Detection of Copper Ion Based on the Interaction Between DNA Molecules and Copper Ions†

doi:10.7503/cjcu20160116

Abstract

Abstract:

Copper ion(Cu²⁺) is one of the essential trace elements of human, which plays an important role in life. However, excessive amounts of copper ions may cause serious damage to health. In this work, Cu²⁺ ions were determined by differential pulse voltammetry(DPV) based on its concentration on DNA modified electrode due to the complexation of Cu²⁺ ions with the base of DNA. Furthermore, because ethylenediaminetetraacetic acid(EDTA) shows stronger complexing ability to Cu²⁺ ions than DNA, Cu²⁺ concentrated on DNA modified electrode can be eluted with EDTA. Thus, the modified electrode was reusable. The results showed that under optimum conditions, the relative reduction current(I-I₀) was linear with the concentration of copper ions in the range of 2.0×10^-6—1.0×10^-5 mol/L and 2.0×10^-5—1.0×10^-4 mol/L. The proposed electrochemical sensor for Cu²⁺ ions was simple, stable and reusable.

Key words: DNA modified electrode, Electrochemical sensor, Differential pulse voltammetry, Copper ion

CLC Number:

O657.1

TrendMD:

LI Min, KONG Huifang, GUO Zhihui. Detection of Copper Ion Based on the Interaction Between DNA Molecules and Copper Ions^†[J]. Chem. J. Chinese Universities, 2016, 37(7): 1269.

Figures/Tables 12

Fig.1 CV curves of 1 mmol/L K3[Fe(CN)6]/K4 [Fe(CN)6] at bare Au(a), Au-ssDNA(b) and Au-ssDNA-MCH(c) electrodesScan potential: -0.2—0.6 V; scan rate: 100 mV/s.

Fig.2 Differential pulse voltammograms of DNA modified electrodes without Cu2+(a) and with Cu2+(b) in 10 mmol/L PBS containing 0.1 mol/L NaCl(pH=7.0)

Fig.3 Schematic representation of detecting Cu2+

Fig.4 Effect of adsorption time of Cu2+ on DPV response signal(cCu2+= 5×10-6 mol/L)

Fig.5 Effect of pH value on the DPV response signal in 10 mmol/L Na2HPO4-NaH2PO4 solution

Fig.6 Influence of the self-assembly time of DNA on the DPV response signal(cDNA=5.0×10-5 mol/L)

Fig.7 DPV response of the DNA modified electrode at different concentration of Cu2+ in 10 mmol/L PBS(pH=7.0) and 0.1 mol/L NaCl (A) cCu2+/(mol·L-1): a—f. 0, 2.0×10-6, 4.0×10-6, 6.0×10-6, 8.0×10-6, 1.0×10-5; (B) cCu2+/(mol·L-1): a—f. 0, 2.0×10-5 , 4.0×10-5, 6.0×10-5, 8.0×10-5, 1.0×10-4. Insets are the linear relationship between the peak current and the Cu2+ concentration.

Table 1 Comparison of the electrochemical sensor in this work and other sensors

Electrode	Linear range/(mol·L^-1)	Detection limit/(mol·L^-1)	Ref.
ssIDNA modified electrode DPV	2.0×10^-6—1.0×10^-5, 2.0×10^-5— 1.0×10^-4	6.4×10^-7	This work
Bismuth film modified electrode ASV	3.1×10^-7—3.1×10^-6	3.1×10^-7	[31]
Pd/PAC-modified GCE DPV	5×10^-7—5.0×10^-6	6.6×10^-8	[32]
IP₆ MWCNTs ITO DNPASV	1.0×10^-8—8.0×10^-7	2.5×10^-9	[33]
DSP-AuNPs/PAMAM/MWCNT GCE DPV	1.0×10^-9—1.0×10^-6	4.8×10^-10	[34]

Fig.8 Differential pulse voltammograms of the DNA modified electrodes without Cu2 +(a)and with Cu2 +(b) and after being immersed into 10 mmol/L Tris-HCl(pH=9.0) buffer solution containing excessive EDTA for 40 min(c)

Fig.9 Relative reduction current(I-I0) of Cu2+ for 4 times repetitive detections of DNA modified electrodecCu2+=5.0×10-6 mol/L.

Fig.10 Reduction current of the DNA modified electrode after adding different metal ions orderly

Table 2 Recovery analysis of Cu2+ in lake water samples

Sample	Cu²⁺ concentration/(μmol·L^-1)		Recovery(%)	Sample	Cu²⁺ concentration/(μmol·L^-1)		Recovery(%)
Sample	Added		Recovery(%)	Found		Added	Found
Lake water 1	0	0		Lake water 4	5	5.26	105.2
Lake water 2	5	4.71	94.2	Lake water 5	5	5.55	111.1
Lake water 3	5	4.76	95.2

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