CN109608364B - 一种用于检测汞离子的荧光探针制备方法与应用 - Google Patents
一种用于检测汞离子的荧光探针制备方法与应用 Download PDFInfo
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- C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
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Abstract
本发明涉及一种用于检测汞离子的荧光探针制备方法与应用,该荧光探针是一类点亮型的α‑氰基二苯乙烯类衍生物。本发明所述荧光探针,化学名为(Z)‑2‑(4‑(2‑氰基‑2‑(4‑硝基苯基)乙烯基)苯基氨甲酰基苯甲酸。本发明所述荧光探针由对乙酰氨基苯甲醛和对硝基苯乙腈在哌啶的催化下缩合生成α‑氰基二苯乙烯类中间产物后,再用盐酸脱去乙酰基保护基后与邻苯二甲酸酐反应得到。该荧光探针在溶液中显浅黄色,在四氢呋喃和水体积比为1:4的溶液体系中在550nm处几乎不发出荧光,识别汞离子后,荧光显著增强,对汞离子能高灵敏选择性识别,最低检测限为0.1μM,其它离子干扰小,是一种理想的汞离子快速检测传感器。
Description
技术领域
本发明属于有机合成与分析化学技术领域,具体涉及一种用于检测汞离子的荧光探针制备方法与应用。
背景技术
由于荧光探针的高选择性和灵敏度,现已广泛应用于阳离子和阴离子的检测当中。这些荧光探针很容易被修饰,以适应不同的测试环境和测试物,但常见的有机荧光探针在水溶液中容易荧光猝灭,限制了其应用范围。聚集诱导发光效应能克服不良溶剂中的荧光猝灭现象,在水溶液中作为荧光探针有很好的应用前景。α-氰基二苯乙烯类化合物具有较强的聚集诱导发光能力,通过适当结构修饰与离子配合后可以发出明显荧光,展现出很好的应用前景。
汞是在自然环境中毒性最强的重金属之一,汞单质及汞的二价阳离子(Hg2+)在排入环境后,可被微生物转化为甲基汞,它可以通过食物链在生物体内富集,当汞离子或者有机汞被人体吸收后容易使人产生恶心、呕吐、腹痛以及肾功能的损伤,同时对脑部也有很大的伤害。目前,人类活动造成的全球汞污染十分严重,世界各地对汞的排放有着严格的要求,所以在环境或者生物样品中能快速简便地检测汞离子显得尤为重要。本发明设计合成的一种α-氰基二苯乙烯类汞离子荧光探针,在四氢呋喃和水的体积比为1:4的溶液中形成的纳米聚集态几乎不发光,在与二价汞离子络合后,发出强烈荧光,能高选择性灵敏检测二价汞离子。
发明内容
本发明的一个目的在于提供一种能够用于汞离子检测的荧光探针及其制备方法,通过明显的荧光增强可以灵敏地检测到汞离子的存在,有很好的应用前景。
为实现本发明的目的采用以下技术方案。
1)本发明所述的一种用于检测汞离子的荧光探针,其化学名为(Z)-2-(4-(2-氰基-2-(4-硝基苯基)乙烯基)苯基氨甲酰基苯甲酸(化合物3),该荧光探针是一种链端带羧基的α-氰基二苯乙烯类化合物,其具体结构为:
2)所述荧光探针(化合物3)的制备方法。
(1)本发明所述荧光探针合成路线如下:
(2)荧光探针的制备方法,具体包括以下步骤:
①将对乙酰氨基苯甲醛和对硝基苯乙腈以摩尔比1:1的比例,溶解于二氯甲烷中,加入催化剂哌啶,常温反应后过滤得到化合物1,所述化合物1为(Z)-3-(4-乙酰氨基苯基)-2-(4-硝基苯基)丙烯腈,化合物1的结构式如下:
催化剂哌啶与对硝基苯乙腈摩尔比为1:0.1~10,常温反应时间3~20小时;
②将化合物1和浓盐酸加到1,4-二氧六环中,回流反应,过滤得化合物1的盐酸盐,用碳酸氢钠中和处理后得到化合物2;所述化合物2为(Z)-3-(4-氨基苯基)-2-(4-硝基苯基)丙烯腈,化合物2的结构式如下:
其中:盐酸与化合物1的摩尔比为40:0.5~3,回流反应温度100℃,回流反应6-24小时;
③将化合物2与邻苯二甲酸酐混合加入四氢呋喃中,反应后过滤得所述荧光探针,所述荧光探针为(Z)-2-(4-(2-氰基-2-(4-硝基苯基)乙烯基)苯基氨甲酰基苯甲酸(化合物3)。
其中化合物2与邻苯二甲酸酐的摩尔比为1:1~10,反应时间3~12小时。
本发明的一个较优公开例中,所述荧光探针合成反应步骤1)中,对硝基苯乙腈和催化剂哌啶的摩尔比为1:1,常温反应时间8小时。
本发明的一个较优公开例中,所述荧光探针合成反应步骤2)中,盐酸与化合物1的摩尔比为40:1,100℃反应12小时。
本发明的一个较优公开例中,所述荧光探针合成反应步骤3)中,邻苯二甲酸酐与化合物2的摩尔比为4:1,室温反应10个小时。
本发明制得的荧光探针(化合物3),其分子式为C23H15N3O5,红外光谱(KBr),v/cm-1:3315(O-H),1688(O=C),1589(N-H),1518(NO2),1413(C-N),1344(NO2),1260(C-O).核磁氢谱(400MHz,d6-DMSO)δ:13.19(bs,1H,COOH),10.77(s,1H,NH),8.33(d,J=8.8Hz,2H,ArH),8.23(s,1H,C=CH),8.06-7.97(m,4H,ArH),7.96-7.85(m,3H,ArH),7.73-7.65(m,1H,ArH),7.64-7.55(m,2H,ArH).核磁碳谱(100MHz,d6-DMSO)δ:173.14,172.51,152.28,151.11,147.79,145.66,143.76,137.12,136.05,135.01,134.88,133.21,133.03,131.87,129.53,124.50,122.94,111.16.高分辨质谱(m/s):计算值C23H15N3O5 413.1012(M)+,测量值413.2749。
(3)荧光探针的应用,具体包括以下步骤:
本发明所制备的荧光探针在不含汞离子溶液中显浅黄色,在550nm几乎无荧光发射;该荧光探针在含汞离子溶液中与汞离子形成1:1络合物,发出高荧光,据此可用于环境中汞离子的灵敏检测,其它离子干扰小,是一种理想的汞离子快速检测传感器。
本发明所制备的荧光探针可对汞离子进行定性、定量的检测,将浓度呈梯度变化的汞离子溶液与荧光探针溶液混合后,测定相应的荧光强度,然后以汞离子的浓度为横坐标,荧光强度为纵坐标作图,可根据荧光强度从图中读出待测溶液中的汞离子浓度。
本发明的有益成果:所制备的荧光探针在汞离子存在下荧光发生显著改变,其它离子的存在不干扰汞离子的检测,检测限为0.1μM,低于汞离子国家安全排放标准,可用于高选择性高灵敏性地检测汞离子,这对于复杂环境中汞离子的检测有重要的现实应用价值。
附图说明
图1为荧光探针与多种离子的紫外吸收图谱。
图2为荧光探针与不同浓度的汞离子的紫外吸收图谱。
图3为荧光探针与多重离子激发波长400nm的荧光发射图谱。
图4为荧光探针与不同浓度的汞离子的荧光图谱。
图5为荧光探针与汞离子和干扰离子的荧光强度比值图。
图6为荧光探针的红外光谱图。
图7为荧光探针络合汞离子后络合物的红外光谱图。
图8为羧基探针的核磁共振氢谱图,确定了羧基探针的结构。
图9为羧基探针的核磁共振碳谱图,确定了羧基探针的结构。
图10为羧基探针的高分辨质谱图。
图11为羧基探针的maldi质谱图。
图12为羧基探针络合汞离子后的maldi质谱图,说明羧基探针能与汞离子以1:1的计量比络合。
具体实施方式
为了进一步说明本发明,给出以下系列具体实施例,但本发明并不受这些具体实施例的限制,任何了解该领域的技术人员对本发明的些许改动将可以达到类似的结果,这些改动也包含在本发明之中。
图1中,横坐标为波长,纵坐标为吸光度;溶液体系中四氢呋喃和水体积比为4:1的溶液,荧光探针浓度为1×10-5mol/L;多种离子的浓度各自为1×10-5mol/L。
图2中,横坐标为波长,纵坐标为吸光度。溶液体系中四氢呋喃和水体积比为4:1,荧光探针为浓度2×10-5mol/L,不同浓度的汞离子的浓度依次为荧光探针浓度的0、0.1、0.2、0.4、0.5、0.6、0.7、0.8、1、2、4、8、10、20、50倍。
图3中,横坐标为波长、纵坐标为相对荧光强度。溶液体系中四氢呋喃比水体积比为4:1,荧光探针为浓度2×10-5mol/L,多种离子各自浓度为2×10-5mol/L,在激发波长400nm时荧光强度上升越大,表示荧光探针对离子识别响应越高。图中显示,荧光探针只对汞离子有明显响应,说明荧光探针对汞离子能选择性识别。
图4中,横坐标为波长,纵坐标为相对荧光强度。溶液体系中四氢呋喃和水体积比为4:1的溶液,荧光探针为浓度2×10-5mol/L,不同浓度的汞离子浓度依次为荧光探针浓度的0、0.1、0.2、0.4、0.5、0.6、0.7、0.8、1、2、4、8、10、20、50倍。图中显示,荧光探针随着汞离子浓度的升高,荧光发射强度迅速升高。
图5中,纵坐标为荧光强度的比值。溶液体系中四氢呋喃和水体积比为4:1,荧光探针浓度为2x10-5mol/L,汞离子浓度为2x10-5mol/L汞离子或2x10-5mol/L,和干扰离子浓度为2x10-5mol/L。从图5看出,所有比值均接近1,比值越接近1说明干扰离子的干扰能力越小,说明其它离子基本不干扰本发明荧光探针对汞离子的高灵敏检测。
图6确定了荧光探针的各官能团,确定了荧光探针的结构。
图7中,为荧光探针络合汞离子后与络合汞离子之前的红光谱图相比,探针上3315处的羧基上的羟基的伸缩振动峰几乎消失,1688处的碳基伸缩振动峰变弱,1260处的羧基的C-O伸缩振动峰变弱和在1384处多出羧酸根的对称伸缩振动峰,说明了荧光探针的羧基在选择性识别汞离子中发挥了重要作用。
实施例1
1、向装有150mL二氯甲烷的三口烧瓶中加入对乙酰氨基苯甲醛1g(6.1mmol)和对硝基苯乙腈1g(6.1mmol),搅拌均匀后加入0.6mL(6.5mmol)哌啶,常温反应3小时,蒸去溶剂,加入甲醇沉淀,过滤得到化合物1,产率75%。
2、将1.4g(4.5mmol)化合物1和20mL浓盐酸加到20mL 1,4-二氧六环中,回流反应6小时,过滤得化合物的盐酸盐,将其加到50mL水中,加碳酸氢钠中和pH=7,过滤出沉淀,得到化合物2,产率85%。
3、将0.85g(3.2mmol)化合物2与0.48g(3.2mmol)邻苯二甲酸酐加入50mL四氢呋喃中,反应3小时,过滤得所述荧光探针(化合物3),产率85%,其分子式为C23H15N3O5,红外光谱(KBr),v/cm-1:3315(O-H),1688(O=C),1589(N-H),1518(NO2),1413(C-N),1344(NO2),1260(C-O).核磁氢谱(400MHz,d6-DMSO)δ:13.19(bs,1H,COOH),10.77(s,1H,NH),8.33(d,J=8.8Hz,2H,ArH),8.23(s,1H,C=CH),8.06-7.97(m,4H,ArH),7.96-7.85(m,3H,ArH),7.73-7.65(m,1H,ArH),7.64-7.55(m,2H,ArH).核磁碳谱(100MHz,d6-DMSO)δ:173.14,172.51,152.28,151.11,147.79,145.66,143.76,137.12,136.05,135.01,134.88,133.21,133.03,131.87,129.53,124.50,122.94,111.16.高分辨质谱(m/s):计算值C23H15N3O5413.1012(M)+,测量值413.2749。
实施例2
1、向装有150mL二氯甲烷的三口烧瓶中加入对乙酰氨基苯甲醛1g(6.1mmol)和对硝基苯乙腈1g(6.1mmol),搅拌均匀后加入0.06mL(0.65mmol)哌啶,常温反应20小时,蒸去溶剂,加入甲醇沉淀,过滤得到化合物1,产率71%。
2、将1.4g(4.5mmol)化合物1和50mL浓盐酸加到20mL 1,4-二氧六环中,回流反应24小时,过滤得化合物的盐酸盐,将其加到40mL水中,加碳酸氢钠中和pH=7,过滤出沉淀,得到化合物2,产率89%。
3、将0.85g(3.2mmol)化合物2与4.8g(32mmol)邻苯二甲酸酐加入50mL四氢呋喃中,反应12小时,过滤得所述荧光探针(化合物3),产率90%,荧光探针表征结果与实施例1一致。
,实施例3
1、向装有150mL二氯甲烷的三口烧瓶中加入对乙酰氨基苯甲醛1g(6.1mmol)和对硝基苯乙腈1g(6.1mmol),搅拌均匀后加入6mL(65mmol)哌啶,常温反应6小时,蒸去溶剂,加入甲醇沉淀,过滤得到化合物1,产率86%。
2、将1.4g(4.5mmol)化合物1和18mL浓盐酸加到20mL 1,4-二氧六环中,回流反应18小时,过滤得化合物的盐酸盐,将其加到40mL水中,加碳酸氢钠中和pH=7,过滤出沉淀,得到化合物2,产率92%。
3、将0.85g(3.2mmol)化合物2与2.4g(16mmol)邻苯二甲酸酐加入四氢呋喃中,反应6小时,过滤得所述荧光探针(化合物3),产率91%,其结构表征与实施例1一致。
以上所述仅为本发明的实施例,并非因此限制本发明的保护范围,凡是利用本发明说明书及附图内容所作的等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (4)
1.一种用于检测汞离子的荧光探针的制备方法,其特征在于:其包括以下步骤:
1)将对乙酰氨基苯甲醛和对硝基苯乙腈溶解于二氯甲烷中,加入催化剂哌啶,过滤得到化合物1,所述化合物1为(Z)-3-(4-乙酰氨基苯基)-2-(4-硝基苯基)丙烯腈,化合物1的结构式如下:
2)将化合物1和浓盐酸加到1,4-二氧六环中回流反应,过滤得化合物1的盐酸盐,用碳酸氢钠中和处理后得到化合物2;
所述化合物2为(Z)-3-(4-氨基苯基)-2-(4-硝基苯基)丙烯腈,化合物2的结构式如下:
3)将化合物2与邻苯二甲酸酐混合加入四氢呋喃中反应,过滤得所述化合物3荧光探针;所述荧光探针为(Z)-2-(4-(2-氰基-2-(4-硝基苯基)乙烯基)苯基氨甲酰基苯甲酸;荧光探针结构式如下:
步骤1)所述催化剂哌啶与对硝基苯乙腈摩尔比为1:0.1~10,常温反应时间3~20小时;
步骤2)中所述盐酸与化合物1的摩尔比为40:0.5~3;回流反应温度100℃,回流反应6-24小时;
步骤3)所述化合物2与邻苯二甲酸酐以摩尔比为1:1~10比例,反应时间3~12小时。
2.根据权利要求1所述的一种用于检测汞离子的荧光探针的制备方法,其特征在于步骤1)所述对硝基苯乙腈和催化剂哌啶的摩尔比为1:1,常温反应时间8小时。
3.根据权利要求1所述的一种用于检测汞离子的荧光探针的制备方法,其特征在于步骤2)所述盐酸与化合物1的摩尔比为40:1,回流反应时间为12小时。
4.根据权利要求1所述的一种用于检测汞离子的荧光探针的制备方法,其特征在于步骤2)所述邻苯二甲酸酐与化合物2的摩尔比为4:1,室温反应时间10个小时。
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