A colorimetric assay for the determination of heavy metal ions is presented that is based on the regulation of the oxidase-mimicking activity of Mn3O4 nanoparticles (NPs) by oligonucleotides. The chromogenic agent tetramethylbenzidine (TMB) is oxidized by the catalytic action of Mn3O4 NPs to generate products that have a yellow color in acidic solution, with a peak at 450 nm. It is found that random oligonucleotides are absorbed on the regular surface of the Mn3O4 NPs and temporarily inhibit the oxidation of TMB. This leads to a decrease in absorbance and a light-green coloration of the solution. The results show that the purine bases in oligonucleotides play a key role in their regulation of the activity of the NPs. The regulatory effect is assumed to be of the noncompetitive type. In the presence of heavy metal ions like Hg(II) or Cd(II), the inhibition is canceled due to the binding of heavy metal ions to thymine bases, and the color of the solution changes from light green to yellow. The increase in absorbance at 450 nm is related to the amount of heavy metal ions present. The method allows Hg(II) and Cd(II) to be determined visually in concentrations as low as 20 μg·L−1. The detection limit of the colorimetric assay is 3.8 and 2.4 μg·L−1 of Hg(II) and Cd(II), respectively. The assay displays good selectivity over other heavy metal ions. The method was successfully validated by analyzing several water samples.
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Wu JJX, Wang XY, Wang Q, Lou ZP, Li SR, Zhu YY, Qin L, Wei H (2019) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II). Chem Soc Rev 48(4):1004–1076
Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007) Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat Nanotechnol 2(9):577–583
Huang YY, Ren JS, Qu XG (2019) Nanozymes: classification, catalytic mechanisms, activity regulation, and applications. Chem Rev 119(6):4357–4412
Zhang XD, Huang YM (2015) Evaluation of the antioxidant activity of phenols and tannic acid determination with Mn3O4 nano-octahedrons as an oxidase mimic. Anal Methods 7(20):8640–8646
Singh N, Savanur MA, Srivastava S, D'Silva P, Mugesh G (2017) A redox modulatory Mn3O4 nanozyme with multi-enzyme activity provides efficient cytoprotection to human cells in a Parkinson's disease model. Angew Chem Int Ed 56(45):14267–14271
Yao J, Cheng Y, Zhou M, Zhao S, Lin SC, Wang XY, Wu JJX, Li SR, Wei H (2018) ROS scavenging Mn3O4 nanozymes for in vivo anti-inflammation. Chem Sci 9(11):2927–2933
Liu J, Meng LJ, Fei ZF, Dyson PJ, Jing XN, Liu X (2017) MnO2 nanosheets as an artificial enzyme to mimic oxidase for rapid and sensitive detection of glutathione. Biosens Bioelectron 90:69–74
Chen J, Meng HM, Tian Y, Yang R, Du D, Li ZH, Qu LB, Lin YH (2019) Recent advances in functionalized MnO2 nanosheets for biosensing and biomedicine applications. Nanoscale Horiz 4(2):321–338
Zhang XD, Mao XX, Li SQ, Dong WF, Huang YM (2018) Tuning the oxidase mimics activity of manganese oxides via control of their growth conditions for highly sensitive detection of glutathione. Sens Actuator B Chem 258:80–87
Zhan SS, Wu YG, Wang LM, Zhan XJ, Zhou P (2016) A mini-review on functional nucleic acids-based heavy metal ion detection. Biosens Bioelectron 86:353–368
Lin L, Shi DM, Li QF, Wang GF, Zhang XJ (2016) Detection of T4 polynucleotide kinase based on a MnO2 nanosheet-3,3 ',5,5 '-tetramethylbenzidine (TMB) colorimetric system. Anal Methods 8(20):4119–4126
Wu YG, Zhan SS, Wang FZ, He L, Zhi WT, Zhou P (2012) Cationic polymers and aptamers mediated aggregation of gold nanoparticles for the colorimetric detection of arsenic(III) in aqueous solution. Chem Commun 48(37):4459–4461
Zhao J, Wu YE, Tao H, Chen HY, Yang WP, Qiu SY (2017) Colorimetric detection of streptomycin in milk based on peroxidase-mimicking catalytic activity of gold nanoparticles. RSC Adv 7(61):38471–38478
Yang WP, Wu YG, Tao H, Zhao J, Chen HY, Qiu SY (2017) Ultrasensitive and selective colorimetric detection of acetamiprid pesticide based on the enhanced peroxidase-like activity of gold nanoparticles. Anal Methods 9(37):5484–5493
Babamiri B, Salimi A, Hallaj R (2018) Switchable electrochemiluminescence aptasensor coupled with resonance energy transfer for selective attomolar detection of Hg2+ via CdTe@CdS/dendrimer probe and Au nanoparticle quencher. Biosens Bioelectron 102:328–335
Xue SY, Jing P, Xu WJ (2016) Hemin on graphene nanosheets functionalized with flower-like MnO2 and hollow AuPd for the electrochemical sensing lead ion based on the specific DNAzyme. Biosens Bioelectron 86:958–965
Lv M, Liu Y, Geng JH, Kou XH, Xin ZH, Yang DY (2018) Engineering nanomaterials-based biosensors for food safety detection. Biosens Bioelectron 106:122–128
Sitko R, Turek E, Zawisza B, Malicka E, Talik E, Heimann J, Gagor A, Feist B, Wrzalik R (2013) Adsorption of divalent metal ions from aqueous solutions using graphene oxide. Dalton Trans 42(16):5682–5689
Nawab J, Khan S, Wang XP (2018) Ecological and health risk assessment of potentially toxic elements in the major rivers of Pakistan: general population vs. fishermen. Chemosphere 202:154–164
Imhof HK, Laforsch C, Wiesheu AC, Schmid J, Anger PM, Niessner R, Ivleva NP (2016) Pigments and plastic in limnetic ecosystems: a qualitative and quantitative study on microparticles of different size classes. Water Res 98:64–74
Pu F, Ren JS, Qu XG (2018) Nucleobases, nucleosides, and nucleotides: versatile biomolecules for generating functional nanomaterials. Chem Soc Rev 47(4):1285–1306
Willner MR, Vikesland PJ (2018) Nanomaterial enabled sensors for environmental contaminants. J Nanobiotechnol 16:16
Berlina AN, Zherdev AV, Dzantiev BB (2019) Progress in rapid optical assays for heavy metal ions based on the use of nanoparticles and receptor molecules. Microchim Acta 186(3):39
Adarakatti PS, Siddaramanna A, Malingappa P (2019) Fabrication of a new calix 4 arene-functionalized Mn3O4 nanoparticle-based modified glassy carbon electrode as a fast responding sensor towards Pb2+ and Cd2+ ions. Anal Methods 11(6):813–820
Wang ZX, Guo YX, Ding SN (2015) Fluorometric determination of cadmium(II) and mercury(II) using nanoclusters consisting of a gold-nickel alloy. Microchim Acta 182(13–14):2223–2231
Zuo XW, Zhang HG, Zhu Q, Wang WF, Feng J, Chen XG (2016) A dual-color fluorescent biosensing platform based on WS2 nanosheet for detection of Hg2+ and Ag+. Biosens Bioelectron 85:464–470
Ramalingam M, Ponnusamy VK, Sangilimuthu SN (2019) A nanocomposite consisting of porous graphitic carbon nitride nanosheets and oxidized multiwalled carbon nanotubes for simultaneous stripping voltammetric determination of cadmium(II), mercury(II), lead(II) and zinc(II). Microchim Acta 186(2):10
Li Y, Tan HY, Yang XY, Goris B, Verbeeck J, Bals S, Colson P, Cloots R, Van Tendeloo G, Su BL (2011) Well shaped Mn3O4 nano-octahedra with anomalous magnetic behavior and enhanced photodecomposition properties. Small 7(4):475–483
Saputra E, Muhammad S, Sun HQ, Ang HM, Tade MO, Wang SB (2013) A comparative study of spinel structured Mn3O4, Co3O4 and Fe3O4 nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions. J Colloid Interface Sci 407:467–473
Wu YG, Zhan SS, Xing HB, He L, Xu LR, Zhou P (2012) Nanoparticles assembled by aptamers and crystal violet for arsenic(III) detection in aqueous solution based on a resonance Rayleigh scattering spectral assay. Nanoscale 4(21):6841–6849
Chen HY, Wu YG, Yang WP, Zhan SS, Qiu SY, Zhou P (2017) Ultrasensitive and selective detection of isocarbophos pesticide based on target and random ssDNA triggered aggregation of hemin in polar organic solutions. Sens Actuator B Chem 243:445–453
Berti L, Burley GA (2008) Nucleic acid and nucleotide-mediated synthesis of inorganic nanoparticles. Nat Nanotechnol 3(2):81–87
Wu YG, Zhan SS, Xu LR, Shi WW, Xi T, Zhan XJ, Zhou P (2011) A simple and label-free sensor for mercury(II) detection in aqueous solution by malachite green based on a resonance scattering spectral assay. Chem Commun 47(21):6027–6029
Wu YG, Zhan SS, Wang LM, Zhou P (2014) Selection of a DNA aptamer for cadmium detection based on cationic polymer mediated aggregation of gold nanoparticles. Analyst 139(6):1550–1561
Li Y, Ouyang Q, Li HH, Chen M, Zhan ZZ, Chen QS (2018) Turn-on fluoresence sensor for Hg2+ in food based on FRET between Aptamers-functionalized upconversion nanoparticles and gold nanoparticles. J Agric Food Chem 66(24):6188–6195
Chen ZQ, Wang XS, Cheng X, Yang WJ, Wu YN, Fu FF (2018) Specifically and visually detect methyl-mercury and ethyl-mercury in fish sample based on DNA-Templated alloy Ag-Au nanoparticles. Anal Chem 90(8):5489–5495
Hassan KM, Elhaddad GM, AbdelAzzem M (2019) Voltammetric determination of cadmium(II), lead(II) and copper(II) with a glassy carbon electrode modified with silver nanoparticles deposited on poly(1,8-diaminonaphthalene). Microchim Acta 186(7):10
Li W, Bin C, Zhang HX, Sun YH, Wang J, Zhang JL, Fu Y (2015) BSA-stabilized Pt nanozyme for peroxidase mimetics and its application on colorimetric detection of mercury(II) ions. Biosens Bioelectron 66:251–258
Liu R, Zuo L, Huang XR, Liu SM, Yang GY, Li SY, Lv CY (2019) Colorimetric determination of lead(II) or mercury(II) based on target induced switching of the enzyme-like activity of metallothionein-stabilized copper nanoclusters. Microchim Acta 186(4):8
Yang HG, Zha JQ, Zhang P, Xiong YH, Su LJ, Ye FG (2016) Sphere-like CoS with nanostructures as peroxidase mimics for colorimetric determination of H2O2 and mercury ions. RSC Adv 6(71):66963–66970
Huang LJ, Zhu QR, Zhu J, Luo LP, Pu SH, Zhang WT, Zhu WX, Sun J, Wang JL (2019) Portable colorimetric detection of mercury(II) based on a non-noble metal nanozyme with tunable activity. Inorg Chem 58(2):1638–1646
Wang CH, Tang GG, Tan HL (2018) Colorimetric determination of mercury(II) via the inhibition by ssDNA of the oxidase-like activity of a mixed valence state cerium-based metal-organic framework. Microchim Acta 185(10):8
Du JW, Hu X, Zhang GW, Wu XQ, Gong DM (2018) Colorimetric detection of cadmium in water using L-cysteine functionalized gold-silver nanoparticles. Anal Lett 51(18):2906–2919
Singh K, Kukkar D, Singh R, Kukkar P, Kim KH (2018) Exceptionally stable green-synthesized gold nanoparticles for highly sensitive and selective colorimetric detection of trace metal ions and volatile aromatic compounds. J Ind Eng Chem 68:33–41
This work was financially supported by the National Natural Science Foundation of China (31760486, 21565009); the Natural Science Foundation of Guizhou Province (1403); the Science and Technology Support Program of Guizhou Province for Social Development (2795, 2805); the Science and Technology Program of Guizhou Province for Talent Team Building (5781, 5788); the Construction Program of Biology First-class Discipline in Guizhou (GNYL009); the Foundation of Key Laboratory of Wuliangye-flavor Liquor Solid-state Fermentation (2018JJ002), China National Light Industry; and the Foundation of Key Laboratory of Urban Agriculture (UA201701), Ministry of Agriculture, China.
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Wang, J., Wang, J., Zhou, P. et al. Oligonucleotide-induced regulation of the oxidase-mimicking activity of octahedral Mn3O4 nanoparticles for colorimetric detection of heavy metals. Microchim Acta 187, 99 (2020). https://doi.org/10.1007/s00604-019-4069-2
- Visual assay