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To improve the effectiveness and durability of wastewater treatment technologies, researchers are showing a growing interest in 3D printing technology. This technology has attracted significant interest owing to its ability to fabricate challenging complex geometries using different material compositions. This manuscript is focused on the development of 3D monoliths from noncommercial filaments, i.e., a powder blend of iron oxide and polylactic acid (PLA) at 15 wt% of the former. Different monolith designs have been prepared to improve the fluid dynamics of the process, so a simple cylinder (15-Fe 3 O 4 @PLA) and a cylinder with double the length and an internal mesh (15-Fe 3 O 4 @PLA-DM) were used. These monoliths were characterized by Scanning electron microscopy (SEM), Differential scanning calorimetry (DSC) and Mössbauer spectroscopy, then used for water-based ofloxacin degradation in a continuous down-up flow configuration. Additionally, computational fluid dynamics simulations were performed to estimate the degradation rate constants and analyze the distribution of fluid velocity and pollutant concentration along the 15-Fe 3 O 4 @PLA-reactor. The oxidant dose was also optimized to develop the highest degradation rate. The degradation of the target pollutant for those monoliths was 55 and 82 % under optimized conditions. In addition, the 15-Fe 3 O 4 @PLA-DM monolith was operated for long term experiments, keeping the degradation performance at a good 67 % for up to 120 h. Finally a fixed-bed reactor was mounted with printed pellets of the mixture (15:85), Fe 3 O 4 :PLA, after being ground in a range of 125-200 μm. Under this setup configuration, we observed the total degradation of ofloxacin. 3D printing technology is cheap, reproducible and time saving in the development of supported catalysts in comparison with conventional deposition techniques. Moreover, the leaching of active sites on streams was largely diminished. In fact under continuous operation the leached Fe concentration is below 0.1 ppm, corroborating the good adhesion of the catalyst in the PLA support., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Catalyst stability has become a challenging issue for advanced oxidation processes (AOPs). Herein, we report an alternative method based on 3D printing technology to obtain zero-valent iron polylactic acid prototypes (ZVI@PLA) in a single step and without post etching treatment. ZVI@PLA was used to activate persulfate (PS) for the removal of Tetracycline (TC) in recirculating mode under two different heating methodologies, thermal bath and contactless heating promoted by magnetic induction (MIH). The effect of both heating methodologies was systematically analysed by comparing the kinetic constant of the degradation processes. It was demonstrated that the non-contact heating of ZVI by MIH reactivates the surface of the catalyst, renewing the surface iron content exposed to the pollutant solution, which makes the ZVI@PLA catalyst reusable up to 10 cycles with no efficiency reduction. In contrast, by using a conventional thermal bath, the kinetic constant gradually decreases over the 10 cycles, because of the superficial iron consumption, being the kinetic constant 5 times lower in the 10th run compared to MIH experiment. X-ray diffraction and Mössbauer spectroscopy confirmed the presence of metallic iron embedded in the ZVI@PLA prototype, whose crystalline structure remained unchanged for 10th cycles of MIH. Moreover, it was proven that with no contact heating technology at low magnetic fields (12.2 mT), the solution temperature does not increase, but only the surface of the catalyst does. Under these superficial heated conditions, kinetic rate is increased up to 0.016 min -1 compared to the value of 0.0086 min -1 obtained for conventional heating at 20 °C. This increase is explained not only by PS activation by iron leaching but also by the contribution of ZVI in the heterogeneous activation of persulfate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The use of magnetic nanoparticles (MNPs) to locally increase the temperature at the nanoscale under the remote application of alternating magnetic fields (magnetic particle hyperthermia, MHT) has become an important subject of nanomedicine multidisciplinary research, focusing among other topics on the optimization of the heating performance of MNPs and their assemblies under the effect of the magnetic field. We report experimental data of heat released by MNPs using a wide range of anisometric shapes and their assemblies in different media. We outline a basic theoretical investigation, which assists the interpretation of the experimental data, including the effect of the size, shape and assembly of MNPs on the MNPs' hysteresis loops and the maximum heat delivered. We report heat release data of anisometric MNPs, including nanodisks, spindles (elongated nanoparticles) and nanocubes, analysing, for a given shape, the size dependence. We study the MNPs either acting as individuals or assembled through a magnetic-field-assisted method. Thus, the physical geometrical arrangement of these anisometric particles, the magnetization switching and the heat release (by means of the determination of the specific adsorption rate, SAR values) under the application of AC fields have been analysed and compared in aqueous suspensions and after immobilization in agar matrix mimicking the tumour environment. The different nano-systems were analysed when dispersed at random or in assembled configurations. We report a systematic fall in the SAR for all anisometric MNPs randomly embedded in a viscous environment. However, certain anisometric shapes will have a less marked, an almost total preservation or even an increase in SAR when embedded in a viscous environment with certain orientation, in contrast to the measurements in water solution. Discrepancies between theoretical and experimental values reflect the complexity of the systems due to the interplay of different factors such as size, shape and nanoparticle assembly due to magnetic interactions. We demonstrate that magnetic assembly holds great potential for producing materials with high functional and structural diversity, as we transform our nanoscale building blocks (anisometric MNPs) into a material displaying enhanced SAR properties.

Advanced oxidation processes constitute a promising alternative for the treatment of wastewater containing organic pollutants. Still, the lack of cost-effective processes has hampered the widespread use of these methodologies. Iron oxide magnetic nanoparticles stand as a great alternative since they can be engineered by different reproducible and scalable methods. The present study consists of the synthesis of single-core and multicore magnetic iron oxide nanoparticles by the microwave-assisted polyol method and their use as self-heating catalysts for the degradation of an anionic (acid orange 8) and a cationic dye (methylene blue). Decolorization of these dyes was successfully improved by subjecting the catalyst to an alternating magnetic field (AMF, 16 kA/m, 200 kHz). The sudden temperature increase at the surface of the catalyst led to an intensification of 10% in the decolorization yields using 1 g/L of catalyst, 0.3 M H 2 O 2 and 500 ppm of dye. Full decolorization was achieved at 90 °C, but iron leaching (40 ppm) was detected at this temperature leading to a homogeneous Fenton process. Multicore nanoparticles showed higher degradation rates and 100% efficiencies in four reusability cycles under the AMF. The improvement of this process with AMF is a step forward into more sustainable remediation techniques.

Uniform cobalt ferrite nanoparticles have been synthesized using an electrochemical synthesis method in aqueous media. Their colloidal, magnetic, and relaxometric properties have been analyzed. The novelty of this synthesis relies on the use of iron and cobalt foils as precursors, which assures the reproducibility of the iron and cobalt ratio in the structure. A stable and biocompatible targeting conjugate nanoparticle-folic acid (NP-FA) was developed that was capable of targeting FA receptor positivity in HeLa (human cervical cancer) cancer cells. The biocompatibility of NP-FA was assessed in vitro in HeLa cells using the MTT assay, and morphological analysis of the cytoskeleton was performed. A high level of NP-FA binding to HeLa cells was confirmed through qualitative in vitro targeting studies. A value of 479 Fe+Co mM -1 s -1 of transverse relaxivity (r 2 ) was obtained in colloidal suspension. In addition, in vitro analysis in HeLa cells also showed an important effect in negative T2 contrast. Therefore, the results show that NP-FA can be a potential biomaterial for use in bio medical trials, especially as a contrast agent in magnetic resonance imaging (MRI).

The present study describes the preparation of 50.3 nm superparamagnetic nanosorbents with high surface area for the adsorptive removal of lead and methyl orange from water. This material is based on the surface modification of iron oxide superparamagnetic nanoparticles with a double-shell coating of mesoporous silica whose porosity was increased up to 570 m 2 /g by the addition of a porogenic material and its calcination. The adsorptive performance of the nanosorbent was evaluated as a function of several parameters (e.g. solution pH, pollutant initial concentration, and contact time), concluding that pHs around 5 are needed to avoid precipitation of Pb 2+ as Pb(OH) 2 and the equilibrium adsorption capacity is reached after 2 h in all cases. The experimental data on the adsorption capacity of lead and methyl orange onto the nanosorbent were fit to a pseudo-second order kinetic model and Langmuir isotherm model. The maximum adsorption capacity value increases from 35 up to 50 mg/g NS for lead removal with increasing nanosorbent surface area. Contrary, for methyl orange the maximum adsorption goes up to 240 mg/g NS , indicating a larger nanosorbent surface affinity for the organic matter that is able to diffuse through the silica pores as probed by the intraparticle diffusion model. In addition, we found an good reusability (100% recovering after 4 sorption/desorption cycles for methyl orange removal), which makes of this magnetic nanosorbent suitable for remediation technologies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Targeting TRAIL (Tumor necrosis factor (TNF)-Related Apoptosis-Inducing Ligand) receptors for cancer therapy remains challenging due to tumor cell resistance and poor preparations of TRAIL or its derivatives. Herein, to optimize its therapeutic use, TRAIL was grafted onto iron oxide nanoclusters (NCs) with the aim of increasing its pro-apoptotic potential through nanoparticle-mediated magnetic hyperthermia (MHT) or photothermia (PT). Methods : The nanovector, NC@TRAIL, was characterized in terms of size, grafting efficiency, and potential for MHT and PT. The therapeutic function was assessed on a TRAIL-resistant breast cancer cell line, MDA-MB-231, wild type (WT) or TRAIL-receptor-deficient (DKO), by combining complementary methylene blue assay and flow cytometry detection of apoptosis and necrosis. Results : Combined with MHT or PT under conditions of "moderate hyperthermia" at low concentrations, NC@TRAIL acts synergistically with the TRAIL receptor to increase the cell death rate beyond what can be explained by the mere global elevation of temperature. In contrast, all results are consistent with the idea that there are hotspots, close to the nanovector and, therefore, to the membrane receptor, which cause disruption of the cell membrane. Furthermore, nanovectors targeting other membrane receptors, unrelated to the TNF superfamily, were also found to cause tumor cell damage upon PT. Indeed, functionalization of NCs by transferrin (NC@Tf) or human serum albumin (NC@HSA) induces tumor cell killing when combined with PT, albeit less efficiently than NC@TRAIL. Conclusions : Given that magnetic nanoparticles can easily be functionalized with molecules or proteins recognizing membrane receptors, these results should pave the way to original remote-controlled antitumoral targeted thermal therapies., Competing Interests: Competing Interests: The authors have declared that no competing interest exists.

Environmental pollution caused by heavy metals constitutes a serious public health problem. In the case of uranium depletion, amidoxime groups are important because of their high affinity for uranium(VI). New series of bis(amidoxime)s with catechol-derived anchor groups were tested (b-AMD-1 and b-AMD-2). The catechol groups were designed to bind to the surface of maghemite nanoparticles (MNPs), and two nanohybrid devices MNP-b-AMD-1 and MNP-b-AMD-2 were obtained. This strategy makes for efficient removal of U(VI) via its complexation with the bis(amidoxime)s (b-AMD) and also its extraction from aqueous solution by magnetic harvesting of the MNPs. The assynthesized and b-AMD-grafted MNPs were characterized by several techniques: X-ray diffraction (XRD), high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM), X-ray photoelectron spectrophotometry (XPS), thermal analysis (TG/DTA) and Fourier transform infrared spectroscopy (FTIR). Sorption tests were run at pH 6.5, which corresponds to the highest affinity and selectivity of b-AMD for U(VI). After magnetic separation, the chelation ability and the selectivity of MNP-b-AMD-1 and MNP-b-AMD-2 towards U(VI) were evaluated by measuring the residual U(VI) concentration in the supernatant by inductively coupled plasma-mass spectrometry (ICP-MS). The data were plotted according to the Langmuir and Freundlich isotherms; the maximal sorption capacity (qmax) was 29 and 60 mg U g-1 for MNP-b-AMD-1 and MNP-b-AMD-2, respectively. This confirms that bis(amidoxime) groups are good candidates for uranium depletion of aqueous solution.

Magnetic nanoparticles (MNPs), and in particular iron oxide nanoparticles (mainly magnetite and maghemite), are being widely used in the form of aqueous colloids for biomedical applications. In such colloids, nanoparticles tend to form assemblies, either aggregates, if the union is permanent, or agglomerates, if it is reversible. These clustering processes have a strong impact on the MNPs' properties that are often not well understood. In this review, the causes and consequences of MNPs aggregation/agglomeration are reviewed and discussed. Special attention has been paid to the impact of the MNPs aggregation/agglomeration on their magnetic properties and heating properties, when exposed to an alternating magnetic field in the frame of magnetic hyperthermia. In addition, a model system with MNPs of two different sizes coated with three different molecules oleic acid, meso-2, 3-dimercaptosuccinic acid and poly(maleic anhydride-alt-1-octadecene) has been characterized and the results used to support the ideas reviewed.

Human serum albumin (HSA), the most abundant plasma protein in human blood, is a natural transport vehicle with multiple ligand binding sites. It, therefore, constitutes an attractive candidate for drug delivery. Targeting may occur via the most known interaction of the protein with the neonatal Fc receptor (FcRn). Here, we investigate another HSA delivery path, involving the transferrin receptor, and we elaborate a maghemite-HSA nanohybrid, opening up new opportunities for medical applications. Fluorescence spectrophotometric titration and size-exclusion chromatography were used to substantiate, in cell-free assays, an interaction between HSA and the transferrin receptor R1. This occurs with a dissociation constant, K D of 6.7 nM. This interaction was confirmed in HeLa cell culture where, by confocal microscopy, rhodamine-labeled HSA is shown to be internalized. HSA was then covalently conjugated onto maghemite nanoparticles (NPs) to give a NP-HSA nanohybrid. The therapeutic potential of this hybrid was demonstrated through its heating capacity in magnetic hyperthermia (MH) and near-infrared (NIR) photothermia (PT). In particular, the Specific Absorption Rate (SAR) in the PT Therapy (PTT) mode, using a 808 nm NIR-LASER (1 W cm -2 ) and at iron concentration as low as 2.5 mM, was found to be very high, equal to 1870 W g -1 with a temperature increment of 9.2 °C. The nanohybrids incubated with HeLa cells were mainly localized at the cell surface. When the PTT mode was applied under the same conditions as in vitro, mortality was higher in HeLa cells than in fibroblasts (non-malignant cells). Cytotoxicity was checked in both cell lines without the PTT mode; the nanohybrids do not seem to affect cell viability. These results make the nanohybrids very promising agents for NIR-PT and for targeting in cancer therapy, since non-malignant cells were not damaged.

Uniform size cobalt ferrite nanoparticles have been synthesized in one step using an electrochemical technique. Synthesis parameters such as the current density, temperature and stirring were optimized to produce pure cobalt ferrite. The nanoparticles have been investigated by means of magnetic measurements, Mössbauer spectroscopy, x-ray powder diffraction and transmission electron microscopy. The average size of the electrosynthesized samples was controlled by the synthesis parameters and this showed a rather narrow size distribution. The x-ray analysis shows that the CoFe(2)O(4) obtained presents a totally inverse spinel structure. The magnetic properties of the stoichiometric nanoparticles show ferromagnetic behavior at room temperature with a coercivity up to 6386 Oe and a saturation magnetization of 85 emu g(-1).