Abstract
Single-crystal 15 nm size magnetite nanoparticles were synthesized and coated with Yerba Mate (Ilex paraguariensis) extract to evaluate their use as versatile antioxidant magnetic nanoadsorbents. The obtained particles, Mnp@YM, were found to be composed of a crystalline magnetite core surrounded by a shell composed of Fe3O4, FeO, and Fe2O3 oxides. YM extract resulted an effective protective coating for Mnp incorporating surface carboxylates, phenols, and organic N groups which improve the particles stability in aqueous suspensions. Mnp@YM antioxidant capacity (1.8 µM Trolox equivalent per 0.1 mg YM coating contained in 1 mgL− 1 particle suspension) is of the order reported for polyphenols. \({\text{S}}{{\text{O}}_{\text{4}}}^{{ \cdot - }}\) scavenging rate constant (1.5 × 104 g− 1 L s− 1) is within the diffusion controlled regime for 15 nm spherical nanoparticles with homogeneously distributed reactive sites. Mnp@YM reversibly adsorbs MB with maximum adsorption of 50 mg g− 1. As a consequence of these capacities, Mnp@YM resulted effective in preventing MB oxidation by peroxodisulfate.
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L. Ai et al., Removal of methylene blue from aqueous solution with magnetite loaded multi-wall carbon nanotube: Kinetic, isotherm and mechanism analysis. J. Hazard. Mater. 198, 282–290 (2011)
O.A. Attallah et al., Removal of cationic and anionic dyes from aqueous solution with magnetite/pectin and magnetite/silica/pectin hybrid nanocomposites: kinetic, isotherm and mechanism analysis. RSC Adv., 6(14), 11461–11480 (2016). https://doi.org/10.1039/C5RA23452B
P. Avetta et al., Activation of persulfate by irradiated magnetite: implications for the degradation of phenol under heterogeneous photo-fenton-like conditions. Environ. Sci. Technol. 49(2), 1043–1050 (2015)
W.J. Barreto, S. Regina, G. Barreto, Iron oxide and pyrocatechol: a spectroscopy study of the reaction products. Quim. Nov 29(6), 1255–1258 (2006)
D.H.M. Bastos et al., Phenolic antioxidants identified by ESI-MS from yerba maté (Ilex paraguariensis) and green tea (Camellia sinensis) extracts. Molecules 12(3), 423–432 (2007)
K.G. Bhattacharya, A. Sharma, Kinetics and thermodynamics of methylene blue adsorption on Neem (Azadirachta indica) leaf powder. Dyes Pigm. 65(1), 51–59 (2005)
L. Bravo, L. Goya, E. Lecumberri, LC/MS characterization of phenolic constituents of mate (Ilex paraguariensis, St. Hil.) and its antioxidant activity compared to commonly consumed beverages. Food Res. Int. 40(3), 393–405 (2007)
G.V. Buxton, T.N. Malone, & G.A. Salmon. Reaction of SO4− with Fe2+, Mn2+ and Cu2+ in aqueous solution. J. Chem. Soc. Faraday Trans. 93(16), 2893–2897 (1997). https://doi.org/10.1039/A701472D
W. Cai, J. Wan, Facile synthesis of superparamagnetic magnetite nanoparticles in liquid polyols. J. Colloid Interface Sci. 305, 366–370 (2007)
Q. Chaudhry, R. Watkins, L. Castle, Nanotechnologies in the food arena: new opportunities, new questions, new concerns. in Nanotechnologies in Food, ed. by Q. Chaudhry, C. Laurence, R. Qasim (Springer, Berlin, 2010), pp. 1–17
E.D. Cömert, V. Gökmen, Antioxidants bound to an insoluble food matrix: their analysis, regeneration behavior, and physiological importance. Compr. Rev. Food Sci. Food Saf. (2017). https://doi.org/10.1111/1541-4337.12263
R.M. Cornell & U. Schwertmann, The Iron Oxides. Structure, Properties, Reactions, Occurrences and Uses. 2nd edn. (Wiley-VCH Verlag, Weinheim, 2003). Available at http://scholar.google.com/scholar?hl=en&btnG=Search&q=intitle:Iron+Oxides+in+the+Laboratory#3
S.E. Favela-Camacho et al., Stability of magnetite nanoparticles with different coatings in a simulated blood plasma. J. Nanoparticle Res. 18(7), 176 (2016). https://doi.org/10.1007/s11051-016-3482-2
A. Ghauch et al., Methylene blue discoloration by heated persulfate in aqueous solution. Chem. Eng. J. 213, 259–271 (2012)
P.R. Ginimuge, Methylene Blue 26(4), 517–520 (2017)
X.H. Guan, C. Shang, G.H. Chen, ATR-FTIR investigation of the role of phenolic groups in the interaction of some NOM model compounds with aluminum hydroxide. Chemosphere 65(11), 2074–2081 (2006)
S. Gunasekaran, G. Sankari, S. Ponnusamy, Vibrational spectral investigation on xanthine and its derivatives—Theophylline, caffeine and theobromine. Spectrochimica Acta 61(1–2), 117–127 (2005)
C.I. Heck, E.G. De Mejia, Yerba mate tea (Ilex paraguariensis): a comprehensive review on chemistry, health implications, and technological considerations. J. Food Sci. 72(9), (2007)
P.C. Hiemenz, R. Rajagopalan, Principles of Colloid and Surface Chemistry, 3rd Edn. (CRC Press, New York, 1997). Available at https://www.crcpress.com/Principles-of-Colloid-and-Surface-Chemistry-Third-Edition-Revised-and/Hiemenz-Rajagopalan/9780824793975#googlePreviewContainer
J.-D. Hu et al., Effect of dissolved organic matter on the stability of magnetite nanoparticles under different pH and ionic strength conditions. Sci. Total Environ. 408(16), 3477–3489 (2010). Available at https://www.scopus.com/inward/record.uri?eid=2-s2.0-77953703572&partnerID=40&md5=020aac6b78f74e159a17a96cfc1b6d99
A.M. Jubb, H.C. Allen, Vibrational spectroscopic characterization of hematite, maghemite, and magnetite thin films produced by vapor deposition. ACS Appl. Mater. Interfaces 2(10), 2804–2812 (2010)
H. Jung, D.B. Kittelson, M.R. Zachariah, The influence of a cerium additive on ultrafine diesel particle emissions and kinetics of oxidation. Combust. Flame 142(3), 276–288 (2005)
G. Magnacca et al., Novel magnetite nanoparticles coated with waste-sourced biobased substances as sustainable and renewable adsorbing materials. ACS Sustain. Chem. Eng. 2(6), 1518–1524 (2014). https://doi.org/10.1021/sc500213j
D.F. Mercado et al., Paramagnetic iron-doped hydroxyapatite nanoparticles with improved metal sorption properties. A bioorganic substrates-mediated synthesis. ACS Appl. Mater. Interfaces 6, 3937–3946 (2014)
D.F. Mercado Castro, M.C. Gonzalez, F.H. Sánchez, Yerba Mate applications: magnetic response of powders and colloids of magnetite nanoparticles coated with Ilex Paraguariensis derivatives. (2017) (under review)
V.C. Mora et al., Thermally activated peroxydisulfate in the presence of additives: a clean method for the degradation of pollutants. Chemosphere 75(10), 1405–1409 (2009)
H. Muthukumar, M. Matheswaran, Amaranthus spinosus leaf extract mediated FeO nanoparticles: physicochemical traits, photocatalytic and antioxidant activity. ACS Sustain. Chem. Eng. 3(12), 3149–3156 (2015)
T.S. Natarajan, H.C. Bajaj, R.J. Tayade, Preferential adsorption behavior of methylene blue dye onto surface hydroxyl group enriched TiO2 nanotube and its photocatalytic regeneration. J. Colloid Interface Sci. 433, 104–114 (2014). https://doi.org/10.1016/j.jcis.2014.07.019
Nist, NIST X-ray Photoelectron Spectroscopy Database, Version 4.1 (National Institute of Standards and Technology, Gaithersburg, 2012), http://srdata.nist.gov/xps/
M. Rafatullah et al., Adsorption of methylene blue on low-cost adsorbents: a review. J. Hazard. Mater. 177(1–3), 70–80 (2010). https://doi.org/10.1016/j.jhazmat.2009.12.047
M. Rafatullah et al., Adsorption of methylene blue on low-cost adsorbents: a review. J. Hazard. Mater. 177(1–3), 70–80 (2010)
C. Rice-Evans et al., The relative antioxidant activities of plant-derived polyphenolic flavonoids. Free Radic. Res. 22(4), 375–383 (1995)
J.A. Rosso et al., Reaction of sulfate and phosphate radicals with α,α,α-trifluorotoluene. J. Chem. Soc. Perkin Trans. 2 2, 205–210 (1999)
M. Rudolph, J. Erler, U.A. Peuker, A TGA-FTIR perspective of fatty acid adsorbed on magnetite nanoparticles-Decomposition steps and magnetite reduction. Colloids Surf. A 397, 16–23 (2012)
S.P. Schwaminger et al., Oxidation of magnetite nanoparticles: impact on surface and crystal properties. CrystEngComm 19(2), 246–255 (2017). Available at http://xlink.rsc.org/?DOI=C6CE02421A
C. Socaci et al., Developing novel strategies for the functionalization of core-shell magnetic nanoparticles with folic acid derivatives. Mater. Chem. Phys. 162, 131–139 (2015). Available at https://doi.org/10.1016/j.matchemphys.2015.05.046
K. Song et al., Comprehensive design of carbon-encapsulated Fe3O4 nanocrystals and their lithium storage properties. Nanotechnology 23(50), 505401 (2012). Available at http://www.ncbi.nlm.nih.gov/pubmed/23186940
C. Su, Environmental implications and applications of engineered nanoscale magnetite and its hybrid nanocomposites: a review of recent literature. J. Hazard. Mater. 322, 48–84 (2017). Available at http://www.sciencedirect.com/science/article/pii/S030438941630615X
E. Tombácz et al., Magnetite in aqueous medium: coating its surface and surface coated with it. Rom. Rep. Phys. 58(3), 281–286 (2006)
S. Trifunschi et al., Determination of flavonoid and polyphenol compounds in Viscum album and Allium Sativum extracts. Int. Curr. Pharm. J. 4, 382–385 (2015)
M.A. Vieira et al., Phenolic acids and methylxanthines composition and antioxidant properties of mate (Ilex paraguariensis) residue. J. Food Sci. 75(3), 280–285 (2010)
L.S. Villata et al., One-electron oxidation of antioxidants : a kinetic-thermodynamic correlation. Redox Rep. 18(5), 205–209 (2013). Available at http://hdl.handle.net/11336/5237
T. Yamashita, P. Hayes, Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl. Surf. Sci. 254(8), 2441–2449 (2008)
L. Zhang, R. He, H.C. Gu, Oleic acid coating on the monodisperse magnetite nanoparticles. Appl. Surf. Sci. 253(5), 2611–2617 (2006)
X. Zhang et al., Adsorption of methylene blue onto humic acid-coated Fe3O4 nanoparticles. Colloids Surf. A 435, 85–90 (2013)
Acknowledgements
DFM thanks Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, Argentina) for a graduate studentship. MCG and PC are research members of CONICET, LSV is a research member from CICPBA, Argentina.
Funding
This study was supported by grant PICT 2012-1795 from ANPCyT.
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Online Resource—List of reactants, description of standard equipment and methods, HRTEM micrographs, XRD patterns, Raman spectra, XPS O1s and Fe2p peaks, depletion of ABTS+•, absorption experiments, and estimation of the particles molar mass and diffusion controlled rate constants is provided (DOCX 36080 KB)
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Mercado, D.F., Caregnato, P., Villata, L.S. et al. Ilex paraguariensis Extract-Coated Magnetite Nanoparticles: A Sustainable Nano-adsorbent and Antioxidant. J Inorg Organomet Polym 28, 519–527 (2018). https://doi.org/10.1007/s10904-017-0757-8
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DOI: https://doi.org/10.1007/s10904-017-0757-8