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Nanomaterials (Basel) ; 9(7)2019 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-31261832


Superparamagnetic iron oxide nanoparticles (SPIONs) have shown great potential in biomedicine due to their high intrinsic magnetization behaviour. These are small particles of magnetite or maghemite, and when coated, their surface oxidation is prevented, their aggregation tendency is reduced, their dispersity is improved, and the stability and blood circulation time are increased, which are mandatory requirements in biomedical applications. In this work, SPIONs were synthesized in air through a reduction-precipitation method and coated with four different polymers (Polyethylene glycol(PEG) 1000/6000 and dextran T10/T70). All the synthesized samples were structurally and magnetically characterized by transmission electron microscopy, Fourier transform infra-red spectroscopy, X-ray powder diffraction, Mössbauer spectroscopy, and Superconducting Quantum Interference Device (SQUID) magnetometry. SPIONs centrifuged and dried in vacuum with an average diameter of at least 7.5 nm and a composition ≤60% of maghemite and ≥40% of magnetite showed the best magnetization results, namely a saturation magnetization of ~64 emu/g at 300 K, similar to the best reported values for SPIONs prepared in controlled atmosphere. As far as SPIONs' coatings are concerned, during their preparation procedure, surface polymers must be introduced after the SPIONs' precipitation. Furthermore, polymers with shorter chains do not affect the SPIONs' magnetization performance, although longer chain polymers significantly decrease the coated particle magnetization values, which is undesirable.

Chemosphere ; 223: 171-179, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30776762


Old mine tailings from Northern and Central Portugal were studied in order to perform a radiological and chemical characterization. The evaluation of massic activity of natural radionuclides and concentrations in tailings of polymetallic and Ra/U mines was performed by gamma spectrometry and neutron activation analysis. Iron speciation was carried out by Mössbauer spectroscopy. In polymetallic tailings with physical ore processing (Cumieira and Verdes - exploited for Sn, Nb-Ta) higher contents of Th, 228Ra and 226Ra in the coarser materials occur, probably due to their presence in host rock and ore fragments. In finer tailings, washing may explain the lower 226Ra and 210Pb massic activity. In tailings with physical/chemical ore processing (Covas - exploited for W and Sn) high U contents and a tendency for higher 226Ra and 210Pb massic activity in the fine materials is observed, probably due to their incorporation in nano-sized particles of iron oxides. A high variation of the 210Pb/226Ra ratio occurs in polymetallic tailings; a deficit of 210Pb can be observed particularly in deposits of settling tanks drained from dumps of chemically treated ore. In Ervideira-Mestras tailings (Ra/U exploitation) where no ore process in situ was performed, a near equilibrium between 210Pb and 226Ra occurs. Dose risk assessment was carried out by calculating external outdoor Annual Effective Dose Rate; the dose rates in air due to terrestrial gamma radiation are low for the polymetallic tailings (<47 nGy/h), and higher for tailings of Ra/U (up to 4130 nGy/h), in the worst scenario.

Mineração , Radioisótopos/análise , Poluentes Radioativos do Solo/análise , Raios gama , Radioisótopos de Chumbo/análise , Portugal , Rádio (Elemento)/análise , Medição de Risco , Espectrometria gama , Urânio/análise
Inorg Chem ; 58(1): 133-142, 2019 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-30547570


We report the synthesis and characterization of three fluoride-rich barium iron phosphates Ba xFe x(PO4)F y (1 ≤ x ≤ 3, 2 ≤ y ≤ 12), which exhibited abundant structural chemistry, exhibiting diverse frameworks and connecting modes between [FeO nF6- n] m- octahedra surrounding Fe2+ or Fe3+ ions. BaFe(PO4)F2 (I) consisted of two-dimensional [Fe(PO4)F2]2- sheets built from linear ∞[Fe2O6F4]10- moieties formed by fluorine corner-sharing FeO4F2 and FeO2F4 octahedra with linking PO4 tetrahedra. Mixed-valence Ba2Fe2(PO4)F6 (II) possessed a three-dimensional framework containing Fe4O6F12 tetramers formed by the edge-sharing oxygen or fluorine atoms of cis-FeF4O2 octahedra. Ba3Fe3(PO4)F12 (III) contained one-dimensional columns of ∞[Fe3(PO4)F12]6- infinite sections built from cis-FeF4O2 and FeF5O octahedra and tetrahedral PO4 linkers. The magnetic characterization of Ba xFe x(PO4)F y unveiled diverse magnetism: an S = 5/2 spin chain for (I), a weak ferrimagnet or canted antiferromagnet for (II) thanks to the presence of distinct Fe2+ and Fe3+ sites identified by Mössbauer spectroscopy, and coupled spin-trimers for (III).

Phys Chem Chem Phys ; 18(31): 21881-92, 2016 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-27439896


The results reported here represent the first direct experimental observations supporting the existence of a solid-to-solid phase transition induced by thermal treatment in magnetic ionic liquids (MILs). The phase transitions of the solid phases of 1,3-dimethylimidazolium tetrachloroferrate, DimimFeCl4, are closely related to its thermal history. Two series of solid-to-solid phase transitions can be described in this MIL: (i) from room temperature (RT) phase II [space group (s.g.) = P21] to phase I-a [s.g. = P212121] via thermal quenching or via fast cooling at T > 2 K min(-1); (ii) from phase I-a to phase I-b [s.g. = P21/c] when the temperature was kept above 180 K for several minutes. The latter involves a slow translational and reorientational dynamical process of both the imidazolium cation and the tetrachloroferrate anion and has been characterized using synchrotron and neutron powder diffraction and DFT (density functional theory) studies. The transition is also related to the modification of the super-exchange pathways of low-temperature phases which show a overall antiferromagnetic behavior. A combination of several experimental methods such as magnetometry, Mössbauer and muon spectroscopy together with polarized and non-polarized neutron powder diffraction has been used in order to characterize the different features observed in these phases.

J Am Chem Soc ; 137(37): 11924-7, 2015 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-26340106


Reaction of the polysulfonated triazole ligand L = 4-(1,2,4-triazol-4-yl)ethanedisulfonate) with iron(II) salts in water yields the trimeric species [Fe3(µ-L)6(H2O)6](6-). This polyanion, as the dimethylammonium salt, shows a thermally induced spin transition above room temperature for the central Fe position in the trimer with a large hysteresis cycle (>85 K) and remarkably slow dynamics. This allows easy quenching of the metastable high-spin (HS) state via gradual cooling (5 K min(-1)). Once it is trapped, the HS state remains metastable. Thermal energy is not able to promote relaxation into the low-spin ground state below 215 K, with a characteristic TTIESST = 250 K, the highest temperature ever observed for thermal trapping of an excited spin state in a switchable molecular material.

Inorg Chem ; 53(16): 8384-96, 2014 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-25079377


We present the first magnetic phase of an ionic liquid with anion-π interactions, which displays a three-dimensional (3D) magnetic ordering below the Néel temperature, TN = 7.7 K. In this material, called Dimim[FeBr4], an exhaustive and systematic study involving structural and physical characterization (synchrotron X-ray, neutron powder diffraction, direct current and alternating current magnetic susceptibility, magnetization, heat capacity, Raman and Mössbauer measurements) as well as first-principles analysis (density functional theory (DFT) simulation) was performed. The crystal structure, solved by Patterson-function direct methods, reveals a monoclinic phase (P21 symmetry) at room temperature with a = 6.745(3) Å, b = 14.364(3) Å, c = 6.759(3) Å, and ß = 90.80(2)°. Its framework, projected along the b direction, is characterized by layers of cations [Dimim](+) and anions [FeBr4](-) that change the orientation from layer to layer, with Fe···Fe distances larger than 6.7 Å. Magnetization measurements show the presence of 3D antiferromagnetic ordering below TN with the existence of a noticeable magneto-crystalline anisotropy. From low-temperature neutron diffraction data, it can be observed that the existence of antiferromagnetic order is originated by the antiparallel ordering of ferromagnetic layers of [FeBr4](-) metal complex along the b direction. The magnetic unit cell is the same as the chemical one, and the magnetic moments are aligned along the c direction. The DFT calculations reflect the fact that the spin density of the iron ions spreads over the bromine atoms. In addition, the projected density of states (PDOS) of the imidazolium with the bromines of a [FeBr4](-) metal complex confirms the existence of the anion-π interaction. Magneto-structural correlations give no evidence for direct iron-iron interactions, corroborating that the 3D magnetic ordering takes place via superexchange coupling, the Fe-Br···Br-Fe interplane interaction being defined as the main exchange pathway.