CN114920762A - 一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法 - Google Patents
一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法。一种有机杂化碘化亚铜双响应荧光探针材料的化学名称为四碘·二(1‑四唑‑4‑咪唑‑苯)合四铜(I)，化学式为[Cu4I4(C10H8N6)2]n，分子量为1186.2g/mol，属于单斜晶系，空间群为C2/c，晶胞参数为
α＝γ＝90°，β＝92.384(2)°，
Z＝8。该材料具有强的发光强度。以碘化亚铜、1‑四唑‑4‑咪唑‑苯为原料通过溶剂热反应法合成。制备方法具有工艺简单、高效、廉价、无污染、重复性好等优点。本发明的有机杂化碘化亚铜双响应荧光探针材料对水溶液中Fe3+和Cr2O7 2‑离子的检测具有高的选择性和灵敏度，且可以重复使用，在荧光探针材料领域可以得到广泛应用。
Description
技术领域
本发明涉及一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法，属于荧光探针材料技术领域。
背景技术
铁和铬是人体必需的微量生物元素，维持人体多种生理功能，缺铁或缺铬可引起严重疾病。铁主要以Fe3+离子的形式存在，其在人体中的浓度失衡可引起组织损伤、肝脾功能障碍、糖尿病、某些肿瘤、皮肤色素沉着等疾病。铬通常以Cr3+和Cr2O7 2-离子的形式存在。Cr3+离子浓度在正常范围内对人体有益，但过量的Cr3+离子可转化为有剧毒的Cr2O7 2-离子，可以诱发皮疹，癌症，鼻炎，基因突变和其他重大疾病。随着Fe3+和Cr2O7 2-离子在不同行业的广泛应用，它们对生态环境的影响日益严重。因此，Fe3+和Cr2O7 2-离子的高选择性检测对保护人类健康和生态环境具有重要意义。
目前，大多数荧光探针材料是由π共轭芳基有机配体与d10过渡金属(如 Ag+、Zn2+和Cd2+)或镧系离子配位获得。相比之下，用于荧光探针的有机杂化 d10金属(I)碘化物相对较少。尤其是能够在水溶液中作为Fe3+和Cr2O7 2-离子双响应荧光探针材料的d10金属(I)碘化物尚未出现。申请人通过采用溶剂热法合成了一种能够在水溶液中对Fe3+和Cr2O7 2-离子具有双响应荧光探针性能的碘化亚铜(I)聚合物。
发明内容
本发明的目的在于，提供一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法和用途。
1.一种有机杂化碘化亚铜双响应荧光探针材料，化学名称为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，化学式为[Cu4I4(C10H8N6)2]n，分子量为1186.2g/mol，属于单斜晶系，空间群为C2/c，晶胞参数为
α＝γ＝90°，β＝92.384(2)°，
Z＝8。结构图如图1所示,其结构中的不对称单元由两个I–阴离子、两个Cu+阳离子和一个有机配体1-四唑-4-咪唑-苯组成。该化合物外观为黄色块状晶体，无味道，难溶于有机溶剂和水。
2.四碘·二(1-四唑-4-咪唑-苯)合四铜(I)的制备方法，具体操作如下：
将CuI 0.0101g、1-四唑-4-咪唑-苯0.0052g、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h，将混合物密封在15mL不锈钢反应器中，在温度100～120℃的烘箱中保温8～10天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为37～51％(按CuI计算)。
3.四碘·二(1-四唑-4-咪唑-苯)合四铜(I)的用途。
荧光探针性能测试表明，四碘·二(1-四唑-4-咪唑-苯)合四铜(I)对Fe3+和Cr2O7 2-离子的检测具有高选择性和灵敏性。在对金属阳离子和阴离子的荧光探针检测实验中，化合物对Fe3+和Cr2O7 2-离子有明显的淬灭效果，并且化合物在其它常见离子的存在下，对Fe3+和Cr2O7 2-离子具有良好的抗干扰性。通过化合物的三次回收并进行荧光测试，发光强度几乎没有变化，证明化合物可以重复使用。因此，对Fe3+和Cr2O7 2-离子具有荧光探针性能的四碘·二(1-四唑-4-咪唑- 苯)合四铜(I)，可以替代价格昂贵，开采困难的稀土荧光探针材料，可以说明其在荧光探针材料技术领域具有明显的应用价值。
本发明的优点：
本发明提供的荧光探针材料[Cu4I4(C10H8N6)2]n是通过溶剂热合成方法制备所得。本发明所采用的制备方法具有工艺简单、高效、廉价、无污染、重复性好等优点。该材料的优点是发光强度强，具有高的选择性，灵敏度以及可回收性。
附图说明
图1为本发明四碘·二(1-四唑-4-咪唑-苯)合四铜(I)化合物的结构图；
图2为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)对Fe3+离子的荧光测试 Stern-Volmer图；
图3为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)对Cr2O7 2-离子的荧光测试 Stern-Volmer图；
具体实施方式
以下结合实施例对本发明作进一步描述。需要说明的是，下述实施例不能作为对本发明保护范围的限制，任何在本发明基础上做出的改进都不违背本发明精神。本发明所用原料或设备，如无特殊说明，均是商业上可以购买得到的。
实施例1
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4ml)溶液中搅拌0.5h。将混合物密封在15mL不锈钢反应器中，在温度100℃的烘箱中保温8天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为37％ (按CuI计算)。
实施例2
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h。将混合物密封在15ml不锈钢反应器中，在温度100℃的烘箱中保温9天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为56％(按 CuI计算)。
实施例3
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4ml)溶液中搅拌0.5h。将混合物密封在15mL不锈钢反应器中，在温度100℃烘箱中保温10天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为49％(按 CuI计算)。
实施例4
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h。将混合物密封在15ml不锈钢反应器中，在温度110℃烘箱中保温8天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为42％(按CuI 计算)。
实施例5
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h。将混合物密封在15ml不锈钢反应器中，在温度110℃烘箱中保温9天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为51％(按CuI 计算)。
实施例6
将CuI(0.0101g,0.053mmol)、1-四唑-4-咪唑-苯(0.0052g,0.024mmol)、苯甲醇(0.5mL)和HI水溶液(0.2mL,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h。将混合物密封在15ml不锈钢反应器中，在温度120℃烘箱中保温9天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为48％(按CuI 计算)。
实施例7
将实施例1-6中所得的任意的四碘·二(1-四唑-4-咪唑-苯)合四铜(I)进行荧光探针检测实验。具体操作步骤如下：
1)取3mg实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I) 充分研磨分散到0.01mol/L MClx(M＝Li+,Na+,K+,Mn2+,Fe2+,Ni2+,Co2+,Cu2+, Zn2+,Fe3+)的水溶液中0.5小时，通过超声方法得到均匀分散的悬浮液，测定它们的荧光发光光谱。结果表明大多数金属阳离子略微降低了所述化合物的发光强度，但Fe3+离子对其发光强度表现出明显的淬灭效应，即表明所述化合物可以检测Fe3+离子。
2)对9种干扰金属阳离子(0.01mol/L)在0.01mol/L Fe3+离子存在下进行了所述化合物对Fe3+离子检测的抗干扰实验。没有Fe3+离子存在的情况下，干扰金属阳离子只会导致发光强度轻微降低，而加入Fe3+离子后，发光强度迅速下降，说明9种干扰金属阳离子对化合物的发光没有影响，即表明所述化合物对 Fe3+离子的检测具有良好的抗干扰性能。
3)研究了实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)化合物分散在不同浓度Fe3+离子水溶液中的发射光谱，随着Fe3+离子浓度的增加，化合物的发光强度降低。结果表明:Stern-Volmer常数KSV值约为5.52×103M-1，以3σ/k计算出检测限(k为斜率，σ为标准误差)，得到所述化合物对水溶液中 Fe3+的检测限为1.08ppm(图2)。
4)取3mg实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I) 充分研磨分散到0.01mol/L[Xn -](X＝I-,Br-,Cl-,SCN-,IO3 -,SO3 2-,SO4 2-,Cr2O7 2-) 的水溶液中，测定其发射光谱，观察到Cr2O7 2-离子对所述化合物的发光强度表现出明显的淬灭效应，即表明所述化合物还可以检测Cr2O7 2-离子。
5)对7种干扰阴离子(0.01mol/L)在0.01mol/L Cr2O7 2-离子存在下进行了所述化合物对Cr2O7 2-离子检测的抗干扰实验。没有Cr2O7 2-离子存在的情况下，干扰阴离子只会导致发光强度轻微降低，而加入Cr2O7 2-离子后，发光强度迅速下降，说明7种干扰阴离子对化合物的发光没有影响，即表明所述化合物对 Cr2O7 2-离子的检测具有良好的抗干扰性能。
6)研究了实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)化合物分散在不同浓度Cr2O7 2-离子水溶液中的发射光谱。结果表明：Cr2O7 2-阴离子的Stern-Volmer常数Ksv值为3.95×103M-1，检出限为3.12ppm(图3)。
基于以上，所述化合物四碘·二(1-四唑-4-咪唑-苯)合四铜(I)可能是一种实用的、有前景的荧光探针材料，其可以用于检测Fe3+和Cr2O7 2-离子，具有高选择性和灵敏度。
Claims (3)
1.一种有机杂化碘化亚铜双响应荧光探针材料，其特征在于该材料的化学名称为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，化学式为[Cu4I4(C10H8N6)2]n，分子量为1186.2g/mol，属于单斜晶系，空间群为C2/c，晶胞参数为
α＝γ＝90°，β＝92.384(2)°，
Z＝8，外观为黄色块状晶体，无味道，难溶于有机溶剂和水。
2.根据权利要求1所述的四碘·二(1-四唑-4-咪唑-苯)合四铜(I)的制备方法，其特征在于采用溶剂热法制备该材料，具体操作按下列步骤进行：
将CuI 0.0101g、1-四唑-4-咪唑-苯0.0052g、苯甲醇(0.5mL)和HI水溶液(0.2ml,V(H2O):V(HI)＝10:1)加入乙腈(4mL)溶液中搅拌0.5h，将混合物密封在15mL不锈钢反应器中，在温度100～120℃的烘箱中保温8～10天，待自然冷却到室温后取出样品，用蒸馏水洗涤、抽滤，再常温干燥，得到的黄色晶体即为四碘·二(1-四唑-4-咪唑-苯)合四铜(I)，产率为37～56％(按CuI计算)。
3.根据权利要求2所述的四碘·二(1-四唑-4-咪唑-苯)合四铜(I)的制备方法，其特征在于将权利要求2的实施例1-6中所得的任意的四碘·二(1-四唑-4-咪唑-苯)合四铜(I)进行荧光探针检测实验，具体操作步骤如下：
1)取3mg实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)充分研磨分散到0.01mol/L MClx(M＝Li+,Na+,K+,Mn2+,Fe2+,Ni2+,Co2+,Cu2+,Zn2+,Fe3+)的水溶液中0.5小时，通过超声方法得到均匀分散的悬浮液，测定它们的荧光发光光谱，结果表明大多数金属阳离子略微降低了所述化合物的发光强度，但Fe3+离子对其发光强度表现出明显的淬灭效应，即表明所述化合物可以检测Fe3+离子：
2)对9种干扰金属阳离子(0.01mol/L)在0.01mol/L Fe3+离子存在下进行了所述化合物对Fe3+离子检测的抗干扰实验，没有Fe3+离子存在的情况下，干扰金属阳离子只会导致发光强度轻微降低，而加入Fe3+离子后，发光强度迅速下降，说明9种干扰金属阳离子对化合物的发光没有影响，即表明所述化合物对Fe3+离子的检测具有良好的抗干扰性能：
3)研究了权利要求2的实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)化合物分散在不同浓度Fe3+离子水溶液中的发射光谱，随着Fe3+离子浓度的增加，化合物的发光强度降低，结果表明:Stern-Volmer常数KSV值约为5.52×103M-1，以3σ/k计算出检测限(k为斜率，σ为标准误差)，得到所述化合物对水溶液中Fe3+的检测限为1.08ppm：
4)取3mg权利要求2的实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)充分研磨分散到0.01mol/L[Xn -](X＝I-,Br-,Cl-,SCN-,IO3 -,SO3 2-,SO4 2-,Cr2O7 2-)的水溶液中，测定其发射光谱，观察到Cr2O7 2-离子对所述化合物的发光强度表现出明显的淬灭效应，即表明所述化合物还可以检测Cr2O7 2-离子：
5)对7种干扰阴离子(0.01mol/L)在0.01mol/L Cr2O7 2-离子存在下进行了所述化合物对Cr2O7 2-离子检测的抗干扰实验，没有Cr2O7 2-离子存在的情况下，干扰阴离子只会导致发光强度轻微降低，而加入Cr2O7 2-离子后，发光强度迅速下降，说明7种干扰阴离子对化合物的发光没有影响，即表明所述化合物对Cr2O7 2-离子的检测具有良好的抗干扰性能：
6)研究了权利要求2的实施例1-6中所得的任意四碘·二(1-四唑-4-咪唑-苯)合四铜(I)化合物分散在不同浓度Cr2O7 2-离子水溶液中的发射光谱，结果表明：Cr2O7 2-阴离子的Stern-Volmer常数Ksv值为3.95×103M-1，检出限为3.12ppm：
基于以上，所述化合物四碘·二(1-四唑-4-咪唑-苯)合四铜(I)可能是一种实用的、有前景的荧光探针材料，其可以用于检测Fe3+和Cr2O7 2-离子，具有高选择性和灵敏度。
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