Magnetite and maghemite multi-core nanoflowers (NFs) synthesized using the modified polyol-mediated routes are to date among the most effective nano-heaters in magnetic hyperthermia (MHT). Recently, magnetite NFs have also shown high photothermal (PT) performances in the most desired second near infra-red (NIR-II) biological window making them attractive in the field of nanoparticle-activated thermal therapies. However, what makes magnetic NFs efficient heating agents in both modalities still remain an open question. In this work, we investigate the role of many parameters of the polyol synthesis on the final NFs size, shape, chemical composition, number of cores and crystallinity. These nanofeatures are later correlated to the magnetic, optical and electronic properties of the NFs as well as their collective macroscopic thermal properties in MHT and PT to find relationships between their structure, properties and function. We evidence the critical role of iron(III) and heating ramps on the elaboration of well-defined NFs with high number of multi-cores. While MHT efficiency is found to be proportional to the average number of magnetic cores within the assemblies, the optical responses of the NFs and their collective photothermal properties depend directly on the mean volume of the NFs (as supported by optical cross sections numerical simulations) and strongly on the structural disorder in the NFs, rather than the stoichiometry. The concentration of defects in the nanostructures, evaluated by photoluminescence and Urbach energy (EU), evidences a switch in the optical behavior for a limit value of EU = 0.4 eV where a discontinuous transition from high to poor PT efficiency is also observed. Keywordsmulti-core iron oxides, nanoflowers, magnetic nanoparticles, magnetic hyperthermia, photothermia, nanothermal agents, thermal therapies distributions histograms, powder XRD diffraction data and Rietveld refinements, XANES data, 57 Fe Mössbauer spectra, SQUID, TGA, ZFC/FC measurements and DLS measurements, ILP values, Python codes, Beer-Lambert plots at 1064 nm, Urbach and Tauc plots, MHT and PT measurements, fluorescence emission spectra and additional tables.
One of the most versatile routes for the elaboration of nanomaterials in materials science, including the synthesis of magnetic iron oxide nanoclusters, is the high-temperature polyol process. However, despite its versatility, this process still lacks reproducibility and scale-up, in addition to the low yield obtained in final materials. In this work, we demonstrate a home-made multiparametric continuous flow millifluidic system that can operate at high temperatures (up to 400 °C). After optimization, we validate its potential for the production of nanomaterials using the polyol route at 220 °C by elaborating ferrite iron oxide nanoclusters called nanoflowers (CoFe2O4, Fe3O4, MnFe2O4) with well-controlled nanostructure and composition, which are highly demanded due to their physical properties. Moreover, we demonstrate that by using such a continuous process, the chemical yield and reproducibility of the nanoflower synthesis are strongly improved as well as the possibility to produce these nanomaterials on a large scale with quantities up to 45 g per day.
Oriented attachment of nanobricks into hierarchical multi-scale structures such as inorganic nanoclusters is one of the crystallization mechanisms that has revolutionized the field of nano and materials science. Herein, we show that the mosaicity, which measures the misalignment of crystal plane orientation between the nanobricks, governs their magneto-optical properties as well as the magnetic heating functions of iron oxide nanoclusters. Thanks to high-temperature and time-resolved millifluidic, we were able to isolate and characterize (structure, properties, function) the different intermediates involved in the diverse steps of the nanocluster’s formation, to propose a detailed dynamical mechanism of their formation and establish a clear correlation between changes in mosaicity at the nanoscale and their resulting physical properties. Finally, we demonstrate that their magneto-optical properties can be described using simple molecular theories.
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