Paramagnetic Fe3 Research Articles

Effect of polymer coating on magnetocaloric properties of garnet

In this study, Gd3Fe5O12 nanoparticles were synthesized using the sol–gel autocombustion method and subsequently coated with polyvinylpyrrolidone (PVP) polymer. The study focuses on understanding the influence of PVP coating on garnet particles’ magnetic and magnetocaloric properties. The crystallite size upon PVP-coating remained unaltered, but the grain size and surface area of coated particles increased. The magnetization of PVP-coated particles decreased by around 11% as compared to the uncoated particles at 5 K. Mössbauer and photoelectron spectroscopy confirmed the presence of a paramagnetic phase Fe3+ in the PVP-coated nanoparticles responsible for the reduction in magnetization value. The maximum value of magnetic entropy change (−ΔS m ) for uncoated Gd3Fe5O12 was 3.78 Jkg−1 K−1 at 37.5 K with a 5T applied field, accompanied by a relative cooling power (RCP) of 382 Jkg−1. On the other hand, for PVP-coated Gd3Fe5O12, the maximum −ΔS m was 3.38 Jkg−1 K−1 at 57.5 K with a 5T applied field, and the RCP was 308 Jkg−1. The observed maximum magnetic entropy changes at higher temperatures for the PVP-coated Gd3Fe5O12 sample are noteworthy. This characteristic indicates that the PVP-coated garnet may have an advantage in terms of usability over a wider temperature range compared to the uncoated counterpart, which can potentially be a promising material for applications in cryogenic temperature magnetic refrigeration.

Iron-based compounds coordinated with phospho-polymers as biocompatible probes for dual 31P/1H magnetic resonance imaging and spectroscopy

In this work, we present the synthesis and evaluation of magnetic resonance (MR) properties of novel phosphorus/iron-containing probes for dual 31P and 1H MR imaging and spectroscopy (MRI and MRS). The presented probes are composed of biocompatible semitelechelic and multivalent phospho-polymers based on poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC) coordinated with small paramagnetic Fe3+ ions or superparamagnetic maghemite (γ-Fe2O3) nanoparticles via deferoxamine group linked to the end or along the polymer chains. All probes provided very short 1H T1 and T2 relaxation times even at low iron concentrations. The presence of iron had a significant impact on the shortening of 31P relaxation, with the effect being more pronounced for probes based on γ-Fe2O3 and multivalent polymer. While the water-soluble probe having one Fe3+ ion per polymer chain was satisfactorily visualized by both 31P-MRS and 31P-MRI, the probe with multiple Fe3+ ions could only be detected by 31P-MRS, and the probes consisting of γ-Fe2O3 nanoparticles could not be imaged by either technique due to their ultra-short 31P relaxations. In this proof-of-principle study performed on phantoms at a clinically relevant magnetic fields, we demonstrated how the different forms and concentrations of iron affect both the 1H MR signal of the surrounding water molecules and the 31P MR signal of the phospho-polymer probe. Thus, this double contrast can be exploited to simultaneously visualize body anatomy and monitor probe biodistribution.

Structural and Electrical Properties of Novel Cr/Fe Mixed Transition-Metal Phosphates.

The phosphate KCoCr(PO4)2 and iron-substituted variants KCoCr1-xFex(PO4)2 (x = 0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route, while a high substitution level of Fe was achieved. Their structures were refined using powder X-ray diffraction and indexed in a monoclinic system with a P21/n space group. A 3D framework with six-sided tunnels parallel to the [101] direction was formed in which the K atoms are located. Mössbauer spectroscopy confirms the exclusive presence of octahedral paramagnetic Fe3+ ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr3+ ions. The activation energy, determined by dielectric measurements, shows that the iron-containing samples present higher ionic activity. Relative to the electrochemical activity of K, these materials could be good candidates for positive and/or negative electrode materials for energy storage applications.

Chitosan based sorafenib tosylate loaded magnetic nanoparticles: Formulation and in-vitro characterization

Biocompatible magnetic nanoparticles are used for various biomedical applications. This study reported the development of nanoparticles with magnetic properties by embedding magnetite particles in the drug-loaded, crosslinked matrix of chitosan. Sorafenib tosylate-loaded magnetic nanoparticles were prepared by a modified ionic-gelation method. Particle size, zeta potential, polydispersity index, and entrapment efficiency of nanoparticles were in the range of 95.6 ± 3.4 nm to 440.9 ± 7.3 nm, 12.8 ± 0.8 mV to 27.3 ± 1.1 mV, 0.289 ± 0.011 to 0.571 ± 0.011, and 54.36 ± 1.26 % to 79.67 ± 1.40 %, respectively. The XRD spectrum of formulation CMP-5 confirmed the amorphous nature of the loaded drug in nanoparticles. TEM image confirmed the spherical shape of nanoparticles. Atomic force microscopic image of formulation CMP-5 indicated a mean surface roughness of 10.3597 nm. The magnetization saturation of formulation CMP-5 was 24.74 emu/g. Electron paramagnetic resonance spectroscopy revealed that formulation CMP-5's g-Lande's factor was 4.27, which was extremely near to the 4.30 (usual for Fe3+ ions). Residual paramagnetic Fe3+ ions may be responsible for paramagnetic origin. The data suggests superparamagnetic nature of particles. Formulations released 28.66 ± 1.22 % to 53.24 ± 1.95 % and 70.13 ± 1.72 % to 92.48 ± 1.32 % of the loaded drug after 24 h in pH 6.8 and pH 1.2, respectively. The IC50 value of formulation CMP-5 was 54.75 μg/mL in HepG2 (human hepatocellular carcinoma cell lines).

SiCNFe Ceramics as Soft Magnetic Material for MEMS Magnetic Devices: A Mössbauer Study.

Polymer-derived SiCNFe ceramics is a prospective material that can be used as soft magnets in MEMS magnetic applications. The optimal synthesis process and low-cost appropriate microfabrication should be developed for best result. Homogeneous and uniform magnetic material is required for developing such MEMS devices. Therefore, the knowledge of exact composition of SiCNFe ceramics is very important for the microfabrication of magnetic MEMS devices. The Mössbauer spectrum of SiCN ceramics, doped with Fe (III) ions, and annealed at 1100 °C, was investigated at room temperature to accurately establish the phase composition of Fe-containing magnetic nanoparticles, which were formed in this material at pyrolysis and which determine their magnetic properties. The analysis of Mössbauer data shows the formation of several Fe-containing magnetic nanoparticles in SiCN/Fe ceramics, such as α-Fe, FexSiyCz, traces of Fe-N and paramagnetic Fe3+ with octahedral oxygen environment. The presence of iron nitride and paramagnetic Fe3+ ions shows that the pyrolysis process was not completed in SiCNFe ceramics annealed at 1100 °C. These new observations confirm the formation of different Fe-containing nanoparticles with complex composition in SiCNFe ceramic composite.

Iminobenzophenone-thiophen hydrazide schiff base: a selective turn on sensor for paramagnetic Fe3+ ion and application in real sample analysis.

A highly selective turn-on sensor for paramagnetic Fe3+ ions based on (E)-N'-((2-aminophenyl)(phenyl)methylene)thiophene-2-carbohydrazide is successfully synthesized. The sensor BPTH is significantly selective and sensitive towards Fe3+ ions over other interfering metal ions especially Cu2+ and Co2+ ions with a lowest limit of recognition 1.48 × 10-7M. The turn-on sensing mechanism involves enhanced charge transfer. Fe3+ ion forms strong binding with the ligand with a Ka value about 8.23 × 104M-1 and a 1:1 stoichiometric ratio is confirmed by Job's plot experiment. With Fe3+ ion, the yellow ligand BPTH change to a green fluorescent and reversible with 1 equivalent of EDTA. Practical application of sensor is demonstrated in real sample analysis.

Theoretical and experimental studies on mechanochromic triphenylamine based fluorescent “ON-OFF-ON” sensor for sequential detection of Fe3+ and deferasirox

A novel triphenylamine (TPA) based sensor TTU was rationally designed and synthesized that exhibited reversible mechanochromic and aggregation induced emission enhancement (AIEE) properties. The AIEE active sensor was employed for fluorometric detection of Fe3+ in aqueous medium, with distinguished selectivity. The sensor showed a highly selective quenching response towards Fe3+ that is ascribed to complex formation with paramagnetic Fe3+. Subsequently, TTU-Fe3+ complex acted as a fluorescence sensor for the detection of deferasirox (DFX). The subsequent addition of DFX to TTU-Fe3+ complex led to the recovery of fluorescence emission intensity of sensor TTU that was attributed to the displacement of Fe3+ by DFX and release of sensor TTU. The proposed sensing mechanisms for Fe3+ and DFX was confirmed through 1H NMR titration experiment and DFT calculations. Frontier molecular orbitals (FMO), density of states (DOS), natural bond orbital (NBO), non-covalent interaction (NCI) and electron density difference (EDD) analysis were performed using DFT calculations to support the experimental results. Moreover, sensor TTU displayed colorimetric detection of Fe3+. Further, the sensor was employed for the detection of Fe3+ and DFX in real water samples. Finally, logic gate was fabricated by using sequential detection strategy.

Preferential preservation of pre-aged terrestrial organic carbon by reactive iron in estuarine particles and coastal sediments of a large river-dominated estuary

Reactive iron (FeR) plays an important role in the preservation of organic carbon (OC) in coastal sediments, yet changes in the OC bound to FeR (OC-FeR), during transport and deposition, remain poorly understood. The main goal of this work is to investigate the variation of the age and composition of OC-FeR from estuarine suspended particulate matter (SPM) to coastal sediments, to further understand the role of FeR in the preservation of terrestrial OC exported from large rivers into marginal seas. We examined OC and its carbon isotopic composition (Δ14Cbulk, δ13Cbulk), specific surface area (SSA), grain size composition, lignin phenols, FeR, Mössbauer spectroscopy, and isotopic signatures of OC-FeR (Δ14COC-FeR, δ13COC-FeR) in SPM and surface sediments of the Changjiang Estuary. Particulate OC (POC) and FeR concentrations in SPM are significantly higher than in surface sediments, with no significant differences between surface- and bottom-water SPM. This indicates that loss of OC and FeR largely occurs at the sediment–water interface due in part, to rapid Fe cycling. The percentage of OC-FeR (fOC-FeR) in SPM (6.6 ± 1.9%) is similar to that in mobile-mud sediment (8.8 ± 1.8%). There are no significant differences in OC-FeR content (p > 0.05) from SPM to mobile-mud sediments, but non-OC-FeR largely decreases, suggesting that terrestrial OC-FeR has greater stability compared to terrestrial non-OC-FeR. Both δ13COC-FeR and Δ14COC-FeR are lower than bulk OC, indicating that FeR is mainly associated with pre-aged soil OC of terrestrial plant origin, especially in estuarine SPM and mobile-mud sediments. Taken together, binding with FeR is a potential long-term protection mechanism for terrestrial OC. Both Δ14Cbulk and Δ14COC-FeR decrease with an increase in the ratio of hematite to (super)paramagnetic Fe3+, indicating that high-crystallinity iron oxide is largely associated with pre-aged terrestrial OC, and there is a potential joint maturation mechanism between FeR and its associated OC. Based on literature comparisons of soils, estuarine SPM, and marine sediments, OC-FeR associations are controlled mainly by sedimentary regimes, FeR compositions, and OC sources. This work supports the notion that FeR plays an important role in the stabilization and transport of river-derived terrestrial OC.

Thermostimulated crystal structure transformation of the polymineral clay submicron particles

Changes in the structure of phyllosilicate microparticles of submicron fractions of polymineral clay with an average size of 290 nm, as well as changes in the positions of impurity ions of transition metals in the crystal lattice, were studied by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and high-resolution electron paramagnetic resonance spectroscopy. The main composition of microparticles included clinochlore, montmorillonite, calcite, and quartz. Structural transformations were stimulated by heating the samples to 1200 K at a rate of 10 K/min. A decrease in the number of crystal structures of microparticles was recorded due to the amorphization of montmorillonite, the decomposition of calcite, and the formation of sillimanite. Structural rearrangements of crystal cells containing impurity paramagnetic ions Fe3+ and Mn2+ in submicron particles of clinochlore and montmorillonite, accompanied by displacements and changes in the chemical bonds of these ions, were recorded by the ion-electron paramagnetic resonance method. It is shown that when microparticles were heated to 1200 K, the impurity paramagnetic ions of transition metals did not go beyond their crystal cells.

19F MRI-fluorescence imaging dual-modal cell tracking with partially fluorinated nanoemulsions.

As a noninvasive "hot-spot" imaging technology, fluorine-19 magnetic resonance imaging (19F MRI) has been extensively used in cell tracking. However, the peculiar physicochemical properties of perfluorocarbons (PFCs), the most commonly used 19F MRI agents, sometimes cause low sensitivity, poor cell uptake, and misleading results. In this study, a partially fluorinated agent, perfluoro-tert-butyl benzyl ether, was used to formulate a 19F MRI-fluorescence imaging (FLI) dual-modal nanoemulsion for cell tracking. Compared with PFCs, the partially fluorinated agent showed considerably improved physicochemical properties, such as lower density, shorter longitudinal relaxation times, and higher solubility to fluorophores, while maintaining high 19F MRI sensitivity. After being formulated into stable, monodisperse, and paramagnetic Fe3+-promoted nanoemulsions, the partially fluorinated agent was used in 19F MRI-FLI dual imaging tracking of lung cancer A549 cells and macrophages in an inflammation mouse model.

Iron-doped calcium phytate nanoparticles as a bio-responsive contrast agent in 1H/31P magnetic resonance imaging

We present the MR properties of a novel bio-responsive phosphorus probe doped with iron for dual proton and phosphorus magnetic resonance imaging (1H/31P-MRI), which provide simultaneously complementary information. The probes consist of non-toxic biodegradable calcium phytate (CaIP6) nanoparticles doped with different amounts of cleavable paramagnetic Fe3+ ions. Phosphorus atoms in the phytate structure delivered an efficient 31P-MR signal, with iron ions altering MR contrast for both 1H and 31P-MR. The coordinated paramagnetic Fe3+ ions broadened the 31P-MR signal spectral line due to the short T2 relaxation time, resulting in more hypointense signal. However, when Fe3+ was decomplexed from the probe, relaxation times were prolonged. As a result of iron release, intensity of 1H-MR, as well as the 31P-MR signal increase. These 1H and 31P-MR dual signals triggered by iron decomplexation may have been attributable to biochemical changes in the environment with strong iron chelators, such as bacterial siderophore (deferoxamine). Analysing MR signal alternations as a proof-of-principle on a phantom at a 4.7 T magnetic field, we found that iron presence influenced 1H and 31P signals and signal recovery via iron chelation using deferoxamine.

Insights into the Gelation Mechanism of Metal-Coordinated Hydrogels by Paramagnetic NMR Spectroscopy and Molecular Dynamics

Metal-coordination complexes are attracting increasing attention as supramolecular cross-linkers to develop polymeric hydrogel networks with tunable and dynamic mechanical properties. Nonetheless, the rational design of these materials is still hindered by the limited mechanistic understanding of how metal–ligand interactions influence the structure and properties of the hydrogel. Here, we report a detailed mechanistic investigation using nuclear magnetic resonance (NMR) spectroscopy combined with molecular dynamics (MD) simulations to explore the formation of cellulose-based hydrogels induced by coordination with paramagnetic Fe3+ ions. We demonstrate how NMR paramagnetic relaxation enhancement can be used to probe the distances between the metal center and NMR active nuclei on the polymer chain, informing on the metal–ligand coordination network. Experimental results, together with supporting MD simulations, allow us to uncover a structuration of water around the cross-linked metals within the hydrogel, in addition to the establishment of different orientations of the chains governed by hydrogen bonds networks. Progress in understanding the gelation mechanism of metal-coordinated hydrogels will fuel their exploitation for a wide variety of biomedical applications.

An investigation on the heat dissipation in Zn-substituted magnetite nanoparticles, coated with citric acid and pluronic F127 for hyperthermia application

Zinc substituted spinel ferrite nanoparticles are appropriate for magnetic fluid hyperthermia. Stable suspensions of Zn2+ substituted magnetite (ZnxFe3-xO4, 0 ≤ x ≤ 0.20) nanoparticles in aqueous solutions (pH 5.5) were synthesized by means of co-precipitation approach, using citric acid (CA) and pluronic F127 as surfactants for hyperthermia application. The specimens were characterized by different methods. XRD patterns of the precipitates confirmed that all specimens have single phase cubic spinel structures and their lattice parameters increased as Zn2+ content increased. Mean crystallite sizes of the uncoated specimens were determined to be around 28 nm, using Scherrer's formula. By increasing the Zn2+ content, Curie temperature of the uncoated specimens reduced from 545 to 410 °C monotonically caused by reduction in super-exchange interactions. Room temperature saturation magnetizations of the uncoated specimens increased to 98.8 emu/g for x = 0.10 initially, and then decreased to 79.6 emu/g for x = 0.20. It is attributed to the replacement of paramagnetic Fe3+ ions by diamagnetic Zn2+ ones and spin canting. FTIR spectra reconfirmed formation of pure magnetite and Zn2+ substituted magnetite nanoparticles and also proved the presence of ligands on the surface of the nanoparticles. TEM investigation showed that mean particle sizes of the coated nanoparticles were in the range of 35–40 nm. The obtained ferrofluids showed a good stability in aqueous medium (pH 5.5) and according to the room temperature magnetic measurements, heating efficiency is scarcely released due to relaxation processes. Maximum obtained specific loss power (SLP) was 539 W/g and that of intrinsic loss power (ILP) was 7.26 nHm2/kg for x = 0.05 (f = 290 kHz, H = 16 kA/m) with a nanoparticle concentration as low as 1.2 mg/ml, which is a promising candidate for magnetic hyperthermia applications potentially.

Effect of magnetic field on stress corrosion cracking induced by Sulfate-reducing bacteria

Buried pipes are often affected by microorganisms and magnetic fields. In this paper, the stress corrosion cracking (SCC) behavior of X80 steel under the combined effect of magnetic field (MF) and sulfate-reducing bacteria (SRB) was studied by electrochemical and slow strain rate tensile testing. The synergistic effect of MF and SRB on SCC was expounded for the first time. Results confirmed that the sensitivity of SCC increased under 0~20 mT, which was attributable to the fact that the MF promoted the entry of diamagnetic corrosion anions into the corrosion pit and accelerated the paramagnetic Fe2+ to detach from the steel surface. MF and SRB not only independently improved the stress corrosion sensitivity of steel, but also had a synergistic effect. MF changed the arrangement of the biofilm. At 30 mT, the sensitivity of SCC decreased, which was due to the excessive MF inhibited the growth of SRB.

Investigation of low-energy electronic excitations in quasi-one-dimensional Ising antiferromagnet CsFeCl3 · 2H2O via Raman spectroscopy

The frequencies of low-lying electronic excitations in the quasi-one-dimensional antiferromagnet CsFeCl3 · 2H2O were determined by Raman spectroscopy. The lowest of them (57 cm−1) was attributed to the magnon-like excitation of the chain of Ising spins of paramagnetic Fe2+ ions. And the next one (77 cm−1) can most likely be attributed to the exciton-like one, associated with the electronic transition to the lower level of the excited orbital quasi-doublet dzx, dzy split by the spin-orbit interaction. Investigations of the splittings and shifts of Raman lines in an external magnetic field allowed us to estimate the values of the magnetic moments of the sublattices in the ground state and to determine their spatial orientation relative to the crystallographic directions.

Сolloidal probe based on iron(III)-doped calcium phytate nanoparticles for 31P NMR monitoring of bacterial siderophores

A conceptually new class of probes was developed for detection of bacterial siderophores (BSPs), important determinants of virulence and pathogenicity, using 31P nuclear magnetic resonance (31P NMR). These probes are based on biodegradable nontoxic nanoparticles of calcium phytate (CaIP6), which possess measurable signal on 31P NMR spectra. The nanoparticles were doped with paramagnetic Fe3+ ions broadening the magnetic resonance signal of 31P. Therefore, the nanoparticles were not detectable by 31P NMR in the environment not containing BSPs, however, in the presence of BSPs, the Fe3+ ion is released from the nanoparticles, and the 31P NMR signal become detectable. In vitro demonstration of this Fe3+ release was performed with BSP deferoxamine (DFO), exhibiting a complete depletion of Fe3+ within 2 h for the nanoparticles containing 17.7 mol% Fe (III). The Fe3+ depletion was accompanied with a restoration of 31P NMR signal.

Structural, magnetic and Mössbauer studies of Nd 0.6Sr0.4FexMn1-xO3 perovskites

The effect of iron doping on the structural and magnetic properties of the manganite perovskites Nd0.6Sr0.4FexMn1-xO3 (0.1 ≤ x ≤ 1.0) was studied. Auto-combustion sol-gel method was used to prepare the compounds. X-ray diffraction refinement indicated that all the compounds crystallized in orthorhombic single-phase with Pnma space group. Scanning electron microscopy micrographs revealed a group of packed grains of about 0.2–1.0 μm whereas the average particle size was found to be in the range of about 40–80 nm via transmission electron microscopy. The zero-field cooled and field cooled magnetization curves, under an applied magnetic field of 0.02 T, revealed that the samples with 0.1 ≤ x ≤ 0.4 exhibit a paramagnetic to ferromagnetic transition with decreasing temperature while the samples with (0.5 ≤ x ≤ 1.0) do not demonstrate such phase transition. At room temperature the dependence of magnetization on the x iron concentration, as revealed by the corresponding M − H curves, can be interpreted as the cumulative result of changes in superparamagnetic, paramagnetic and antiferromagnetic contributions. 57Fe transmission Mӧssbauer spectra were recorded at room-temperature (295 K) and liquid nitrogen temperature (78 K) for all the samples. Iron ions were found to be present in these compounds exclusively in a paramagnetic high-spin Fe3+ state for 0.1 ≤ x ≤ 0.5 at 295 K and for 0.1 ≤ x ≤ 0.3 at 78 K. At higher iron concentrations an antiferromagnetic state of iron clusters is formed due to the Fe3+ – Fe3+ superexchange interaction. Room temperature 57Fe quadrupole splitting was found to increase near linearly with the x iron concentration up to x = 0.6. For x ≥ 0.6 the formation of paramagnetic Fe4+ is observed at 295 K, which at lower temperatures undergoes charge disproportionation leading to the appearance of Fe5+ species as observed at 78 K. Perturbations of the magnetic state of iron ions was found to lead to substantial broadening of the Mössbauer absorption peaks of magnetic components, which is interpreted as the effect of nearest neighbor Fe5+ and Mn ions at 78 K, and as that of electron-hopping related Fe3+ - Fe4+ valence fluctuations at 295 K.

Valleriite, a Natural Two-Dimensional Composite: X-ray Absorption, Photoelectron, and Mössbauer Spectroscopy, and Magnetic Characterization.

Valleriite is of interest as a mineral source of basic and precious metals and as an unusual material composed of two-dimensional (2D) Fe–Cu sulfide and magnesium hydroxide layers, whose characteristics are still very poorly understood. Here, the mineral samples of two types with about 50% of valleriites from Noril’sk ore provenance, Russia, were examined using Cu K- and Fe K-edge X-ray absorption fine structure (XAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), 57Fe Mössbauer spectroscopy, and magnetic measurements. The Cu K X-ray absorption near-edge structures (XANES) spectra resemble those of chalcopyrite, however, with a higher electron density at Cu+ centers and essentially differ from those of bornite Cu5FeS4; the Fe K-edge was less informative because of accompanying oxidized Fe-containing phases. The post-edge XANES and extended XAFS (EXAFS) analysis reveal differences in the bond lengths, e.g., additional metal–metal distances in valleriites as compared with chalcopyrite. The XPS spectra confirmed the Cu+ and Fe3+ state in the sulfide sheets and suggest that they are in electron equilibrium with (Mg, Al) hydroxide layers. Mössbauer spectra measured at room temperature comprise central doublets of paramagnetic Fe3+, which decreased at 78 K and almost disappeared at 4.2 K, producing a series of hyperfine Zeeman sextets due to internal magnetic fields arising in valleriites. Magnetic measurements do not reveal antiferromagnetic transitions known for bornite. The specific structure and properties of valleriite are discussed in particular as a platform for composites of the 2D transition metal sulfide and hydroxide (mono)layers stacked by the electrical charges, promising for a variety of applications.

Oscillations of EPR Signals Accompanying Belousov–Zhabotinsky Reaction

Periodical transformation of ferroin to ferriin is accompanied by changes in magnetic properties of liquids during Belousov–Zhabotinsky (BZ) reaction malonic acid, sodium bromide, sodium bromate, ferroin, and sulfuric acid. Instead of the earlier studied oscillation of microwave conductivity accompanying an oscillating reaction, we propose a flash technique to interrupt the BZ reaction by rapid freezing. Rapid cooling of a solution during chemical oscillations results in a frozen system with a fixed concentration of paramagnetic centers Fe3+. EPR spectrum recorded at different stages of the interrupted reaction corresponds to the exact concentration of the ferroin and ferriin components. Following unfreezing unblocks the BZ reaction, and oscillations are still observed. A simulated spectrum allows one to distinguish two groups of Fe3+ ions of different symmetries. The obtained results are important to explain the earlier observed effect of inhomogeneous magnetic field on BZ reaction front velocity.

Magnetic nanocomposite based on montmorillonite, Fe oxides, and hydrothermal carbon: Synthesis, characterization and pollutants adsorption tests

This work presents the synthesis and characterization of montmorillonite-Fe oxides (Mt-Mag) and Mt-Fe oxides-carbon (Mt-Mag-C) systems as adsorbent materials, prepared by efficient and low-cost procedures. Fe oxides were synthesized by alkaline oxidation in the presence of nitrates while carbonization was hydrothermally synthesized. The adsorption capacity of the synthesized materials was tested against different pollutants (norfloxacin, thiabendazole, thiophanate-methyl, oxytetracycline, P4R and Cr(VI)). Fe particles and carbon were not homogeneously distributed while Mt-Mag-C sample presented a lower specific surface area and porosity than Mt-Mag, related to carbon presence, while magnetic nanoparticles seem not to block Mt external pores. Both materials revealed negative surface charge, indicating that is dominated by montmorillonite. Besides, Mt structure seems to be modified by both Fe oxides and carbon synthesis. The magnetic response was higher in Mt-Mag-C than in Mt-Mag, indicating Fe phases modifications during carbonization. The principal identified Fe oxide was magnetite, with minor contributions of paramagnetic Fe3+, goethite, and paramagnetic relaxation, with a significantly increased of the spectral area of the latter in Mt-Mag-C. Fe concentration determined by Mössbauer spectroscopy resulted higher on Mt-Mag-C than Mt-Mag, indicating that Fe atoms located at the interlayer space of montmorillonite, that give not Mössbauer signal, are exposed by sonication and carbon synthesis, and new magnetite particles are formed through the reduction of Fe3+ atoms in dextrose aqueous solution. The paramagnetic relaxation increase is related to new magnetite particles, that, because of carbon presence, cannot be magnetically coupled. A significant sorption capacity was found for cationic and zwitterionic compounds, revealing the relevance of electrostatic interaction. The magnetic response of Mt-Mag-C and the results of sorption tests for cationic and zwitterionic compounds, claims Mt-Mag-C as a promising sorbent material.