一种简单快速检测汞离子的1,4-二硫苏糖醇膜修饰金平板电极

doi:10.7503/cjcu20140288

摘要/Abstract

摘要：

将1,4-二硫苏糖醇(DTT)自组装在100 nm厚的平整金膜表面, 形成DTT膜修饰金平板电极(GPE), 构建了一种新颖的简单、快速测定汞离子的选择性电极分析方法. 通过电化学交流阻抗和循环伏安法探讨了该电极的响应原理, 即固定在Au表面的DTT通过另一端的巯基与汞离子发生强配位作用而吸附结合带正电荷的汞离子, 引起电极表面膜电位的变化, 从而选择性地识别汞离子. 实验结果表明, 该电极在pH=6.0的Tris-HCl缓冲溶液中对汞离子有良好的电位响应性能, 其线性范围为1.0×10^-8~1.0×10^-3 mol/L, 能斯特响应斜率为(29.62±0.2) mV/-pc(25 ℃), 检出限为5.1×10^-9 mol/L. 该汞离子检测电极的响应时间仅为20 s, 且有较好的重现性和稳定性. 通过测定各种离子的选择性系数, 发现Cu²⁺, Fe²⁺, Na⁺, K⁺, Mg²⁺, Ba²⁺, Ca²⁺, Zn²⁺, Sn²⁺, Pb²⁺, Ag⁺, Al³⁺, Fe³⁺, Ni²⁺, N $O 2 -$ , I $O 3 -$ , Br $O 3 -$ 和Cl $O 3 -$ 等离子不干扰该电极对汞离子的检测. 此外, 将该电极用于实际水样中微量汞离子含量的测定, 结果与双硫腙分光光度方法一致, 且回收率为98.20%~101.75%.

关键词: 金平板电极, 1, 4-二硫苏糖醇, 自组装膜, 汞离子, 选择性识别

Abstract:

A simply gold plate electrode(GPE) based on 1,4-dithiothreitol(DTT), which was self-assembled on a surface of flat gold film with a thickness of 100 nm, was developed to construct a novel selective electrode method for rapid detection of mercury ion. Through electrochemical impedance analysis and cyclic voltamme-tric method, the response mechanism of the electrode for selective recognition of Hg²⁺ was investigated, that the other terminal sulfhydryl group of DTT binding to Au surface can coordinate with Hg²⁺ due to their strong complexing interaction, resulting in change of membrane potential of the electrode surface. The proposed electrode possesses good potential performance responding to Hg²⁺ with a linear range of 1.0×10^-8—1.0×10^-3mol/L, a Nernst slope of (29.62±0.2) mV/-pc(25 ℃), and a detection limit of 5.1×10^-9mol/L in Tris-HCl buffer solution(pH=6.0). The electrode has short response time(20 s), good reproducibility and stability. No interference can be observed from most common ions like Cu²⁺, Fe²⁺, Na⁺, K⁺, Mg²⁺, Ba²⁺, Ca²⁺, Zn²⁺, Sn²⁺, Pb²⁺, Ag⁺, Al³⁺, Fe³⁺, Ni²⁺, N $O 2 -$ , I $O 3 -$ , Br $O 3 -$ and Cl $O 3 -$ . Compared with spectrophotometric method with dithizone, the proposed electrode can be well utilized to the determination of trace amount of Hg²⁺ in real water samples with a recovery rate of 98.20%—101.75%, showing promising application in environmental and other fields.

Key words: Gold plate electrode, 1, 4-Dithiothreitol, Self-assembled monolayer, Mercury ion, Selective recognition

中图分类号:

TrendMD:

曹婷婷, 曹忠, 何婧琳, 梁海琴, 肖忠良. 一种简单快速检测汞离子的1,4-二硫苏糖醇膜修饰金平板电极. 高等学校化学学报, 2014, 35(7): 1388.

CAO Tingting, CAO Zhong, HE Jinglin, LIANG Haiqin, XIAO Zhongliang. Simple and Rapid Determination of Mercury Ions Based on 1,4-Dithiothreitol Assembled Gold Plate Electrode^†. Chem. J. Chinese Universities, 2014, 35(7): 1388.

图/表 12

Fig.1 Structure of DTT

Fig.2 Design of gold plate electrode(A) and SEM image of its section structure(B) (A) 1. Base plate; 2. gold film; 3. gold-film pin; 4. plastics film; 5. copper wire; 6. soldering tin; 7. silicone sealant.

Fig.3 SEM images of electrode surfaces for bare GPE(A), GPE/DTT(B) and GPE/DTT/Hg2+(C)

Fig.4 Schematic illustration of the response process of the electrode

Fig.5 Impedance(A) and cyclic voltammetry(B) plots of the electrodes for bare GPE(a), GPE/DTT(b) and GPE/DTT/Hg2+(c) in the media solution containing 2.0 mmol/L K3Fe(CN)6 and 0.2 mol/L Na2SO4

Fig.6 XPS spectra of the electrode surfaces for bare GPE(a), GPE/DTT(b) and GPE/DTT/Hg2+(c)

Fig.7 Effect of pH on sensitivity of GPE/DTT electrode

Fig.8 Potential response curve(A) and its linear relation plot(B) of GPE/DTT electrode to Hg2+ in Tris-HCl buffer(pH=6.0)

Fig.9 Dynamic response of the electrode to various concentrations of Hg2+ in Tris-HCl buffer(pH=6.0) c(Hg2+)/(mol·L-1): A. 0; B. 1.0×10-8; C. 1.0×10-7; D. 1.0×10-6; E. 1.0×10-5; F. 1.0×10-4.

Table 1 Reproducibility of GPE/DTT electrode

No.	Potential/mV
No.	1.0×10^-6mol/L Hg²⁺	1.0×10^-4mol/L Hg²⁺
1	131	189
2	130	188
3	131	189
4	131	189
5	129	188
6	130	187
7	130	188
8	131	188
9	130	189
10	131	190
AV	130.4	188.5
SD	±0.70	±0.85

Table 2 Selectivity coefficient of GPE/DTT electrode to Hg2+

Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$
Na⁺	-4.95	Cu²⁺	-2.85	Sn²⁺	-3.25
K⁺	-3.20	Zn²⁺	-3.15	Ni²⁺	-3.48
Mg²⁺	-4.32	Pb²⁺	-3.65	N $O 2 -$	-4.69
Ba²⁺	-4.29	Ag⁺	-3.83	I $O 3 -$	-4.32
Ca²⁺	-3.58	Al³⁺	-3.63	Br $O 3 -$	-3.47
Fe²⁺	-3.15	Fe³⁺	-2.85	Cl $O 3 -$	-3.06

Table 2 Selectivity coefficient of GPE/DTT electrode to Hg2+

Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$
Na⁺	-4.95	Cu²⁺	-2.85	Sn²⁺	-3.25
K⁺	-3.20	Zn²⁺	-3.15	Ni²⁺	-3.48
Mg²⁺	-4.32	Pb²⁺	-3.65	N $O 2 -$	-4.69
Ba²⁺	-4.29	Ag⁺	-3.83	I $O 3 -$	-4.32
Ca²⁺	-3.58	Al³⁺	-3.63	Br $O 3 -$	-3.47
Fe²⁺	-3.15	Fe³⁺	-2.85	Cl $O 3 -$	-3.06

Table 3 Recovery of the proposed GPE/DTT electrode for the determination of Hg2+ in real water samples compared with spectrophotometric method with dithizone

Sample	Concentration added/(μmol·L^-1)	Spectrophotometric method with dithizone		GPE/DTT electrode		Recovery(%)
Sample	Concentration added/(μmol·L^-1)	Mean/(μmol·L^-1)	SD		Mean/(μmol·L^-1)	SD
A	0.400	0.402	±0.016	0.407	±0.015	101.75
B	0.500	0.510	±0.013	0.491	±0.019	98.20
C	0.600	0.594	±0.014	0.604	±0.014	100.67
D	0.800	0.794	±0.013	0.797	±0.022	99.63
E	1.200	1.210	±0.015	1.206	±0.014	100.50
F	1.800	1.798	±0.011	1.796	±0.016	99.89

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