CN110243898B - 一种基于环金属铱配合物光电化学分子探针pH传感器的制备方法 - Google Patents
一种基于环金属铱配合物光电化学分子探针pH传感器的制备方法 Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
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- G01N27/28—Electrolytic cell components
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- G—PHYSICS
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Abstract
本发明公开了一种基于环金属铱配合物光电化学分子探针的pH传感器的制备方法。先在ITO电极表面形成TiO2簇,进而涂覆纳米TiO2的分散溶液,自然干燥后煅烧,制得TiO2修饰的ITO电极,然后在其表面吸附含有罗丹明B结构的环金属铱配合物分子层作为识别元件,采用三电极系统,制得pH传感器。在H+存在下,罗丹明B内酰胺环开环使得环金属铱配合物的吸收增强,进而使得配合物的光电信号增强实现对pH值的传感。该传感器在pH=2.5‑8.0范围内呈现非常好的响应,具有制备简单、检测精确性高的特点。
Description
技术领域
本发明属于分子探针光电化学检测领域,具体涉及一种含有罗丹明B结构的环金属铱配合物作为光电化学分子探针用于检测pH值的传感器的制备方法。
背景技术
pH值在工业生产、生理学或临床实践中是一个非常重要的定性、诊断指标,因此pH传感器被广泛应用于食品分析、环境检测、临床诊断以及生物医学等领域,而这些应用通常需要高度可信且精确的pH值检测方法。目前用于pH检测的传感技术主要包括光学与电化学两大类。其中光学传感器最为普遍,但背景干扰严重,且检测相对复杂、仪器成本高;而电化学方法虽仪器简单,但存在灵敏度、特异性不够高,重现性差的缺点(Anal.Chem.,2014,86,15-29)。
光电化学传感器融合了光学和电化学技术的优点,因具有灵敏度高、设备简单、成本低、易于微型化等优点而备受瞩目,在多种领域取得了巨大的进展。而将其用于pH值的检测还是一个崭新的领域,目前仅有一种半导体聚合物量子点作为光电活性材料用于光电化学pH传感器(Anal.Chem.,2018,90,8300-8303)。与量子点型传感相比,分子型的识别探针具有结构及传感机理明确、重现性好的优点。大量的分子型识别探针已被广泛用于荧光pH传感,而用于光电化学的pH传感的分子探针至今未见报道。为弥补现有技术的不足,鉴于环金属配合物固有的光电化学活性及优异的化学、热稳定性(Anal.Chem.,2017,87,4283-4291;Anal.Chem.2018,90,14239-14246),本发明通过引入罗丹明B基团作为识别单元合成了环金属铱配合物,并将其作为光电化学分子识别探针用于pH值的检测。
发明内容:
本发明旨在提供一种基于环金属铱配合物光电化学分子探针构建pH传感的方法,具有制备简单、响应快、选择性高的特点。
基于上述目的,本发明所涉及的技术方案为:将制备好的环金属铱配合物分子探针键合在修饰有纳米TiO2的ITO电极表面形成分子层,制得pH传感的工作电极,采用三电极系统获得光电化学pH传感器,具体步骤如下:
(1)环金属铱配合物分子探针的制备:首先罗丹明B酰肼与4'-甲基-2,2'-联吡啶-4-甲醛反应制得辅助配体。铱配合物的制备采用传统的两步法进行合成,三氯化铱与环金属化配体4-(2-吡啶基)苯甲酸在乙氧基乙醇中回流制得氯桥联中间体,接着与已制得的辅助配体反应得到环金属铱配合物分子探针。
(2)工作电极的制备:将面积固定的ITO电极依次采用丙酮、乙醇、去离子水超声清洗干净并干燥后,将其浸入TiCl4溶液中加热,在电极表面形成小的TiO2团簇,进而涂覆纳米TiO2的分散溶液,自然干燥后,450℃煅烧2小时,制得TiO2修饰的ITO电极(TiO2/ITO)。将制得的TiO2/ITO电极浸入环金属铱配合物溶液中吸附2小时,在TiO2/ITO表面形成环金属铱配合物分子层,自然干燥后制得传感器的工作电极(Ir/TiO2/ITO)。
优选的,环金属铱配合物溶液的浓度为5.0×10-6mol/L。
(3)pH值的检测:将步骤(2)制得的工作电极浸入不同pH值的缓冲溶液中,以Pt丝为对电极,Ag/AgCl为参比电极,采用560nm可见光进行激发,每20s开关光源一次,记录光电流响应,实现对不同pH值的检测。
本发明的有益效果:
(1)本发明公开了一种环金属铱配合物作为光电化学分子识别探针用于pH传感器的制备,该探针具有稳定性好、采用可见光进行激发、光电转换效率高的特点。
(2)采用公开的环金属铱配合物作为光电化学分子识别探针制备的传感器用于pH值的检测,在2.5-8.0范围呈现非常好的响应,具有制备简单、检测精确性高的特点。
附图说明:
图1pH传感器工作电极示意图;
图2环金属配合物的紫外-可见吸收对不同pH值响应示意图;
图3传感器对不同pH值光电流响应示意图;
图4传感器对pH的线性关系图。
具体实施方式
结合实施例对本发明作进一步的说明,应该说明的是,下述说明仅是为了解释本发明,并不对其内容进行限定。
实施例1
环金属铱配合物分子探针的合成与表征:
在50mL圆底烧瓶中将罗丹明B酰肼(0.8mmol,0.41g)和4'-甲基-2,2'-联吡啶-4-甲醛(1.2mmol,0.29g)溶于无水乙醇(12mL)中,在N2气氛下将混合物在60℃加热12h。之后自然冷却至室温,抽滤得到的滤饼,用冷乙醇洗涤,得到砖红色固体,无水乙醇重结晶,得到辅助配体。1H NMR(CDCl3,500MHz)δ:8.58(d,1H);8.51(d,1H);8.42(s,1H);8.20(s,1H);8.16(s,1H);8.01(d,1H);7.75(d,1H);7.48(dt,2H);7.12(d,2H);6.54(d,2H);6.47(s,2H);6.24(d,2H);3.32(q,8H,);2.42(s,3H);1.16(t,12H)。
称取IrCl3·3H2O(0.6mmol,0.21g)溶于水(5mL)中,加入4-(2-吡啶基)苯甲酸(2.4mmol,0.44g)的乙二醇乙醚溶液15mL,充分搅拌后,反应混合液在氮气保护下于130-140℃反应24h。冷却至室温,抽滤得到的滤饼,用95%的乙醇洗涤后,真空干燥,硅胶柱色谱提纯(200-300目,洗脱剂:二氯甲烷/甲醇=10/1),得橙黄色的氯桥联中间体。将以上制备的辅助配体(0.1mmol,0.06g)和氯桥联中间体(0.05mmol,0.04g)溶于二氯甲烷和甲醇(50mL)(1:1v/v)中,回流4小时。减压除去溶剂后,将红色固体残余物溶于热甲醇中,加入六氟磷酸铵的饱和甲醇溶液搅拌2小时,过滤得到的固体通过将二乙醚蒸气扩散到配合物的二氯甲烷溶液中重结晶,得到橙色固体为环金属铱配合物分子探针。1H NMR(CDCl3,500MHz)δ:9.71(s,2H);8.85(s,1H);8.55(s,1H);8.34(s,1H);7.96-8.09(m,2H);7.79-7.92(m,4H);7.66-7.78(m,4H);7.57(dt,4H);7.41(d,2H);7.28(dd,2H);7.19(d,1H);7.13(t,1H);6.69(d,2H);6.50(d,2H);6.31(s,2H);3.32(q,8H);2.43(s,3H);1.13(t,12H)。
实施例2
ITO工作电极的制备:
将ITO电极依次用丙酮、乙醇、超纯水进行超声清洗,然后在氮气氛围下充分干燥。将清洗好的ITO电极浸入冷TiCl4溶液中30min,然后在空气中加热至80℃反应2小时,在ITO表面形成小的TiO2簇。将乙基纤维素(81mg)在搅拌的状态下缓慢加入松油醇(4.26mL)后保持搅拌状态直至乙基纤维素完全溶解,然后加入商品化的纳米TiO2(25nm,75mg),搅拌均匀后制得了TiO2凝胶。将制备好的TiO2凝胶(10μL)滴涂在修饰有TiO2簇的ITO电极上,室温干燥后,450℃煅烧2小时后自然冷却,制得TiO2修饰的ITO电极(TiO2/ITO)。将制备好的TiO2/ITO电极浸入铱配合物的甲醇溶液(5.0×10-6mol/L)中吸附2小时,在TiO2/ITO表面形成环金属铱配合物分子层,自然干燥后制得该传感器的工作电极(Ir/TiO2/ITO)。
实施例3
将实施例2制备好的Ir/TiO2/ITO工作电极浸入0.1mol/L的Tris-HCl缓冲液中,不断加入盐酸调节缓冲溶液的pH值。采用饱和Ag/AgCl为参比电极;铂丝为对电极;由光电化学分析仪记录和检测光电流。采用560nm可见光进行激发,每20s自动开关光源一次。光电流强度与pH值在1fM至1000fM范围内成良好的线性关系,线性方程为I=-0.28pH+2.50,R2=0.992,其中I为光电流强度(μA)。
Claims (2)
1.一种以环金属铱配合物作为光电化学分子探针的pH传感器的制备方法,其特征在于,包括以下步骤:
(1)环金属铱配合物分子探针的制备,采用含有罗丹明B结构的联吡啶作为辅助配体,其化学结构如下图所示:
(2)pH传感器工作电极的制备:ITO电极清洗干净并干燥后,将其浸入TiCl4溶液中加热,在电极表面形成TiO2簇,进而涂覆纳米TiO2的分散溶液,自然干燥后,450℃煅烧2小时,制得TiO2/ITO电极;将制得的TiO2/ITO电极浸入环金属铱配合物分子探针溶液中吸附2小时,在TiO2/ITO表面形成环金属铱配合物分子探针层,自然干燥后制得pH传感器工作电极;
(3)pH值的检测:将步骤(2)制得的传感器工作电极浸入不同pH值的缓冲溶液中,以Pt丝为对电极,Ag/AgCl为参比电极,采用560nm可见光进行激发,每20s开关光源一次,记录光电流响应,实现对不同pH值的检测。
2.如权利要求1所述方法制备的pH传感器在pH值检测中的应用。
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