Effect of Fe:ligand ratios on hydroponic conditions and calcareous soil in Solanum lycopersicum L. and Glycine max L. fertilized with heptagluconate and gluconate.

BACKGROUND: The environmental risk from the application of synthetic chelates has led to the use of biodegradable complexes to correct Fe deficiency in plants. In this article, the Fe oxidation state, the Fe:ligand ratio, and the molecular weight distribution for heptagluconate (G7) and gluconate (G6) are considered as key factors for the efficacy of complexes as fertilizers. Complexes with different Fe:ligand ratios were prepared and analyzed by gel filtration chromatography (GFC). The ability of Fe:ligand ratios to provide Fe to tomato in hydroponics and soybean in calcareous soil was tested and compared with synthetic chelates (Fe3+ :HBED and Fe3+ :EDTA). RESULTS: G7 presented greater capacity to complex both Fe(II) and Fe(III) than G6, but the Fe(II) complexes exhibited poor stability at pH 9 and oxidation in solution. Gel filtration chromatography demonstrated the polynuclear nature of the Fe3+ :G7 at various ratios. The effectiveness of the Fe fertilizers depend on the Fe3+ :ligand ratio and the ligand type, the Fe3+ :G7 (1:1 and 1:2) being the most effective. Fe3+ :G7 (1:1) also presented a better response for the uptake of other micronutrients. CONCLUSION: Fe3+ :G7 molar ratios have been shown to be critical for plant Fe uptake under hydroponic conditions and with calcareous soil. Thus, the Fe3+ :G7 at equimolar ratio and 1:2 molar ratio can be an environmentally friendly alternative to less degradable synthetic chelates to correct Fe chlorosis in strategy I plants. © 2019 Society of Chemical Industry.

Micromotors of MnO2 for the Recovery of Microplastics.

Plastics, primarily microplastics, are among the greatest pollutants in aquatic environments. Their removal and/or degradation in these environments are crucial to ensure an optimal future of these ecosystems. In this work, MnO2 particles were synthesized and characterized for the removal of polystyrene microplastics as a model. MnO2 catalyzes the peroxide reaction, resulting in the formation of oxygen bubbles that propel the pollutants to the surface, achieving removal efficiencies of up to 80%. To achieve this, hydrothermal synthesis was employed using various methods. Parameters such as MnO2, pH, microplastics, and H2O2 concentrations were varied to determine the optimal conditions for microplastics recovering. The ideal conditions for a low microplastic concentrations (10 mg L-1) are 0.2 g L-1 MnO2, 1.6% of H2O2 and 0.01 triton as a surfactant. In these conditions, the micromotors can recover approximately 80% of 300 nm sized polystyrene microplastic within 40 min.

Highly Efficient T2 Cobalt Ferrite Nanoparticles Vectorized for Internalization in Cancer Cells.

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-1s-1 of transverse relaxivity (r2) 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).

New Highly Charged Iron(III) Metal-Organic Cube Stabilized by a Bulky Amine.

In this work, we report a new octanuclear cluster based on FeIII and the ligand 1H-imidazole-4,5-dicarboxylic acid, [Et3NH]12[Fe8(IDC)12]·10DMF·13H2O (1), with a metal core containing eight FeIII connected by only one type of organic ligand. A peak at 573 m/z in the mass spectra of the compound suggests the adduct species {[Fe8(IDC)12]+8H}4-. By X-ray photoelectron spectroscopy, the oxidation state of the iron cation was confirmed to be 3+, also identifying the presence of a quaternary nitrogen species, which act as a countercation of the anionic metal core [Fe8(IDC)12]12-. Mössbauer spectra recorded at different temperatures show an isomer shift and quadrupole splitting parameters that confirm the existence of only FeIII-HS in the structure of 1. X-ray analysis reveals that compound 1 crystallizes in the orthorhombic system space group Ibam, confirming a molecular cluster structure with an almost regular cube as geometry, with the FeIII atoms located at the corners of the cube and connected by µ-1κ2 N,O:2κ2 N',O‴-IDC3- bridges. Additionally, the magnetic measurements reveal a weak antiferromagnetic coupling in the Fe8 III coordination cluster (J = -3.8 cm-1). To the best of our knowledge, 1 is the first member of the family of cubes assembled with 1H-imidazole-4,5-dicarboxylic acid and FeIII cation, exhibiting high pH stability over a broad pH range, making it an ideal candidate for the design of supramolecular structures and metal-organic frameworks.

Composition, speciation and distribution of iron minerals in Imperata cylindrica.

A comparative study of the roots, rhizomes and leaves of an iron hyperaccumulator plant, Imperata cylindrica, isolated from the banks of an extreme acidic environment, using complementary techniques: Mösbauer spectroscopy (MS), X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled to energy-dispersive X-ray microanalysis (EDAX) and transmission electron microscopy (TEM), has shown that two main biominerals, jarosite and ferrihydrate-ferritin, accumulate in the different tissues. Jarosite accumulates mainly in roots and rhizomes, while ferritin has been detected in all the structures. A model of iron management in I. cylindrica is presented.

Long-Term Effect of a Leonardite Iron Humate Improving Fe Nutrition As Revealed in Silico, in Vivo, and in Field Experiments.

Novel, cheap and ecofriendly fertilizers that solve the usual iron deficiency problem in calcareous soil are needed. The aim of this work is to study the long-term effect of an iron leonardite fertilizer on citrus nutrition taking into account a properly characterization, kinetic response with a ligand competition experiment, efficiency assessment using Saccharomyces cerevisiae strain and finally, in field conditions with citrus as test plants. Its efficiency was compared with the synthetic iron chelate FeEDDHA. Leonardite iron humate (LIH) is mainly humic acid with a high-condensed structure where iron is present as ferrihydrite and Fe3+ polynuclear compounds stabilized by organic matter. Iron and humic acids form aggregates that decrease the iron release from these kinds of fertilizers. Furthermore, LIH repressed almost 50% of the expression of FET3, FTR1, SIT1, and TIS11 genes in Saccharomyces cerevisiae cells, indicating increasing iron provided in cells and improved iron nutrition in citrus.

New insights into the chemistry of di- and trimetallic iron dithiolene derivatives. Structural, Mössbauer, magnetic, electrochemical and theoretical studies.

Reaction of Fe3(CO)12 with 1,2-dithiolene HSC6H2Cl2SH affords a mixture of complexes [Fe2(CO)6(µ-SC6H2Cl2S)] 1, [Fe2(SC6H2Cl2S)4] 2 and [Fe3(CO)7(µ3-SC6H2Cl2S)2] 3. In the course of the reaction the trimetallic cluster 3 is first formed and then converted into the known dinuclear compound 1 to afford finally the neutral diiron tetrakis(dithiolato) derivative 2. Compounds 2 and 3 have been studied by Mössbauer spectroscopy, X-ray crystallography and theoretical calculations. In compound 2 the metal atoms are in an intermediate-spin Fe(III) state (S(Fe) = 3/2) and each metal is bonded to a bridging dithiolene ligand and a non-bridging thienyl radical (S = 1/2). Magnetic measurements show a strong antiferromagnetic coupling in complex 2. Cyclic voltammetry experiments show that the mixed valence trinuclear cluster 3 undergoes a fully reversible one electron reduction. Additionally, compound 3 behaves as an electrocatalyst in the reduction process of protons to hydrogen.

Exchange bias in iron oxide nanoclusters.

Iron oxide nanoclusters have been prepared by the gas-phase aggregation technique to form thin film structures with very high exchange bias values (up to 3000 Oe at low temperatures). Composition has been analysed by x-ray absorption and Mössbauer spectroscopies in order to elucidate the actual origin of the observed magnetic behaviour. The formation of a metal-oxide core-shell arrangement to explain the observed exchange bias has to be discarded since results show no metallic iron content and the main presence of α-Fe(2)O(3). The observed weak ferromagnetism and exchange bias are in agreement with the obtained size of α-Fe(2)O(3) nanoparticles: weak ferromagnetism because of the well-known spin canting in this antiferromagnetic structure and exchange bias because of the interaction between different spin sublattice configurations promoted by the modification of iron coordination in α-Fe(2)O(3) nanoparticles. Moreover, the preparation method is proposed for tuning both magnetization and exchange bias values by modification of the preparation conditions of α-Fe(2)O(3) nanoparticles, which open new possibilities in the design of new materials with required properties.

Nonstoichiometric spinel ferrites obtained from alpha-NaFeO2 via molten media reactions.

Different solid/liquid "exchange" reactions involving divalent cations, protons, or ammonium ions have been performed at low/moderate temperatures (between 80 and 500 degrees C) on alpha-NaFeO2 dipped in molten salts (or acid) media. Several ferrites have been obtained which are nonstoichiometric with partially inverse spinel structures. When sodium is replaced by divalent cations (Mg2+, Co2+, Ni2+, and Zn2+), the obtained ferrites are hyperstoichiometric (cation/oxygen ratio higher than 3/4) whereas proton or ammonium reactions result in hypostoichiometric materials (cation/oxygen lower than 3/4). All these ferrites present a platelet-like morphology and show ferrimagnetic, soft magnet behavior.

[C-reactive protein and orosomucoid as parameters of developmental monitoring and therapeutic effectiveness in neonatal sepsis]. / Proteína-C-reactiva y orosomucoide como parámetros de control evolutivo y eficacia terapéutica en la sepsis neonatal.

Authors develop a comparative study of two acute phase reactants behaviour, in the follow up on 27 neonates with confirmed sepsis of favourable evolution and in 15 cases with fatal evolution. Results show that sera levels C-reactive-protein follow a parallel course with clinical significance in patients reaching normal concentrations soon after favourable evolution and persisting in high level or even increasing previous ones, in cases of lethal evolution. Orosomucoid did show the same clinical-biological correlation maintaining generally in high levels independent of normalization of symptoms and C-reactive protein. They propose serial determination of C-reactive-protein and an efficient control of treatment in neonatal sepsis.