Observation of magnetic vortex configuration in non-stoichiometric Fe3O4 nanospheres.

Theoretical and micromagnetic simulation studies of magnetic nanospheres with vortex configurations suggest that such nanostructured materials have technological advantages over conventional nanosystems for applications based on high-power-rate absorption and subsequent emission. However, full experimental evidence of magnetic vortex configurations in spheres of submicrometer size is still lacking. Here, we report the microwave irradiation fabrication of Fe3O4 nanospheres and establish their magnetic vortex configuration based on experimental results, theoretical analysis, and micromagnetic simulations. Detailed magnetic and electrical measurements, together with Mössbauer spectroscopy data, provide evidence of a loss of stoichiometry in vortex nanospheres owing to the presence of a surface oxide layer, defects, and a higher concentration of cation vacancies. The results indicate that the magnetic vortex spin configuration can be established in bulk spherical magnetite materials. This study provides crucial information that can aid the synthesis of magnetic nanospheres with magnetically tailored properties; consequently, they may be promising candidates for future technological applications based on three-dimensional magnetic vortex structures.

Iron Oxide Nanoparticles in a Dynamic Flux: Magnetic Hyperthermia Effect on Flowing Heavy Crude Oil.

An essential part for crude oil extraction is flow assurance, being critical to maintain a financially sustainable flow while getting the petroleum to the surface. When not well managed, it can develop into a significant issue for the O&G industry. By heating the fluids, problems with flow assurance, including paraffin deposition, asphaltene, and methane hydrate, can be reduced. Also, as the temperature rises, a liquid's viscosity decreases. Research focusing on the application of magnetic nanoparticles (NPs) in the oil industry is very recent. When magnetic nanofluids are exposed to an alternating magnetic field, the viscosity decreases by several orders of magnitude as a result of the fluid's temperature rising due to a phenomenon known as magnetic hyperthermia. This work focuses on the use of magnetic NPs (9 nm) in heavy crude oil (API 19.0). The frequency and strength of the magnetic field, as well as the characteristics of the fluid and the NPs intrinsic properties all affect the heating efficiency. For all of the experimental settings in this work, the flowloop's temperature increased, reaching a maximum of ΔT = 16.3 °C, using 1% wt NPs at the maximum available frequency of the equipment (533 kHz) and the highest field intensity for this frequency (14 kA/m), with a flow rate of 1.2 g/s. This increase in temperature causes a decrease of nearly 45% on the heavy crude oil viscosity, and if properly implemented, could substantially increase oil flow in the field during production.

In vitro and in vivo acute toxicity of a novel citrate-coated magnetite nanoparticle.

Magnetic nanoparticles (MNps) have become powerful tools for multiple biomedical applications such as hyperthermia drivers, magnetic resonance imaging (MRI) vectors, as well as drug-delivery systems. However, their toxic effects on human health have not yet been fully elucidated, especially in view of their great diversity of surface modifications and functionalizations. Citrate-coating of MNps often results in increased hydrophilicity, which may positively impact their performance as drug-delivery systems. Nonetheless, the consequences on the intrinsic toxicity of such MNps are unpredictable. Herein, novel magnetite (Fe3O4) nanoparticles covered with citrate were synthesized and their potential intrinsic acute toxic effects were investigated using in vitro and in vivo models. The proposed synthetic pathway turned out to be simple, quick, inexpensive, and reproducible. Concerning toxicity risk assessment, these citrate-coated iron oxide nanoparticles (IONps) did not affect the in vitro viability of different cell lines (HaCaT and HepG2). Moreover, the in vivo acute dose assay (OECD test guideline #425) showed no alterations in clinical parameters, relevant biochemical variables, or morphological aspects of vital organs (such as brain, liver, lung and kidney). Iron concentrations were slightly increased in the liver, as shown by Graphite Furnace Atomic Absorption Spectrometry and Perls Prussian Blue Staining assays, but this finding was considered non-adverse, given the absence of accompanying functional/clinical repercussions. In conclusion, this study reports on the development of a simple, fast and reproducible method to obtain citrate-coated IONps with promising safety features, which may be used as a drug nanodelivery system in the short run. (263 words).

Sciatic nerve regeneration after traumatic injury using magnetic targeted adipose-derived mesenchymal stem cells.

Traumatic peripheral nerve injuries constitute a huge concern to public health. Nerve damage leads to a decrease or even loss of mobility of the innervated area. Adult stem cell therapies have shown some encouraging results and have been identified as promising treatment candidates for nerve regeneration. A major obstacle to that approach is securing a sufficient number of cells at the injured site to produce measurable therapeutic effects. The present work tackles this issue and demonstrates enhanced nerve regeneration ability promoted by magnetic targeted cell therapy in an in vivo Wallerian degeneration model. To this end, adipose-derived mesenchymal stem cells (AdMSC) were loaded with citric acid coated superparamagnetic iron oxide nanoparticles (SPIONs), systemically transplanted and magnetically recruited to the injured sciatic nerve. AdMSC arrival to the injured nerve was significantly increased using magnetic targeting and their beneficial effects surpassed the regenerative properties of the stand-alone cell therapy. AdMSC-SPIONs group showed a partially conserved nerve structure with many intact myelinated axons. Also, a very remarkable restoration in myelin basic protein organization, indicative of remyelination, was observed. This resulted in an improvement in nerve conduction, demonstrating functional recovery. In summary, our results demonstrate that magnetically assisted delivery of AdMSC, using a non-invasive and non-traumatic method, is a highly promising strategy to promote cell recruitment and sciatic nerve regeneration after traumatic injury. Last but not least, our results validate magnetic targeting in vivo exceeding previous reports in less complex models through cell magnetic targeting in vitro and ex vivo. STATEMENT OF SIGNIFICANCE: Traumatic peripheral nerve injuries constitute a huge public health concern. They can lead to a decrease or even loss of mobility of innervated areas. Due to their complex pathophysiology, current pharmacological and surgical approaches are only partially effective. Cell-based therapies have emerged as a useful tool to achieve full tissue regeneration. However, a major bottleneck is securing enough cells at injured sites. Therefore, our proposal combining biological (adipose derived mesenchymal stem cells) and nanotechnological strategies (magnetic targeting) is of great relevance, reporting the first in vivo experiments involving "magnetic stem cell" targeting for peripheral nerve regeneration. Using a non-invasive and non-traumatic method, cell recruitment in the injured nerve was improved, fostering nerve remyelination and functional recovery.

Hybrid magneto-luminescent iron oxide nanocubes functionalized with europium complexes: synthesis, hemolytic properties and protein corona formation.

The use of hybrid nanostructures based on magneto-luminescent properties is a promising strategy for nano-bio applications and theranostics platforms. In this work, we carried out the synthesis and functionalization of iron oxide nanocubes (IONCs) to obtain multifunctional hybrid nanostructures towards biomedical applications. The IONCs were functionalized with tetraethylorthosilicate, thenoyltrifluoroacetone-propyl-triethoxysilane and europium(iii)-dibenzoylmethane complexes to obtain the materials termed as IOCNCs@SiO2, IONCs@SiO2TTA, IONCs@SiO2TTA-Eu and IONCs@SiO2-TTA-Eu-DBM, respectively. Then, the biological interactions of these nanostructures with red blood cells - RBCs (hemolysis) and human blood plasma (protein corona formation) were evaluated. The XPS spectrocopy and EDS chemical mapping analysis showed that each domain is homogeneously occupied in the hybrid material, with the magnetic core at the center and the luminescent domain on the surface of the hybrid nanomaterial with a core@shell like structure. Futhermore, after each functionalization step, the nanomaterial surface charge drastically changed, with critical impact on RBC lysis and corona formation. While IONCs@SiO2 and IONCs@SiO2-TTA-Eu-DBM showed hemolytic properties in a dose-dependent manner, the IONCs@SiO2TTA-Eu did not present any hemolytic effect up to 300 µg mL-1. Protein corona results showed a pattern of selective adsorption of proteins with each surface of the synthesized hybrid materials. However, as a general result, a suppression of hemolysis after protein corona formation in all tests was verified. Finally, this study provides a solid background for further applications of these hybrid magneto-luminescent materials containing new surface functionalities in the emerging field of medical nanobiotechnology.

Magnetic mesoporous silica nanospheres with dual probe & release fluorescent functionality.

The combination of different nanomaterials through step-by-step synthesis procedures has turned into a promising alternative to fabricate high-quality nanosystems in order to satisfy the increasingly demanding requirements of the biomedical field. In this work, we report a detailed study on the synthesis and characterization of a complex nanosystem composed of nanoparticles with a single magnetic nanoparticle core and a shell of dense and mesoporous silica arranged in layers. The procedure designed to fabricate these systems lead us to the formation of a dispersion of non-agglomerated spherical nanoparticles of nearly 100 nm. The structural characterization performed over the final samples confirmed both the prevalence of single-core systems and the presence of the mesoporous silica shell in the outer layer. The performance of the nanosystem in a specific technological application was tested by sequentially loading two different fluorescents molecules by covalent and non-covalent bonding strategies. Due to the distinct loading strategies, the resulting nanosystem presented a magnetically-assisted probe & release functionality as analyzed in a magnetophoretic experiment.

Highly fluorescent few atoms silver nanoclusters with strong photocatalytic activity synthesized by ultrashort light pulses.

While there are conventional chemical synthesis methods to generate metal nanoclusters (NCs), many of them are adversely affected by the unavoidable contamination of the nanoproduct solution, resulting in aggregation, background noise in analytical chemistry, toxicity, and deactivation of the catalyst. In this work, physical method of ultrafast laser ablation as a "green" synthesis approach together with mechanical centrifugation to obtain silver NCs, simplifying widely the chemical synthesis requirements, is proposed. Remarkably, compared with conventional methods for synthesizing Ag NCs, this new approach starts with a colloid that contains nanosized particles as well as smaller species, managing to obtain colloids with few atoms NCs by centrifugation. Those colloids were analyzed by fluorescence spectroscopy observing UV bands corresponding with HOMO-LUMO cluster transitions. Besides, independent HRTEM measurements were made confirming the presence of few atoms Ag NCs, as well as small NPs in different formation stages. Equally important, photocatalytic efficiency of the obtained NCs was studied through degradation of Methylene Blue (MB) when it was mixed with as-prepared or highly centrifuged colloid, showing an enhanced photocatalytic efficiency of 79% as compared to 57% for pure MB after 180 min of illumination. Consequently, this work contributes to establishing a simple approach to synthesize highly fluorescent and photocatalytic NCs.

Control of Multiferroic properties in BiFeO3 nanoparticles.

BiFeO3 (BFO) nanoparticles (NPs) were synthesized using the sol-gel method at different calcination temperatures from 400 °C to 600 °C. XRD studies have confirmed that all BFO NPs show distorted rhombohedral crystals that match the R3c space group. We found evidence of local structural strain that develops with increasing particle size as suggested by TEM and Raman spectroscopy measurements. Magnetic measurements suggest that NPs have two distinct regimes: a ferromagnetic-like one at low temperatures and a superparamagnetic-like one at room temperature. The crossover temperature increases with NPs size, suggesting a size-dependent blocking magnetic regime. Similarly, local piezoelectric measurements at room temperature in single NP have confirmed a ferroelectric order with a NP size-dependent d33 coefficient. An analysis of both the ferroelectric and the magnetic results suggest that ferromagnetism and ferroelectricity coexist at room temperature in NPs. Our results lead to the possibility of tailoring the ferroic order in multifunctional materials by means of NP size.

In situ electron microscopy observation of the redox process in plasmonic heterogeneous-photo-sensitive nanoparticles.

Observation of relevant phenomena related with dynamical redox process in a plasmonic heterogeneous-photocatalyst system composed by silver nanoparticles (NPs) around and in contact with amorphous silver chloride NPs are reported by in situ transmission electron microscopy. During this process, nanobubbles are initially produced inside the silver chloride NPs, which immediately begin to move within the amorphous phase. Besides, silver atoms inside the silver chloride NPs start to migrate out the occupied volume leaving a space behind, which is filled by crystalline regions of silver chloride located between the pre-existing silver NPs. During the observation time, fast-nucleation, movement, growth, and fast-dissolution of silver NPs take place. Specific space correlation with silver mass loss (or gain) when a new NP is formed (or dissolved), was detected in different regions during the reaction. This mass loss (or gain) takes place on certain places of pre-existing silver NPs. All these phenomena were observed for a configuration comprising at least two silver NPs separated few nanometers apart by a silver chloride NP.

Selective contrast agents with potential to the earlier detection of tumors: Insights on synthetic pathways, physicochemical properties and performance in MRI assays.

Magnetic iron oxide nanoparticles (MNPs) have been prepared and stabilized with three organic acids (tartaric, malic and ascorbic) in order to obtain biocompatible and water dispersible MNPs with potential to bind specifically to tumoral cancer cells. An in deep characterization was performed aiming to verify the presence and effect of the coating and stabilizer on MNPs surface. Besides the mechanisms followed by the different acids to bind MNPs were elucidated and used to justify the differences in the physicochemical properties of each formulation. Data related to characterization revealed that MNPs coated with ascorbic acid (MNPs-AA) resulted the most suitable in terms of their size, surface charge and stability along the time. Besides, ascorbic acid may be recognized by GLUTs receptors that are overexpressed in several kinds of tumoral cells. Therefore, MNPs-AA was selected to explore its performance in both MRI and in vitro assays using human colon cancer cells HCT 116. MRI experiments were performed in clinical equipment using a series of aqueous dispersions of MNPs-AA that were evaluated as T2 contrast agent. The T2- weighted images obtained as well as the calculated r2, indicated that MNPs-AA could act as efficient T2 contrast agent for MRI. Regarding in vitro assays, MNPs-AA did not alter the cellular function neither exert cytotoxicity using the three explored doses. The internalization of the nanoparticles on the cellular structure was confirmed quanti and qualitatively using atomic absorption spectroscopy and Prussian blue techniques respectively. From these results, it emerges that ascorbic acid coated-magnetite nanoparticles may be used as alternative contrast agent to avoid or minimize some toxicological issues related to the widely used gadolinium.

Synthesis and magnetic properties of cobalt-iron/cobalt-ferrite soft/hard magnetic core/shell nanowires.

A straightforward method for the synthesis of CoFe2.7/CoFe2O4 core/shell nanowires is described. The proposed method starts with a conventional pulsed electrodeposition procedure on alumina nanoporous template. The obtained CoFe2.7 nanowires are released from the template and allowed to oxidize at room conditions over several weeks. The effects of partial oxidation on the structural and magnetic properties were studied by x-ray spectrometry, magnetometry, and scanning and transmission electron microscopy. The results indicate that the final nanowires are composed of 5 nm iron-cobalt alloy nanoparticles. Releasing the nanowires at room conditions promoted surface oxidation of the nanoparticles and created a CoFe2O4 shell spinel-like structure. The shell avoids internal oxidation and promotes the formation of bi-magnetic soft/hard magnetic core/shell nanowires. The magnetic properties of both the initial single-phase CoFe2.7 nanowires and the final core/shell nanowires, reveal that the changes in the properties from the array are due to the oxidation more than effects associated with released processes (disorder and agglomeration).

Optical and Magnetic Properties of Fe Nanoparticles Fabricated by Femtosecond Laser Ablation in Organic and Inorganic Solvents.

Magnetic nanoparticles have attracted much interest due to their broad applications in biomedicine and pollutant remediation. In this work, the optical, magnetic, and structural characteristics of colloids produced by ultrashort pulsed laser ablation of a solid Fe target were studied in four different media: HPLC water, an aqueous solution of trisodium citrate, acetone, and ethanol. Optical extinction spectroscopy revealed an absorption band in the UV region for all, in contrast to the results obtained with nanosecond lasers. Micro-Raman spectroscopy showed that the samples are heterogeneous in their composition, with hematite, maghemite, and magnetite nanoparticles in all four solvents. Similar results were obtained by electron diffraction, which also found α-Fe. Magnetic properties were studied by vibrating-sample magnetometry, and showed nanoparticles in the superparamagnetic state. Under certain experimental conditions, submicrometer-sized iron oxide nanoparticles agglomerate into fractal patterns that show self-similar properties. Self-assembled annular structures on the nanometer scale were also observed and are reported for the first time.

Red-green emitting and superparamagnetic nanomarkers containing Fe3O4 functionalized with calixarene and rare earth complexes.

The design of bifunctional magnetic luminescent nanomaterials containing Fe3O4 functionalized with rare earth ion complexes of calixarene and ß-diketonate ligands is reported. Their preparation is accessible through a facile one-pot method. These novel Fe3O4@calix-Eu(TTA) (TTA = thenoyltrifluoroacetonate) and Fe3O4@calix-Tb(ACAC) (ACAC = acetylacetonate) magnetic luminescent nanomaterials show interesting superparamagnetic and photonic properties. The magnetic properties (M-H and ZFC/FC measurements) at temperatures of 5 and 300 K were explored to investigate the extent of coating and the crystallinity effect on the saturation magnetization values and blocking temperatures. Even though magnetite is a strong luminescence quencher, the coating of the Fe3O4 nanoparticles with synthetically functionalized rare earth complexes has overcome this difficulty. The intramolecular energy transfer from the T1 excited triplet states of TTA and ACAC ligands to the emitting levels of Eu(3+) and Tb(3+) in the nanomaterials and emission efficiencies are presented and discussed, as well as the structural conclusions from the values of the 4f-4f intensity parameters in the case of the Eu(3+) ion. These novel nanomaterials may act as the emitting layer for the red and green light for magnetic light-converting molecular devices (MLCMDs).

Compact Ag@Fe3O4 core-shell nanoparticles by means of single-step thermal decomposition reaction.

A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine.