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Mechanism of in Situ Surface Polymerization of Gallic Acid in an Environmental-Inspired Preparation of Carboxylated Core–Shell Magnetite Nanoparticles

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Department of Physical Chemistry and Materials Science, University of Szeged, Aradi vt 1, 6720 Szeged, Hungary
National Institute R&D for Isotopic and Molecular Technology, 65-103 Donath Street, Cluj-Napoca 400293, Romania
Cite this: Langmuir 2014, 30, 51, 15451–15461
Publication Date (Web):December 3, 2014
Copyright © 2014 American Chemical Society

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    Magnetite nanoparticles (MNPs) with biocompatible coatings are good candidates for MRI (magnetic resonance imaging) contrasting, magnetic hyperthermia treatments, and drug delivery systems. The spontaneous surface induced polymerization of dissolved organic matter on environmental mineral particles inspired us to prepare carboxylated core–shell MNPs by using a ubiquitous polyphenolic precursor. Through the adsorption and in situ surface polymerization of gallic acid (GA), a polygallate (PGA) coating is formed on the nanoparticles (PGA@MNP) with possible antioxidant capacity. The present work explores the mechanism of polymerization with the help of potentiometric acid–base titration, dynamic light scattering (for particle size and zeta potential determination), UV–vis (UV–visible light spectroscopy), FTIR-ATR (Fourier-transformed infrared spectroscopy by attenuated total reflection), and XPS (X-ray photoelectron spectroscopy) techniques. We observed the formation of ester and ether linkages between gallate monomers both in solution and in the adsorbed state. Higher polymers were formed in the course of several weeks both on the surface of nanoparticles and in the dispersion medium. The ratio of the absorbances of PGA supernatants at 400 and 600 nm (i.e., the E4/E6 ratio commonly used to characterize the degree of polymerization of humic materials) was determined to be 4.3, similar to that of humic acids. Combined XPS, dynamic light scattering, and FTIR-ATR results revealed that, prior to polymerization, the GA monomers became oxidized to poly(carboxylic acid)s due to ring opening while Fe3+ ions reduced to Fe2+. Our published results on the colloidal and chemical stability of PGA@MNPs are referenced thoroughly in the present work. Detailed studies on biocompatibility, antioxidant property, and biomedical applicability of the particles will be published.

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    21. Ke Song, Yu Huang, Jiewen Yang. Goethite enhanced the Cr(VI) reduction by gallic acid through the stabilisation of free radicals: spectroscopic evidences and implication for transformation of Cr(VI) in an Oxisol. International Journal of Environmental Analytical Chemistry 2022, 102 (16) , 4535-4549.
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    53. Corina Vasilescu, M. Latikka, K. D. Knudsen, V. M. Garamus, V. Socoliuc, Rodica Turcu, Etelka Tombácz, Daniela Susan-Resiga, R. H. A. Ras, L. Vékás. High concentration aqueous magnetic fluids: structure, colloidal stability, magnetic and flow properties. Soft Matter 2018, 14 (32) , 6648-6666.
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    55. Syed Tawab Shah, Wageeh A Yehya, Omer Saad, Khanom Simarani, Zaira Chowdhury, Abeer A. Alhadi, Lina Al-Ani. Surface Functionalization of Iron Oxide Nanoparticles with Gallic Acid as Potential Antioxidant and Antimicrobial Agents. Nanomaterials 2017, 7 (10) , 306.
    56. Sunghyun Nam, Brian D. Condon, Zhiyu Xia, Ramaswamy Nagarajan, Doug J. Hinchliffe, Crista A. Madison. Intumescent flame-retardant cotton produced by tannic acid and sodium hydroxide. Journal of Analytical and Applied Pyrolysis 2017, 126 , 239-246.
    57. Hung-Pang Lee, Da-Jun Lin, Ming-Long Yeh. Phenolic Modified Ceramic Coating on Biodegradable Mg Alloy: The Improved Corrosion Resistance and Osteoblast-Like Cell Activity. Materials 2017, 10 (7) , 696.
    58. Ildikó Y. Tóth, Dániel Nesztor, Levente Novák, Erzsébet Illés, Márta Szekeres, Tamás Szabó, Etelka Tombácz. Clustering of carboxylated magnetite nanoparticles through polyethylenimine: Covalent versus electrostatic approach. Journal of Magnetism and Magnetic Materials 2017, 427 , 280-288.
    59. Chunming Su. Environmental implications and applications of engineered nanoscale magnetite and its hybrid nanocomposites: A review of recent literature. Journal of Hazardous Materials 2017, 322 , 48-84.
    60. Tamara A. Vico, Valeria B. Arce, María F. Fangio, Liesel B. Gende, Celso A. Bertran, Daniel O. Mártire, María S. Churio. Two choices for the functionalization of silica nanoparticles with gallic acid: characterization of the nanomaterials and their antimicrobial activity against Paenibacillus larvae. Journal of Nanoparticle Research 2016, 18 (11)
    61. J. Rácz, P. F. de Châtel, I. A. Szabó, L. Szunyogh, I. Nándori. Improved efficiency of heat generation in nonlinear dynamics of magnetic nanoparticles. Physical Review E 2016, 93 (1)
    62. Ahmed H. Nadim, Medhat A. Al-Ghobashy, Marianne Nebsen, Mostafa A. Shehata. Gallic acid magnetic nanoparticles for photocatalytic degradation of meloxicam: synthesis, characterization and application to pharmaceutical wastewater treatment. RSC Advances 2015, 5 (127) , 104981-104990.