CN113372356A - 一种吲哚花菁荧光探针及其制备方法 - Google Patents
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Abstract
Description
技术领域
本发明涉及氰根离子检测技术领域,具体是一种吲哚花菁荧光探针及其制备方法。
背景技术
过去几十年,阴离子类受体的荧光探针设计及合成受到广泛关注,这使得阴离子识别成为化学领域发展最快的方向之一。在各种阴离子中,氰化物广泛用于合成纤维、树脂、除草剂和金属提取工艺中,并且它是毒性最大的无机阴离子。氰基或氰根离子(CN-)由碳、氮两种原子组成一价原子团—C≡N或—CN。无机化合物中的氰化物(如氰化钠)与有机化合物中的烃基腈(如丙烯腈)和氰基酸(如氰基乙酸)等分子中都含有氰基。氰基(CN)中的碳原子和氮原子通过叁键连接,在通常的化学反应中都以一个整体形式存在,由于该基团具有与卤素类似的化学性质,常被称为拟卤素。氰根离子广泛存在于自然界和生物体中,在化学、医学、生物学及环境领域都具有重要的作用,但是过量存在的氰根离子又会带来生物体的危害以及环境的污染。
日常生活中接触到的发芽的土豆、木薯等植物本身也会产生氰化物来抵抗害虫;工业废水、汽车尾气中也都含有氰化物。当氰化物进入人体后,会分解出具有毒性的CN-,氰根离子能抑制组织细胞内多种酶的活性,例如细胞色素氧化酶、过氧化物酶、脱羧酶、琥珀酸脱氢酶及乳酸脱氢酶等,其中细胞色素氧化酶对氰根离子最为敏感,氰根离子能迅速与氧化型细胞素色氧化酶中的Fe3+结合,阻止其还原成二价铁,使氧化过程的电子传递中断,组织细胞不能利用血液中的氧而造成窒息,进而导致中枢性呼吸衰竭而死亡。
氰根离子的检测方法有很多,例如离子色谱法、电位分析法、电化学法、滴定法、伏安法等,这些方法通常耗时长、检测限偏高。荧光探针法作为一种新的检测技术,具有检测迅速、处理简单、灵敏度高、检测限低以及可生物应用等优点,广泛用于化学分析、环境检测和生物成像等领域,是近些年研究的热点。目前,已经公开了大量荧光探针法检测离子,其检测机制主要是氢键作用、脱金属的络合物反应以及氰根离子与荧光探针的亲核加成反应。
发明内容
本发明以吲哚花菁染料为荧光母体,利用氰根离子的强亲核性,与亲电基团发生亲核加成反应,设计并制备了一类吲哚花菁荧光探针,实现对氰根离子的特异性识别,具有很好的选择性。
本发明保护一种吲哚花菁荧光探针,其结构式为
本发明还保护上述吲哚花菁荧光探针的制备方法,
步骤1,通过3-甲氧基苯胺和1-溴-3-氯丙烷反应制得化合物2,
步骤2,通过化合物2反应制得化合物3,
步骤3,通过化合物3和丙酸二乙酯反应制得化合物4,
步骤4,通过化合物4反应制得化合物5,
步骤5,通过化合物5和甲基吲哚盐反应制得权利要求1所述的吲哚花菁荧光探针,
优选的,通过3-甲氧基苯胺和1-溴-3-氯丙烷反应制得化合物2的具体步骤为:将3-甲氧基苯胺和1-溴-3-氯丙烷在氮气气氛下室温搅拌0.5h,将温度升高至95℃反应1h,升高温度至140℃反应23h,再加热回流21h,完全反应后形成反应液1;将反应液1冷却至80℃,反应液1中有固体生成,加入HI,继续加热回流6h,再加入水进行淬灭反应,萃取,保留有机相,减压除去有机溶剂,纯化得到化合物2。
优选的,通过化合物2反应制得化合物3的具体步骤为:将新蒸馏的DMF在氮气气氛下,室温下滴加至POCl3中,室温下搅拌30min,形成溶液1;将化合物2溶于DMF中,加入到溶液1中,室温下搅拌30min,升温至60℃继续搅拌30min,再加入冰水中静置2h,过滤得到黄色固体化合物3。
优选的,通过化合物3和丙酸二乙酯反应制得化合物4的具体步骤为:将化合物3和丙酸二乙酯溶解于无水乙醇中,再滴入哌啶,加热回流24h,减压除去乙醇;再加入浓HCl和冰醋酸,继续加热8h,停止反应后,冷却至室温,加入冰水中,再用0.1M的NaOH调节pH至7.0,有黄色固体析出,继续搅拌30min,然后过滤、洗涤、干燥,再利用甲苯重结晶得到化合物4。
优选的,通过化合物4反应制得化合物5的具体步骤为:将新蒸馏的DMF在氮气气氛下,室温下滴加到POCl3中,在室温下搅拌30min,形成溶液2;将化合物4溶于DMF中,加入到溶液2中,室温下搅拌30min,升温至60℃继续搅拌12h,再加入冰水中,利用20%的NaOH溶液调节pH至7.0,产生沉淀,收集所得固体,利用无水乙醇重结晶得到化合物5。
优选的,通过化合物5和甲基吲哚盐反应制得吲哚花菁荧光探针的具体步骤为:将化合物5和甲基吲哚盐溶于乙醇中,加热回流14h,反应结束后,冷却至室温,有大量固体析出,通过减压抽滤收集固体,固体利用无水乙醇洗涤多次、真空干燥,得到吲哚花菁荧光探针。
氰根离子具有很强的亲核性,容易与亲电基团发生亲核加成反应。本发明利用氰根离子与探针HNOC发生加成反应,使得探针分子内的共轭结构遭到破坏,阻止分子内的电荷转移,氰根粒子本身属于吸电子基团,从而使得探针分子电子结构发生变化,又进一步导致紫外吸收和荧光信号的变化,实现对氰根离子的高选择性裸眼识别。
探针HNOC在测试体系中稳定性好,对氰根离子具有很好的选择性,较高的灵敏度,加成后的产物也比较稳定,可用于复杂样品的快速实时定性检测。
附图说明
图1为荧光探针HNOC的1H NMR图谱;
图2为荧光探针HNOC的13C NMR图谱;
图3(a)为荧光探针HNOC检测氰根离子的紫外可见光谱图和随氢根离子浓度变化线性关系图;
图3(b)为荧光探针(HNOC)检测氰根离子的荧光发射谱图和随氰根离子浓度变化线性关系图;
图4为荧光探针HNOC与氰根离子响应的时间曲线图;
图5为荧光探针HNOC在不同pH环境下检测氢根离子的荧光响应图;
图6为荧光探针HNOC与氰根离子反应荧光滴定线性拟合曲线;
图7为荧光探针HNOC与氰根离子及其他分析物的荧光图谱;
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细的说明。本发明的实施例是为了示例和描述起见而给出的,而并不是无遗漏的或者将本发明限于所公开的形式。很多修改和变化对于本领域的普通技术人员而言是显而易见的。选择和描述实施例是为了更好说明本发明的原理和实际应用,并且使本领域的普通技术人员能够理解本发明从而设计适于特定用途的带有各种修改的各种实施例。
实施例1
经测试,荧光探针HNOC的1HNMR图谱如图1所示,1HNMR(300MHz,DMSO-d6):δ(ppm):8.65(s,Ar-H,C=C-H,1H),8.24(d,C=C-H,1H,J=15.5Hz),7.88(d,C=C-H,1H,J=5.1Hz),7.53(s,Ar-H,1H),7.54(s,Ar-H,1H),7.52(s,Ar-H,1H),7.47(s,Ar-H,1H),7.56(s,Ar-H,1H),1.74(s,6H),1.91(s,4H),3.44(s,4H),2.75(s,4H),1.51(s,3H)。荧光探针HNOC的13CNMR图谱如图2所示,13CNMR(75MHz,DMSO-d6):δ(ppm):171.8,147.2,144.6,141.4,138.9,132.4,129.4,126.6,123.1,120.2,114.5,112.8,109.8,107.2,75.6,71.6,51.1,46.2,45.2,31.4,31.1,30.4,28.5,23.7,22.8,21.1。
氰根离子具有很强的亲核性,容易与亲电基团发生亲核加成反应。本发明利用氰根离子与探针HNOC发生加成反应,使得探针分子内的共轭结构遭到破坏,阻止分子内的电荷转移,氰根粒子本身属于吸电子基团,从而使得探针分子电子结构发生变化,又进一步导致紫外吸收和荧光信号的变化,实现对氰根离子的高选择性裸眼识别。
探针HNOC在测试体系中稳定性好,对氰根离子具有很好的选择性,较高的灵敏度,加成后的产物也比较稳定,可用于复杂样品的快速实时定性检测。
氰根离子检测效果验证:
1、测试样品的配制
探针HNOC用HEPES(10mM,pH=9.3)/CH3OH(v:v,1:1)配制成10mL10-3M的溶液,室温下混匀,放入冰箱中备用。
现配制CN-和常见分析物离子F-、Br-、I-、NO3-、SCN-、Cl-、S2O3 2-、AcO-、CO3 2-、SO4 2-、HSO3 -、ClO4 -、HCO3 -、Citrate、HS-、Cys,所有离子用去离子水配置成10mL 10-2M的溶液。将上述配置好的待测溶液,室温下混匀,放入冰箱中备用。
2、紫外光谱测试和荧光光谱测试
将5μM探针HNOC加入到HEPES(10mM,pH=9.3)/CH3OH(v:v,1:1)的溶液中,在600nm处有较强的最大吸收峰,荧光光谱在激发波长为400nm下,几乎没有荧光信号;随着CN-(0-15μM)的浓度增加,600nm处的吸收逐渐减少,在440nm处出现了新的吸收峰,体系的颜色也从蓝色变为黄绿色。荧光光谱图在发射波长为500nm处表现出荧光信号增强,在365nm紫外灯的照射下,溶液的颜色从几乎无色变为绿色。图3(a)为荧光探针HNOC检测氰根离子的紫外可见光谱图和随氢根离子浓度变化线性关系图;图3(b)为荧光探针HNOC检测氰根离子的荧光发射谱图和随氰根离子浓度变化线性关系图。
3、CN-的响应时间和pH滴定
从探针HNOC与CN-的时间曲线(参照图4)中可以看出,在加入CN-15s后,荧光信号基本不在发生变化,表明探针HNCO可以对CN-快速检测,优于现有技术。
此外,研究pH在2-13的范围内,pH对体系荧光强度的影响,从图5中可以看出,pH在9.3-11.0范围内,探针HNCO对CN-的响应最好。
4、探针HNOC检测CN-的检出限
将不同浓度的CN-(0-16μM)加入到5μM探针HNCO,收集500nm处的相对荧光强度,并绘制成与CN-浓度的线性关系Y=41.858C+33.838,R2=0.989,参照图6。荧光响应曲线的线性范围为0-16μM。根据CDL=3σ/s,计算出探针HNOC对CN-的检出限为0.069μM。
5、探针HNOC对CN-的选择性
研究探针HNOC对CN-的传感性能,在5μM探针HNOC的HEPES(10mM,pH=9.3)/CH3OH(v:v,1:1)中加入其他离子,包括HNOC、F-、Br-、I-、NO3-、SCN-、Cl-、S2O3 2-、AcO-、CO3 2-、SO4 2-、HSO3 -、ClO4 -、HCO3 -、Citrate、HS-、Cys结果(参照图7)表明,这些离子并没有导致探针HNOC有明显的紫外和荧光响应,而只有CN-表现出明显的紫外和荧光信号的变化。
实施例2
实施例1公开的吲哚花菁荧光探针的制备方法,包括以下步骤:
1、通过3-甲氧基苯胺和1-溴-3-氯丙烷反应制得化合物2,合成路线为
具体步骤为:将3-甲氧基苯胺(0.65g,5.0mmol)和1-溴-3-氯丙烷(11.80g,75.0mmol)在氮气气氛下室温搅拌0.5h,将温度升高至95℃反应1h,升高温度至140℃反应23h,再加热回流21h,完全反应后形成反应液1;
将反应液1冷却至80℃,反应液1中有固体生成,加入HI,继续加热回流6h,再加入水进行淬灭反应,萃取,保留有机相,减压除去有机溶剂,纯化得到化合物2。
步骤2,通过化合物2反应制得化合物3,合成路线为
具体步骤为:将新蒸馏的DMF(2.0mL)在氮气气氛下,室温下滴加至POCl3(2.0mL)中,室温下搅拌30min,形成溶液1;
将化合物2(500.0mg,2.6mmol)溶于10mL DMF中,加入到溶液1中,室温下搅拌30min,升温至60℃继续搅拌30min,再加入冰水中静置2h,过滤得到黄色固体化合物3。
步骤3,通过化合物3和丙酸二乙酯反应制得化合物4,合成路线为
具体步骤为:将化合物3(500.0mg,2.3mmol)和丙酸二乙酯(738.2mg,4.6mmol)溶解于无水乙醇中,再滴入4滴哌啶,加热回流24h,减压除去乙醇;
再加入浓HCl(8mL)和冰醋酸(8mL),继续加热8h,停止反应后,冷却至室温,加入40mL冰水中,再用0.1M的NaOH调节pH至7.0,有黄色固体析出,继续搅拌30min,然后过滤、洗涤、干燥,再利用甲苯重结晶得到化合物4。
步骤4,通过化合物4反应制得化合物5,合成路线为
具体步骤为:将新蒸馏的DMF(2.0mL)在氮气气氛下,室温下滴加到POCl3(2.0mL)中,在室温下搅拌30min,形成溶液2;
将化合物4(500.0mg,2.6mmol)溶于10mL DMF中,加入到溶液2中,室温下搅拌30min,升温至60℃继续搅拌12h,再加入100mL冰水中,利用20%的NaOH溶液调节pH至7.0,产生沉淀,收集所得固体,利用无水乙醇重结晶得到化合物5。
步骤5,通过化合物5和甲基吲哚盐反应制得实施例1公开的吲哚花菁荧光探针,合成路线为
具体步骤为:将化合物5(270mg,1mmol)和甲基吲哚盐(300mg,1mmol)溶于乙醇中,加热回流14h,反应结束后,冷却至室温,有大量固体析出,通过减压抽滤收集固体,固体利用无水乙醇洗涤多次、真空干燥,得到吲哚花菁荧光探针(192.1mg,产率45.2%)。
显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域及相关领域的普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例,都应属于本发明保护的范围。
Claims (7)
3.根据权利要求2所述的吲哚花菁荧光探针的制备方法,其特征在于,通过3-甲氧基苯胺和1-溴-3-氯丙烷反应制得化合物2的具体步骤为:
将3-甲氧基苯胺和1-溴-3-氯丙烷在氮气气氛下室温搅拌0.5h,将温度升高至95℃反应1h,升高温度至140℃反应23h,再加热回流21h,完全反应后形成反应液1;
将反应液1冷却至80℃,反应液1中有固体生成,加入HI,继续加热回流6h,再加入水进行淬灭反应,萃取,保留有机相,减压除去有机溶剂,纯化得到化合物2。
4.根据权利要求2所述的吲哚花菁荧光探针的制备方法,其特征在于,通过化合物2反应制得化合物3的具体步骤为:
将新蒸馏的DMF在氮气气氛下,室温下滴加至POCl3中,室温下搅拌30min,形成溶液1;
将化合物2溶于DMF中,加入到溶液1中,室温下搅拌30min,升温至60℃继续搅拌30min,再加入冰水中静置2h,过滤得到黄色固体化合物3。
5.根据权利要求2所述的吲哚花菁荧光探针的制备方法,其特征在于,通过化合物3和丙酸二乙酯反应制得化合物4的具体步骤为:
将化合物3和丙酸二乙酯溶解于无水乙醇中,再滴入哌啶,加热回流24h,减压除去乙醇;
再加入浓HCl和冰醋酸,继续加热8h,停止反应后,冷却至室温,加入冰水中,再用0.1M的NaOH调节pH至7.0,有黄色固体析出,继续搅拌30min,然后过滤、洗涤、干燥,再利用甲苯重结晶得到化合物4。
6.根据权利要求2所述的吲哚花菁荧光探针的制备方法,其特征在于,通过化合物4反应制得化合物5的具体步骤为:
将新蒸馏的DMF在氮气气氛下,室温下滴加到POCl3中,在室温下搅拌30min,形成溶液2;
将化合物4溶于DMF中,加入到溶液2中,室温下搅拌30min,升温至60℃继续搅拌12h,再加入冰水中,利用20%的NaOH溶液调节pH至7.0,产生沉淀,收集所得固体,利用无水乙醇重结晶得到化合物5。
7.根据权利要求2所述的吲哚花菁荧光探针的制备方法,其特征在于,通过化合物5和甲基吲哚盐反应制得吲哚花菁荧光探针的具体步骤为:
将化合物5和甲基吲哚盐溶于乙醇中,加热回流14h,反应结束后,冷却至室温,有大量固体析出,通过减压抽滤收集固体,固体利用无水乙醇洗涤多次、真空干燥,得到吲哚花菁荧光探针。
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