Simultaneous Detection of Mercury, Lead and Strontium Ions Based on Conformational Conversion Sensor †

doi:10.7503/cjcu20180868

Abstract

Abstract:

A high-sensitive and specific electrochemical biosensor was designed for simultaneous detection of mercury ion(Hg ²⁺), lead ion(Pb ²⁺) and strontium ion(Sr ²⁺) by oligonucleotide conformational transformation. The biosensor was based on porous anodic alumina(PAA) modified with two oligonucleotide aptamers which could capture Hg ²⁺, Pb ²⁺ and Sr ²⁺, respectively. The aptamers can block [Fe(CN)₆] ^3-/4- ion conduction in the nanochannels of PAA. In the presence of Hg ²⁺, Pb ²⁺ and Sr ²⁺, the aptamers could bend and wrap around those metal ions to make the nanochannel unobstructed, and then, the redox current of [Fe(CN)₆] ^3-/4- could be increased. When the biosensor eluted with β-mercaptoethanol(βME), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid(DOTA) and kryptofix 222(KP) successively, the aptamers stretched and released Hg ²⁺, Pb ²⁺ and Sr ²⁺ in sequence, leading to the re-blockage of nanochannel with the decrease of the redox current. The calibration curves of Hg ²⁺, Pb ²⁺ and Sr ²⁺ were obtained in the range of 0.05—2.50 nmol/L, and the detection limits were 0.013, 0.017 and 0.022 nmol/L, respectively. Furthermore, the biosensor is easily constructed, stable and reusable. It is hopeful to apply in the daily monitoring of harmful metal ions in drinking water or environmental water.

Key words: Porous anodic alumina, Hg ²⁺, Pb ²⁺, Sr ²⁺, Biosensor

CLC Number:

O657.1

TrendMD:

ZHOU Yuting, TANG Yujiao, SHAO Shuang, DAI Shiyan, CHENG Guifang, HE Pingang, FANG Yuzhi. Simultaneous Detection of Mercury, Lead and Strontium Ions Based on Conformational Conversion Sensor ^†[J]. Chem. J. Chinese Universities, 2019, 40(8): 1621.

Figures/Tables 10

Fig.1 Schematic illustration of the proposed Hg2+/Pb2+/Sr2+-biosensor

Fig.2 SEM image of the bare PAA on the biosensor surfaces

Fig.3 DPV(A) and EIS(B) curves for bare PAA(a), PAA modified with oligonucleotide H1(b), the biosensor incubated with Hg2+(c) and then eluted by βME(d) Experimental conditions: 5×10-4 mol/L K3Fe(CN)6; 1×10-7 mol/L Hg2+; 1×10-8 mol/L βME.

Fig.4 Effect of the size of PAA nanopore on the differences of the current between before and after incubation with Hg2+ Experimental conditions: 5×10-4 mol/L K3Fe(CN)6; 1×10-7 mol/L Hg2+; 1×10-8 mol/L βME.

Fig.5 DPV curves of the entire detection process for PAA/H1/H2(a), incubated with the mixture of Hg2+, Pb2+ and Sr2+(b), eluted by βME(c), DOTA(d), and KP(e) Experimental conditions: 5×10-4 mol/L K3Fe(CN)6; 1×10-7 mol/L Hg2+; 1×10-7 mol/L Pb2+ and Sr2+; 1×10-8 mol/L βME; 1×10-7 mol/L DOTA and KP.

Eluent	Ion	k/(nmol·s^-1)
βME	Hg²⁺	4.95×10^-3
	Pb²⁺	5.60×10^-4
	Sr²⁺	7.29×10^-4
DOTA	Pb²⁺	3.10×10^-3
	Sr²⁺	6.11×10^-4
KP	Sr²⁺	2.16×10^-3

Fig.6 Specificity of the biosensor for the detection of Hg2+(A), Pb2+(B) and Sr2+(C) a. Zn2+; b. Sn2+; c. Cu2+; d. Mn2+; e. Ni2+; f. Co2+; g. Cd2+; h. Ca2+; i. Mg2+; j. F-; k. Cl-; l. NO 3 - ; m. SO 4 2 - ; n. Ac-; o. P O 4 3 - ; p. CO 3 2 - ; q. S2-; r. Pb2+; s. Sr2+; t. the mixture of all the co-existent ions; u. the solution contains 10.0 nmol/L Hg2+, Pb2+ and Sr2+. Experimental conditions: 5×10-4 mol/L K3Fe(CN)6; 1×10-8 mol/L βME; 1×10-7 mol/L DOTA and KP.

Fig.7 Regeneration of the biosensor

Fig.8 Calibration curves of the biosensor for the detection of Hg2+(A), Pb2+(B) and Sr2+(C) and linear relationships between the currents and the concentration of Hg2+(A'), Pb2+(B') and Sr2+(C')

Sample	Contentration of M²⁺/nmol				Recovery(%)
Sample	Ion	Original	Add	Found	Recovery(%)
Tap water	Hg²⁺	Not detected	1.00	0.98	98
	Pb²⁺	Not detected	1.00	1.11	111
	Sr²⁺	Not detected	1.00	1.08	107
Drinking water	Hg²⁺	Not detected	1.00	0.90	90
	Pb²⁺	Not detected	1.00	0.93	93
	Sr²⁺	Not detected	1.00	1.03	103
River water	Hg²⁺	0.04	1.00	1.16	112
	Pb²⁺	Not detected	1.00	0.97	97
	Sr²⁺	0.16	1.00	1.11	95

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