Abstract
The present paper reports the synthesis of iron-oxide nanoparticles (diameter 12.8±2.2 nm) coated with silica shell doped with paramagnetic Gd(III)-based complexes. The resulting nanoparticles with a silica shell thickness of about 45 nm have an average diameter of 113.1±14.3 nm and feature high transverse and longitudinal relaxivities (356 and 25 mM−1 s−1, respectively) at 1.5 T and 25 °C on a medical whole body NMR scanner. It has been also revealed using magnetic heating measurements that the prepared core-shell nanoparticles possess a high specific adsorption rate of around 236 W/g in aqueous media. The surface of the composite nanoparticles was decorated by amino-groups for a greater cellular uptake behaviour. The cell viability measurements reveal the concentration-dependent cytotoxicity of the nanoparticles, which agrees well with the high content of Gd(III) complexes in the nanomaterial. The obtained results show that the core-shell design of nanoparticles with superparamagnetic and paramagnetic parts can be promising for high transverse (and longitudinal) relaxivity as well as magnetic hyperthermia.
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Jedlovszky-Hajdu A, Tombacz E, Banyai I, Babos M and Palko A 2012 Carboxylated magnetic nanoparticles as MRI contrast agents: Relaxation measurements at different field strengths J. Magn. Magn. Mater. 324 3173
Xiao N, Gu W, Wang H, Deng Y, Shi X and Ye L 2014 T1–T2 dual-modal MRI of brain gliomas using PEGylated Gd-doped iron oxide nanoparticles J. Colloid Interface Sci. 417 159
Sulek S, Mammadov B, Mahcicek D I, Sozeri H, Atalar E, Tekinay A B and Guler M O 2011 Peptide functionalized superparamagnetic nanoparticles as MRI contrast agents J. Mater. Chem. 21 15157
Huang J, Wang L, Lin R, Wang A Y, Yang L, Kuang M, et al. 2013 Casein-coated iron oxide nanoparticles for high MRI contrast enhancement and efficient cell targeting ACS App. Mater. Interfaces. 5 4632
Ansari L and Malaekeh-Nikouei B 2017 Magnetic silica nanocomposites for hyperthermia applications Int. J. Hyperth. 33 354
Laurent S, Dutz S, Häfeli U O and Mahmoudi M 2011 Magnetic fluid hyperthermia: focus on superparamagnetic iron-oxide nanoparticles Adv. Colloid Interface Sci. 166 8
Gonzales-Weimuller M, Zeisberger M and Krishnan K M 2009 Size-dependent heating rates of iron oxide nanoparticles for magnetic fluid hyperthermia J. Magn. Magn. Mater. 321 1947
Hedayatnasab Z, Abnisa F and Duad W M A W 2017 Review on magnetic nanoparticles for magnetic nanofluid hyperthermia applications Mater. Des. 123 174
Guibert C, Dupuis V, Peyre V and Fresnais J 2015 Hyperthermia of magnetic nanoparticles: experimental study of the role of aggregation J. Phys. Chem. C 119 28148
Müller R, Dutz S, Neeb A, Cato A C B and Zeisberger M 2013 Magnetic heating effect of nanoparticles with different sizes and size distributions J. Magn. Magn. Mater. 328 80
Ramimoghadam D, Bagheri S and Hamid S B A 2014 Progress in electrochemical synthesis of magnetite iron oxide nanoparticles J. Magn. Magn. Mater. 368 207
Yang M, Gao L, Liu K, Luo C, Wang Y, Yu L and Peng H 2015 Characterization of Fe3O4/SiO2/Gd2O(CO3)2 core/shell/shell nanoparticles as T1 and T2 dual mode MRI contrast agent Talanta 131 661
Xiao W, Gu H, Li D, Chen D, Deng X, Jiao Z and Lin J 2012 Microwave-assisted synthesis of magnetite nanoparticles for MRI blood pool contrast agents J. Magn. Magn. Mater. 324 488
Rohrer M, Bauer H, Mintorovitch J, Requardt M and Weinmann H J 2005 Comparison of magnetic properties of MRI contrast media solutions at different magnetic field strengths Invest. Radiol. 40 715
Shin T-H, Choi J S, Yun S, Kim I S, Song H T, Kim Y, et al. 2014 T1 and T2 dual-mode MRI contrast agent for enhancing accuracy by engineered nanomaterials ACS Nano 8 3393
Choi J-S, Lee J H, Shin T H, Song H T, Kim E Y and Cheon J 2010 Self-confirming “AND” logic nanoparticles for fault-free MRI J. Am. Chem. Soc. 132 11015
Stepanov A, Fedorenko S, Amirov R, Nizameev I, Kholin K, Voloshina A, et al. 2018 Silica-coated iron-oxide nanoparticles doped with Gd(III) complexes as potential double contrast agents for magnetic resonance imaging at different field strengths J. Chem. Sci. 130 125
Fedorenko S, Stepanov A, Zairov R, Kaman O, Amirov R, Nizameev I, Kholin K, Ismaev I, Voloshina A, Sapunova A, Kadirov M and Mustafina A 2018 One-pot embedding of iron oxides and Gd(III) complexes into silica nanoparticles—Morphology and aggregation effects on MRI dual contrasting ability Colloids Surf., A 559 60
Fedorenko S V, Grechkina S L, Mustafina A R, Kholin K V, Stepanov A S, Nizameev I R, Ismaev I E, Kadirov M K, Zairov R R, Fattakhova A N, Amirov R R and Soloveva S E 2017 Tuning the non-covalent confinement of Gd(III) complexes in silica nanoparticles for high T1-weighted MR imaging capability Colloids Surf., B 149 243
Abenojar E C, Wickramasinghe S, Bas-Concepcion J and Samia A C S 2016 Structural effects on the magnetic hyperthermia properties of iron oxide nanoparticles Prog. Nat. Sci. 26 440
Parmar H, Smolkova IS, Kazantseva N E, Babayan V, Smolka P, Moucka R, et al. 2015 Size dependent heating efficiency of iron-oxide single domain nanoparticles Proced. Eng. 102 527
Nemati Z, Das R, Alonso J, Clements E, Phan M H and Srikanth H 2017 Iron oxide nanospheres and nanocubes for magnetic hyperthermia therapy: a comparative study J. Electron. Mater. 46 3764
Xiao L L, Fan H M, Yi J B, Yang Y, Choo E S G, Xue J M, et al. 2012 Optimization of surface coating on Fe3O4 nanoparticles for high performance magnetic hyperthermia agents J. Mater. Chem. 22 8235
Fedorenko S V, Mustafina A R, Mukhametshina A R, Jilkin M E,. Mukhametzyanov T A, Solovieva A O, Pozmogova T N, Shestopalova L V, Shestopalov M A, Kholin K V, Osin Y N and Sinyashin O G 2017 Cellular imaging by green luminescence of Tb(III)-doped aminomodified silica nanoparticles Mater. Sci. Eng., C 76 551
Beddoes C M, Case C P and Briscoe W H 2015 Understanding nanoparticle cellular entry: a physicochemical perspective Adv. Colloid Interface Sci. 218 48
Salatin S, Dizaj S M and Khosroushahi A Y 2015 Effect of the surface modification, size, and shape on cellular uptake of nanoparticles Cell Biol. Int. 39 881
Saha K, Kim S T, Yan B, Miranda O R, Alfonso F S, Shlosman D and Rotello V M 2013 Surface functionality of nanoparticles determines cellular uptake mechanisms in mammalian cells Small 9 300
Iki N, Fujimoto T and Miyano S 1998 A new water-soluble host molecule derived from thiacalixarene Chem. Lett. 27 625
Bronstein L M, Huang X, Retrum J, Schmucker A, Pink M, Stein B D and Dragnea B 2007 Influence of iron oleate complex on iron oxide nanoparticle formation Chem. Mater. 19 3624
Dutz S, Kettering M, Hilger I, Müller R and Zeisberger M 2011 Magnetic multicore nanoparticles for hyperthermia—influence of particle immobilization in tumour tissue on magnetic properties Nanotechnology 22 265102
Dutz S, Müller R, Eberbeck D, Hilger I and Zeisberger M 2015 Magnetic nanoparticles adapted for specific biomedical applications Biomed. Eng.-Biomed. Tech. 60 405
Voloshina D, Semenov V E, Strobykina A S, Kulik N V, Krylova E S, Zobov V V and Reznik V S 2017 Synthesis and antimicrobial and toxic properties of novel 1,3-bis(alkyl)-6-methyluracil derivatives containing 1,2,3- and 1,2,4-triazolium fragments Russ. J. Bioorg. Chem. 43 170
Fedorenko S, Stepanov A, Sibgatullina G, Samigullin D, Mukhitov A, Petrov K, et al. 2019 Fluorescent magnetic nanoparticles for modulating the level of Ca2+ in motoneurons Nanoscale 11 16103
Iqbal Y, Bae H, Rhee I and Hong S 2016 Magnetic heating of silica-coated manganese ferrite nanoparticles J. Magn. Magn. Mater. 409 80
Zhu X M, Wang Y X, Leung K C, Lee S F, Zhao F, Wang D W, et al. 2012 Enhanced cellular uptake of aminosilane-coated superparamagnetic iron oxide nanoparticles in mammalian cell lines Int. J. Nanomed. 7 953
Fedorenko S V, Mustafina A R, Mukhametshina A R, Jilkin M E, Mukhametzyanov T A, Solovieva A O, et al. 2017 Cellular imaging by green luminescence of Tb(III)-doped aminomodified silica nanoparticles Mater. Sci. Eng. C 76 551
Davydov N, Mustafina A, Burilov V, Zvereva E, Katsyuba S, Vagapova L, et al. 2012 Complex formation of d-metal ions at the interface of TbIII-doped silica nanoparticles as a basis of substrate-responsive TbIII-centered luminescence ChemPhysChem. 13 3357
Mukhametshina A R, Fedorenko S V, Petrov A M, Zakyrjanova G F, Petrov K A, Nurullin L F, et al. 2018 Targeted nanoparticles for selective marking of neuromuscular junctions and ex vivo monitoring of endogenous acetylcholine hydrolysis ACS Appl. Mater. Interfaces 10 14948
Rosensweig R E 2002 Heating magnetic fluid with alternating magnetic field J. Magn. Magn. Mater. 252 370
Lübbe A S, Alexiou C and Bergemann C 2001 Clinical applications of magnetic drug targeting J. Surg. Res. 95 200
Mendes R G, Koch B, Bachmatiuk A, El-Gendy A A, Krupskaya Y, Springer A, et al. 2014 Synthesis and toxicity characterization of carbon coated iron oxide nanoparticles with highly defined size distributions Biochim. Biophys. Acta 1840 160
Haddad P S, Santos M C, Guzzi Cassago C A, Bernardes JS , Jesus M D and Seabra A B 2016 Synthesis, characterization, and cytotoxicity of glutathione-PEG-iron oxide magnetic nanoparticles J. Nanopart Res. 18 369
Acknowledgement
The work was funded by the Government assignment for FRC Kazan Scientific Center of Russian academy of Science (Reg. Nr. AAAA-A18-118041760011-2). M.R. thanks National Science Foundation of China (Grant No. 52071225) and the Czech Republic under the ERDF program “Institute of Environmental Technology—Excellent Research” (No. CZ.02.1.01/0.0/0.0/16_019/0000853).
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STEPANOV, A., FEDORENKO, S., MENDES, R. et al. T2- and T1 relaxivities and magnetic hyperthermia of iron-oxide nanoparticles combined with paramagnetic Gd complexes. J Chem Sci 133, 43 (2021). https://doi.org/10.1007/s12039-021-01904-7
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DOI: https://doi.org/10.1007/s12039-021-01904-7