CN105566247A - 一种苯并噻唑克酮酸菁比色探针、制备方法及应用 - Google Patents
一种苯并噻唑克酮酸菁比色探针、制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种苯并噻唑克酮酸菁比色探针,苯并噻唑克酮酸菁比色探针的制备方法为3-乙基-2甲基苯并噻唑-3碘盐的制备和苯并噻唑克酮酸菁染料的制备。本发明的有益效果是:苯并噻唑克酮酸菁染料合成过程较为简单,反应条件容易控制,通过简单的后处理就能够得到纯的产物,并且苯并噻唑克酮酸菁染料具有优良的光学性能和光学稳定性;苯并噻唑克酮酸箐染料为固体粉末,便于储存,具有良好的前景;通过加入EDTA,考察其对探针识别的影响,发明了一种开关式的铁离子和铜离子传感器。
Description
技术领域
本发明涉及一种苯并噻唑克酮酸菁比色探针、制备方法及应用。
背景技术
铁和铜是维持人体正常生理机能和组织结构所必须的微量元素,铁是人体血红蛋白、肌球蛋白和细胞色素中的重要成分。研究表明,缺铁会引起缺铁性贫血和再生障碍性贫血,容易使人产生四肢无力和气喘症状;当机体内的铜离子浓度超出或低于细胞所需的浓度范围时就会扰乱生命系统的正常活动而使细胞中毒,从而引起严重的铜代谢障碍疾病,比如肝豆状核变性疾病,阿尔茨海默氏早老性痴呆病,Menkes氏综合症等。为此各国政府部门都采取了各种有效措施来改善国民的摄铁、摄铜的生理环境,如在人们日常必须的食盐或食品中添加微量铁。然而,过多的摄入铁或铜会在脑、肾、肝等部位聚集而引起病变,环境中微量的铜离子污染,可以通过生物链而产生富集,当人饮用或食用受铜离子污染的水和食物,导致体内铜离子含量过高时,便会引发各种不治之症。因此,就有必要对自然环境和生物体内的铜离子进行检测。设计与合成对铜离子具有选择性识别功能的化学传感器近年来备受关注,已经成为化学科学、环境科学和生命科学等领域的研究热点。
近年来有关采用荧光化学传感器来识别Fe3+的文献已经有所报道。例如国外的ShinhyoBae等(TetrahedronLetters,2007,48,5389-5392)报道了一种通过水合肼改性的罗丹明B类Fe3+荧光化学传感器,虽然其选择性比较高,但是其灵敏度不理想。国内易卫国等人(分析化学,2012,40,1241-1246)报道了一种芳基吡啶类Fe3+荧光探针,但是其合成原料价格较高,过程复杂,不利于实际应用。
克酮酸染料作为一种新型的有机功能染料分子,其近红外吸收波长在800nm左右,且该类染料光、热稳定性好,因此在光学记录与存贮、液晶显示等领域显示出优异的应用性能。由于克酮酸分子五元环也是一个具有推-拉电子能力的芳香共轭体系,具有电子给体-受体分子结构,分子内存在着很大的电荷分离,因此克酮酸箐染料具有识别某些金属离子的特性。
本发明具体涉及一种用于Fe3+和Cu2+检测的克酮酸染料化学传感器,合成方法较为简单,反应条件容易控制,反应结束后通过简单的处理就能够得到纯的产物,此外作为Fe3+和Cu2+的检测的化学传感器,克酮酸染料具有灵敏度高,选择性好等优点。
发明内容
本发明要解决的技术问题是:基于上述问题,本发明提供一种苯并噻唑克酮酸菁比色探针、制备方法及应用。
本发明解决其技术问题所采用的一个技术方案是:一种苯并噻唑克酮酸菁比色探针,该比色探针为2,5-二[3-乙基-2-甲基苯并噻唑]克酮酸箐染料,结构式如下:
一种苯并噻唑克酮酸菁比色探针的制备方法,包括以下步骤:
该制备方法具有如下步骤:
(1)将2-甲基苯并噻唑和碘乙烷按照摩尔比1:1~1.05加入到反应容器中,加入溶剂Ⅰ,78~80℃条件下回流反应20~24h,冷却至室温,旋蒸,固体析出,洗涤,抽滤,烘干,得到3-乙基-2甲基苯并噻唑-3碘盐;
(2)将步骤(1)制备得到的3-乙基-2甲基苯并噻唑-3碘盐和克酮酸按照摩尔比2:1加入反应容器中,加入溶剂Ⅱ,连接冷凝管和斯托克分水器,通入氮气,105~115℃加热回流反应6~8h,反应中生成的水用分水器分出,冷却至室温,旋蒸,洗涤,烘干,得到苯并噻唑克酮酸菁粗品;
(3)将步骤(2)制备得到的苯并噻唑克酮酸菁粗品以二氯甲烷和甲醇混合溶剂作为洗脱剂,柱层析洗脱分离提纯,得到苯并噻唑克酮酸菁产品。
进一步地,步骤(1)中溶剂Ⅰ为乙腈或乙醇。
进一步地,步骤(2)中溶剂Ⅱ为正丁醇和甲苯混合溶剂,正丁醇和甲苯的体积比为3:1~4:1。
进一步地,步骤(3)中二氯甲烷和甲醇的体积比为40:1。
苯并噻唑克酮酸菁比色探针的应用,比色探针用于识别溶液中的Fe3+和Cu2+。
本发明的有益效果是:(1)本发明的苯并噻唑克酮酸菁染料合成过程较为简单,反应条件容易控制,通过简单的后处理就能够得到纯的产物,并且苯并噻唑克酮酸菁染料具有优良的光学性能和光学稳定性;(2)本发明的苯并噻唑克酮酸箐染料为固体粉末,便于储存,具有良好的前景;(3)本发明通过加入EDTA,考察其对探针识别的影响,发明了一种开关式的铁离子和铜离子传感器。
附图说明
下面结合附图对本发明进一步说明。
图1为实施例1制备的苯并噻唑克酮酸菁比色探针与不同浓度铁离子络合后的紫外吸收光谱图;
图2为实施例1制备的苯并噻唑克酮酸菁比色探针与不同浓度铜离子络合后的紫外吸收光谱图;
图3为加入EDTA后,实施例1制备的苯并噻唑克酮酸菁比色探针与铁离子络合的可逆作用图;
图4为加入EDTA后,实施例1制备的苯并噻唑克酮酸菁比色探针与铜离子络合的可逆作用图。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
将2-甲基苯并噻唑和碘乙烷按照摩尔比1:1加入到三口烧瓶中,加入乙醇做为溶剂,78℃条件下回流20h,溶液慢慢从无色变为橘黄色。反应结束后,停止加热,待其冷却至室温,用旋转蒸发仪旋蒸出大部分溶剂,加入乙酸乙酯,有蓝色固体析出。用乙酸乙酯洗涤并抽滤。滤饼放入蒸发皿中,烘箱60℃下干燥。
称取0.05g的克酮酸(0.000352mol)和0.22g制得的3-乙基-2甲基苯并噻唑-3碘盐(0.000704mol)加入到100mL三口烧瓶中,加入10mL甲苯与30mL正丁醇,连接冷凝管和斯托克分水器,通氮气,105℃下加热回流搅拌6个小时,溶液由黄色变为深褐色,反应中生成的水用分水器分出。反应结束后,停止加热,待溶液冷却至室温后,减压条件下用旋转蒸发仪旋去溶剂。乙醚洗涤几次,得到褐色粉末。将粉末放入蒸发皿中,烘箱60℃下干燥。将所得的褐色粉末以二氯甲烷和甲醇混合溶剂(体积比V二氯甲烷:V甲醇=40:1)作为洗脱剂,300目硅胶为固定相,柱层析洗脱分离提纯后,得到棕色的固体,即苯并噻唑克酮酸菁染料。
实施例2
将2-甲基苯并噻唑和碘乙烷按照摩尔比1:1.05加入到三口烧瓶中,加入乙腈做为溶剂,80℃条件下回流24h,溶液慢慢从无色变为橘黄色。反应结束后,停止加热,待其冷却至室温,用旋转蒸发仪旋蒸出大部分溶剂,加入乙酸乙酯,有蓝色固体析出。用乙酸乙酯洗涤并抽滤。滤饼放入蒸发皿中,烘箱60℃下干燥。
称取0.1g的克酮酸(0.000704mol)和0.43g制得的3-乙基-2甲基苯并噻唑-3碘盐(0.001408mol)加入到100mL三口烧瓶中,加入10mL甲苯与40mL正丁醇,连接冷凝管和斯托克分水器,通氮气,115℃下加热回流搅拌8个小时,溶液由黄色变为深褐色,反应中生成的水用分水器分出。反应结束后,停止加热,待溶液冷却至室温后,减压条件下用旋转蒸发仪旋去溶剂。乙醚洗涤几次,得到褐色粉末。将粉末放入蒸发皿中,烘箱60℃下干燥。将所得的褐色粉末以二氯甲烷和甲醇混合溶剂(体积比V二氯甲烷:V甲醇=40:1)作为洗脱剂,300目硅胶为固定相,柱层析洗脱分离提纯后,得到棕色的固体,即苯并噻唑克酮酸菁染料。
应用例1
为了检测实施例1制备的苯并噻唑克酮酸菁探针对铁离子的识别性能,以无水乙醇和水体积比为4:1的混合溶液作溶剂,将合成的苯并噻唑克酮酸菁染料配制成浓度为2×10-5mol/L,取50mL,向溶液中逐滴加入1×10-2mol/L的铁离子溶液,利用紫外-可见光分度计依次测定其吸收光谱的变化,其吸收光谱如图1所示。由图可以看出,随着铁离子滴加量的增加,苯并噻唑克酮酸菁化合物的吸收光谱发生改变,位于756nm处的吸收峰逐渐降低,而在475、585nm处的吸收峰则逐渐增加。
为了检测EDTA对整个体系可逆性的影响,以无水乙醇和水体积比为4:1的混合溶液作溶剂,将合成的苯并噻唑克酮酸菁染料配制成浓度为2×10-5mol/L,分别取3mL配制的溶液于三支试管中,标号分别是1、2和3号。将2号试管滴入0.1mL1×10-2mol/L的铁离子溶液,3号试管先后滴入0.1mL1×10-2mol/L的铁离子溶液和0.05mL1×10-2mol/L的EDTA溶液,分别测其吸光度,其吸收光谱如图3所示。由图可以看出,体系加入EDTA后,吸光度增加但小于苯并噻唑克酮酸菁染料的吸光度。这说明,这个体系可以作为一种开关式的铁离子传感器。
应用例2
为了检测实施例1制备的苯并噻唑克酮酸菁探针对铜离子的识别性能,以无水乙醇和水体积比为4:1的混合溶液作为溶剂,将合成的苯并噻唑克酮酸菁染料配制成浓度为2×10-5mol/L,取50mL,向溶液中逐滴加入1×10-3mol/L的铜离子溶液,利用紫外-可见光分度计依次测定其吸收光谱的变化,其吸收光谱如图2所示。由图可以看出,随着铜离子滴加量的增加,苯并噻唑克酮酸菁染料的吸收光谱发生了变化。位于756nm处的吸收峰逐渐降低,而在471nm处的吸收峰则逐渐增加。
为了检测EDTA对整个体系可逆性的影响,无水乙醇和水体积比为4:1的混合溶液作溶剂,将合成的苯并噻唑克酮酸菁染料配制成浓度为2×10-5mol/L,分别取3mL配好的溶液于三支试管中,标号分别是1、2和3号。将2号试管滴入0.1mL1×10-2mol/L的铜离子溶液,3号试管先后滴入0.1mL1×10-2mol/L的铜离子溶液和0.05mL1×10-2mol/L的EDTA溶液,分别测其吸光度,其吸收光谱如图4所示。由图可以看出,体系加入EDTA后,吸光度增加但小于苯并噻唑克酮酸菁染料的吸光度,这说明,这个体系可以作为一种开关式的铜离子传感器。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (6)
1.一种苯并噻唑克酮酸菁比色探针,其特征是:该比色探针为2,5-双[3-乙基-2甲基苯并噻唑]克酮酸箐,结构式如下:
2.权利要求1所述的苯并噻唑克酮酸菁比色探针的制备方法,其特征是:包括以下步骤:
(1)将2-甲基苯并噻唑和碘乙烷按照摩尔比1:1~1.05加入到反应容器中,加入溶剂Ⅰ,78~80℃条件下回流反应20~24h,冷却至室温,旋蒸,固体析出,洗涤,抽滤,烘干,得到3-乙基-2甲基苯并噻唑-3碘盐;
(2)将步骤(1)制备得到的3-乙基-2甲基苯并噻唑-3碘盐和克酮酸按照摩尔比2:1加入反应容器中,加入溶剂Ⅱ,连接冷凝管和斯托克分水器,通入氮气,105~115℃加热回流反应6~8h,反应中生成的水用分水器分出,冷却至室温,旋蒸,洗涤,烘干,得到苯并噻唑克酮酸菁粗品;
(3)将步骤(2)制备得到的苯并噻唑克酮酸菁粗品以二氯甲烷和甲醇混合溶剂作为洗脱剂,柱层析洗脱分离提纯,得到苯并噻唑克酮酸菁产品。
3.根据权利要求1所述的苯并噻唑克酮酸菁比色探针的制备方法,其特征是:所述的步骤(1)中溶剂Ⅰ为乙腈或乙醇。
4.根据权利要求1所述的苯并噻唑克酮酸菁比色探针的制备方法,其特征是:所述的步骤(2)中溶剂Ⅱ为正丁醇和甲苯混合溶剂,正丁醇和甲苯的体积比为3:1~4:1。
5.根据权利要求1所述的苯并噻唑克酮酸菁比色探针的制备方法,其特征是:所述的步骤(3)中二氯甲烷和甲醇的体积比为40:1。
6.权利要求1所述的苯并噻唑克酮酸菁比色探针的应用,其特征是:所述的比色探针用于识别溶液中的Fe3+和Cu2+。
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