Charge ordering and dielectric properties in the near half-doped Pr0.79Na0.21MnO3 perovskite

[Abstract] The Pr0.79Na0.21MnO3 perovskite has been prepared in polycrystalline form by a ceramic method. We have carried out its structural characterization by synchrotron X-ray powder diffraction (SXRPD) at room temperature and at 150 K (T<TCO). In the charge ordering (CO) state, the SXRPD data can be refined both on the basis of the site-centred model and the bond-centred model proposed for half-doped manganites, without a clear advantage of one model over the other. From the dielectric point of view, at the CO temperature this manganite shows a maximum in the dielectric constant whose origin is intrinsic, and cannot be attributed to the presence of extrinsic factors. We relate this dielectric behaviour to the formation of polar entities at the temperature of charge condensation, due to an asymmetric charge distribution intermediate between site-centred and bond-centred type.Xunta de Galicia; PGIDIT06PXB103298PRMinisterio de Educación y Ciencia; Project FEDER MAT 2004-0513

Efficient Separation of Heavy Metals by Magnetic Nanostructured Beads

This study reports the ability of magnetic alginate activated carbon (MAAC) beads to remove Cd(II), Hg(II), and Ni(II) from water in a mono-metal and ternary system. The adsorption capacity of the MAAC beads was highest in the mono-metal system. The removal efficiency of such metal ions falls in the range of 20–80% and it followed the order Cd(II) > Ni(II) > Hg(II). The model that best fitted in the ternary system was the Freundlich isotherm, while in the mono-system it was the Langmuir isotherm. The maximum Cd(II), Hg(II), and Ni(II) adsorption capacities calculated from the Freundlich isotherm in the mono-metal system were 7.09, 5.08, and 4.82 (mg/g) (mg/L)1/n, respectively. Lower adsorption capacity was observed in the ternary system due to the competition of metal ions for available adsorption sites. Desorption and reusability experiments demonstrated the MAAC beads could be used for at least five consecutive adsorption/desorption cycles. These findings suggest the practical use of the MAAC beads as efficient adsorbent for the removal of heavy metals from wastewaterThis research was supported by EP-INTERREG V A (POCTEP) Funds (project NANOEATERS/1378) and by the Consellería de Educación Program for Reference Research Groups project (GPC2017/015 and the Development of Strategic Grouping in Materials—AEMAT at the University of Santiago de Compostela under Grant No. ED431E2018/08, of the Xunta de GaliciaS

Apparent colossal dielectric constants in nanoporous Metal Organic Frameworks

[Abstract] In this work, we show that the hybrid material Co2(1,4-bdc)2(dabco)•[4DMF•1H2O], shows an apparent colossal dielectric constant at room temperature (r5000 at 300 K for =100 Hz). Nevertheless, such response does not imply colossal polarizability processes, as its dielectric constant is not purely intrinsic, but is greatly enhanced by the activation of extrinsic dielectric effects close to room temperature associated to the diffusion of numerous guest molecules through the channels. If such extrinsic contributions are eliminated or reduced, the values of the dielectric constant turn to be much smaller, as observed in the closely related Co2(1,4-bdc-NH2)2(dabco)•[7/2DMF•1H2O], Co2(1,4-ndc)2(dabco) •[3DMF•2H2O] and Ni2(1,4-bdc)2(dabco)•[3DMF•1/2H2O] compounds. Therefore, we warn about the imperious necessity of distinguishing between intrinsic and extrinsic effects in electrically inhomogenous MOF materials that display a certain conductivity in order to adequately interpret their dielectric behaviorMinisterio de Economía y Competitividad; MAT2010-21342-C02-01Xunta de Galicia; PGIDIT10PXB103272P

Multiferroic behavior in the new double-perovskite Lu2_2MnCoO6_6

We present a new member of the multiferroic oxides, Lu$_2$MnCoO$_6$, which we have investigated using X-ray diffraction, neutron diffraction, specific heat, magnetization, electric polarization, and dielectric constant measurements. This material possesses an electric polarization strongly coupled to a net magnetization below 35 K, despite the antiferromagnetic ordering of the $S = 3/2$ Mn$^{4+}$ and Co$^{2+}$ spins in an $\uparrow \uparrow \downarrow \downarrow$ configuration along the c-direction. We discuss the magnetic order in terms of a condensation of domain boundaries between $\uparrow \uparrow$ and $\downarrow \downarrow$ ferromagnetic domains, with each domain boundary producing a net electric polarization due to spatial inversion symmetry breaking. In an applied magnetic field the domain boundaries slide, controlling the size of the net magnetization, electric polarization, and magnetoelectric coupling

A simple solvothermal synthesis of MFe2O4 (M=Mn, Co and Ni) nanoparticles

This is the accepted manuscript of the following article: Yáñez-Vilar, S., Sánchez-Andújar, M., Gómez-Aguirre, C., Mira, J., Señarís-Rodríguez, M., & Castro-García, S. (2009). A simple solvothermal synthesis of MFe2O4 (M=Mn, Co and Ni) nanoparticles. Journal Of Solid State Chemistry, 182(10), 2685-2690. doi: 10.1016/j.jssc.2009.07.028Nanoparticles of MFe2O4 (M=Mn, Co and Ni), with diameters ranging from 5 to 10 nm, have been obtained through a solvothermal method. In this synthesis, an alcohol (benzyl alcohol or hexanol) is used as both a solvent and a ligand; it is not necessary, therefore, to add a surfactant, simplifying the preparation of the dispersed particles. We have studied the influence of the synthetic conditions (temperature, time of synthesis and nature of solvent) on the quality of the obtained ferrites and on their particle size. In this last aspect, we have to highlight that the solvent plays an important role on the particle size, obtaining the smallest diameters when hexanol was used as a solvent. In addition, the magnetic properties of the obtained compounds have been studied at room temperature (RT). These compounds show a superparamagnetic behaviour, as was expected for single domain nanoparticles, and good magnetization values. The maxima magnetization values of the MFe2O4 samples are quite high for such small nanoparticles; this is closely related to the high crystallinity of the particles obtained by the solvothermal methodThe authors are grateful for financial support from the MEC of Spain (Project CSD2006-00012 of Consolider-Ingenio 2010 Programme and FPI fellowship to S. Yáñez-Vilar), from the Xunta de Galicia (Project PGIDIT06PXIB103298PR, Rede Galega de Nanomedicina and Parga Pondal Programme) and from the EU (FEDER)S

Magnetoelectric behavior in the complex CaMn7O12 perovskite

This is the accepted manuscript of the following article: Sánchez-Andújar, M., Yáñez-Vilar, S., Biskup, N., Castro-García, S., Mira, J., Rivas, J., & Señarís-Rodríguez, M. (2009). Magnetoelectric behavior in the complex CaMn7O12 perovskite. Journal Of Magnetism And Magnetic Materials, 321(11), 1739-1742. doi: 10.1016/j.jmmm.2009.02.018We report a magnetoelectric effect in the double perovskite CaMn7O12, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (TN2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (TN2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic fieldThe authors are grateful from financial support for MEC (Spain) under project FEDER MAT 2007-66696 and Xunta de Galicia under project PGIDIT06PXB103298PR. S. Yáñez-Vilar want to thank to MEC of Spain for her FPI fellowship and M. Sánchez-Andújar acknowledges to Xunta de Galicia for support under program Parga PondalS

Development of Superparamagnetic Nanoparticles Coated with Polyacrylic Acid and Aluminum Hydroxide as an Efficient Contrast Agent for Multimodal Imaging

Early diagnosis of disease and follow-up of therapy is of vital importance for appropriate patient management since it allows rapid treatment, thereby reducing mortality and improving health and quality of life with lower expenditure for health care systems. New approaches include nanomedicine-based diagnosis combined with therapy. Nanoparticles (NPs), as contrast agents for in vivo diagnosis, have the advantage of combining several imaging agents that are visible using different modalities, thereby achieving high spatial resolution, high sensitivity, high specificity, morphological, and functional information. In this work, we present the development of aluminum hydroxide nanostructures embedded with polyacrylic acid (PAA) coated iron oxide superparamagnetic nanoparticles, Fe3O4@Al(OH)3, synthesized by a two-step co-precipitation and forced hydrolysis method, their physicochemical characterization and first biomedical studies as dual magnetic resonance imaging (MRI)/positron emission tomography (PET) contrast agents for cell imaging. The so-prepared NPs are size-controlled, with diameters below 250 nm, completely and homogeneously coated with an Al(OH)3 phase over the magnetite cores, superparamagnetic with high saturation magnetization value (Ms = 63 emu/g-Fe3O4), and porous at the surface with a chemical affinity for fluoride ion adsorption. The suitability as MRI and PET contrast agents was tested showing high transversal relaxivity (r2) (83.6 mM−1 s −1 ) and rapid uptake of 18F-labeled fluoride ions as a PET tracer. The loading stability with 18F-fluoride was tested in longitudinal experiments using water, buffer, and cell culture media. Even though the stability of the 18F-label varied, it remained stable under all conditions. A first in vivo experiment indicates the suitability of Fe3O4@Al(OH)3 nanoparticles as a dual contrast agent for sensitive short-term (PET) and high-resolution long-term imaging (MRI).This work was supported by the European Commission under the PANA project, Call H2020-NMP2015-two-stage, Grant 686009, and partially supported by the Consellería de Educación Program for the Development of Strategic Grouping in Materials—AEMAT at the University of Santiago de Compostela under Grant No. ED431E2018/08, Xunta de Galicia, and the Flemish Agency for Innovation by Science and Technology (IWT grant agreement n◦ 140061, SBO ‘NanoCoMIT’). Furthermore, we acknowledge infrastructure funding for the preclinical PET/MRI scanner from ‘Stichting tegen Kanker’ (STK 2015-145) and from the Hercules Stichting (AKUL/13/29). Frederik Cleeren is a Postdoctoral Fellow of The Research Foundation—Flanders (FWO; 12R3119N)S

Hybrid nanostructured magnetite nanoparticles: From bio-detection and theragnostics to regenerative medicine

Nanotechnology offers the possibility of operating on the same scale length at which biological processes occur, allowing to interfere, manipulate or study cellular events in disease or healthy conditions. The development of hybrid nanostructured materials with a high degree of chemical control and complex engineered surface including biological targeting moieties, allows to specifically bind to a single type of molecule for specific detection, signaling or inactivation processes. Magnetite nanostructures with designed composition and properties are the ones that gather most of the designs as theragnostic agents for their versatility, biocompatibility, facile production and good magnetic performance for remote in vitro and in vivo for biomedical applications. Their superparamagnetic behavior below a critical size of 30 nm has allowed the development of magnetic resonance imaging contrast agents or magnetic hyperthermia nanoprobes approved for clinical uses, establishing an inflection point in the field of magnetite based theragnostic agents.Fil: Piñeiro, Yolanda. Universidad de Santiago de Compostela; EspañaFil: González Gómez, Manuel. Universidad de Santiago de Compostela; EspañaFil: de Castro Alves, Lisandra. Universidad de Santiago de Compostela; EspañaFil: Arnosa Prieto, Angela. Universidad de Santiago de Compostela; EspañaFil: García Acevedo, Pelayo. Universidad de Santiago de Compostela; EspañaFil: Seco Gudiña, Román. Universidad de Santiago de Compostela; EspañaFil: Puig, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Teijeiro, Carmen. Universidad de Santiago de Compostela; EspañaFil: Yáñez Vilar, Susana. Universidad de Santiago de Compostela; EspañaFil: Rivas, José. Universidad de Santiago de Compostela; Españ

Multiple phase and dielectric transitions on a novel multi-sensitive [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) hybrid inorganic–organic perovskite family

The hybrid inorganic–organic [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) compounds, where TPrA is the tetrapropylammonium cation and dca is the dicyanamide anion, are unique multi-sensitive compounds that display multiple phases and dielectric transitions. These materials exhibit up to three first-order structural transitions (between the polymorphs I, Ia, Ib and II) associated with the same number of dielectric transitions in the temperature range of 210–360 K. The mechanisms responsible for these dielectric responses are found to be novel within the hybrid perovskites, involving ionic displacements of the A-site cations (TPrA) and order/disorder processes of the X anions (dca). In addition, the phase transitions and dielectric transition temperatures can be tuned by applying external hydrostatic pressure or by inducing internal pressure by modifying the tolerance factor through ionic substitution in the B-sites. This multi-sensitive response towards temperature, external and internal pressure opens up promising technological applications for this family of materials, such as dielectric transductors or multistimuli-sensors, whose response can be modulated in a wide range of temperatures and pressuresThe authors are grateful for the financial support from Ministerio de Economía y Competitividad MINECO (MINECO) ENE2014-56237-C4-4-R and Xunta de Galicia under the project GRC2014/042. J. M. B.-G. also wants to thank Barrié Foundation for a predoctoral fellowship and S. Y.-V. to the Xunta de Galicia for a postdoctoral grant (Plan I2C)S

Carbon-Coated Superparamagnetic Nanoflowers for Biosensors Based on Lateral Flow Immunoassays

Superparamagnetic iron oxide nanoflowers coated by a black carbon layer (Fe3O4@C) were studied as labels in lateral flow immunoassays. They were synthesized by a one-pot solvothermal route, and they were characterized (size, morphology, chemical composition, and magnetic properties). They consist of several superparamagnetic cores embedded in a carbon coating holding carboxylic groups adequate for bioconjugation. Their multi-core structure is especially efficient for magnetic separation while keeping suitable magnetic properties and appropriate size for immunoassay reporters. Their functionality was tested with a model system based on the biotin–neutravidin interaction. For this, the nanoparticles were conjugated to neutravidin using the carbodiimide chemistry, and the lateral flow immunoassay was carried out with a biotin test line. Quantification was achieved with both an inductive magnetic sensor and a reflectance reader. In order to further investigate the quantifying capacity of the Fe3O4@C nanoflowers, the magnetic lateral flow immunoassay was tested as a detection system for extracellular vesicles (EVs), a novel source of biomarkers with interest for liquid biopsy. A clear correlation between the extracellular vesicle concentration and the signal proved the potential of the nanoflowers as quantifying labels. The limit of detection in a rapid test for EVs was lower than the values reported before for other magnetic nanoparticle labels in the working range 0–3 × 107 EVs/μL. The method showed a reproducibility (RSD) of 3% (n = 3). The lateral flow immunoassay (LFIA) rapid test developed in this work yielded to satisfactory results for EVs quantification by using a precipitation kit and also directly in plasma samples. Besides, these Fe3O4@C nanoparticles are easy to concentrate by means of a magnet, and this feature makes them promising candidates to further reduce the limit of detectionThis work was supported in part by Spanish Ministry of Economy and Competitiveness under projects MAT2017-84959-C2-1-R and the Principality of Asturias (Spain) under project IDI/2018/000185 and the Consellería de Educación Program for Development of a Strategic Grouping in Materials (AEMAT) at the University of Santiago de Compostela under Grant No. ED431E208/08, Xunta de Galicia. Amanda Moyano was supported by a “Severo Ochoa” fellowship (Consejería de Educación y Cultura del Gobierno del Principado de Asturias, grant BP17-152)S