Abstract
The enhancement of nanoparticle’s magnetic properties with a suitable coating is the main tool to increase their potential as an effective candidate for applications in different areas, especially in biomedicine. In the work here reported, Fe3O4 nanoparticles coated with natural oils were synthesized by iron (III) acetylacetonate thermal decomposition and the effects of the coating on the magnetic properties of these particles have been investigated. The oils were extracted from three Amazon fruits seeds: açaí, ucuúba, and bacaba by CO2 supercritical extraction process, and the relative percentage composition of fatty acids were determined by gas chromatography. A systematic study of crystalline, morphological, and magnetic properties revealed a saturation magnetization (Ms) enhancement and high values of the anisotropy constant for Fe3O4 samples when coated with açaí and ucuúba oils, which present a large percentage of saturated total fatty acid. Our results indicate that nanoparticles with sizes smaller than around 5 nm present Ms values as high as that found for bulk Fe3O4 and, consequently, much higher than Ms values for nanoparticles usually coated with oleic acid. The nuclear techniques neutron activation analysis and perturbed angular correlations were used to better characterize the nanoparticles.
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Abbreviations
- Ms:
-
saturation magnetization
- XRD:
-
X-ray diffraction
- TEM:
-
transmission electron microscopy
- NAA:
-
neutron activation analysis
- TGA:
-
thermogravimetric analyzes
- SAXS:
-
small-angle X-ray scattering
- PAC:
-
perturbed angular correlation
- ASABE:
-
American Society of Agricultural and Biological Engineers
- ZFC:
-
zero-field-cooled
- FC:
-
field-cooled
- DTG:
-
differential thermogravimetric
References
Abadio Finco FDB, Kammerer DR, Carle R, Tseng W-H, Boser S, Graeve L (2012) Antioxidant activity and characterization of phenolic compounds from Bacaba (Oenocarpus bacaba Mart.) fruit by HPLC-DAD-MSn. J Agric Food Chem 60:7665–7673. https://doi.org/10.1021/jf3007689
Ahmed S, Saifullah AM, Swami BL, Ikram S (2016) Green synthesis of silver nanoparticles using Azadirachta indica aqueous leaf extract. J Radiat Res Appl Sci 9:1–7. https://doi.org/10.1016/j.jrras.2015.06.006
American Society of Agricultural and Biological Engineers, ANSI/ASAE S319: method of determining and expressing fineness of feed materials by sieving, St. Joseph: ASABE, 1998, 547
Andrzejewski B, Bednarski W, Kazmierczak M, Lapinski A, Pogorzelec-Glaser K, Hilczer B, Jurga S, Nowaczyk G, Zaleski K, Matczak M, Leska B, Pankiewicz R, Kepinski L (2014) Magnetization enhancement in magnetite nanoparticles capped with alginic acid. Compos Part B Eng 64:147–154. https://doi.org/10.1016/j.compositesb.2014.04.022
Asai K, Okada T, Sekizawa H (1985) TDPAC of γ-rays emitted from 111Cd(←111In) in Fe3O4. J Phys Soc Jpn 54:4325–4330. https://doi.org/10.1143/JPSJ.54.4325
Barbeta VB, Jardim RF, Kiyohara PK, Effenberger FB, Rossi LM (2010) Magnetic properties of Fe3O4 nanoparticles coated with oleic and dodecanoic acids. J Appl Phys 107:073913-1–073913-7. https://doi.org/10.1063/1.3311611
Batista CCR, Oliveira MS, Araújo ME, Rodrigues AMC, Botelho JRS, Souza Filho APS, Machado NT, Carvalho Junior RN (2016) Supercritical CO2 extraction of açaí (Euterpe oleracea) berry oil: global yield, fatty acids, allelopathic activities, and determination of phenolic and anthocyanins total compounds in the residual pulp. J Supercrit Fluids 107:364–369. https://doi.org/10.1016/j.supflu.2015.10.006
Bedanta S, Kleemann W (2009) Supermagnetism. J Phys D Appl Phys 42:013001. https://doi.org/10.1088/0022-3727/42/1/013001
Bosch-Santos B, Carbonari AW, Cabrera-Pasca GA, Saxena RN, Freitas RS (2015) The magnetic behavior of the intermetallic compound NdMn2Ge2 studied by magnetization and hyperfine interactions measurements. J Appl Phys 117:17E304-1–17E304-4. https://doi.org/10.1063/1.4907330
Brollo MEF, López-Ruiz R, Muraca D, Figueroa SJA, Pirota KR, Knobel M (2014) Compact Ag@Fe3O4 Core-shell nanoparticles by means of single-step thermal decomposition reaction. Sci Rep 4:6839. https://doi.org/10.1038/srep06839
Caruntu D, Caruntu G, O’Connor CJ (2007) Magnetic properties of variable-sized Fe3O4 nanoparticles synthesized from non-aqueous homogeneous solutions of polyols. J Phys D Appl Phys 40:5801–5809. https://doi.org/10.1088/0022-3727/40/19/001
Carvalho AA, Galdino PM, Nascimento MV, Kato MJ, Valadares MC, Cunha LC, Costa EA (2010) Antinociceptive and antiinflammatory activities of grandisin extracted from Virola surinamensis. Phytother Res 24:113–118. https://doi.org/10.1002/ptr.2882
Chen Y, Song B, Liv LL, Xue J (2014) Fe3O4 nanoparticles embedded in uniform mesoporous carbon spheres for superior high-rate battery applications. Adv Funct Mater 24:319–326. https://doi.org/10.1002/adfm.201300872
Corrêa EL, Bosch-Santos B, Freitas RS, Potiens MPA, Saiki M, Carbonari AW (2018) Synthesis and atomic scale characterization of Er2O3 nanoparticles: enhancement of magnetic properties and changes in the local structure. Nanotechnology 29:205704.1–205704.20570410. https://doi.org/10.1088/1361-6528/aab3f8
Costa WA, Oliveira MS, Silva MP, Cunha VMB, Pinto RHH, Bezerra FWF, Carvalho Junior RN (2017) Açaí (Euterpe oleracea) and Bacaba (Oenocarpus bacaba) as functional food. In: Shiomi N (ed) Superfood and Functional Food - An Overview of Their Processing and Utilization Publisher. InTech, pp 155–172. https://doi.org/10.5772/65881
Cuong ND, Hoa TT, Khieu DQ, Lam TD, Hoa ND, Hieu NV (2012) Synthesis, characterization, and comparative gas-sensing properties of Fe2O3 prepared from Fe3O4 and Fe3O4-chitosan. J Alloys Compd 523:120–126. https://doi.org/10.1016/j.jallcom.2012.01.117
Da Rocha Filho GN, Bentes MHS, Brodzki D, Djega-Mariadassou G (1992) Catalytic conversion of Hevea brasiliensis and Virola sebifera oils to hydrocarbons oils. J Am Oil Chem Soc 69:266–271. https://doi.org/10.1007/BF02635899
De Soete D, Gijbels R, Hoste J (1972) Neutron activation analysis. Wiley, New York
Dogra R, Junqueira AC, Saxena RN, Carbonari AW, Mestnik-Filho J, Moralles M (2001) Hyperfine interaction measurements in LaCrO3 and LaFeO3 perovskites using perturbed angular correlation spectroscopy. Phys Rev B 63:224104-1–224104-9. https://doi.org/10.1103/PhysRevB.63.224104
Effenberger FB, Carbonari AW, Rossi LM (2016) The influence of 1, 2-alkanediol on the crystallinity of magnetite nanoparticles. J Magn Magn Mater 417:49–55. https://doi.org/10.1016/j.jmmm.2016.05.028
Fregonesi A, Scanavez C, Santos L, De Oliveira A, Roesler R, Escudeiro C, Moncayo P, De Sanctis D, Gesztesi JL (2009) Brazilian oils and butters: the effect of different fatty acid chain composition on human hair physiochemical properties. J Cosmet Sci 60:273–280. https://doi.org/10.1111/j.1468-2494.2010.00534_16.x
Gordon A, Cruz APG, Cabral LMC, Freitas SC, Dib Taxi CMA, Donangelo CM, Mattietto RA, Friedrich M, Matta VM, Marx F (2012) Chemical characterization and evaluation of antioxidant properties of Açaí fruits (Euterpe oleraceae Mart.) during ripening. Food Chem 133:256–263. https://doi.org/10.1016/j.foodchem.2011.11.150
Guivar JAR, Fernandes EGR, Zucolotto V (2015) A peroxidase biomimetic system based on Fe3O4 nanoparticles in non-enzymatic sensors. Talanta 141:307–314. https://doi.org/10.1016/j.talanta.2015.03.017
Hiruma-Lima CA, Batista LM, Almeida ABA, Magri LP, Santos LC, Vilegas W, Brito ARMS (2009) Antiulcerogenic action of ethanolic extract of the resin from Virola surinamensis Warb. (Myristicaceae). J Ethnopharmacol 122:406–409. https://doi.org/10.1016/j.jep.2008.12.023
Holderness J, Schepetkin IA, Freedman B, Kirpotina LN, Quinn MT, Hedges JF, Jutila MA (2011) Polysaccharides isolated from açaí fruit induce innate immune responses. PLoS One 6(2):e17301.1–e1730114. https://doi.org/10.1371/journal.pone.0017301
Hou Y, Yu J, Gao S (2003) Solvothermal reduction synthesis and characterization of superparamagnetic magnetite nanoparticles. J Mater Chem 13:1983–1987. https://doi.org/10.1039/B305526D
Hussain I, Singh NB, Singh A, Singh H, Singh SC (2016) Green synthesis of nanoparticles and its potential application. Biotechnol Lett 38:545–560. https://doi.org/10.1007/s10529-015-2026-7
Iizumi M, Koetzle TF, Shirane G, Chikazumi S, Matsui M, Todo S (1982) Structure of magnetite (Fe3O4) below the Verwey transition temperature. Acta Cryst B38:2121–2133. https://doi.org/10.1107/S0567740882008176
Inglot Z, Wiarda D, Lieb KP, Wenzel T, Uhrmacher M (1991) Defects in Fe1-xO and the Fe1-xO to Fe3O4 phase transition studied by the perturbed angular correlation method. J Phys Condens Matter 3:4569–4585. https://doi.org/10.1088/0953-8984/3/25/006
Iravani S (2011) Green synthesis of metal nanoparticles using plants. Green Chem 13:2638–2650. https://doi.org/10.1039/C1GC15386B
Issa B, Obaidat IM, Albiss BA, Haik Y (2013) Magnetic nanoparticles: surface effects and properties related to biomedicine applications. Int J Mol Sci 14:21266–21305. https://doi.org/10.3390/ijms141121266
Jiao M, Zeng J, Jing L, Liu C, Gao M (2015) Flow synthesis of biocompatible Fe3O4 nanoparticles: insight into the effects of residence time, fluid velocity, and tube reactor dimension on particle size distribution. Chem Mater 27:1299–1305. https://doi.org/10.1021/cm504313c
Jun Y-W, Huh Y-M, Choi J-S, Lee J-H, Song H-T, Kim S, Yoon S, Kim K-S, Shin JS, Suh JS, Cheon J (2005) Nanoscale size effect of magnetic nanocrystals and their utilization for cancer diagnosis via magnetic resonance imaging. J Am Chem Soc 127:5732–5733. https://doi.org/10.1021/ja0422155
Knobel M, Nunes WC, Socolovsky LM, De Biasi E, Vargas JM, Denardin JC (2008) Superparamagnetism and other magnetic features in granular materials: a review on ideal and real systems. J Nanosci Nanotechnol 8:2836–2857. https://doi.org/10.1166/jnn.2008.15348
Lee K, Lee S, Ahn B (2019) Understanding high anisotropic magnetism by ultrathin shell layer formation for magnetically hard–soft core–shell nanostructures. Chem Mater 31:728–736. https://doi.org/10.1021/acs.chemmater.8b03591
Liao H, Shelor CP, Chen Y, Sabaa-Srur AUO, Smith RE, Dasgupta PK (2013) Anion composition of açaí extracts. J Agric Food Chem 61:5928–5935. https://doi.org/10.1021/jf4014185
Lopes NP, Blumenthal EEA, Cavalheiro AJ, Kato MJ, Yoshida M (1996) Lignans, γ-lactones and propiophenones of Virola surinamensis. Phytochemistry 43:1089–1092. https://doi.org/10.1016/S0031-9422(96)00408-6
Lopes NP, Kato MJ, Yoshida M (1999) Antifungal constituents from roots of Virola surinamensis. Phytochemistry 51:29–33. https://doi.org/10.1016/S0031-9422(98)00709-2
Matos IT, Bosch-Santos B, Cabrera-Pasca GA, Carbonari AW (2015) Magnetic behavior of La-doped Fe3O4 studied by perturbed angular correlation spectroscopy with 111Cd and 140Ce. J Appl Phys 117:17D511-1–17D511-4. https://doi.org/10.1063/1.4916023
Mercurio ME, Carbonari AW, Cordeiro MR, Saxena RN, D’Agostino LZ (2010) Local investigation of hyperfine interactions in pure and Co-doped ZnO. J Magn Magn Mater 322:1195–1197. https://doi.org/10.1016/j.jmmm.2009.06.051
Morales MP, Veintemillas-Verdaguer S, Montero MI, Serna CJ, Roig A, Casas LI, Martínez B, Sandiumenge F (1999) Surface and internal spin canting in γ-Fe2O3 nanoparticles. Chem Mater 11:3058–3064. https://doi.org/10.1021/cm991018f
Nemala H, Thakur JS, Naik VM, Vaishnava PP, Lawes G, Naik R (2014) Investigation of magnetic properties of Fe3O4 nanoparticles using temperature dependent magnetic hyperthermia in ferrofluids. J Appl Phys 116:034309-1–034309-6. https://doi.org/10.1063/1.4890456
Oliveira FCC, Effenberger FB, Sousa MH, Jardim RF, Kiyohara PK, Dupont J, Rubim JC, Rossi LM (2011) Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles. Phys Chem Chem Phys 13:13558–13564. https://doi.org/10.1039/C1CP21518C
O'Neill HSC, Dollase WA (1994) Crystal structures and cation distributions in simple spinels from powder XRD structural refinements: MgCr2O4, ZnCr2O4, Fe3O4 and the temperature dependence of the cation distribution in ZnAl2O4. Phys Chem Miner 20:541–555. https://doi.org/10.1007/BF00211850
Parvin K, Ma J, Ly J, Sun XC, Nikles DE, Sun K, Wang LM (2004) Synthesis and magnetic properties of monodisperse Fe3O4 nanoparticles. J Appl Phys 95:7121–7123. https://doi.org/10.1063/1.1682783
Pérez-Dieste V, Castellini OM, Crain JN, Eriksson MA, Kirakosian A, Lin J-L, McChesney JL, Himpsel FJ, Black CT, Murray CB (2003) Thermal decomposition of surfactant coatings on Co and Ni nanocrystals. Appl Phys Lett 83:5053–5055. https://doi.org/10.1063/1.1633971
Pistone A, Piperno A, Iannazzo D, Donato N, Latino M, Spadaro D, Neri G (2013) Fe3O4-MWCNT-PhCOOH composites for ammonia resistive sensors. Sens Actuators B Chem 186:333–342. https://doi.org/10.1016/j.snb.2013.06.027
Ramirez FEN, Cabrera-Pasca GA, Mestnik-Filho J, Carbonari AW, Souza JA (2015) Magnetic and transport properties assisted by local distortions in Bi2Mn4O10 and Bi2Fe4O9 multiferroic compounds. J Alloys Compd 651:405–413. https://doi.org/10.1016/j.jallcom.2015.08.165
Ren X, Chen H, Yang V, Sun D (2014) Iron oxide nanoparticle-based theranostics for cancer imaging and therapy. Front Chem Sci Eng 8:253–264. https://doi.org/10.1007/s11705-014-1425-y
Roca AG, Morales MP, Grady KO, Serna CJ (2006) Structural and magnetic properties of uniform magnetite nanoparticles prepared by high temperature decomposition of organic precursors. Nanotechnology 17:2783–2788. https://doi.org/10.1088/0957-4484/17/11/010
Rodrigues AMC, Darnet S, Silva LHM (2010) Fatty acid profiles and tocopherol contents of buriti (Mauritia flexuosa), patawa (Oenocarpus bataua), tucuma (Astrocaryum vulgare), mari (Poraqueiba paraensis) and inaja (Maximiliana maripa) fruits. J Braz Chem Soc 21:2000–2004. https://doi.org/10.1590/S0103-50532010001000028
Sahoo Y, Pizem H, Fried T, Golodnitsky D, Burstein L, Sukenik CN, Markovich G (2001) Alkyl phosphonate/phosphate coating on magnetite nanoparticles: a comparison with fatty acids. Langmuir 17:7907–7911. https://doi.org/10.1021/la010703+
Sales TSN, Cavalcante FHM, Bosch-Santos B, Pereira LFD, Cabrera-Pasca GA, Freitas RS, Saxena RN, Carbonari AW (2017) Stable tetragonal phase and magnetic properties of Fe-doped HfO2 nanoparticles. AIP Adv 7:056315-1–056315-6. https://doi.org/10.1063/1.4976583
Sato W, Ida T, Komatsuda S, Fujisawa T, Takenaka S, Ohkubo Y (2016) Thermal stability of nonmagnetic Cd and in impurities in Fe3O4. J Appl Phys 120:145104. https://doi.org/10.1063/1.4964694
Schauss AG, Wu X, Prior RL, Ou B, Patel D, Huang D, Kababick JP (2006) Phytochemical and nutrient composition of the freeze-dried Amazonian palm berry, Euterpe oleraceae Mart. (Açaí). J Agric food Chem 54:8598–8603. https://doi.org/10.1021/jf060976g
Sena C, Costa MS, Muñoz EL, Cabrera-Pasca GA, Pereira LFD, Mestnik-Filho J, Carbonari AW, Coaquira JAH (2015) Charge distribution and hyperfine interactions in the vicinity of impurity sites in In2O3 doped with Fe, Co, and Ni. J Magn Magn Mater 387:165–178. https://doi.org/10.1016/j.jmmm.2015.03.092
Shen M, Cai H, Wang X, Cao X, Li K, Wang SH, Guo R, Zheng L, Zhang G, Shi X (2012) Facile one-pot preparation, surface functionalization, and toxicity assay of APTS-coated iron oxide nanoparticles. Nanotechnology 23:105601.1–105601.10560110. https://doi.org/10.1088/0957-4484/23/10/105601
Soares BMC, Gamarra FMC, Paviani LC, Gonçalves LAG, Cabral FA (2007) Solubility of triacylglycerols in supercritical carbon dioxide. J Supercrit Fluids 43:25–31. https://doi.org/10.1016/j.supflu.2007.03.013
Stoner EC, Wohlfarth EP (1948) A mechanism of magnetic hysteresis in heterogeneous alloys Phil. Trans. Roy. Soc. London A, 240:599-642. https://doi.org/10.1098/rsta.1948.0007; Reprinted by IEEE Trans Magn (1991) 27:3475-3518. https://doi.org/10.1109/TMAG.1991.1183750
Sun S, Zeng H, Robinson DB, Raoux S, Rice PM, Wang SX, Li G (2004) Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. J Am Chem Soc 126:273–279. https://doi.org/10.1021/ja0380852
Svergun DI (1992) Determination of the regularization parameter in indirect-transform methods using perceptual criteria. J Appl Crystallogr 25:495–503. https://doi.org/10.1107/S0021889892001663
Teixeira-Neto AA, Izumi CMS, Temperini MLA, Ferreira AMC, Constantino VRL (2012) Hybrid materials based on Smectite clays and nutraceutical anthocyanins from the Açaí fruit. Eur J Inorg Chem 32:5411–5420. https://doi.org/10.1002/ejic.201200702
Uhrmacher M (2011) Can PAC measurements be used to investigate defects in nanostructures? Defects Diffus Forum 311:105–133. https://doi.org/10.4028/www.scientific.net/DDF.311.105
Unni M, Uhl A, Savliwala S, Savitzky BH, Dhavalikar R, Garraud N, Arnold DP, Kourkoutis LF, Andrew J, Rinaldi C (2018) Thermal decomposition synthesis of iron oxide nanoparticles with diminished magnetic dead layer by controlled addition of oxygen. ACS Nano 11:2284–2303. https://doi.org/10.1021/acsnano.7b00609
Yamaguchi KKL, Pereira LFR, Lamarão CV, Lima ES, Da Veiga Junior VF (2015) Amazon acai: chemistry and biological activities: a review. Food Chem 179:137–151. https://doi.org/10.1016/j.foodchem.2015.01.055
Yuan Y, Rende D, Altan CL, Bucak S, Ozisik R, Borca-Tasciuc D-A (2012) Effect of surface modification on magnetization of Iron oxide nanoparticle colloids. Langmuir 28:13051–13059. https://doi.org/10.1021/la3022479
Zhang L, He R, Hong-Chen G (2006) Oleic acid coating on the monodisperse magnetite nanoparticles. Appl Surf Sci 253:2611–2617. https://doi.org/10.1016/j.apsusc.2006.05.023
Zhang Y, Zeng G-M, Tang L, Huang D-L, Jiang X-Y, Chen Y-N (2007) A hydroquinone biosensor using modified core–shell magnetic nanoparticles supported on carbon paste electrode. Biosens Bioelectron 22:2121–2126. https://doi.org/10.1016/j.bios.2006.09.030
Acknowledgments
The authors acknowledge the Centro de Radiofarmacia do IPEN by the supply of 111InCl3 solution and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES).
Funding
Financial support of this study was partially provided by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) [grant numbers 473477/2013-0, 304627/2017-8, 430060/2018–1]; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) [grant numbers 2015/16191-5, 2017/50332-0].
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BSC and APSS: extraction and characterization of natural oils, synthesis of Fe3O4 nanoparticles, characterization of synthesized nanoparticles with XRD and TEM, and preparation of samples with radioactive 111In and measurements of PAC spectroscopy; MSC: synthesis of Fe3O4 nanoparticles, characterization of synthesized nanoparticles with XRD and TEM, and preparation of samples with radioactive 111In and measurements of PAC spectroscopy; GAC: synthesis of Fe3O4 nanoparticles, characterization of synthesized nanoparticles with XRD and TEM, preparation of samples with radioactive 111In and measurements of PAC spectroscopy and drafted the manuscript; CS: synthesis of Fe3O4 nanoparticles, characterization of synthesized nanoparticles with XRD and TEM, preparation of samples with radioactive 111In and measurements of PAC spectroscopy and drafted the manuscript; RHHP and RNCJ: extraction and characterization of natural oils; LI and JGAR: characterization of nanoparticles with SAXS and measurements of magnetization; RSF: characterization of nanoparticles with SAXS and measurements of magnetization, drafted the manuscript; MS: determination of the Fe concentration by NAA; ITM: synthesis of Fe3O4 nanoparticles and preparation of samples with radioactive 111In and measurements of PAC spectroscopy; and ELC: determination of the Fe concentration by NAA and preparation of samples with radioactive 111In and measurements of PAC spectroscopy; AWC: drafted the manuscript and revised and organized the full final manuscript.
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Corrêa, B.S., Costa, M.S., Cabrera-Pasca, G.A. et al. High-saturation magnetization in small nanoparticles of Fe3O4 coated with natural oils. J Nanopart Res 22, 68 (2020). https://doi.org/10.1007/s11051-020-4761-5
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DOI: https://doi.org/10.1007/s11051-020-4761-5