In order to understand the properties involved in the heating performance of magnetic nanoparticles during hyperthermia treatments, a systematic study of different γ-Fe2O3 and Fe3O4 nanoparticles has been done. High-frequency hysteresis loops at 50 kHz carried out on particles with sizes ranging from 6 to 350 nm show susceptibility χ increases from 9 to 40 for large particles and it is almost field independent for the smaller ones. This suggests that the applied field induces chain ordering in large particles but not in the smaller ones due to the competition between thermal and dipolar energy. The specific absorption rate (SAR) calculated from hysteresis losses at 60 mT and 50 kHz ranges from 30 to 360 W/gFe, depending on particle size, and the highest values correspond to particles ordered in chains. This enhanced heating efficiency is not a consequence of the intrinsic properties like saturation magnetization or anisotropy field but to the spatial arrangement of the particles.
24 August 2018 in Physical Chemistry Chemical Physics
The present manuscript reports the use of hybrid magneto-plasmonic nanoparticles (HMPNPs) based on iron oxide nanoparticles and Au nanorods as colloidal nanoheaters.
Magnetite nanoparticles (MNPs) with 12, 34 and 53 nm sizes have been measured by AC-magnetometry at 50 kHz and 57 mT maximum applied field. The MNPs form chains under the AC-field, and the dynamics of the formation can be studied by measuring hysteresis cycles at different times. The measurement time has been varied from 5 ms to 10 s and for different initial temperatures of 5, 25 and 50 °C. The chain formation, identified by the increase of susceptibility and remanence with the measurement time, appears only for 34 nm particles. It has been observed that saturation, remanence and susceptibility at low (high) fields increase (decrease) with time. For the other two samples, these magnitudes are independent of time. At low fields, the heating efficiency is higher at 5 °C than at 50 °C, whereas it shows an opposite behaviour at higher fields; the origin of this behaviour is discussed in the article. Additionally, the relaxation times, τN and τB, have been calculated by considering the influence of the applied field. Chain formation requires translation and rotation of MNPs; therefore, the Brownian mechanism plays a fundamental role. It is found that magnetic reversal for 12 nm MNPs is mainly due to Néel relaxation. However, in the case of 34 nm MNPs, both mechanisms, Néel and Brownian relaxation, can be present depending on the amplitude of the field; for μ0H < 22 mT, the physical rotation of the particle is the dominant mechanism; on the other hand, for μ0H > 22 mT, both mechanisms are present within the size distribution. This highlights the importance of taking the field intensity into account to calculate relaxation times when analysing the relaxation mechanisms of magnetic colloids subjected to AC fields.
It is well stablished that heating efficiency of magnetic nanoparticles under radiofrequency fields is due to the hysteresis power losses. In the case of microwires (MWs), it is not clear at all since they undergo non-coherent reversal mechanisms that decrease the coercive field and, consequently, the heating efficiency should be much smaller than the nanoparticles. However, colossal heating efficiency has been observed in MWs with values ranging from 1000 to 2800 W/g, depending on length and number of microwires, at field as low as H = 36 Oe at f = 625 kHz. It is inferred that this colossal heating is due to the Joule effect originated by the eddy currents induced by the induction field B = M + χH parallel to longitudinal axis. This effect is observed in MWs with nearly zero magnetostrictive constant as Fe2.25Co72.75Si10B15 of 30 μm magnetic diameter and 5 mm length, a length for which the inner core domain of the MWs becomes axial. This colossal heating is reached with only 24 W of power supplied making these MWs very promising for inductive heating applications at a very low energy cost.
Macroscopic materials with nanoscopic properties have recently been synthesized by self-assembling defined nanoparticles to form self-supported networks, so-called aerogels. Motivated by the promising properties of this class of materials, the search for versatile routes toward the controlled assembly of presynthesized nanoparticles into such ultralight macroscopic materials has become a great interest. Overcoating procedures of colloidal nanoparticles with polymers offer versatile means to produce aerogels from nanoparticles, regardless of their size, shape, or properties while retaining their original characteristics. Herein, we report on the surface modification and assembly of various building blocks: photoluminescent nanorods, magnetic nanospheres, and plasmonic nanocubes with particle sizes between 5 and 40 nm. The polymer employed for the coating was poly(isobutylene-alt-maleic anhydride) modified with 1-dodecylamine side chains. The amphiphilic character of the polymer facilitates the stability of the nanocrystals in aqueous media. Hydrogels are prepared via triggering the colloidally stable solutions, with aqueous cations acting as linkers between the functional groups of the polymer shell. Upon supercritical drying, the hydrogels are successfully converted into macroscopic aerogels with highly porous, open structure. Due to the noninvasive preparation method, the nanoscopic properties of the building blocks are retained in the monolithic aerogels, leading to the powerful transfer of these properties to the macroscale. The open pore system, the universality of the polymer-coating strategy, and the large accessibility of the network make these gel structures promising biosensing platforms. Functionalizing the polymer shell with biomolecules opens up the possibility to utilize the nanoscopic properties of the building blocks in fluorescent probing, magnetoresistive sensing, and plasmonic-driven thermal sensing.