CN108640867B - 一种含有氰基-咔唑基席夫碱荧光探针化合物及其制备方法和用途 - Google Patents
一种含有氰基-咔唑基席夫碱荧光探针化合物及其制备方法和用途 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种含有氰基-咔唑基席夫碱荧光探针化合物及其制备方法和用途,属于金属离子检测和荧光分子探针领域。
背景技术
重金属离子污染已经在全球范围内成为一个非常严重的问题,这是由于有些重金属离子即使在浓度非常低的情况下也会对环境和人体产生潜在危害,其中的许多元素能够在各种生物体中积累起来,严重地威胁着人类和各种生命体的安全,对它们的识别和检测在分析化学中占有重要地位。
近年来,随着化学传感器的迅速发展,荧光探针研究在化学、生物、医学及环境等诸多领域的应用受到人们越来越多的关注,成为目前的一大研究热点。荧光探针技术因具有选择性好、灵敏度高、简单快速且不需要借助昂贵仪器的优点而被广泛地应用于各种金属离子的检测。利用紫外/荧光性能与离子浓度的关系可以对离子进行定量或定性的分析,方便、快捷,具有较高的选择性和灵敏度,非常适合于重金属离子的实时或原位检测。
铜是生命系统中重要的微量元素和必需的营养素。铜的毒性很小,但铜缺乏可导致生长和代谢的紊乱。铜在细胞中平衡的改变会导致抑制神经性疾病,如Menkes综合症、Wilson病、家族遗传性脊侧索硬化、Alzheimers病和Prion病等。正是由于铜对于生命的重要,铜在细胞中的分布受到严格的控制。此外,铜具有可变价态,在生命体中参与电子传递、氧化还原等一系列过程,直接研究以及模拟铜蛋白和铜酶一直是科学家研究的热点。因此,建立一种简便、灵敏的方法检测铜离子是很有必要的。
荧光检测法具有灵敏度高、选择性专一及响应时间短等优点,近几年来备受人们的关注。近年来,荧光探针的研究和应用已经取得了很大的进展。荧光探针是利用探针与目标物质结合前后荧光性质的变化实现对目标物质的识别检测,具有选择性好、灵敏度高、实时原位检测及操作方法简便等优势。
发明内容
本发明旨在提供一种含有氰基-咔唑基席夫碱荧光探针化合物及其制备方法和用途。由于荧光探针的识别性能与探针分子的空间结构有关,所以本发明基于C=N异构化机理,以咔唑基-氰基取代的胺为荧光发色团母体,设计并合成了具有C=N结构的席夫碱衍生物,同时分子中含有O和N配位原子,可以与一些金属离子形成配位分子,产生特定的紫外、荧光现象。
本发明含有氰基-咔唑基席夫碱荧光探针化合物,是席夫碱化合物其结构中含有N-取代咔唑基团、氰基基团和(N,N-二乙氨基)苯酚基团,该探针化合物具有C=N结构的席夫碱衍生物,同时分子中含有O和N配位原子,可以与一些金属离子形成配位分子,产生特定的紫外、荧光现象。
本发明含有氰基-咔唑基席夫碱荧光探针化合物,结构式如下:
本发明含有氰基-咔唑基席夫碱荧光探针化合物的制备方法,是由基于咔唑的氰基取代胺的化合物与4-(N,N-二乙氨基)水杨醛缩合反应得到的。具体包括如下步骤:
步骤1:中间体的制备
取咔唑单醛0.502g(2mmol)于100mL的圆底烧瓶中,加入3mL二氯甲烷完全溶解,然后加入对氨基苯乙腈0.3g和30mL乙醇,再滴加1.5mL的TBAH(四丁基氢氧化铵)作为催化剂,用薄层色谱法监测反应进程,80℃反应12小时;反应结束后冷却至室温,有黄色沉淀析出,旋干有机相得黄色固体,用二氯甲烷溶解后倒入烧杯中,再加入100mL乙醇搅拌,有大量黄色固体析出,过滤,乙醇洗涤,收集固体干燥后得中间体——2-(4-氨基苯基)-3-(9-丁基-9H-咔唑基)-丙烯腈0.44g,为桔红色固体,产率约60%。
步骤2:目标产物的制备
取步骤1制备的中间体0.365g(1mmol)于50mL圆底烧瓶中,用CH2Cl2完全溶解后再加入0.233g(1.2mmol)4-(二乙氨基)水杨醛和20mL无水乙醇,80℃反应12小时,有黄色沉淀析出,冷却后过滤,将所得的固体放入200mL烧杯中加入少量CH2Cl2溶解,再倒入100mL石油醚中搅拌10分钟,过滤,滤渣用乙醇冲洗三次,干燥后称量得红褐色固体0.41g,即为目标产物CN1,产率约为75.6%。
本发明合成路线如下:
本发明含有氰基-咔唑基席夫碱荧光探针化合物的用途,是在定性或定量检测Cu2+时作为检测试剂应用。
本发明含有氰基-咔唑基席夫碱荧光探针化合物的应用,是在含水介质中进行紫外-可见吸收光谱测定,通过溶液颜色的变化实现对Cu2+的定性或定量检测。
所述含水介质为乙腈和水按体积比1:1构成的混合溶液。
本发明含有氰基-咔唑基席夫碱荧光探针化合物的应用,是在含水介质中进行荧光光谱测定,通过荧光强度的变化实现对Cu2+的定性或定量检测。
所述含水介质为乙腈和水按体积比1:1构成的混合溶液。
本发明目标产物具有C=N结构,含有取代氰基-咔唑基席夫碱荧光探针席夫碱衍生物,其分子结构特征是席夫碱化合物结构中含有亲水的氰基基团,同时分子中含有O和N配位原子,可以在含水介质中与一些金属离子结合形成配位分子,产生特定的紫外、荧光现象。
本发明荧光探针化合物可用于Cu2+离子的识别、检测,对多种金属离子有较强的抗干扰能力,并且本发明荧光探针化合物与Cu2+离子混合产生明显的颜色变化现象可以实现裸眼识别和比色分析。
本发明的效果体现在:
本发明荧光探针化合物具有多功能性,可以通过紫外-可见分光光度法和荧光光谱法分别实现对Cu2+离子的识别。本发明荧光探针化合物可用于在含水的介质中对Cu2+离子的快速识别、定量检测,而且对Cu2+离子识别具有较高的选择性和较好的抗干扰能力,并且明显的颜色变化现象可以实现裸眼识别和比色分析。
附图说明
图1为化合物CN1在乙腈和水体积比为1:1的混合溶液中加入不同金属离子的紫外吸收光谱。
图2为加入Cu2+后CN1的颜色变化(左1为CN1+Cu2+,右依次为CN1中加入不同的金属离子)。
图3为加入Cu2+离子的荧光探针化合物CN1在乙腈和水体积比为1:1的混合溶液紫外-可见吸收光谱滴定光谱图。
图4为化合物CN1在乙腈和水体积比为1:1的混合溶液中的金属离子选择性和抗干扰柱状图;代表CN1在乙腈和水体积比为1:1的混合溶液中的紫外吸收强度;代表CN1在乙腈和水体积比为1:1的混合溶液中加入不同金属离子的紫外吸收强度;代表在CN1乙腈和水体积比为1:1的混合溶液中加入不同金属离子和Cu2+离子的紫外吸收强度(λmax=430nm)。
图5为荧光探针化合物CN1在乙腈和水体积比为1:1的混合溶液中加入不同金属离子的荧光光谱(λex=430nm)(左1为CN1+Cu2+,右为CN1)。
图6为加入Cu2+后在紫外灯照射下CN1的颜色变化图像。
图7中为荧光探针化合物CN1在乙腈和水体积比为1:1的混合溶液中Cu2+的荧光滴定光谱(λex=430nm)。
图8为荧光探针化合物CN1在乙腈和水体积比为1:1的混合溶液中金属离子选择性和抗干扰柱状图;代表CN1在乙腈和水体积比为1:1的混合溶液中的荧光强度;代表CN1乙腈溶液中加入不同金属离子的荧光强度;代表在乙腈和水体积比为1:1的混合溶液中加入不同金属离子和Cu2+离子的荧光强度(λem=530nm)。
具体实施方式
本发明可以通过以下的实施例进一步说明,但不仅仅局限于实施例。
实施例1:化合物CN1的合成
取咔唑单醛0.502g(2mmol)于100mL的圆底烧瓶中加入约3mL二氯甲烷完全溶解,然后向该烧瓶中加入对氨基苯乙腈0.3g和30mL乙醇,再滴加1.5mL的TBAH(四丁基氢氧化铵)作为催化剂,用薄层色谱法监测反应进程,80℃反应12小时。冷却反应混合物,有少量黄色沉淀析出,旋干有机相得黄色固体,用少量二氯甲烷溶解后倒入烧杯中,再加入100mL乙醇搅拌,有大量黄色固体析出快速抽滤,用乙醇洗涤抽滤所得固体三次,收集固体干燥后称量得桔红色固体0.44g,产率约60%。
FT-IR(KBr,cm-1):3450(-N-H),2964,2875(-CH2,-CH3),2208(-CN),1631,1516(-C=C-),715(-Ar).1H NMR(600MHz,DMSO):δ(ppm)8.85(s,1H),8.12(d,1H,J=7.80),8.08(d,1H,J=8.40),7.84(s,1H),7.73(d,1H,J=8.40),7.66(d,1H,J=8.40),7.51(t,1H,J=7.20),7.46(d,2H,J=8.40),7.27(t,1H,J=7.20),6.67(d,2H,J=8.40),5.57(s,2H,-NH2),4.44(t,2H),1.77(m,2H),1.33(m,2H),0.89(t,3H).MS(ESI)m/z:[M+H]+,366.1968for C25H23N3.
取2-(4-氨基苯基)-3-(9-丁基-9H-咔唑基)-丙烯腈0.365g(1mmol)于50mL圆底烧瓶中用少量CH2Cl2完全溶解后再加入0.233g(1.2mmol)4-(二乙氨基)水杨醛和20mL无水乙醇,80℃反应12小时,有大量黄色沉淀析出,冷却之后过滤,将所得的固体放入200mL烧杯中加入少量CH2Cl2溶解后,再倒入100mL石油醚中搅拌10分钟,过滤,滤渣用乙醇冲洗三次,干燥后称量得红褐色固体0.41g,产率约为75.6%。
FT-IR(KBr,cm-1):3448(-OH),2962,2872(-CH3、-CH2),2208(-CN),1626(-C=N),1585,1522(-Ar),1350(-C-H),1211,1130(-C-N),745(-N-H)。1H NMR(600MHz,CDCl3):δ(ppm)8.67(s,1H),8.49(s,1H),8.18(t,2H),7.75(t,2H,J=7.80),7.54~7.47(m,4H),7.34(m,3H),7.21(s,1H),6.30(d,2H,J=7.20),4.36(t,2H),3.46(d,4H),1.91(m,2H),1.45(m,2H),1.26(m,6H),0.99(t,3H).MS-ESI:m/z[M+H]+,541.2946for C36H36N4O.
实施例2:荧光探针化合物CN1的紫外-可见吸收光谱测定
准确称量荧光探针化合物CN1 5.4mg,溶解并配制成浓度为1.0×10-2mol/L的乙腈储备溶液;用乙腈和水体积比为1:1的混合溶液将储备液稀释成浓度为1.0×10-5mol/L的待测溶液。取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中(石英比色皿的厚度为1cm),然后分别加入3μL浓度为1.0×10-2mol/L的各种金属离子(Na+,K+,Ag+,Ca2+,Mg2+,Mn2+,Cd2+,Cr3+,Cu2+,Ni2+,Co2+,Fe3+,Hg2+)的水溶液,摇匀,1分钟后测定溶液的紫外-可见吸收光谱(见附图图1)。加入金属离子前,化合物CN1的紫外-可见吸收光谱显示在430nm有一个明显的吸收峰,当加入Cu2+离子之后,CN1在430nm处的吸收峰减弱,在418nm处出现一个新的吸收峰,其溶液颜色也由黄绿色变为无色(如附图图2所示),肉眼即可观察出,具有“裸眼识别”功能,化合物CN1可以作为紫外识别和裸眼识别Cu2+离子的比色探针;而在相同条件下,其他金属离子如:Na+,K+,Ag+,Ca2+,Mg2+,Mn2+,Cd2+,Cr3+,Zn2+,Ni2+,Co2+,Fe3+,Hg2+的加入对CN1大的紫外-可见吸收光谱均无明显影响,溶液颜色基本没有发生变化。
实施例3:化合物CN1的紫外-可见吸收光谱滴定实验及检测限的测定
取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中,分别加入3、6、9μL浓度为1.0×10-3mol/L的Cu2+离子水溶液及1.2、1.5、1.8、2.1、2.4、2.7、3.0μL浓度为1.0×10- 2mol/L的Cu2+离子水溶液,摇匀后测定溶液的紫外-可见吸收光谱(如附图图3所示)。随着Cu2+离子的加入,化合物CN1在430nm处的吸光度逐渐减弱并蓝移至418nm处,且在478nm处出现一个明显的等量点,说明在乙腈和水体积比为1:1的混合溶液中化合物CN1能与Cu2+离子形成稳定的配合物,Cu2+离子在1.0×10-6~1.2×10-5mol/L范围内,Cu2+离子浓度与418nm处吸光度变化量呈较好的线性关系(R2=0.99),通过计算得出化合物CN1对Cu2+离子的检测限为1.14×10-5mol/L。
实施例4:荧光探针化合物CN1对Cu2+离子识别的选择性和抗干扰性
取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中,加入3μL浓度为1.0×10-2mol/L的Cu2+离子后,再分别加入3μL浓度为1.0×10-2mol/L的各种金属离子(Na+,K+等)溶液,摇匀,1分钟后测定其紫外吸收光谱(如附图图4所示),结果显示加入其它金属离子如:Na+,K+等均对荧光探针化合物CN1的紫外吸收性能几乎没有影响,这就表明了荧光探针化合物CN1对Cu2+离子识别具有较高的选择性和较好的抗干扰能力。
实施例5:荧光探针化合物CN1的荧光光谱测定
取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中,然后分别加入3μL浓度为1.0×10-2mol/L的各种金属离子(Na+,K+,Ag+,Ca2+,Mg2+,Mn2+,Cd2+,Cr3+,Cu2+,Ni2+,Co2+,Fe3+,Hg2+)溶液,摇匀,1分钟后在λ=430nm的激发波长下测定其荧光发射光谱(如附图图5所示),结果显示没有加入金属离子时,荧光探针化合物CN1在λ=530nm处有个较强的荧光峰,Cu2+离子加入后化合物CN1在530nm处荧光几乎完全猝灭,而其它金属离子如:Na+,K+等均无明显荧光增强或猝灭现象;同时在365nm荧光灯的照射下可以看到溶液的颜色发生明显变化,由蓝绿色变成明亮的蓝色(如附图图6所示)。
实施例6:荧光探针化合物CN1的荧光光谱滴定实验及检测限的测定
取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中,分别加入3、6、9μL浓度为1.0×10-3mol/L的Cu2+离子水溶液及1.2、1.5、1.8、2.1、2.4、2.7、3.0、3.3、3.6、3.9、4.2、4.5μL浓度为1.0×10-2mol/L的Cu2+离子水溶液,摇匀,平衡后测定溶液的荧光光谱(如附图图7所示),随着Cu2+离子的加入,化合物CN1在λem=530nm处的荧光强度逐渐减弱。通过离子浓度与荧光强度的关系曲线可知,在0.5×10-6~1.5×10-5mol/L范围内,Cu2+离子浓度与荧光强度呈较好的线性关系(R=0.99),化合物CN1对Cu2+离子的检测限为1.26×10-5mol/L。
实施例7:荧光探针化合物CN1对Cu2+离子识别的选择性和抗干扰性
取3mL浓度为1.0×10-5mol/L的待测溶液于石英比色皿中,加入3μL浓度为1.0×10-2mol/L的Cu2+离子后,再分别加入3μL浓度为1.0×10-2mol/L的各种金属离子(Na+,K+等)溶液,摇匀,1分钟后在λ=500nm的激发波长下测定其荧光发射光谱(如附图图8所示),结果显示加入其它金属离子如:Na+,K+等均对荧光探针化合物CN1的荧光强度几乎没有影响,这就表明了荧光探针化合物CN1对Cu2+离子识别具有较高的选择性和较好的抗干扰能力。
Claims (8)
2.一种权利要求1所述的含有氰基-咔唑基席夫碱荧光探针化合物的制备方法,其特征在于:是由基于咔唑的氰基取代胺的化合物与4-(N,N-二乙氨基)水杨醛缩合反应得到。
3.根据权利要求2所述的制备方法,其特征在于包括如下步骤:
步骤1:中间体的制备
取咔唑单醛2mmol于圆底烧瓶中,加入二氯甲烷完全溶解,然后加入对氨基苯乙腈0.3g和30mL乙醇,再滴加1.5mL的四丁基氢氧化铵作为催化剂,用薄层色谱法监测反应进程,80℃反应12小时;反应结束后冷却至室温,有黄色沉淀析出,旋干有机相得黄色固体,用二氯甲烷溶解后倒入烧杯中,再加入乙醇搅拌,有大量黄色固体析出,过滤,乙醇洗涤,收集固体干燥后得中间体——2-(4-氨基苯基)-3-(9-丁基-9H-咔唑基)-丙烯腈,为桔红色固体;
步骤2:目标产物的制备
取步骤1制备的中间体1mmol于圆底烧瓶中,用CH2Cl2完全溶解后再加入1.2mmol 4-(二乙氨基)水杨醛和无水乙醇,80℃反应12小时,有黄色沉淀析出,冷却后过滤,将所得的固体放入烧杯中加入CH2Cl2溶解,再倒入石油醚中搅拌10分钟,过滤,滤渣用乙醇冲洗三次,干燥后称量得红褐色固体,即为目标产物。
4.一种权利要求1所述的含有氰基-咔唑基席夫碱荧光探针化合物在制备用于定性或定量检测Cu2+的检测试剂中的应用。
5.根据权利要求4所述的应用,其特征在于:
是在含水介质中进行紫外-可见吸收光谱测定,通过溶液颜色的变化实现对Cu2+的定性或定量检测。
6.根据权利要求5所述的应用,其特征在于:
所述含水介质为乙腈和水按体积比1:1构成的混合溶液。
7.根据权利要求4所述的应用,其特征在于:
是在含水介质中进行荧光光谱测定,通过荧光强度的变化实现对Cu2+的定性或定量检测。
8.根据权利要求7所述的应用,其特征在于:
所述含水介质为乙腈和水按体积比1:1构成的混合溶液。
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CN104498022A (zh) * | 2014-10-10 | 2015-04-08 | 安徽大学 | 一种用于Cr3+检测与识别的含有咔唑-苯并咪唑基比率荧光探针化合物及其制备方法 |
CN107417681A (zh) * | 2017-06-15 | 2017-12-01 | 安徽大学 | 一种含有香豆素‑噻二唑基席夫碱荧光探针化合物及其制备方法和用途 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN107417681A (zh) * | 2017-06-15 | 2017-12-01 | 安徽大学 | 一种含有香豆素‑噻二唑基席夫碱荧光探针化合物及其制备方法和用途 |
Non-Patent Citations (2)
Title |
---|
Fluorescein-based fluorescent and colorimetric chemosensors for copper in aqueous media;Fasil A. Abebe,等;《Tetrahedron Letters》;20110803;5234-5237 * |
基于咔唑衍生物离子受体的合成及识别研究;赵国有;《渤海大学硕士学位论文》;20151231;全文 * |
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