High-sensitive Fluorescent Enhancement Detection of Hg(Ⅱ) Ions Based on Poly(thymine)-templated Copper Nanoclusters†

doi:10.7503/cjcu20160319

Abstract

Abstract:

A rapid sensitive fluorescent sensor was developed for Hg(Ⅱ) ions detection based on the specific thymine-Hg²⁺-thymine structure and photoluminescent property of DNA copper nanoclusters. Upon the addition of Hg²⁺, poly thymine single strand DNA(P1) is transformed into double strand DNA through the formation of T-Hg²⁺-T configuration. Sodium ascorbate is effective to reduce Cu²⁺ to Cu⁰, and this reduction process is accompanied by formation of intermediate Cu⁺. However, Cu⁺has a strong binding site within hydrogen-bonding moieties in the helix of dsDNA which facilating Cu⁰ gathered in dsDNA to form stronger fluorescent copper nanoclusters than ssDNA copper nanoclusters, and these changes in fluorescence intensity of DNA-CuNCs are allowed for sensitive analysis of Hg(Ⅱ) ions. Satisfactory linear relationship and detection limit were obtained. The resulting calibration plots exhibited good linear correlations in the range from 1.0 nmol/L to 10 μmol/L for Hg(Ⅱ) ions, and the detection limits of Hg(Ⅱ) ions was 0.4 nmol/L. The proposed method was highly selective and other metal ions have no interfering effects on the determination. Moreover, satisfactory results were obtained while the proposed method was applied to determination of Hg²⁺ in real lake samples.

Key words: Fluorescence enhancement, Environmental water sample, Copper nanoclusters, T-Hg²⁺-T, Mercury ion

CLC Number:

O657.3

TrendMD:

LI Ting, CAO Zhong, LI Panpan, HE Jinglin, XIAO Hui, YANG Chan. High-sensitive Fluorescent Enhancement Detection of Hg(Ⅱ) Ions Based on Poly(thymine)-templated Copper Nanoclusters^†[J]. Chem. J. Chinese Universities, 2016, 37(9): 1616.

Figures/Tables 6

Fig.1 Schematic illustration of the Hg2+ sensing strategy based on the fluorescence enhancing of copper nanoclusters

Fig.2 Fluorescence emission spectra of different systems The final concentrations of P1, sodium ascorbate, Hg2+ and Cu2+ were 500 nmol/L, 2.0 mmol/L, 100 nmol/L, and 1.0 mmol/L, respectively. a. P1; b. P1+sodium ascorbate; c. P1+Hg2+; d. P1+sodium ascorbate+Hg2+; e. P1+Cu2++sodium ascorbate; f. P1+ Cu2++sodium ascorbate+Hg2+.

Fig.3 Effect of incubation time on the fluorescence intensity of DNA-CuNCs in the presence of 100 nmol/L Hg2+

Fig.4 Fluorescence spectra of DNA-CuNCs with addition of different concentrations of Hg2+ ions c(Hg2+)/(nmol·L-1): a. 0, b. 1.0, c. 10, d. 100,e. 103, f. 104.

Fig.5 Selectivity of DNA-CuNCs in the presence of 5 μmol/L Hg2+ ions and 50 μmol/L other metal ions a. Hg2+; b. blank; c. Ni2+; d. Zn2+; e. Mg2+; f. Co2+; g. Ce2+; h. Ca2+; i. Fe3+; j. Fe2+; k. Cd2+; l. Ba2+; m. Al3+; n. Mn2+; o. Ag+; p. Cr3+.

Table 1 Determination results of Hg2+ in Yunying lake water samples

Sample No.	Spiked/(nmol·L^-1)	Founded/(nmol·L^-1)	Recovery(%)	RSD(n=3, %)
1	2.000	1.973	98.7	2.6
2	5.000	5.232	104.6	4.1
3	10.00	9.722	97.2	8.0
4	80.00	85.26	106.6	6.1

References 28

[1]	Nolan E. M., Lippard S. J., Chem. Rev., 2008, 108(9), 3443—3480
[2]	Hao Y. L., Guo Q. Q., Wu H. Y., Guo L. Q., Zhong L. S., Wang J., Lin T. R., Fu F. F., Chen G. N., Biosens. Bioelectron., 2014, 52, 261—264
[3]	Wang D., Liu X. M., Fang Z. X., Li J., Sun M. J., Chem. Res. Chinese Universities,2015, 31(4), 581—584
[4]	Tang W. Q., Chase D. B., Sparks D. L., Rabolt J. F., Appl. Spectros., 2015, 69(7), 843—849
[5]	Wang L., Li T., Du Y., Chen C. G., Li B. L., Zhou M., Dong S. J., Biosens. Bioelectron., 2010, 25(12), 2622—2626
[6]	Das N. K., Ghosh S., Priya A., Datta S., Mukherjee S., J. Phys. Chem. C,2015, 119(43), 24657—24664
[7]	Chen J. Y., Su W., Wang E. J., Chem. J. Chinese Universities,2016, 37(2), 232—238
	(陈家逸, 苏伟, 王恩举. 高等学校化学学报, 2016, 37(2), 232—238)
[8]	Liu X. F., Tang Y. L., Wang L. H., Zhang J., Song S. P., Fan C. H., Wang S., Adv. Mater., 2007, 19(11), 1471—1474
[9]	Freeman R., Finder T., Willner I., Angew. Chem. Int. Ed., 2009, 48(42), 7818—7821
[10]	Huang C. C., Yang Z., Lee K. H., Chang H. T., Angew. Chem., 2007, 119(36), 6948—6952
[11]	Tao Y., Li M. Q., Ren J. S., Qu X. G., Chem. Soc. Rev., 2015, 44(24), 8636—8663
[12]	Zhang L. B., Wang E. K., Nano Today,2014, 9(1), 132—157
[13]	Guo Y. M., Cao F. P., Lei X. L., Mang L. H., Cheng S. J., Song J. T., Nanoscale,2016, 8(48), 4852—4863
[14]	Wang G. F., Xu G., Zhu Y. H., Zhang X. J., Chem. Commun., 2014, 50(6), 747—750
[15]	Gao F. P., Cai P. J., Yang W. J., Xue J. Q., Gao L., Liu R., Wang Y. L., Zhao Y. W., He X., Zhao L., Huang G. D., Wu F. S., Zhao Y. L., Chai Z. F., Gao X. Y., ACS Nano,2015, 9(5), 4976—4986
[16]	Zhong Y. P., Wang Q. P., He Y., Ge Y. L., Song G. W., Sens. Actuators B,2015, 209, 147—153
[17]	Bhamore J. R., Jha S. J., Munngara A. K., Singhal R. K., Sonkeshariya D., Kailasa S. K., Biosens. Bioelectron., 2016, 80, 243—248
[18]	Rotaru A., Dutta S., Jentzsch E., Gothelf K., Mokhir A., Angew. Chem. Int. Ed., 2010, 49(33), 5665—5667
[19]	Jia X. F., Li J., Han L., Ren J. T., Yang X., Wang E. K., ACS Nano,2012, 6(4), 3311—3317
[20]	Hu R., Liu Y. R., Kong R. M., Donovan M. J., Zhang X. B., Tan W. H., Shen G. L., Yu R. Q., Biosens. Bioelectron., 2013, 42, 31—35
[21]	Zhou Z. X., Du Y., Dong S. J., Anal. Chem., 2011, 83(13), 5122—5127
[22]	Chen J. H., Liu J., Fang Z. Y., Zeng L. W., Chem. Commun., 2012, 48(7), 1057—1059
[23]	Wang H. B., Zhang H. D., Chen Y., Huang K. J., Liu Y. M., Sens. Actuators B,2015, 220, 146—153
[24]	Qing Z. H., He X. X., He D. G., Wang K. M., Xu F. Z., Qing T. P., Yang X., Angew. Chem. Int. Ed., 2013, 52(37), 9719—9722
[25]	Qing Z. H., Mao Z. G., Qing T. P., He X. X., Zou Z., He D. G., Shi H., Huang J., Liu J. B., Wang K. M., Anal. Chem., 2014, 86(22), 11263—11268
[26]	Ou L. J., Li X. Y., Liu H. W., Li L. J., Chu X., Anal. Sci., 2014, 30(7), 723—727
[27]	Russo N., Toscano M., Grand A., J. Mass Spectrom., 2003, 38, 265—270
[28]	Berti L., Burley G. A., Nature Nanotech., 2008, 3, 81—87