CN105461741A - 含巯甲基二核铜(ⅱ)配合物的用途 - Google Patents
含巯甲基二核铜(ⅱ)配合物的用途 Download PDFInfo
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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Abstract
本发明公开了一种含巯甲基二核铜(Ⅱ)配合物的用途，产品为蓝色晶体，以2-(巯甲基）苯并[d]噁唑-5-羧酸为主要配体，1,10-菲啰啉为辅助配体，室温下，pH值为7-8，CuCl2的甲醇-水溶液中得到。本发明制备方法简便，在功能配合物外围引入巯甲基，通过硫原子和金属电极相互作用，含巯甲基金属配合物通过自组装到金属电极的表面，实现功能配合物在电极上对多巴胺样品的快速、灵敏检测。
Description
本申请是申请号：201410375373.7、名称“含巯甲基二核铜(Ⅱ)配合物及制备方法和用途”的分案申请。
技术领域
本发明涉及一种含巯甲基二核铜(Ⅱ)配合物及制备方法和用途。
背景技术
铜与蛋白残基以单，二，或四核配合物形式，形成一些蛋白质和酶(如血蓝素，儿茶酚氧化酶，多巴胺一氧化物酶等)的活性位点，充当氧的载体和氧化还原反应的催化活性中心。通过体外研究铜氧化酶簇合物在电极上的氧化还原反应，对于生物催化的理论研究以及高灵敏生物传感器的构建有着非常重要的意义。多巴胺(DA)是哺乳动物中枢神经系统中重要的神经递质之一，影响生物的认知和行为功能。人体内DA水平的异常与精神分裂症，老年性痴呆和帕金森氏病有着密切的关系。在众多的DA分析方法中，电化学方法是最直接，快速，低成本的检测技术。然而，电化学检测DA过程中存在三个问题：(1)DA的超低生理浓度；(2)吸附氧化产物而导致电极钝化；(3)生物样品中共存的物质(尤其是抗坏血酸和尿酸)对DA检测的干扰。为此，人们采用共价键固定酶，金属纳米粒子，碳纳米管，导电聚合物膜，自组装修饰电极等方法，以提高DA检测的灵敏度和选择性。
设计合成的有机-金属配合物具有特定的功能，能模仿金属蛋白的活性位点，从而构造高灵敏的人工酶电化学生物传感器，为体外研究蛋白质/酶反应提供了一种有效的途径。然而，常用滴涂-干燥方法来修饰电极，电化学信号响应慢、检测结果重现性差，其主要原因：(1)修饰膜物理稳定性差，电化学测量时容易被洗脱至电解液中；(2)制备过程中难以控制修饰物薄膜的厚度和电催化活性物质的量，造成检测结果的重现性差。(3)由于修饰层的阻碍作用，待测分子透过修饰层扩散到电极表面的扩散系数相对较低，直接影响待测物在电极表面的电子传输速率。
发明内容
本发明的目的在于提供一种制备方法简便，能实现功能配合物在电极上对多巴胺样品的快速、灵敏检测的含巯甲基二核铜(Ⅱ)配合物及制备方法和用途。
本发明的技术解决方案是：
一种含巯甲基二核铜(Ⅱ)配合物([Cu2Cl2(mtboc)2(C12H8N2)2][mtboc＝2-(甲硫基)苯并[d]恶唑-5-羧酸](铜))，其特征是：为蓝色晶体，其制备方法：以2-(巯甲基)苯并[d]噁唑-5-羧酸为主要配体，1,10-菲啰啉为辅助配体，室温下，pH值为7-8，CuCl2的甲醇-水溶液中得到。
一种含巯甲基二核铜(Ⅱ)配合物的制备方法，其特征是：以2-(巯甲基)苯并[d]噁唑-5-羧酸为主要配体，1,10-菲啰啉为辅助配体，室温下，pH值为7-8，CuCl2的甲醇-水溶液中得到。
一种含巯甲基二核铜(Ⅱ)配合物在多巴胺检测中的应用，其特征是：(1)将裸金圆盘电极，用氧化铝的含水浆料分别进行抛光，然后依次在水、氯仿、水中超声波清洗；(2)在0.5mol/L硫酸溶液中，0.00到1.50V间，采用循环伏安法将电极进行电化学清洗，直到出现稳定的循环伏安图；(3)将洗净后的金电极浸入二核铜(Ⅱ)配合物的N，N-二甲基甲酰胺溶液中24小时，通过形成Au-S键将二核铜(Ⅱ)配合物自组装到金电极表面；(4)用三次蒸馏水冲洗金电极表面，除去电极表面可能物理吸附的二核铜(Ⅱ)配合物，得到修饰电极；(5)电化学测量采用三电极体系，工作电极为上述得到的修饰电极，参比电极为银/氯化银电极，辅助电极为铂片电极；多巴胺的定量检测采用示差脉冲的方法，起始电位和终止电位分别为-0.2V和0.7V，电位增量4mV，脉冲周期0.2s，脉冲宽度和样品宽度分别为0.05s和0.0167s。
本发明制备方法简便，在功能配合物外围引入巯甲基，通过硫原子和金属电极相互作用，含巯甲基金属配合物通过自组装到金属电极的表面，实现功能配合物在电极上对多巴胺样品的快速、灵敏检测。
本发明利用自组装修饰电极(Au/Cu2)与其它电极相比，具有良好的电催化活性、电子传输速率快、能有效防止DA的氧化产物污染电极表面、能有效防止高浓度尿酸、葡萄糖、柠檬酸以及常见的无机离子对多巴胺检测的干扰。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1是含巯甲基二核铜(Ⅱ)配合物的FT-IR谱图。
图2是含巯甲基二核铜(Ⅱ)配合物的晶体结构图。
图3是修饰电极(Au/Cu2)检测不同浓度多巴胺标准溶液的示差脉冲曲线，浓度范围为(5×10-4-1mmol/L)。插图为示差脉冲法测定不同浓度标液所制标准曲线。
图4是多巴胺、尿酸及其混合液的循环伏安图。
具体实施方式
实施例1：含巯甲基二核铜(Ⅱ)配合物的制备
在100mL烧杯中加入0.3345g(1.5mmol)2-(巯甲基)苯并[d]噁唑-5-羧酸，25mL甲醇，用0.2mol·L-1氢氧化钠溶液调节pH值为7-8，搅拌溶解，再依次加入0.139g(0.7mmol)1,10-菲啰啉，0.1364g(0.8mmol)CuCl2·2H2O，15mL甲醇，常温下搅拌1h，过滤，滤液在室温下静置数周，析出蓝色晶体。FT-IR(KBr压片):2929,2819,2671,2545,1676,1593,1559,1422,1294,1191,1129,1093,928,839,818,760,687,549,515,470。
X-射线单晶衍射表明，含巯甲基二核铜(Ⅱ)配合物属于三斜晶系，空间点群为P-1，晶体学参数详见表1，含巯甲基二核铜配合物的晶体结构见图2，在二核铜(Ⅱ)配合物中，Cu-N键的平均键长为Cu-O键的平均键长为Cu-Cl键的平均键长为
表1含巯甲基二核铜簇合物晶体学参数
实施例2：修饰电极(Au/Cu2)的制备
第一步，将裸金圆盘电极(直径2mm)，用氧化铝(1.0，0.3，0.05微米)的含水浆料分别进行抛光，然后依次在水、氯仿、水中超声波清洗5分钟；第二步，在0.5mol/L硫酸溶液中，0.00到1.50V间，采用循环伏安法将电极进行电化学清洗(～40个循环，50毫伏/秒)，直到出现稳定的循环伏安图；第三步，将洗净后的金电极浸入二核铜(Ⅱ)配合物(5mmol/L)的N，N-二甲基甲酰胺溶液中24小时，通过形成Au-S键将二核铜(Ⅱ)配合物自组装到金电极表面；第四步，用三次蒸馏水彻底冲洗金电极表面，以除去电极表面可能物理吸附的二核铜(Ⅱ)配合物。
实施例3：修饰电极(Au/Cu2)重现性及抗干扰能力检测
电化学测量采用三电极体系，工作电极为修饰电极(Au/Cu2)，参比电极为银/氯化银电极，辅助电极为铂片电极。多巴胺的定量检测采用示差脉冲的方法，起始电位和终止电位分别为-0.2V和0.7V，电位增量4mV，脉冲周期0.2s，脉冲宽度和样品宽度分别为0.05s和0.0167s。
图3为不同浓度的DA在Au/Cu2电极上的部分DPV响应曲线。由图3可见，DA的电化学氧化大约在0.17V处，增加DA的浓度会引起催化电流同时增加，催化电流和DA浓度之间存在线性关系，线性回归公式可表示为：y＝0.06287x+0.3043(R＝0.9975)，线性范围从0.2到30微摩尔/升。检测限采用IUPAC的定义LOD＝3SB/q，计算为0.08μM，以30微摩尔/升DA的氧化峰电流进行计算，连续检测15次，结果表明相对标准偏差仅为3.6％，说明此电极的重现性和稳定性好。。对于六种平行制备的修饰电极，RSD为7.9％。该修饰电极在4℃保存30天以上，观察其原有的峰值电流的92％。如表2所示，干扰物质葡萄糖、柠檬酸，K+,Na+,Ca2+,Mg2+,Zn2+,SO4 2-,NO3 -,及Cl-在浓度大于100倍条件下也不会对检测造成干扰。从图4可以看出，修饰电极(Au/Cu2)能有效防止尿酸对多巴胺检测的干扰。当使用裸金电极进行检测时，尿酸和多巴胺氧化峰峰电位严重重叠，导致两者不能实现选择性检测；而使用修饰电极(Au/Cu2)时，两者氧化峰位差可达270毫伏，完全避免了尿酸对多巴胺检测的干扰。
表2干扰物质对多巴胺检测的影响
实施例4：修饰电极(Au/Cu2)巴胺注射液及尿液样品电化学检测
10mg·mL-1盐酸多巴胺注射液及尿液样品采用磷酸缓冲液稀释到一定浓度。采用加入一定浓度，一定体积的多巴胺标准溶液，结合修饰电极(Au/Cu2)和示差脉冲方法对回收率及精密度进行了检测，如表3所示其结果满足微量检测的要求。
表3盐酸多巴胺注射液及尿液样品中多巴胺含量的测定
由此可见本发明的优异效果。
Claims (1)
1.一种含巯甲基二核铜(Ⅱ)配合物在多巴胺检测中的应用，其特征是：（1）将裸金圆盘电极，用氧化铝的含水浆料分别进行抛光，然后依次在水、氯仿、水中超声波清洗；（2）在0.5mol/L硫酸溶液中，0.00到1.50V间，采用循环伏安法将电极进行电化学清洗，直到出现稳定的循环伏安图；（3）将洗净后的金电极浸入二核铜(Ⅱ)配合物的N，N-二甲基甲酰胺溶液中24小时，通过形成Au-S键将二核铜(Ⅱ)配合物自组装到金电极表面；（4）用三次蒸馏水冲洗金电极表面，除去电极表面可能物理吸附的二核铜(Ⅱ)配合物，得到修饰电极；（5）电化学测量采用三电极体系，工作电极为上述得到的修饰电极，参比电极为银/氯化银电极，辅助电极为铂片电极；多巴胺的定量检测采用示差脉冲的方法，起始电位和终止电位分别为-0.2V和0.7V，电位增量4mV，脉冲周期0.2s，脉冲宽度和样品宽度分别为0.05s和0.0167s；所述含巯甲基二核铜(Ⅱ)配合物为蓝色晶体。
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