Abstract
In this study, a nanocomposite consisting of three-dimensional reduced graphene oxide (3D-rGO) and plasma-polymerized propargylamine (3D-rGO@PpPG) was prepared and used as a highly sensitive and selective DNA sensor for detecting Hg2+. Given the high density of amino groups in the resultant 3D-rGO@PpPG nanocomposite, thymine-rich and Hg2+-targeted DNA was preferentially immobilized on the fabricated sensor surface via the strong electrostatic interaction between DNA strands and the amino-functionalized nanocomposites, followed by detecting Hg2+ through T–Hg2+–T coordination chemistry between DNA and Hg2+. The results of electrochemical measurements revealed that the anchored amount of DNA strands anchored on the 3D-rGO@PpPG nanofilm surface affects the determination of Hg2+ in aqueous solution. It showed high sensitivity and selectivity toward Hg2+ within concentrations ranging from 0.1 to 200 nM and displayed a low detection limit of 0.02 nM. The new strategy proposed also provides high selectivity of Hg2+ against other interfering metal ions, good stability, and repeatability. The excellent applicability of the developed sensor confirms the potential use of plasma-modified nanofilms for the detection of heavy metal ions in real environmental samples and water.
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Yoon S, Miller EW, He Q, Do PH, Chang CJ (2007) A bright and specific fluorescent sensor for mercury in water, cells, and tissue. Angew Chem Int Ed 46:6658–6661
Clarkson TW, Laszlo M, Myers GJ (2003) The toxicology of mercury—current exposures and clinical manifestations. New Engl J Med 349:1731–1737
Harris HH, Pickering IJ, George GN (2003) The chemical form of mercury in fish. Science 301:1203
Morel FM, Kraepiel AM, Amyot M (1998) The chemical cycle and bioaccumulation of mercury. Annu Rev Ecol Evol Syst 29:543–566
Caballero A, Martínez R, Lloveras V, Ratera I, Vidal-Gancedo J, Wurst K, Tárraga A, Molina P, Veciana J (2005) Highly selective chromogenic and redox or fluorescent sensors of Hg2+ in aqueous environment based on 1, 4-disubstituted azines. J Am Chem Soc 127:15666–15667
Chen P, He C (2004) A general strategy to convert the MerR family proteins into highly sensitive and selective fluorescent biosensors for metal ions. J Am Chem Soc 126:728–729
Coronado E, Galan-Mascaros JR, Marti-Gastaldo C, Palomares E, Durrant JR, Vilar R, Gratzel M, Nazeeruddin MK (2005) Reversible colorimetric probes for mercury sensing. J Am Chem Soc 127:12351–12356
Guo X, Qian X, Jia L (2004) A highly selective and sensitive fluorescent chemosensor for Hg2+ in neutral buffer aqueous solution. J Am Chem Soc 126:2272–2273
Nolan MA, Kounaves SP (1999) Microfabricated array of iridium microdisks as a substrate for direct determination of Cu2+ or Hg2+ using square-wave anodic stripping voltammetry. Anal Chem 71:3567–3573
Xu L, Yin H, Ma W, Kuang H, Wang L, Xu C (2015) Ultrasensitive SERS detection of mercury based on the assembled gold nanochains. Biosens Bioelectron 67:472–476
Angupillai S, Hwang JY, Lee JY, Rao BA, Son YA (2015) Efficient rhodamine-thiosemicarbazide-based colorimetric/fluorescent ‘turn-on’ chemodosimeters for the detection of Hg2+ in aqueous samples. Sensor Actuat B Chem 214:101–110
Hong YS, Rifkin E, Bouwer EJ (2011) Combination of diffusive gradient in a thin film probe and IC-ICP-MS for the simultaneous determination of CH3Hg+ and Hg2+ in Oxic Water. Environ Sci Technol 45:6429–6436
Liu S, Kang M, Yan F, Peng D, Yang Y, He L, Wang M, Fang S, Zhang Z (2015) Electrochemical DNA biosensor based on microspheres of cuprous oxide and nano-chitosan for Hg(II) detection. Electrochim Acta 160:64–73
Tanaka Y, Oda S, Yamaguchi H, Kondo Y, Kojima C, Ono A (2007) 15N-15NJ-coupling across Hg II: direct observation of Hg II-mediated TT base pairs in a DNA duplex. J Am Chem Soc 129:244–245
Miyake Y, Togashi H, Tashiro M, Yamaguchi H, Oda S, Kudo M, Tanaka Y, Kondo Y, Sawa R, Fujimoto T (2006) MercuryII-mediated formation of thymine-Hg II-thymine base pairs in DNA duplexes. J Am Chem Soc 128:2172–2173
Chang CC, Lin S, Wei SC, Chu SY, Lin CW (2012) Surface plasmon resonance detection of silver ions and cysteine using DNA intercalator-based amplification. Anal Bioanal Chem 402:2827–2835
Huy GD, Zhang M, Zuo P, Ye BC (2011) Multiplexed analysis of silver(I) and mercury(II) ions using oligonucletide-metal nanoparticle conjugates. Analyst 136:3289–3294
Li T, Dong S, Wang E (2010) A lead (II)-driven DNA molecular device for turn-on fluorescence detection of lead (II) ion with high selectivity and sensitivity. J Am Chem Soc 132:13156–13157
Yang X, Xu J, Tang X, Liu H, Tian D (2010) A novel electrochemical DNAzyme sensor for the amplified detection of Pb2+ ions. Chem Communications 46:3107–3109
Chen J, Zhou X, Zeng L (2013) Enzyme-free strip biosensor for amplified detection of Pb2+ based on a catalytic DNA circuit. Chem Commun 49:984–986
Long Y, Jiang D, Zhu X, Wang J, Zhou F (2009) Trace Hg2+ analysis via quenching of the fluorescence of a CdS-encapsulated DNA nanocomposite. Anal Chem 81:2652–2657
Ding X, Kong L, Wang J, Fang F, Li D, Liu J (2013) Highly sensitive SERS detection of Hg2+ ions in aqueous media using gold nanoparticles/graphene heterojunctions. ACS Appl Mater Interfaces 5:7072–7078
Liu X, Tang Y, Wang L, Zhang J, Song S, Fan C, Wang S (2007) Optical detection of mercury (II) in aqueous solutions by using conjugated polymers and label-free oligonucleotides. Adv Mater 19:1471–1474
Peng H, Zhang L, Soeller C, Travas-Sejdic J (2009) Conducting polymers for electrochemical DNA sensing. Biomater 30:2132–2148
Goddard JM, Hotchkiss J (2007) Polymer surface modification for the attachment of bioactive compounds. Prog Poly Sci 32:698–725
Qiu S, Gao S, Liu Lin Z, Qiu B, Chen G (2011) Electrochemical impedance spectroscopy sensor for ascorbic acid based on copper (I) catalyzed click chemistry. Biosensor Bioelectron 26:4326–4330
Liu C, Li F, Ma LP, Cheng HM (2010) Advanced materials for energy storage. Adv Mater 22:E28–E62
Pumera M (2011) Graphene-based nanomaterials for energy storage. Energy Environ Sci 4:668–674
Wang Y, Li Z, Wang J, Li J, Lin Y (2011) Graphene and graphene oxide: biofunctionalization and applications in biotechnology. Trends Biotech 29:205–212
Shao Y, Wang J, Wu H, Liu J, Aksay IA, Lin Y (2010) Graphene based electrochemical sensors and biosensors: a review. Electroanal 22:1027–1103
Cao X, Shi Y, Shi W, Lu G, Huang X, Yan Q, Zhang Q, Zhang H (2011) Preparation of novel 3D graphene networks for supercapacitor applications. Small 7:3163–3168
Xu Y, Wu Q, Sun Y, Bai H, Shi G (2010) Three-dimensional self-assembly of graphene oxide and DNA into multifunctional hydrogels. ACS Nano 4:7358–7362
He L, Zhang Y, Liu S, Fang S, Zhang Z (2014) A nanocomposite consisting of plasma-polymerized propargylamine and graphene for use in DNA sensing. Microchim Acta 181:1981–1989
Yang Y, Kang M, Fang S, Wang M, He L, Zhao J, Zhang H, Zhang Z (2015) Electrochemical biosensor based on three-dimensional reduced graphene oxide and polyaniline nanocomposite for selective detection of mercury ions. Sensor Actuator B-Chem 214:63–69
Marx KA (2003) Quartz crystal microbalance: a useful tool for studying thin polymer films and complex biomolecular systems at the solution-surface interface. Biomacromolecules 4:1099–1120
Pajkossy T (1994) Impedance of rough capacitive electrodes. J Electroanal Chem 364:111–125
Wang M, Wang L, Yuan H, Ji X, Sun C, Ma L, Bai Y, Li T, Li J (2004) Immunosensors based on layer-by-layer self-assembled au colloidal electrode for the electrochemical detection of antigen. Electroanalysis 16:757–764
Levie DR (1965) The influence of surface roughness of solid electrodes on electrochemical measurements. Electrochim Acta 10:113–130
Yuan Y, Gao M, Liu G, Chai Y, Wei S, Yuan R (2014) Sensitive pseudobienzyme electrocatalytic DNA biosensor for mercury(II) ion by using the autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification. Anal Chim Acta 811:23–28
Liu S, Nie H, Jiang J, Shen G, Yu R (2009) Electrochemical sensor for mercury (II) based on conformational switch mediated by interstrand cooperative coordination. Anal Chem 81:5724–5730
Noorbakhsh A, Salimi A (2011) Development of DNA electrochemical biosensor based on immobilization of ssDNA on the surface of nickel oxide nanoparticles modified glassy carbon electrode. Biosensor Bioelectron 30:188–196
Seah M (1980) The quantitative analysis of surfaces by XPS: a review. Surf Interface Anal 2:222–239
Dementjev A, De Graaf A, Van de Sanden M, Maslakov K, Naumkin A, Serov A (2000) X-ray photoelectron spectroscopy reference data for identification of the C3N4 phase in carbon–nitrogen films. Diam Relat Mater 9:1904–1907
Wang P, Kang M, Sun S, Liu Q, Zhang Z, Fang S (2014) Imine-linked covalent organic framework on surface for biosensor. Chin J Inorg Chem 32:838–843
Cai S, Lao K, Lau C, Lu J (2011) “Turn-on” chemiluminescence sensor for the highly selective and ultrasensitive detection of Hg2+ ions based on interstrand cooperative coordination and catalytic formation of gold nanoparticles. Anal Chem 83:9702–9708
Lou X, Zhao T, Liu R, Ma J, Xiao Y (2013) Self-assembled DNA monolayer buffered dynamic ranges of mercuric electrochemical sensor. Anal Chem 85:7574–7580
Dong ZM, Zhao GC (2012) Quartz crystal microbalance aptasensor for sensitive detection of mercury(II) based on signal amplification with gold nanoparticles. Sensors 12:7080–7094
Lu X, Dong X, Zhang K, Zhang Y (2012) An ultrasensitive electrochemical mercury (II) ion biosensor based on a glassy carbon electrode modified with multi-walled carbon nanotubes and gold nanoparticles. Anal Methods 4:3326–3331
Wang M, Liu S, Zhang Y, Yang Y, Shi Y, He L, Fang S, Zhang Z (2014) Graphene nanostructures with plasma polymerized allylamine biosensor for selective detection of mercury ions. Sensor Actuator B-Chem 203:497–503
Xu JL, Khor KA (2007) Chemical analysis of silica doped hydroxyapatite biomaterials consolidated by a spark plasma sintering method. J Inorg Biochem 101:187–195
Guo YF, Yan NQ, Yang SJ, Liu P, Wa J, Qu Z, Jia JP (2012) Conversion of elemental mercury with a novel membrane catalytic system at low temperature. J Hazard Mater 213–214:62–70
Stoica A, Manakhov A, Polčák J, Ondračka P, BuršíkováV Zajíčková R, Zajíčková L, Stoica A, Manakhov A (2015) Cell proliferation on modified DLC thin films prepared by plasma enhanced chemical vapor deposition Cell proliferation on modified DLC thin films prepared by plasma enhanced chemical vapor deposition. Biointerphases 10:029520–029529
Manakhov A, Nečas D, Čechal J, Pavliňák D, Eliáš M, Zajíčková L (2015) Deposition of stable amine coating onto polycaprolactone nanofibers by low pressure cyclopropylamine plasma polymerization. Thin Solid Films 581:7–13
Manakhov A, Skládal P, Nečas D, Čechal J, Polčák J, Eliáš M, Zajíčková L (2014) Cyclopropylamine plasma polymers deposited onto quartz crystal microbalance for biosensing application. Phys Status Solidi 211:2801–2808
Kingshot P, Thissen H, Griesser H (2002) Effects of cloud-point grafting, chain length, and densityof PEG layers on competitive adsorption of ocular proteins. Biomaterials 23:2043–2056
Majumder S, Priyadarshini M, Subudhi U, Chainy GBN, Shikha V (2009) X-ray photoelectron spectroscopic investigations of modifacations in plasmid DNA after interaction with Hg nanoparticles. Appl Surf Sci 256:438–442
Acknowledgments
This work was supported by Program for the National Natural Science Foundation of China (NSFC: Account No. 51173172), Science and Technology Opening Cooperation Project of Henan Province (Account No. 132106000076), and Innovative Technology Team of Henan Province.
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Peng, D.L., Ji, H.F., Dong, X.D. et al. Highly Sensitive Electrochemical Bioassay for Hg(II) Detection Based on Plasma-Polymerized Propargylamine and Three-Dimensional Reduced Graphene Oxide Nanocomposite. Plasma Chem Plasma Process 36, 1051–1065 (2016). https://doi.org/10.1007/s11090-016-9707-4
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DOI: https://doi.org/10.1007/s11090-016-9707-4