol)4-羟基苯甲醛和10mL乙酸酐溶液，加热回流12h。反应结束后，加入500mL冰水，搅拌1h，产生沉淀，将沉淀用水洗涤并用乙醇重结晶，随后在含90mL乙醇，(3.780g,0.0675mol)氢氧化钾的溶液中回流1.5h，加醋酸至沉淀产生，水洗并干燥，得到化合物4-(4-羟基苯乙烯基)吡啶，即化合物3，7.232g,产率73.4％。1HNMR(400MHz,DMSO,25℃,TMS)δ9.83(broad,-OH),8.50(d,J＝5.6,2H),7.51(d,J＝6.4,4H),7.45(d,J＝16.4,1H),7.02(d,J＝16.4,1H),6.82(d,J＝8.4,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ158.2,149.9,144.8,133.0,128.7,127.2,122.4,120.5,115.7.
实施例二：化合物3的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(5.588g,0.06mol)4-甲基吡啶，(6.100g，0.05mol)4-羟基苯甲醛和10mL乙酸酐溶液，加热回流10h。反应结束后，加入500mL冰水，搅拌0.8h，产生沉淀，将沉淀用水洗涤并用乙醇重结晶，随后在含90mL乙醇，(3.528g,0.063mol)氢氧化钾的溶液中回流1.4h，加醋酸至沉淀产生，水洗并干燥，得到化合物4-(4-羟基苯乙烯基)吡啶，即化合物3，6.895g,产率70.0％。1HNMR(400MHz,DMSO,25℃,TMS)δ9.82(broad,-OH),8.51(d,J＝5.6,2H),7.50(d,J＝6.4,4H),7.46(d,J＝16.4,1H),7.02(d,J＝16.4,1H),6.82(d,J＝8.4,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ158.0,149.9,144.7,133.0,128.7,127.2,122.3,120.5,115.4.
实施例三：化合物3的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(7.264g,0.078mol)4-甲基吡啶，(6.100g，0.05mol)4-羟基苯甲醛和10mL乙酸酐溶液，加热回流11h。反应结束后，加入500mL冰水，搅拌1.2h，产生沉淀，将沉淀用水洗涤并用乙醇重结晶，随后在含90mL乙醇，(4.032g,0.072mol)氢氧化钾的溶液中回流1.6h，加醋酸至沉淀产生，水洗并干燥，得到化合物4-(4-羟基苯乙烯基)吡啶，即化合物3，6.402g,产率65.0％。1HNMR(400MHz,DMSO,25℃,TMS)δ9.83(broad,-OH),8.49(d,J＝5.6,2H),7.52(d,J＝6.4,4H),7.47(d,J＝16.4,1H),7.02(d,J＝16.4,1H),6.80(d,J＝8.4,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ158.1,149.9,144.7,133.1,128.7,127.1,122.4,120.5,115.7.
实施例四：化合物2的合成
在装有磁力搅拌器的25mL圆底烧瓶依次加入(0.0788g,0.4mmol)4-(4-羟基苯乙烯基)吡啶，(0.1052g，0.4mmol)2-(2-二硫吡啶)苯甲酸，(0.0767g,0.4mmol)1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC)，(2.443mg,0.02mmol)4－N,N-二甲氨基吡啶(DMAP)和5mL二氯甲烷，1mL二甲基亚砜，在室温下搅拌8h，反应结束后，水洗干燥混合物，得粗产品。粗产品经硅胶柱色谱分离(展开剂为甲醇：二氯甲烷＝1:10,v/v)得到4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2，0.123g,产率69.5％。1HNMR(400MHz,DMSO,25℃,TMS)δ8.54(d,J＝6.0,2H),8.46-8.48(m,1H),8.30-8.34(m,1H),7.69-7.89(m,5H),7.53-7.62(m,4H),7.46-7.50(m,1H),7.39-7.42(m,2H),7.26-7.30(m,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ164.3,157.3,157.0,150.4,150.0,149.9,149.7,144.2,140.0,139.5,138.1,134.4,132.0,128.3,126.6,126.4,126.2,125.9,125.6,122.4,121.9,121.8,120.9,119.8,119.5.
实施例五：化合物2的合成
在装有磁力搅拌器的25mL圆底烧瓶依次加入(0.0788g,0.4mmol)4-(4-羟基苯乙烯基)吡啶，(0.1157g，0.44mmol)2-(2-二硫吡啶)苯甲酸，(0.0767g,0.4mmol)1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC)，(2.443mg,0.02mmol)4－N,N-二甲氨基吡啶(DMAP)和5mL二氯甲烷，1mL二甲基亚砜，在室温下搅拌6h，反应结束后，水洗干燥混合物，得粗产品。粗产品经硅胶柱色谱分离(展开剂为甲醇：二氯甲烷＝1:10,v/v)得到4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2，0.119g,产率67.2％。1HNMR(400MHz,DMSO,25℃,TMS)δ8.54(d,J＝6.0,2H),8.46-8.47(m,1H),8.30-8.35(m,1H),7.69-7.88(m,5H),7.53-7.61(m,4H),7.46-7.51(m,1H),7.39-7.41(m,2H),7.26-7.31(m,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ164.2,157.3,157.1,150.4,150.0,149.8,149.7,144.1,140.0,139.4,138.0,134.4,132.0,128.4,126.6,126.4,126.3,125.9,125.6,122.5,121.9,121.8,120.8,119.8,119.6.
实施例六：化合物2的合成
在装有磁力搅拌器的25mL圆底烧瓶依次加入(0.0788g,0.4mmol)4-(4-羟基苯乙烯基)吡啶，(0.1262g，0.48mmol)2-(2-二硫吡啶)苯甲酸，(0.0767g,0.4mmol)1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(EDC)，(2.443mg,0.02mmol)4－N,N-二甲氨基吡啶(DMAP)和5mL二氯甲烷，1mL二甲基亚砜，在室温下搅拌7h，反应结束后，水洗干燥混合物，得粗产品。粗产品经硅胶柱色谱分离(展开剂为甲醇：二氯甲烷＝1:10,v/v)得到4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2，0.125g,产率70.6％。1HNMR(400MHz,DMSO,25℃,TMS)δ8.53(d,J＝6.0,2H),8.46-8.47(m,1H),8.30-8.33(m,1H),7.69-7.88(m,5H),7.53-7.60(m,4H),7.46-7.51(m,1H),7.39-7.42(m,2H),7.26-7.31(m,2H).13CNMR(100MHz,CDCl3,25℃,TMS)δ164.2,157.3,157.1,150.4,150.0,149.8,149.7,144.2,140.1,139.4,138.1,134.4,132.1,128.3,126.6,126.5,126.2,125.9,125.6,122.4,121.9,121.8,120.9,119.8,119.5.
实施例七：探针分子1的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(0.221g,0.5mmol)4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶，(34.23μL，0.55mmol)碘甲烷，5mL乙腈和1mL二氯甲烷，加热回流8h。反应结束后，溶液中有沉淀产生，过滤，用二氯甲烷洗涤三次，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针分子1,0.154g,产率64.7％。1HNMR(400MHz,DMSO)δ8.88(d,J＝6.8,2H),8.37(dd,J＝7.6,1.2,1H),8.25(d,J＝6.8,2H),8.07(d,J＝16.4,1H),7.91(d,J＝8.8,2H)，7.73-7.79(m,2H),7.53-7.59(m,4H),4.28(s,3H).13CNMR(100MHz,CDCl3)δ164.1,152.3,151.7,145.1,139.6,139.5,134.6,133.3,132.4,129.4,126.7,126.0,125.4,123.6,122.8,47.0.MS(ESI)[M-I]+calcd for C21H18NO2S+,348.1053,found,348.1070.
实施例八：探针分子1的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(0.221g,0.5mmol)4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶，(34.23μL，0.55mmol)碘甲烷，5mL乙腈和2mL二氯甲烷，加热回流9h。反应结束后，溶液中有沉淀产生，过滤，用二氯甲烷洗涤三次，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针分子1,0.142g,产率59.6％。1HNMR(400MHz,DMSO)δ8.87(d,J＝6.8,2H),8.37(dd,J＝7.6,1.2,1H),8.25(d,J＝6.8,2H),8.08(d,J＝16.4,1H),7.90(d,J＝8.8,2H)，7.73-7.80(m,2H),7.53-7.59(m,4H),4.27(s,3H).13CNMR(100MHz,CDCl3)δ164.0,152.2,151.8,145.1,139.6,139.5,134.6,133.3,132.3,129.2,126.8,126.0,125.3,123.6,122.7,47.1.MS(ESI)[M-I]+calcd for C21H18NO2S+,348.1053,found,348.1070.
实施例九：探针分子1的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(0.221g,0.5mmol)4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，(31.12μL，0.5mmol)碘甲烷，5mL乙腈和1mL二氯甲烷，加热回流10h。反应结束后，溶液中有沉淀产生，过滤，用二氯甲烷洗涤三次，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针分子1,0.131g,产率55.1％。1HNMR(400MHz,DMSO)δ8.87(d,J＝6.8,2H),8.38(dd,J＝7.6,1.2,1H),8.26(d,J＝6.8,2H),8.09(d,J＝16.4,1H),7.91(d,J＝8.8,2H)，7.73-7.82(m,2H),7.53-7.59(m,4H),4.26(s,3H).13CNMR(100MHz,CDCl3)δ164.0,152.2,151.8,145.0,139.6,139.5,134.0,133.3,132.3,129.1,126.8,126.0,125.3,123.6,122.6,47.1.MS(ESI)[M-I]+calcd for C21H18NO2S+,348.1053,found,348.1070.
实施例十：探针分子1的合成
在装有磁力搅拌器的25mL三口瓶中依次加入(0.221g,0.5mmol)4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，(37.34μL，0.60mmol)碘甲烷，5mL乙腈和1mL二氯甲烷，加热回流8h。反应结束后，溶液中有沉淀产生，过滤，用二氯甲烷洗涤三次，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针分子1,0.143g,产率59.9％。1HNMR(400MHz,DMSO)δ8.87(d,J＝6.8,2H),8.37(dd,J＝7.6,1.2,1H),8.25(d,J＝6.8,2H),8.08(d,J＝16.4,1H),7.91(d,J＝8.8,2H)，7.73-7.81(m,2H),7.53-7.58(m,4H),4.27(s,3H).13CNMR(100MHz,CDCl3)δ164.1,152.2,151.7,145.1,139.5,139.5,134.4,133.3,132.3,129.0,126.8,126.0,125.2,123.6,122.7,47.2.MS(ESI)[M-I]+calcd for C21H18NO2S+,348.1053,found,348.1070.
实施例十一：探针分子与Hg2+作用前后的荧光光谱研究
为测试探针分子与Hg2+作用前后的荧光光谱研究，在2mLPBS缓冲溶液(pH＝7.4)中加入4μL探针分子储备液(5mM)，随后滴加20μL Hg2+储备液(10mM),记录荧光强度变化(如图1)。由图1可知，探针分子在加入Hg2+后在520nm出现一个新的发射峰。说明探针分子可与汞离子进行反应，利用荧光强度的变化可检测汞离子的浓度。
实施例十二：探针分子对不同浓度Hg2+条件下荧光强度变化的研究
为测试探针分子对不同浓度Hg2+条件下荧光强度变化的研究，对不同浓度Hg2+条件下((0,2,4,6,8,10,12,14,16,18,20,25,30,35,40,45,50μM)探针分子的荧光强度变化进行了研究(如图2)。由图2可知，线性范围宽(2-18μM)，检出限低(6.5nM)，低于美国环保署(EPA)规定安全饮用水中最大Hg2+浓度(10nM)。说明本发明荧光探针分子对不同浓度的汞离子表现出了较高的灵敏度。
实施例十三：探针分子对Hg2+的时间响应研究
为测试探针分子对Hg2+的时间响应研究，对探针分子与Hg2+反应的荧光强度随时间(0～20分钟)的变化进行了研究(如图3)。由图3可知，探针分子对Hg2+响应速度快。
实施例十四：探针分子对Hg2+的选择性研究
测试探针分子对Hg2+的选择性，对探针分子与不同金属离子(K+,Na+,Ca2+,Mg2+,Ba2 +,Fe2+,Fe3+,Al3+,Zn2+,Li+,Cr3+,Cd2+,Co2+,Pb2+,Cu2+,Ag+,Hg2+)反应前后的荧光强度的变化进行了实验研究，Hg2+和不同金属离子的浓度均为100μM(如图4)。由图4可知，探针分子对Hg2+检测不受其他具有潜在竞争性的金属离子的干扰，对Hg2+检测具有高度的选择性。
实施例十五：探针分子与汞离子反应产物的确定
为了确定探针分子与汞离子的反应产物，在20mLPBS缓冲液加入探针分子(0.10mmol，0.0475g)和Hg2+(0.20mmol，0.0471g)，室温下搅拌20分钟后，反应体系直接通过ESI-MS分析。出现了m/z＝354.0682和m/z＝212.0170的峰，归属为化合物3和4，分子式分别为[C7H4HgO2SH],[C15H14INO2]。

Claims (9)

1.一种turn-on型汞离子荧光探针，其特征在于：它的化学名称为：4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，分子式为C21H18INO2S，结构式如下：
Figure RE-FDA0002457162440000011
2.一种权利要求1所述的turn-on型汞离子荧光探针的制备方法，其特征在于包括以下步骤：
(1)将4-羟基苯甲醛和4-甲基吡啶在乙酸酐中回流10～12小时，反应完后倒入冰水中搅拌0.8～1.2小时，产生沉淀，将沉淀水洗并用乙醇重结晶，在醇钾溶液中回流1.4～1.6小时，加醋酸至沉淀产生，水洗干燥，得到化合物4-(4-羟基苯乙烯基)吡啶；反应过程如下：
Figure RE-FDA0002457162440000012
(2)4-(4-羟基苯乙烯基)吡啶和2-(2-二硫吡啶)苯甲酸溶于二氯甲烷溶液中，加入1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐EDC和4－N,N-二甲氨基吡啶DMAP，在室温下进行酯化反应6～8小时，得到4-[4-(2-二硫吡啶)苯甲酸酯]苯乙烯基吡啶,即化合物2；反应过程如下：
Figure RE-FDA0002457162440000013
(3)将化合物2和碘甲烷在乙腈和二氯甲烷的混合溶剂中回流8～10小时，溶液中有沉淀产生，过滤，用二氯甲烷洗涤，得到4-[4-(2-巯基)苯甲酸酯]苯乙烯基-1-甲基吡啶碘盐，即探针化合物1：
Figure RE-FDA0002457162440000021
3.根据权利要求2所述的turn-on型汞离子荧光探针的制备方法，其特征在于：步骤(1)中4-羟基苯甲醛和4-甲基吡啶的摩尔比为1：1.20～1.30；醇钾溶液是指氢氧化钾的乙醇溶液，其中氢氧化钾的浓度为0.70～0.80M。
4.根据权利要求2所述的turn-on型汞离子荧光探针的制备方法，其特征在于：步骤(2)中4-(4-羟基苯乙烯基)吡啶、2-(2-二硫吡啶)苯甲酸、EDC和DMAP的摩尔比为1：1～1.2：1：0.05。
5.根据权利要求2所述的turn-on型汞离子荧光探针的制备方法，其特征在于：步骤(3)中化合物2和碘甲烷的摩尔比为1：1～1.2；乙腈和二氯甲烷的体积比为5：1～2。
6.根据权利要求5所述的turn-on型汞离子荧光探针的制备方法，其特征在于：步骤(3)中化合物2和碘甲烷的摩尔比为1：1.1。
7.一种权利要求1所述的turn-on型汞离子荧光探针在制备在纯PBS缓冲溶液中检测汞离子的 探针中的应用。
8.根据权利要求7所述的应用，其特征在于：在纯PBS缓冲溶液中将荧光探针与汞离子进行反应，利用520nm处的荧光强度变化来检测汞离子是否存在；在未加入汞离子前，探针溶液没有荧光信号，当加入汞离子后，反应溶液在520nm出现较强的荧光信号。
9.根据权利要求8所述的应用，其特征在于：所述检测汞离子的线性范围为2-18μM，检出限为6.5nM。
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