A system composed of polyethylenimine-capped upconversion nanoparticles, copper(II), hydrogen peroxide and 3,3′,5,5′-tetramethylbenzidine for colorimetric and fluorometric determination of glyphosate Original Paper First Online: 22 November 2019 Abstract
A dual (colorimetric and fluorometric) method is described for sensitive and selective determination of the herbicide glyphosate. It is based on the use of a system composed of polyethylenimine-capped NaGdF
4:Yb,Er upconversion nanoparticles (UCNPs), copper(II) ions, hydrogen peroxide and 3,3′,5,5′-tetramethylbenzidine. The physicochemical and photophysical properties of the polyethylenimine-capped UCNPs were characterized by various spectroscopic and microscopic techniques. The fluorescence of the UCNPs (with main emission peaks at 548 and 660 nm under 980 nm excitation) is reduced in the presence of Cu(II) because of the formation of a blue oxidation product of 3,3′,5,5′-tetramethylbenzidine as a result of the peroxidase mimicking activity of Cu(II). In the presence of glyphosate, its strong affinity for Cu(II) leads to the formation of N-(phosphonomethyl)glycine copper(II) complexes. This inhibits the quenching ability and catalysis activity of Cu(II). Hence, fluorescence is increasingly less reduced. Fluorescence at 660 nm increases linearly in the 0.05 to 125 μg·mL −1 glyphosate concentration range and the detection limit is found 9.8 ng·mL −1. The colorimetric assay (performed at 652 nm) has a detection ranges from 5 to 125 μg·mL −1, and the limit of detection is 1 μg·mL −1. Graphical abstract
Schematic representation of UCNP-H
2O 2-TMB-Cu(II) mixed system for optical determinations of glyphosate. Keywords Fluorometric Upconversion nanoparticles Glyphosate Cu(II) Peroxidase mimicking activity 3,3′,5,5′-tetramethylbenzidine Colorimetric Electronic supplementary material
The online version of this article (
) contains supplementary material, which is available to authorized users. https://doi.org/10.1007/s00604-019-3936-1 Notes Acknowledgements
This work has been financially supported by the National Natural Science Foundation of China (31772063) and (31901772), Key Research and Development of Jiangsu Province (BE2017357), Anhui Provincial of Science and Technology (18030701141) and the China Postdoctoral Science Foundation (2019M651748).
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The author(s) declare that they have no competing interests.
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Gui YX, Fan XN, Wang HM, Wang G, Chen SD (2012) Glyphosate induced cell death through apoptotic and autophagic mechanisms. Neurotoxicol Teratol 34(3):344–349.
https://doi.org/10.1016/j.ntt.2012.03.005 CrossRef PubMed Google Scholar
Marc J, Mulner-Lorillon O, Bellé R (2004) Glyphosate-based pesticides affect cell cycle regulation. Biol Cell 96(3):245–249.
https://doi.org/10.1016/j.biolcel.2003.11.010 CrossRef PubMed Google Scholar
Gasnier C, Dumont C, Benachour N, Clair E, Chagnon MC, Séralini GE (2009) Glyphosate-based herbicides are toxic and endocrine disruptors in human cell lines. Toxicology 262(3):184–191.
https://doi.org/10.1016/j.tox.2009.06.006 CrossRef PubMed Google Scholar
Islas G, Rodriguez JA, Huizar LHM, Moreno FP, Carrillo EG (2014) Determination of glyphosate and aminomethylphosphnic acid in soils by HPLC with pre-column derivatization using 1,2-naphthoquinone-4-sulfonate. J Liq Chromatogr Relat Technol 37(9):1298–1309.
https://doi.org/10.1080/10826076.2013.789801 CrossRef Google Scholar
Saito T, Aoki H, Namera A, Oikawa H, Miyazaki S, Nakamoto A, Inokuchi S (2011) Mix-mode TiO-C(18) monolith spin column extraction and GC-MS for the simultaneous assay of Organophosphorus compounds and Glufosinate, and glyphosate in human serum and urine. Anal Sci 27(10):999.
https://doi.org/10.2116/analsci.27.999 CrossRef PubMed Google Scholar
Şenyuva HZ, Gilbert J (2010) Immunoaffinity column clean-up techniques in food analysis: a review. J Chromatogr B Anal Technol Biomed Life Sci 878(2):115–132.
https://doi.org/10.1016/j.jchromb.2009.05.042 CrossRef Google Scholar
Mörtl M, Németh G, Juracsek J, Darvas B, Kamp L, Rubio F, Székács A (2013) Determination of glyphosate residues in Hungarian water samples by immunoassay. Microchem J 107:143–151.
https://doi.org/10.1016/j.microc.2012.05.021 CrossRef Google Scholar
Sánchez-Bayo F, Hyne RV, Desseille KL (2010) An amperometric method for the detection of amitrole, glyphosate and its aminomethyl-phosphonic acid metabolite in environmental waters using passive samplers. Anal Chim Acta 675(2):125–131.
https://doi.org/10.1016/j.aca.2010.07.013 CrossRef PubMed Google Scholar
Sok V, Fragoso A (2019) Amperometric biosensor for glyphosate based on the inhibition of tyrosinase conjugated to carbon nano-onions in a chitosan matrix on a screen-printed electrode. Microchim Acta 186(8).
Corbera M, Hidalgo M, Salvadó V, Wieczorek PP (2004) Determination of glyphosate and aminomethylphosphonic acid in natural water using the capillary electrophoresis combined with enrichment step. Anal Chim Acta 540(1):3–7.
https://doi.org/10.1016/j.aca.2004.12.028 CrossRef Google Scholar
Chen Q, Chen H, Li Z, Pang J, Lin T, Guo L, Fu FF (2017) Colorimetric sensing of glyphosate in environmental water based on peroxidase mimetic activity of MoS
nanosheets. J Nanosci Nanotechnol 17(8):5730–5734.
https://doi.org/10.1166/jnn.2017.13821 CrossRef Google Scholar
Fang F, Wei RQ, Liu XN (2014) Novel pre-column derivatisation reagent for glyphosate by high-performance liquid chromatography and ultraviolet detection. Int J Environ An Ch 94(7):661–667.
https://doi.org/10.1080/03067319.2013.864648 CrossRef Google Scholar
Aguirre MC, Urreta SE, Gomez CG (2019) A Cu
-Cu/glassy carbon system for glyphosate determination. Sensors Actuators B Chem 284:675–683.
https://doi.org/10.1016/j.snb.2018.12.124 CrossRef Google Scholar
Pérez AL, Tibaldo G, Sánchez GH, Siano GG, Marsili NR, Schenone AV (2019) A novel fluorimetric method for glyphosate and AMPA determination with NBD-Cl and MCR-ALS. Spectrochim Acta A Mol Biomol Spectrosc 214:119–128.
https://doi.org/10.1016/j.saa.2019.01.078 CrossRef PubMed Google Scholar
Liu Y, Ouyang Q, Li HH, Zhang ZZ, Chen QS (2017) Development of an inner filter effects-based Upconversion nanoparticles–Curcumin Nanosystem for the sensitive sensing of fluoride ion. ACS Appl Mater Interfaces 9(21):18314–18321.
https://doi.org/10.1021/acsami.7b04978 CrossRef PubMed Google Scholar
Hu WW, Chen QS, Li HH, Ouyang Q, Zhao JW (2016) Fabricating a novel label-free aptasensor for acetamiprid by fluorescence resonance energy transfer between NH
: Yb, Ho@SiO
and Au nanoparticles. Biosens Bioelectron 80:398–404.
https://doi.org/10.1016/j.bios.2016.02.001 CrossRef PubMed Google Scholar
Long Q, Li HT, Zhang YY, Yao SZ (2015) Upconversion nanoparticle-based fluorescence resonance energy transfer assay for organophosphorus pesticides. Biosens Bioelectron 68:168–174.
https://doi.org/10.1016/j.bios.2014.12.046 CrossRef PubMed Google Scholar
Choi SY, Baek SH, Chang SJ, Song Y, Rafique R, Kang TL, Park TJ (2016) Synthesis of upconversion nanoparticles conjugated with graphene oxide quantum dots and their use against cancer cell imaging and photodynamic therapy. Biosens Bioelectron 93:267–273.
https://doi.org/10.1016/j.bios.2016.08.094 CrossRef PubMed Google Scholar
Ma LN, Liu FY, Lei Z, Wang ZX (2017) A novel upconversion@polydopamine core@shell nanoparticle based aptameric biosensor for biosensing and imaging of cytochrome c inside living cells. Biosens Bioelectron 87:638–645.
https://doi.org/10.1016/j.bios.2016.09.017 CrossRef PubMed Google Scholar
Pan WX, Zhao JW, Chen QS (2015) Fabricating Upconversion fluorescent probes for rapidly sensing foodborne pathogens. J Agric Food Chem 63(36):8068–8074.
https://doi.org/10.1021/acs.jafc.5b02331 CrossRef PubMed Google Scholar
Wu SJ, Duan N, Shi Z, Fang CC, Wang ZP (2014) Dual fluorescence resonance energy transfer assay between tunable upconversion nanoparticles and controlled gold nanoparticles for the simultaneous detection of Pb
. Talanta 128:327–336.
https://doi.org/10.1016/j.talanta.2014.04.056 CrossRef PubMed Google Scholar
Chen HQ, Ren JC (2012) Sensitive determination of chromium (VI) based on the inner filter effect of upconversion luminescent nanoparticles (NaYF4:Yb
). Talanta 99:404–408.
https://doi.org/10.1016/j.talanta.2012.05.071 CrossRef PubMed Google Scholar
Songa EA, Arotiba OA, Owino JHO, Jahed N, Baker PGL, Iwuoha EI (2009) Electrochemical detection of glyphosate herbicide using horseradish peroxidase immobilized on sulfonated polymer matrix. Bioelectrochemistry 75(2):117–123.
https://doi.org/10.1016/j.bioelechem.2009.02.007 CrossRef PubMed Google Scholar
Stefano P, Paola V, Joong Hyun K, Pier Paolo P (2013) Colorimetric detection of human papilloma virus by double isothermal amplification. Chem Commun 49(90):10605–10607
CrossRef Google Scholar
Lin TR, Zhong LS, Guo LQ, Fu FF, Chen GN (2014) Seeing diabetes: visual detection of glucose based on the intrinsic peroxidase-like activity of MoS
nanosheets. Nanoscale 6(20):11856–11862.
https://doi.org/10.1039/c4nr03393k CrossRef PubMed Google Scholar
Zhang L, Han L, Hu P, Wang L, Dong S (2013) TiO
nanotube arrays: intrinsic peroxidase mimetics. Chem Commun 49(89):10480–10482.
https://doi.org/10.1039/c3cc46163g CrossRef Google Scholar
Guan JF, Peng J, Jin XY (2015) Synthesis of copper sulfide nanorods as peroxidase mimics for the colorimetric detection of hydrogen peroxide. Anal Methods 7(13):5454–5461.
https://doi.org/10.1039/C5AY00895F CrossRef Google Scholar
Dutta AK, Das S, Samanta S, Samanta PK, Adhikary B, Biswas P (2013) CuS nanoparticles as a mimic peroxidase for colorimetric estimation of human blood glucose level. Talanta 107:361–367.
https://doi.org/10.1016/j.talanta.2013.01.032 CrossRef PubMed Google Scholar
Zhang LL, Li M, Qin YF, Chu ZD, Zhao SL (2014) A convenient label free colorimetric assay for pyrophosphatase activity based on a pyrophosphate-inhibited Cu
reaction. Analyst 139(23):6298–6303.
https://doi.org/10.1039/c4an01415d CrossRef PubMed Google Scholar
Chang YQ, Zhe Z, Hao JH, Yang WS, Tang JL (2016) A simple label free colorimetric method for glyphosate detection based on the inhibition of peroxidase-like activity of Cu(II). Sensors Actuators B Chem 228:410–415.
https://doi.org/10.1016/j.snb.2016.01.048 CrossRef Google Scholar
Sheals J, Persson P, Hedman B (2001) IR and EXAFS spectroscopic studies of glyphosate protonation and copper(II) complexes of glyphosate in aqueous solution. Inorg Chem 40(17):4302–4309.
https://doi.org/10.1021/ic000849g CrossRef PubMed Google Scholar
Shao H, Xu D, Ding Y, Hong X, Liu Y (2018) An "off-on" colorimetric and fluorometric assay for Cu(II) based on the use of NaYF4:Yb(III),Er(III) upconversion nanoparticles functionalized with branched polyethylenimine. Microchim Acta 185(4):211.
https://doi.org/10.1007/s00604-018-2740-7 CrossRef Google Scholar
Zhou JC, Yang ZL, Dong W, Tang RJ, Sun LD, Yan CH (2011) Bioimaging and toxicity assessments of near-infrared upconversion luminescent NaYF4:Yb,Tm nanocrystals. Biomaterials 32(34):9059–9067.
https://doi.org/10.1016/j.biomaterials.2011.08.038 CrossRef PubMed Google Scholar
Wang FF, Zhang CL, Xue Q, Li HP, Xian YZ (2017) Label-free upconversion nanoparticles-based fluorescent probes for sequential sensing of Cu
, pyrophosphate and alkaline phosphatase activity. Biosens Bioelectron 95:21–26.
https://doi.org/10.1016/j.bios.2017.04.010 CrossRef PubMed Google Scholar
Kassab L, Bomfim F, Martinelli J, Wetter N, Neto J, de Araujo C (2009) Energy transfer and frequency upconversion in Yb
glass containing silver nanoparticles. Appl Phys B Lasers Opt 94(2):239–242.
https://doi.org/10.1007/s00340-008-3249-2 CrossRef Google Scholar
Shyam S, Manjunath C, Venkataramanan M (2014) Highly luminescent colloidal Eu
nanoparticles for the selective and sensitive detection of Cu(II) ions. Chem Eur J 20(12):3311–3316.
https://doi.org/10.1002/chem.201304697 CrossRef Google Scholar Copyright information
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