CN115108966A - 苯并吲哚方酸菁金属离子探针及其制备方法与应用 - Google Patents
苯并吲哚方酸菁金属离子探针及其制备方法与应用 Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 53
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Abstract
本发明公开了苯并吲哚方酸菁金属离子探针及其制备方法与应用,本发明涉及的金属离子探针是一类具有苯并吲哚方酸菁结构的化合物,制备方法简单,原料易得,具有优良的光热稳定性;对Fe3+、Cu2+、Hg2+具有很好的比色及荧光识别能力,在对Fe3+、Cu2+、Hg2+的识别过程中发生明显的颜色变化,同时其吸收光谱和荧光发射光谱也发生变化,响应时间短,灵敏度高,并且不受其他离子的干扰。
Description
技术领域
本发明属于化学分析测试技术领域,具体涉及苯并吲哚方酸菁金属离子探针及其制备方法与应用。
背景技术
铁和铜是人体所必须的两种微量元素,在许多生命活动过程中起着重要的作用。铁参与血液中氧的转运和质子转移等过程,是各种酶和血红蛋白的重要组成部分;一旦人体体内铁元素缺乏,就会导致生理机能***紊乱,从而引起疾病;而过量的铁也存在潜在的危害,可能会促进氧化脂肪、蛋白质和细胞中的其他组分而变得有毒。同样地,体内铜离子的缺乏或过量也会导致生长和代谢的紊乱,从而引起严重的铜代谢障碍疾病。另外,汞是对人类和环境具有高毒害性的重金属元素,其在体内的积累会导致严重的健康问题。因此,开发能高效、高选择性地检测自然环境中和生物体内的Fe3+、Cu2+、Hg2+的方法受到人们的关注。检测金属离子的传统方法有:原子吸收分光光度法,电感耦合等离子体原子发射光谱法和电化学分析法等。上述方法往往需要借助昂贵的仪器和专业的检测人员,不适合大批量检测和实时检测。荧光探针检测方法具有灵敏度高、成本低和易于操作等优点。目前用于检测Fe3+、Cu2+、Hg2+的荧光探针分子往往具有制备复杂、低选择性、吸收和发射波长不够红等缺点。因此开发具有高灵敏度、高选择性、在近红外区有强烈吸收和荧光发射特点的探针分子对检测自然环境中和生物体内的Fe3+、Cu2+、Hg2+至关重要。
方酸菁是一类由两个相同或不同的富电子给电单元(donor,D或D′)和一个强吸电子的方酸核单元(acceptor,A)缩合形成的D-A-D型共轭有机分子,具有共振稳定的两性离子结构。大多数方酸菁在可见及近红外区有强烈吸收和发射,其摩尔消光系数(ε)高达105M-1cm-1;而且方酸菁还具有易聚集、合成路线简单、光/热稳定性好、结构修饰性强等优点。因此,方酸菁分子已在很多领域得到了广泛的应用,如光电导数据存储、有机发光二极管、有机场效应晶体管、有机太阳能电池、双光子吸收、非线性光学、近红外荧光探针、生物标记及光动力学治疗等。事实上,方酸菁中心四元环上有两个氧原子,可以直接作为与金属离子的配位点;氧原子与金属离子的结合是影响中心四元环中电子分布的最有效方法之一,往往导致方酸菁化合物的光物理性质发生显著变化,从而提高探针分子的灵敏度。此外,氧原子可进一步被硫原子、氮原子等取代修饰,从而改变与金属离子的结合能力,调节其光物理性质,获得具有不同响应现象的探针分子。
发明内容
鉴于以上所述现有技术的缺点,本发明的第一目的在于提供苯并吲哚方酸菁金属离子探针;
第二目的在于提供苯并吲哚方酸菁金属离子探针的制备方法;
第三目的在于提供苯并吲哚方酸菁金属离子探针在检测Fe3+、Cu2+、Hg2+中的应用。
为实现上述目的,本发明提供一种苯并吲哚方酸菁金属离子探针,所述金属离子探针具有如下结构式(Ⅰ):
其中,R1、R2为氧原子、硫原子。
进一步地,所述金属离子探针的结构式(Ⅰ)中:
当R1、R2均为氧原子时,为化合物Ⅱ,其结构式如(Ⅱ)所示;
当R1、R2分别为氧原子和硫原子时,为化合物Ⅲ,其结构式如(Ⅲ)所示;
当R1、R2均为硫原子时,为化合物Ⅳ,其结构式如(Ⅳ)所示;
所述化合物Ⅱ、化合物Ⅲ、化合物Ⅳ的结构式分别如下所示:
进一步地,所述化合物Ⅱ、化合物Ⅲ、化合物Ⅳ的制备方法,具体步骤如下:
1)化合物Ⅱ的制备
1,1,2-三甲基-1H-苯并[e]吲哚加入CH3NO2中,搅拌溶解后加入碘代正丁烷,加热至100℃反应14-18h后停止反应,得到反应液Ⅰ,将反应液Ⅰ浓缩后缓慢滴加进乙酸乙酯中,沉淀析出,抽滤,滤饼用石油醚搅拌洗涤后再抽滤得浅灰绿色沉淀B-C4;
将B-C4、方酸、喹啉加入甲苯和正丁醇的体积比为1:1的共混溶剂中,加分水器后回流9h,得到反应液Ⅱ,将反应液Ⅱ减压浓缩后滴入乙酸乙酯中,固体析出,抽滤后将滤液旋干,加入石油醚搅拌洗涤两次,抽滤得棕绿色固体,为金属离子探针即化合物Ⅱ;
2)化合物Ⅲ的制备
室温条件下,将化合物Ⅱ与五硫化二磷在吡啶中反应26h,得到反应液Ⅲ,经过柱层析提纯,得到目标产物后用正己烷洗涤,得到纯净的墨绿色固体,为金属离子探针即化合物Ⅲ;
3)化合物Ⅳ的制备
无水无氧条件下,将化合物Ⅱ、劳森试剂、六甲基磷酰三胺、加入脱气后的甲苯中,回流反应2.5h,停止反应,得到反应液Ⅳ,将反应液Ⅳ滴入无水***中并抽滤得固体,将固体用二氯甲烷溶解后经柱层析提纯,然后重结晶得到亮铜色固体,为金属离子探针即化合物Ⅳ。
进一步地,所述的苯并吲哚方酸菁金属离子探针在检测Fe3+、Cu2+、Hg2+中的应用。
采用以上方案,本发明具有如下有益效果:
1、本发明所涉及的探针在乙腈溶液中呈蓝色或蓝绿色,在600-700nm处有强的吸收,在650-850nm处有强的荧光发射,吸收和发射均处于近红外区域,因此具有光损伤小、组织穿透能力强、自体荧光干扰低等优点。本发明中探针的溶液在分别加入Fe3+、Cu2+、Hg2+后会呈现出明显的颜色变化,可进行裸眼检测,无需借助其他设备,同时相应的吸收光谱和荧光发射光谱也发生变化,因此可通过比色和光谱测试对Fe3+、Cu2+、Hg2+进行双通道检测,且不受其他金属离子的干扰,有很好的应用前景。
2、本发明涉及的金属离子探针的合成路线简单、原料易得、操作简单。
3、本发明涉及的金属离子探针在加入Fe3+、Cu2+、Hg2+后立即出现响应现象,响应时间极短,且具有高的灵敏度,最低检测限为1.14-6.28μM。
本发明的其他优点、目标和特征在某种程度上将在随后的说明书中进行阐述,并且在某种程度上,基于对下文的考察研究对本领域技术人员而言将是显而易见的,或者可以从本发明的实践中得到教导。
附图说明
图1为化合物Ⅱ的制备流程图。
图2为化合物Ⅲ的制备流程图。
图3为化合物Ⅳ的制备流程图。
图4为化合物Ⅱ对不同金属离子选择性测试的吸收光谱。
图5为化合物Ⅳ对不同金属离子选择性测试的荧光发射光谱。
图6为其他金属离子对化合物Ⅱ识别Fe3+时的干扰性测试。
图7为化合物Ⅱ中加入不同当量比的Fe3+溶液后的吸收光谱。
图8为化合物Ⅲ中加入Fe3+后在663nm处吸收波长随时间变化。
图9为化合物Ⅲ对不同金属离子的比色显色。
具体实施方式
下面结合附图和实施例对本发明进行详细的描述,但实施例并不对本发明作任何形式的限定,除非特别说明,本发明所涉及的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1:苯并吲哚方酸菁金属离子探针的制备
1、实验方法
具体步骤如下:
1)化合物Ⅱ的制备,制备流程如图2所示;
1,1,2-三甲基-1H-苯并[e]吲哚(10.00g,47.50mmol)加入80mL CH3NO2中,搅拌溶解后加入碘代正丁烷(21.50g,95.50mmol),加热至100℃反应14h,TLC监测发现体系中仍有部分原料未反应,补加1.8mL碘代正丁烷,继续100℃加热反应4h,停止反应,得到反应液Ⅰ,将反应液Ⅰ浓缩至50mL,然后缓慢滴加进350mL乙酸乙酯中,沉淀析出,抽滤,滤饼用石油醚搅拌洗涤后再抽滤得浅灰绿色沉淀B-C4,B-C4为16g,产率86%;
将B-C4(10.00g,25.4mmol)、方酸(1.45g,12.7mmol)、喹啉(3.30g,25.4mmol)加入150mL甲苯和正丁醇的体积比为1:1的共混溶剂中,沸水中回流9h,得到反应液Ⅱ,将反应液Ⅱ减压浓缩至20mL后滴入300mL乙酸乙酯中,固体析出,抽滤后将滤液旋干,加入200mL石油醚搅拌洗涤两次,抽滤得棕绿色固体,为金属离子探针即化合物Ⅱ,化合物Ⅱ为4.16g,产率54%;
2)化合物Ⅲ的制备,制备流程如图3所示;
室温条件下,将化合物Ⅱ(0.54g,0.89mmol)与五硫化二磷(0.79g,1.80mmol)在吡啶(6mL)中反应26h,得到反应液Ⅲ,经过柱层析(200-300硅胶,洗脱剂为二氯甲烷)提纯,得到目标产物后用正己烷洗涤,得到纯净的墨绿色固体,为金属离子探针即化合物Ⅲ,化合物Ⅲ为0.39g,产率69%;
3)化合物Ⅳ的制备,制备流程如图4所示;
无水无氧条件下,将化合物Ⅱ(0.20g,0.33mmol)、劳森试剂(0.27g,0.66mmol)、六甲基磷酰三胺(HMPA,0.13mL)加入15mL脱气后的甲苯中,回流反应2.5h,停止反应,得到反应液Ⅳ,将反应液Ⅳ滴入100mL无水***中并抽滤得固体,将固体用二氯甲烷溶解后经柱层析(100-200目硅胶,洗脱剂为二氯甲烷:石油醚=1:1)提纯,然后重结晶(二氯甲烷:乙醇=1:3)得到亮铜色固体,为金属离子探针即化合物Ⅳ,化合物Ⅳ为0.07g,产率33%;
将得到的化合物Ⅱ、化合物Ⅲ、化合物Ⅳ分别经过核磁共振氢谱和碳谱进行结构鉴定。
2、实验结果
化合物Ⅱ:1H NMR(400MHz,Chloroform-d,ppm)δ8.20(d,J=8.5Hz,2H,ArH),7.90(d,J=8.6Hz,2H,ArH),7.87(d,J=8.4Hz,2H,ArH)7.58(t,J=7.7Hz,2H,ArH),7.42(t,J=7.6Hz,2H,ArH),7.29(d,J=8.7Hz,2H,ArH),6.03(s,2H,=CH),4.12(s,4H,CH2),2.09(s,12H,CH3),1.90-1.83(m,4H,CH2),1.54-1.46(m,4H,CH2),1.01(t,J=7.4Hz,6H,CH3).13CNMR(101MHz,Chloroform-d,ppm)δ178,171.4,139.7,134.4,131.2,129.7,129.6 128.7,127.3,124.3,122.6,110.2,86.3,51.2,43.7,29.4,26.8,20.4,13.9.
化合物Ⅲ:1H NMR(400MHz,Chloroform-d,ppm)δ8.22(d,J=8.5Hz,2H,ArH),7.90(t,J=7.1Hz,4H,ArH),7.57(t,J=7.8Hz,2H,ArH),7.42(t,J=7.6Hz,2H,ArH),7.34(d,J=8.9Hz,2H,ArH),6.50(s,2H,=CH),4.22(t,J=7.5Hz,4H,CH2),2.11(s,12H,CH3),1.90(q,J=7.8Hz,4H,CH2),1.54-1.47(m,4H,CH2),1.01(t,J=7.5Hz,6H,CH3).13C NMR(101MHz,Chloroform-d,ppm)δ205.7,182.8,177.9,173.2,139.6,134.7,131.4,129.8,129.7,128.6,127.4,124.5,122.5,110.4,88.9,51.3,43.8,29.5,26.7,20.4,14.0.
化合物Ⅳ:1H NMR(400MHz,Chloroform-d,ppm)δ8.21(d,J=8.5Hz,2H,ArH),7.91(t,J=8.0Hz,4H,ArH),7.59(t,J=7.7Hz,2H,ArH),7.45(t,J=7.6Hz,2H,ArH),7.37(d,J=8.0Hz,2H,ArH),6.63(s,2H,=CH),4.36(t,J=7.6Hz,4H,CH2),2.14(s,12H,CH3),1.93-1.86(m,4H,CH2),1.56-1.46(m,4H,CH2),1.02(t,J=6Hz,6H,CH3).13C NMR(101MHz,Chloroform-d,ppm)δ204.5,185.1,174.9,139.4,135.0,131.4,129.7,129.6,128.6,127.3,124.6,122.7,110.7,87.5,51.6,45.2,29.4,27.6,20.3,13.9.
实施例2:金属离子探针对不同金属离子的选择性测试
1、实验材料
实施例1中所制备的金属离子探针化合物Ⅱ、化合物Ⅲ、化合物Ⅳ
2、实验方法
向编号1-21的21支试管中分别加入10mL金属离子探针化合物Ⅱ或化合物Ⅲ或化合物Ⅳ的CH3CN溶液(1.0×10-5mol/L),再往2-21号试管中分别加入50μL不同金属离子的水溶液(Fe3+、Fe2+、Hg2+、Na+、K+、Li+、Ca2+、Ba2+、Al3+、Pb2+、Mn2+、Co2+、Cu2+、Ag+、Zn2+、Cd2+、Mg2+、Ni2+、Cr3+、Cr2+,c=0.04mol/L),振荡后静置30min,进行吸收光谱和荧光发射光谱测试。
3、实验结果
如图1、5、9所示,在加入Fe3+、Cu2+、Hg2+后,金属离子探针化合物Ⅱ或化合物Ⅲ或化合物Ⅳ溶液的颜色有明显变化,其吸收光谱和发射光谱的强度明显降低,而加入其他金属离子后溶液的颜色及光谱无明显变化,表明金属离子探针对Fe3+、Cu2+、Hg2+具有良好的识别能力。
实施例3:其他金属离子对金属离子探针识别Fe3+时的干扰性测试
1、实验材料
实施例1中所制备的金属离子探针化合物Ⅱ
2、实验方法
向编号1-21的21支试管中加入10mL金属离子探针化合物Ⅱ(1.0×10-5mol/L)的CH3CN溶液,往2-21号试管中分别加入50μL的Fe3+水溶液(0.04mol/L),再往3-21号试管中分别加入50μL的不同金属离子(Fe2+、Hg2+、Na+、K+、Li+、Ca2+、Ba2+、Al3+、Pb2+、Mn2+、Co2+、Cu2+、Ag+、Zn2+、Cd2+、Mg2+、Ni2+、Cr3+、Cr2+,c=0.04mol/L)水溶液,振荡后静置30min,进行吸收光谱和荧光发射光谱测试。
3、实验结果
如图6所示,结果表明探针分子对Fe3+识别时不受其他金属离子的干扰。
实施例4:金属离子探针对不同浓度Fe3+、Cu2+、Hg2+水溶液的响应
1、实验材料
实施例1中所制备的金属离子探针化合物Ⅱ
2、实验方法
向编号1-31的31支试管中加入10mL探针化合物Ⅱ(1.0×10-5mol/L)的CH3CN溶液,再依次向每一支试管中加入不同当量比的(0.0-20.0当量)Fe3+或Cu2+或Hg2+(0.01mol/L)水溶液,振荡后静置30min,进行吸收光谱和荧光发射光谱测试。
3、实验结果
如图7所示,随着Fe3+或Cu2+或Hg2+当量的增加,探针分子的吸收光谱和发射光谱的强度都依次降低,对实验数据进行处理和计算可得到探针分子对Fe3+、Cu2+、Hg2+的最低检测限为1.14-6.28μM。
实施例5:金属离子探针对Fe3+、Cu2+、Hg2+水溶液的响应随时间的变化情况
1、实验材料
实施例1中所制备的金属离子探针化合物Ⅲ
2、实验方法
向两面光的石英比色皿中加入2mL探针化合物Ⅲ(1.0×10-5mol/L)的CH3CN溶液,测试其吸收光谱和荧光发射光谱,测试完毕后再向比色皿中加入Fe3+或Cu2+或Hg2+(0.01mol/L)水溶液,振荡后立即进行吸收光谱和荧光发射光谱测试,随后每隔2分钟进行一次吸收光谱和荧光发射光谱测试。
3、实验结果
如图8所示,当加入Fe3+或Cu2+或Hg2+后,探针分子的最大吸收波长和最大发射波长处的强度都立即降低,随后趋于平稳,说明探针分子对金属离子响应速度快。
最后需要说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行同等替换。凡在本发明的精神和原则之内,所作的任何修改、同等替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
3.根据权利要求2所述的一种苯并吲哚方酸菁金属离子探针,其特征在于,所述化合物Ⅱ、化合物Ⅲ、化合物Ⅳ的制备方法,具体步骤如下:
1)化合物Ⅱ的制备
1,1,2-三甲基-1H-苯并[e]吲哚加入CH3NO2中,搅拌溶解后加入碘代正丁烷,加热至100℃反应14-18h后停止反应,得到反应液Ⅰ,将反应液Ⅰ浓缩后缓慢滴加进乙酸乙酯中,沉淀析出,抽滤,滤饼用石油醚搅拌洗涤后再抽滤得浅灰绿色沉淀B-C4;
将B-C4、方酸、喹啉加入甲苯和正丁醇的体积比为1:1的共混溶剂中,加分水器后回流9h,得到反应液Ⅱ,将反应液Ⅱ减压浓缩后滴入乙酸乙酯中,固体析出,抽滤后将滤液旋干,加入石油醚搅拌洗涤两次,抽滤得棕绿色固体,为金属离子探针即化合物Ⅱ;
2)化合物Ⅲ的制备
室温条件下,将化合物Ⅱ与五硫化二磷在吡啶中反应26h,得到反应液Ⅲ,经过柱层析提纯,得到目标产物后用正己烷洗涤,得到纯净的墨绿色固体,为金属离子探针即化合物Ⅲ;
3)化合物Ⅳ的制备
无水无氧条件下,将化合物Ⅱ、劳森试剂、六甲基磷酰三胺、加入脱气后的甲苯中,回流反应2.5h,停止反应,得到反应液Ⅳ,将反应液Ⅳ滴入无水***中并抽滤得固体,将固体用二氯甲烷溶解后经柱层析提纯,然后重结晶得到亮铜色固体,为金属离子探针即化合物Ⅳ。
4.根据权利要求1-3任一项所述的苯并吲哚方酸菁金属离子探针在检测Fe3+、Cu2+、Hg2+中的应用。
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