CN106220531B - 用于识别铜离子的荧光探针、膜材料、制备方法及应用 - Google Patents
用于识别铜离子的荧光探针、膜材料、制备方法及应用 Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 70
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- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 67
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Abstract
本发明公开了一种用于识别铜离子的荧光探针、膜材料、制备方法及应用，属于荧光探针技术领域。该荧光探针具有针对铜离子的荧光敏感性，可与铜离子配位形成配合物，并导致荧光淬灭，通过探测荧光即可快速识别铜离子，检测灵敏度较高，适用于含铜溶液的便捷检测。该荧光探针的结构式如下：
Description
技术领域
本发明涉及一种用于识别铜离子的荧光探针，同时还涉及采用该荧光探针制备的膜材料、制备方法及应用，属于荧光探针技术领域。
背景技术
现代研究发现，过去被认为“没有生命”的金属元素实际上与动植物的多个生命过程有关，且广泛参与到各种生命过程当中，在信息传递和生物催化中发挥关键作用。作为生命体中含量居第三位的微量元素，铜离子具有较高的亲和力，能够与蛋白质结合，明显改变其生化性质。例如，在老年痴呆症患者脑部的异常蛋白质沉积物中，铜离子的含量明显高于正常人。
目前，人们已开发出多种用于铜离子检测的方法，包括核磁共振波谱法、电化学分析法和光学分析法等。其中，光学分析法中的荧光法因具有操作简便、检测灵敏度高、检测成本低等优势，受到了越来越多的关注。如公布号CN104072753A的发明专利公开的一种用于检测Cu2+的罗丹明B基聚合物探针，其结构式为：
式中，n为43～454。该聚合物探针可溶于水，通过裸眼观察水溶液颜色变化即可对水介质中的Cu2+实现高效识别，选择性高、抗干扰能力强，且探针分子可循环使用。但是，目视比色法应用于聚合物体系时，由于聚合物透光性欠佳，检测结果容易出现较大偏差。又如公布号CN103242825A的发明专利公开的一种基于罗丹明6G的Cu2+荧光探针，其结构式为：
该荧光探针检测Cu2+的原理与上述聚合物探针基本相同，Cu2+选择性较强，但同样也存在检测结果偏差大等问题，并且该检测体系难以实现检测的器件化和微型化。
发明内容
本发明的目的是提供一种用于识别铜离子的荧光探针，该探针具有针对铜离子的荧光敏感性，可与铜离子配位形成配合物，并导致荧光淬灭，通过探测荧光即可快速识别铜离子，检测灵敏度高。
其次，本发明还提供一种上述荧光探针的制备方法及应用。
再者，本发明提供一种采用上述荧光探针制备的膜材料。
最后，本发明提供一种上述膜材料的制备方法及应用。
为了实现以上目的，本发明所采用的技术方案是：
用于识别铜离子的荧光探针，其结构式为：
式中，Ar为荧光基团，选自萘基、喹啉基或异喹啉基、芘基、蒽基、苝基，或者取代的萘基、芘基、蒽基，各取代基独立地选自1～4个碳的烷基(如甲基、乙基)或羟基；Ar’选自苯基、萘基、蒽基，或者取代的苯基、萘基、蒽基，各取代基独立地选自1～4个碳的烷基(如甲基、乙基)或烷氧基(如甲氧基、乙氧基)。
优选的，所述荧光探针的结构式中Ar为萘基、Ar’为苯基，或者Ar为芘基，Ar’为甲基取代的苯基或乙基取代的苯基。
用于识别铜离子的荧光探针的制备方法，包括以下步骤：将式Ⅰ、式Ⅱ化合物和催化剂加入溶剂A中，反应即得；
式Ⅰ中，Ar选自萘基、喹啉基或异喹啉基、芘基、蒽基、苝基，或者取代的萘基、芘基、蒽基，各取代基独立地选自1～4个碳的烷基(如甲基、乙基)或羟基；
式Ⅱ中，Ar’选自苯基、萘基、蒽基，或者取代的苯基、萘基、蒽基，各取代基独立地选自1～4个碳的烷基(如甲基、乙基)或烷氧基(如甲氧基、乙氧基)。
所述反应方程式如下：
所述酸性催化剂选自甲酸、乙酸、硫酸、盐酸、SiO2-Al2O3、B2O3-Al2O3中的一种或多种。
所述溶剂A选自苯、甲苯、乙醇、丙醇、乙醚、四氢呋喃、氯仿中的一种或多种。
所述式Ⅰ、式Ⅱ化合物的摩尔比为1:0.3～2.5。
所述酸性催化剂与式Ⅱ化合物的摩尔比为1:1～100。
所述溶剂A的加入量为：每克式Ⅰ化合物对应加入5～100mL溶剂A。
所述反应的温度为65～110℃，时间4～8h。
所述反应完毕，冰冷收集沉淀(如将反应混合物加入5～10倍体积的冰水中)，纯化，即得。纯化可采用重结晶或层析分离的方法。重结晶所用溶剂可与溶剂A相同，如采用氯仿、甲醇、乙醇等。
用于识别铜离子的膜材料，是以成膜材料、上述荧光探针为原料制备得到。
所述成膜材料选自聚乙烯醇、聚氯乙烯、聚丙烯、聚丙烯酸酯(如聚丙烯酸甲酯、聚丙烯酸乙酯等)、聚N-乙烯基吡咯烷酮、纤维素等。所得膜材料(干膜)中，荧光探针(即金属配合物)的含量≥1×10-4mol/g。
用于识别铜离子的膜材料的制备方法，包括以下步骤：将荧光探针、成膜材料加入溶剂B中得铸膜液，取铸膜液制膜，即得。
所述成膜材料选自聚乙烯醇、聚氯乙烯、聚丙烯、聚丙烯酸酯(如聚丙烯酸甲酯、聚丙烯酸乙酯等)、聚N-乙烯基吡咯烷酮、纤维素等。
所述溶剂B选自甲醇、乙醇、氯仿、二氯甲烷、丙酮、水中的一种或多种。
所述制膜为常规技术，如采用旋涂、干燥的方法制膜。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。原理为：荧光探针具有针对铜离子的荧光敏感性，可与铜离子配位形成配合物，并导致荧光淬灭，通过探测荧光即可快速识别铜离子。
反应如下：
本发明的有益效果：
本发明中荧光探针具有针对铜离子的荧光敏感性，可与铜离子配位形成配合物，并导致荧光淬灭，通过探测荧光即可快速识别铜离子，检测灵敏度较高，适用于含铜溶液的便捷检测。同时，该荧光探针也可用于制备铜离子探测用荧光传感器。
本发明中用于识别铜离子的膜材料由荧光探针和高分子成膜材料制得，能快速识别溶液中的铜离子，灵敏度较高，适于含铜溶液的便捷检测。
本发明中荧光探针及膜材料的制备工艺简单，操作简便，适于大规模工业化生产及应用。
附图说明
图1为实施例1中荧光探针及其与铜离子配合后所得金属配合物的红外光谱图；
图2为实施例1中荧光探针对铜离子的荧光光谱识别图；
图3为实施例1中膜材料检测铜离子前后的荧光反应结果图；
图4为实施例1中膜材料检测铜离子前后的荧光光纤光谱图。
具体实施方式
下述实施例仅对本发明作进一步详细说明，但不构成对本发明的任何限制。
实施例1
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g 1-羟基-2-萘甲酰肼、1.5g对羟基苯甲醛加入50mL乙醇中，再加入0.2mL冰乙酸(分析纯)作为催化剂，于65℃下(搅拌)反应6h；
2)反应完毕，将反应混合物加入4倍体积的冰水中，收集沉淀，用乙醇重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，由以下步骤制备得到：
1)将荧光探针溶于乙醇中得到浓度1×10-3mol/L的溶液，同时将聚乙烯醇溶于水中，混合得到铸膜液；
2)将铸膜液旋涂在平板上，自然干燥后揭膜，即得荧光探针含量1.5×10-4mol/g的膜材料。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
图1为上述荧光探针及其与铜离子配合后所得金属配合物的红外光谱图；图2为荧光探针对铜离子的荧光光谱识别图；图3为上述膜材料检测铜离子前后的荧光反应结果图(图中，a)为紫外灯照射下未接触铜离子的膜材料，b)为紫外灯照射下下半部接触铜离子的膜材料，c)为使用EDTA实现荧光恢复的膜材料)；图4为膜材料检测铜离子前后的荧光光纤光谱图(图中，a为未接触铜离子的膜材料，b为接触铜离子后的膜材料，c为使用EDTA实现荧光恢复的膜材料)。
实施例2
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g 3-羟基-2-萘甲酰肼、1.5g香草醛加入50mL乙醇中，再加入0.15mL冰乙酸(分析纯)作为催化剂，于80℃下(搅拌)反应4h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用乙醇重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法基本同实施例1，成膜材料为聚氯乙烯。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例3
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将0.25g式1化合物、14g式2化合物加入150mL乙醚中，再加入0.1mL浓度40％的硫酸作为催化剂，于60℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用乙醚重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法基本同实施例1，成膜材料为聚丙烯。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例4
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g式3化合物、2g式4化合物加入100mL四氢呋喃中，再加入0.4mL浓度28％的盐酸作为催化剂，于80℃下(搅拌)反应6h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用乙醇重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法基本同实施例1，成膜材料为聚丙烯酸甲酯。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例5
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将3g式5化合物、1.5g式6化合物加入150mL氯仿中，再加入0.3g SiO2-Al2O3作为催化剂，于75℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用氯仿重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法基本同实施例1，成膜材料为聚N-乙烯基吡咯烷酮。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例6
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g式7化合物、2.5g式8化合物加入100mL苯中，再加入0.1g B2O3-Al2O3作为催化剂，于80℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用苯重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法基本同实施例1，成膜材料为纤维素。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例7
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将3.5g式9化合物、2g式10化合物加入500mL甲苯中，再加入1.2mL浓度36％的甲酸作为催化剂，于110℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用甲苯重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法同实施例1。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例8
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g式11化合物、5g式12化合物加入100mL乙醇中，再加入1mL冰乙酸(分析纯)作为催化剂，于80℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用乙醇重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法同实施例1。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
实施例9
用于识别铜离子的荧光探针，其结构式为：
上述荧光探针的制备方法，包括以下步骤：
1)将2g式13化合物、2.3g式14化合物加入100mL丙醇中，再加入1mL冰乙酸(分析纯)作为催化剂，于100℃下(搅拌)反应8h；
2)反应完毕，将反应混合物加入5倍体积的冰水中，收集沉淀，用乙醇重结晶，即得。
反应方程式如下：
用于识别铜离子的膜材料，制备方法同实施例1。
上述荧光探针或膜材料在铜离子识别(或检测)中的应用。
Claims (5)
1.荧光探针及含有荧光探针的膜材料在铜离子识别或检测中的应用，其特征在于：所述荧光探针的结构式如下：
2.根据权利要求1所述的应用，其特征在于：所述荧光探针的制备方法包括以下步骤：将式Ⅰ、式Ⅱ化合物和催化剂加入溶剂A中，反应即得；
式Ⅰ、式Ⅱ中，Ar为萘基，Ar’为苯基；
所述催化剂选自甲酸、乙酸、硫酸、盐酸、SiO2-Al2O3、B2O3-Al2O3中的一种或多种；
所述溶剂A选自苯、甲苯、乙醇、丙醇、乙醚、四氢呋喃、氯仿中的一种或多种。
3.根据权利要求2所述的应用，其特征在于：所述反应的温度为65～110℃，时间4～8h。
4.根据权利要求1所述的应用，其特征在于：所述含有荧光探针的膜材料是以荧光探针及成膜材料为原料制备得到的；所述成膜材料选自聚乙烯醇、聚氯乙烯、聚丙烯、聚丙烯酸酯、聚N-乙烯基吡咯烷酮、纤维素。
5.根据权利要求4所述的应用，其特征在于：所述含有荧光探针的膜材料的制备方法包括以下步骤：将荧光探针、成膜材料加入溶剂B中得铸膜液，取铸膜液制膜，即得；所述溶剂B选自甲醇、乙醇、氯仿、二氯甲烷、丙酮、水中的一种或多种。
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| WO2015188130A1 (en) * | 2014-06-05 | 2015-12-10 | The University Of Kansas | Marmelin analogs and methods of use in cancer treatment |
| CN105223176A (zh) * | 2015-10-08 | 2016-01-06 | 河南师范大学 | 一种利用1,4-二羟基-9,10-蒽醌缩水杨酰肼化合物作为荧光探针检测铜离子的方法 |
| CN105647512A (zh) * | 2015-12-18 | 2016-06-08 | 南京理工大学 | 一种Cu2+荧光探针、制备方法及其应用 |
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| Synthesis, characterization and biological evaluation of some novel hydrazide Schiff"s bases and their metal complexes;Hussain, Mazhar等;《Asian Journal of Chemistry》;20131231;第25卷(第5期);第2669页图示1 * |
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