Homo- and Heterogeneous Benzyl Alcohol Catalytic Oxidation Promoted by Mononuclear Copper(II) Complexes: The Influence of the Ligand upon Product Conversion.

The catalytic properties of three copper complexes, [Cu(en)2](ClO4)2 (1), [Cu(amp)2](ClO4)2, (2) and [Cu(bpy)2](ClO4)2 (3) (where en = ethylenediamine, amp = 2-aminomethylpyridine and bpy = 2,2'-bipyridine), were explored upon the oxidation of benzyl alcohol (BnOH). Maximized conversions of the substrates to their respective products were obtained using a multivariate analysis approach, a powerful tool that allowed multiple variables to be optimized simultaneously, thus creating a more economical, fast and effective technique. Considering the studies in a fluid solution (homogeneous), all complexes strongly depended on the amount of the oxidizing agent (H2O2), followed by the catalyst load. In contrast, time seemed to be statistically less relevant for complexes 1 and 3 and not relevant for 2. All complexes showed high selectivity in their optimized conditions, and only benzaldehyde (BA) was obtained as a viable product. Quantitatively, the catalytic activity observed was 3 > 2 > 1, which is related to the π-acceptor character of the ligands employed in the study. Density functional theory (DFT) studies could corroborate this feature by correlating the geometric index for square pyramid Cu(II)-OOH species, which should be generated in the solution during the catalytic process. Complex 3 was successfully immobilized in silica-coated magnetic nanoparticles (Fe3O4@SiO2), and its oxidative activity was evaluated through heterogenous catalysis assays. Substrate conversion promoted by 3-Fe3O4@SiO2 generated only BA as a viable product, and the supported catalyst's recyclability was proven. Reduced catalytic conversions in the presence of the radical scavenger (2,2,6,6-tetrametil-piperidi-1-nil)oxil (TEMPO) indicate that radical and non-radical mechanisms are involved.

The effect of temperature on the synthesis of magnetite nanoparticles by the coprecipitation method.

Magnetic nanoparticles, such as magnetite (Fe3O4), exhibit superparamagnetic properties below 15 nm at room temperature. They are being explored for medical applications, and the coprecipitation technique is preferred for cost-effective production. This study investigates the impact of synthesis temperature on the nanoparticles' physicochemical characteristics. Two types of magnetic analysis were conducted. Samples T 40, T 50, and T 60 displayed superparamagnetic behavior, as evidenced by the magnetization curves. The experiments verified the development of magnetic nanoparticles with an average diameter of approximately dozens of nanometers, as determined by various measurement methods such as XDR, Raman, and TEM. Raman spectroscopy showed the characteristic bands of the magnetite phase at 319, 364, 499, and 680 cm-1. This was confirmed in the second analysis with the ZFC-FC curves, which showed that the samples' blocking temperatures were below ambient temperature. ZFC-FC curves revealed a similar magnetization of about 30 emu/g when applying a magnetic field of 5 kOe.

A fluorescent magnetic core-shell nanosensor for detection of copper ions in natural waters.

A nanosensor based on magnetic core-shell nanoparticles functionalized with rhodamine derivative, N-(3-carboxy)acryloyl rhodamine B hydrazide (RhBCARB), using (3-aminopropyl)triethoxysilane (APTES) as a linker, has been synthesized for detection of Cu(II) ions in water. The magnetic nanoparticle and the modified rhodamine were fully characterized, showing a strong orange emission sensitive to Cu(II) ions. The sensor shows a linear response from 10 to 90 µg L-1, detection limit of 3 µg L-1 and no interference of Ni(II), Co(II), Cd(II), Zn(II), Pb(II), Hg(II) and Fe(II) ions. The nanosensor performance is similar to those described in the literature, being a viable option for the determination of Cu(II) ions in natural waters. In addition, the magnetic sensor can be easily removed from the reaction medium with the aid of a magnet and its signal recovered in acidic solution, allowing its reuse in subsequent analysis.

Static and Dynamic Magnetic Properties of Fe3O4 Nanotubes.

In this paper, our objective was to investigate the static and dynamic magnetic properties of Fe3O4 nanotubes that are 1000 nm long, by varying the external radius and the thickness of the tube wall. We performed a detailed numerical analysis by simulating hysteresis curves with an external magnetic field applied parallel to the axis of the tubes (along the z-axis). Our findings indicate that nanotubes with an external radius of 30 nm exhibit non-monotonic behavior in their coercivity due to a change in the magnetization reversal mechanism, which was not observed in nanotubes with external radii of 80 nm. Additionally, we explored the dynamic susceptibility of these nanotubes and found that the position and number of resonance peaks can be controlled by manipulating the nanotube geometry. Overall, our study provides valuable insights into the behavior of Fe3O4 nanotubes, which can aid in the design and improvement in pseudo-one-dimensional technological devices.

Extraction-assisted voltammetric determination of homocysteine using magnetic nanoparticles modified with molecularly imprinted polymer.

A magnetic graphite-epoxy composite (m-GEC) electrochemical sensor is presented based on magnetic imprinted polymer (mag-MIP) to determine homocysteine (Hcy). Mag-MIP was synthesized via precipitation polymerization, using functionalized magnetic nanoparticles (Fe3O4) together with the template molecule (Hcy), the functional monomer 2-hydroxyethyl methacrylate (HEMA), and the structural monomer trimethylolpropane trimethacrylate (TRIM). For mag-NIP (magnetic non-imprinted polymer), the procedure was the same in the absence of Hcy. Morphological and structural properties of the resultant mag-MIP and mag-NIP were examined using TEM, FT-IR, and Vibrating Sample Magnetometer. Under optimized conditions, the m-GEC/mag-MIP sensor showed a linear range of 0.1-2 µmol L-1, with a limit of detection (LOD) of 0.030 µmol L-1. In addition, the proposed sensor responded selectively to Hcy compared to several interferents present in biological samples. The recovery values determined by differential pulse voltammetry (DPV) were close to 100% for natural and synthetic samples, indicating good method accuracy. The developed electrochemical sensor proves to be a suitable device for determining Hcy, with advantages related to magnetic separation and electrochemical analysis.

Characterization of Fe3O4 Nanoparticles for Applications in Catalytic Activity in the Adsorption/Degradation of Methylene Blue and Esterification.

The aim of this study is to evaluate the applicability of the catalytic activity (CA) of the Fe3O4 magnetic system in the adsorption/degradation of methylene blue and esterification. The thermal decomposition method allowed the preparation of Fe3O4 nanoparticles. The crystallites of the Fe3O4 structural phase present an acicular form confirmed by X-ray diffraction. Transmission electron microscopy results identified the acicular shape and agglomeration of the nanoparticles. Mössbauer spectroscopy showed that the spectrum is composed of five components at room temperature, a hyperfine magnetic field distribution (HMFD), two sextets, a doublet, and a singlet. The presence of the HMFD means that a particle size distribution is present. Fluorescence spectroscopy studied the CA of the nanoparticles with methylene blue and found adsorption/degradation properties of the dye. The catalytic activity of the nanoparticles was evaluated in the esterification reaction by comparing the results in the presence and absence of catalyst for the reaction with isobutanol and octanol, where it is observed that the selectivity for the products MIBP and MNOP is favored in the first three hours of reaction.

Hollow Iron Oxide Nanospheres Obtained through a Combination of Atomic Layer Deposition and Electrospraying Technologies.

In the present study, we report on the successful synthesis of hollow iron oxide nanospheres. The hollow Fe3O4 nanospheres were synthesized following a four-step procedure: electrospraying spherical PVP particles, coating these particles with alumina (Al2O3) and hematite (Fe2O3) through atomic layer deposition and, finally, a thermal reduction process to degrade the polymer (PVP) and convert hematite (Fe2O3) into magnetite (Fe3O4). A structural analysis using X-ray diffraction (XRD) confirmed the effectiveness of the thermal reduction process. A morphological analysis confirmed that the four-step procedure allowed for the obtainment of hollow iron oxide nanospheres, even though the reduction process caused a contraction in the diameter of the particles of almost 300 nm, but did not affect the thickness of the walls of the hollow spheres that remained at approximately 15 nm. Magnetic properties of the hollow iron oxide nanospheres enable their use in applications where the agglomeration of magnetic nanostructures in liquid media is commonly not allowed, such as in drug encapsulation and delivery.

Fortification of water kefir with magnetite nanoparticles.

The aim of this work was to evaluate the suitability of incorporating Fe3O4 (magnetite, M) NPs into water kefir (wKef) beverages. Magnetite NPs were synthesized and coated with pectins (cM), and incorporated into wKef beverages obtained by fermentation of a muscovado sugar solution with wKef grains. FeSO4, usually employed as fortifier, was used as a control. Four different beverages were analyzed: wKef, wKef-cM, wKef-M, wKef-FeSO4, indicating wKef beverages fortified with cM, M or FeSO4, respectively. Their stability was assessed by determining the viability of total lactic acid bacteria and yeasts, and the composition of saccharides along storage at 4 °C for up to 30 days. The toxicity of M and cM was evaluated in an in vivo model of Artemia salina. The absorption of iron was quantified by determining ferritin values on intestinal Caco-2/TC7 cells, and its internalization mechanisms, by employing inhibitors of endocytic pathways and quantifying ferritin. M and cM were non-toxic on Artemia salina up to 500 µg/mL, a toxicity even lower than that of FeSO4, which showed a LD50 of 304.08 µg/mL. After 30 days of storage, no significant decrease on yeasts viability was observed, and bacteria viability was above 6 log CFU/mL for the four beverages. In turn, sucrose decreased to undetectable values, concomitantly to an increase in the concentrations of glucose and fructose. Both wKef-M and wKef-cM led to a significant increase in the ferritin values (up to 2 folds) with regard to the basal state. The internalization of M NPs occurred via clathrins and caveolin pathways, whereas that of cM, by macropinocytosis. Safely incorporating M and cM NPs into wKef beverages appear as an innovative strategy for providing bioavailable iron aiming to ameliorate the nutritional status of populations at risk of iron deficiency (e.g., vegans).

Electrochemical microfluidic immunosensor based on TES-AuNPs@Fe3O4 and CMK-8 for IgG anti-Toxocara canis determination.

We report a microfluidic immunosensor for the electrochemical determination of IgG antibodies anti-Toxocara canis (IgG anti-T. canis). In order to improve the selectivity and sensitivity of the sensor, core-shell gold-ferric oxide nanoparticles (AuNPs@Fe3O4), and ordered mesoporous carbon (CMK-8) in chitosan (CH) were used. IgG anti-T. canis antibodies detection was carried out using a non-competitive immunoassay, in which excretory secretory antigens from T. canis second-stage larvae (TES) were covalently immobilized on AuNPs@Fe3O4. CMK-8-CH and AuNPs@Fe3O4 were characterized by transmission electron microscopy, scanning electron microscopy, energy dispersive spectrometry, cyclic voltammetry, electrochemical impedance spectroscopy, and N2 adsorption-desorption isotherms. Antibodies present in serum samples immunologically reacted with TES, and then were quantified by using a second antibody labeled with horseradish peroxidase (HRP-anti-IgG). HRP catalyzes the reduction from H2O2 to H2O with the subsequent oxidation of catechol (H2Q) to p-benzoquinone (Q). The enzymatic product was detected electrochemically at _100 mV on a modified sputtered gold electrode. The detection limit was 0.10 ng mL-1, and the coefficients of intra- and inter-assay variation were less than 6%, with a total assay time of 20 min. As can be seen, the electrochemical immunosensor is a useful tool for in situ IgG antibodies anti-T. canis determination.

Assessing South American Guadua chacoensis bamboo biochar and Fe3O4 nanoparticle dispersed analogues for aqueous arsenic(V) remediation.

Discarded bamboo culms of Guadua chacoensis were used for biochar remediation of aqueous As(V). Raw biochar (BC), activated biochar (BCA), raw Fe3O4 nanoparticle-covered biochar (BC-Fe), and activated biochar covered with Fe3O4 nanoparticles (BCA-Fe) were prepared, characterized and tested for As(V) aqueous adsorption. The goal is to develop an economic, viable, and sustainable adsorbent to provide safe arsenic-free water. Adsorbents were characterized using scanning electron microscopy (SEM) and energy dispersive analysis by X-ray (SEM-EDX), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (TEM-EDS), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller surface area measurements (SBET), point of zero charge determinations (PZC), and elemental analysis. Activation with KOH increased the O/C ratio and the surface area of BC from 6.7 m2/g to 1239.7 m2/g (BCA). As(V) sorption equilibrium was achieved within <2 h for all four adsorbents and kinetics followed the pseudo-second-order model. At a 10 mg/L initial As(V) concentration, BC-Fe achieved a 100% removal (5 mg/g) over a pH 5 to 9 window. Sorption was endothermic on all four adsorbents and the capacities rose with the increasing temperature. Langmuir capacities at 40 °C for BC, BCA, BC-Fe, and BCA-Fe were 256, 217, 457, and 868 mg/g, respectively, and capacities were compared with other sorbents. Breakthrough fixed-bed column sorption was carried out for BC and BC-Fe producing 6.6 mg/g and 13.9 mg/g bed capacities, respectively. Potassium phosphate was a better As stripping agent than sodium bicarbonate. Performance of the adsorbents in an As(V)-spiked natural water and a naturally As(V)-contaminated domestic water were assessed. Robust arsenate sequestration occurred generating As-safe water (As <0.01 mg/L), despite the presence of competing ions. Stoichiometric precipitation of iron-arsenate complexes triggered by iron dissolution was also established.

Removal of mercury(II) from contaminated water by gold-functionalised Fe3O4 magnetic nanoparticles.

Fe3O4 nanoparticles were prepared by co-precipitation of Fe2+ and Fe3+ and then modified with Au to produce an effective adsorbent (Fe3O4/Au) for aqueous Hg(II) in contaminated water. Rietveld refinement on the XRD pattern confirmed that the Fe3O4/Au was synthesised. Mössbauer spectra exhibited broad and asymmetric resonance lines with two sextets which can be assigned to tetrahedral Fe3+; and octahedral Fe3+/Fe2+. The quantitative analysis of magnetite confirms that the sample shows around 3 wt.% Au and 97 wt.% partially oxidised Fe3O4. High surface area: 121 m2 g-1, average pore sizes: 6.3 nm and pore volume: 1.64 cm3 g-1. The kinetics data were better fitted with a pseudo-second-order and Dubinin-Radushkevich isotherm suggests the Hg(II) adsorption onto Fe3O4/Au nanoparticles was mainly by chemical adsorption forming complex with the Au metal immobilised on Fe3O4 surfaces. Adsorption capacity of 79.59 mg g-1. Ionic strength and co-existing ions had a slight influence on the adsorption capacity.

Síntesis y caracterización de nanocompuestos Fe3O4/Ag: su efecto contra Enterobacter aerogenes y Enterococcus faecaiis / Synthesisandcharacterization of nanocompounds Fe3O4/Ag: its effect against Enterobacter aerogenes and Enterococcus faecaiis / Síntese e caracterização de nanocompósitos Fe3O4/Ag: seu efeito contra Enterobacter aerogenes e Enterococcus faecaiis

Resumen En el presente trabajo, se reporta la síntesis y caracterización de nanopartículas magnéticas de magnetita/plata (Fe3O4/Ag) para el estudio de sus propiedades antibacterianas frente a las bacterias Enterobacter aerogenes (Gram-negativa) y Enterococcus faecaiis (Gram-positiva). Las nanopartículas magnéticas de magnetita (MNPs) se sintetizaron por el método de solgel, usando bromuro de cetiltrimetilamonio (CTAB) como surfactante. Posteriormente, en la dispersión coloidal de magnetita, se llevó a cabo la reducción química in situ de iones de plata, usando glucosa como agente reductor y polivinilpirrolidona (PVP) como agente dispersante, para obtener un nanocompuesto magnético Fe3O4/Ag. El análisis morfológico y espectroscópico de las nanopartículas de Fe3O4 y del nanocompuesto de Fe3O4/Ag fue realizado mediante la espectroscopia infrarroja con transformada de Fourier (FTIR), Raman, y Mössbauer (MS), además de la técnica de difracción de rayos X (DRX), la microscopía electrónica de barrido (SEM) y espectroscopia de energía dispersiva de rayos X (EDS). Las nanopartículas de Fe3O4 resultaron esféricas con un diámetro medio de 10 nm y el nanocompuesto de Fe3O4/Ag con un tamaño medio de 28 nm, el test antibacteriano indicó que el uso del nanocompuesto de Fe3O4/Ag a una concentración de 5 mg'mL-1 permite una inhibición total del crecimiento de los microorganismos estudiados a partir de una concentración inicial 108 bacterias mL-1.

Abstract In the present study, we report the synthesis and characterization of magnetite/silver magnetic nanoparticles (Fe3O4/Ag) and the study of their antibacterial properties against the bacteria Enterobacter aerogenes (Gramnegative) and Enterococcus faecaiis (Grampositive). Magnetite magnetic nanoparticles (MNPs) were prepared by a sol-gel method using cetyltrimethylammonium bromide (CTAB), as a surfactant, followed by in-situ chemical reduction of silver ions by glucose, and polyvinylpyrrolidone (PVP), as a dispersive agent, to obtain the antibacterial nanocomposite of Fe3O4/Ag. Morphological and spectroscopic studies of magnetite nanoparticles and nanocomposite were carried out using the Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Mössbauer spectroscopy (MS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Spherical Fe3O4 MNPs showed an average diameter of 10 nm and the average size for nanocomposite was 28 nm. The antibacterial test indicated that the use of the nanocomposite of Fe3O4/Ag at a concentration of 5 mg'mL-1 allowed a total inhibition of the growth of the microorganisms studied from an initial concentration of 108 bacteria mL-1.

Resumo No presente trabalho, relatamos a síntese e caracterização de nanopartículas magnéticas de magnetita/prata (Fe3O4/Ag) e o estudo de suas propriedades antibacterianas contra as bactérias Enterobacter aerogenes (Gram-negativo) e Enterococcus faecaiis (Gram-positiva). Nanopartículas magnéticas de magnetita (MNPs) foram sintetizadas pelo método solgel usando o bromuro de cetiltrimetilamonio (CTAB) como surfactante. Posteriormente, na dispersão coloidal de magnetita, a redução química in situ dos íons de prata foi realizada utilizando-se glicose, como agente redutor, e polivinilpirrolidona (PVP), como agente dispersante, para obter um nanocompósito magnético Fe3O4/Ag. A análise morfológica e espectroscópica das nanopartículas de Fe3O4 e do nanocompuesto de Fe3O4/Ag conduziu-se através da espectroscopia infravermelha com transformada de Fourier (FTIR), Raman, e Mössbauer (MS), además da técnica de raio X da deformação (DRX), a microscopia eletrônica de barrido (SEM) e a espectroscopia de energia dispersiva de raios X (EDS). As nanopartículas de Fe O têm formas esféricas com um diâmetro médio de 10 nm e o nanocompósito de Fe3O4/Ag com um tamanho promédio de 28 nm. O teste antibacteriano indicou que o uso do nanocompósito Fe3O4/Ag na concentração de 5 mg'mL-1 permitiu inibir totalmente o crescimento dos microrganismos estudados a partir de uma concentração inicial de 108 bactérias mL-1.

Bean Seedling Growth Enhancement Using Magnetite Nanoparticles.

Advanced fertilizers are one of the top requirements to address rising global food demand. This study investigates the effect of bare and polyethylene glycol-coated Fe3O4 nanoparticles on the germination and seedling development of Phaseolus vulgaris L. Although the germination rate was not affected by the treatments (1 to 1 000 mg Fe L-1), seed soaking in Fe3O4-PEG at 1 000 mg Fe L-1 increased radicle elongation (8.1 ± 1.1 cm vs 5.9 ± 1.0 cm for the control). Conversely, Fe2+/Fe3+(aq) and bare Fe3O4 at 1 000 mg Fe L-1 prevented the growth. X-ray spectroscopy and tomography showed that Fe penetrated in the seed. Enzymatic assays showed that Fe3O4-PEG was the least harmful treatment to α-amylase. The growth promoted by the Fe3O4-PEG might be related to water uptake enhancement induced by the PEG coating. These results show the potential of using coated iron nanoparticles to enhance the growth of common food crops.

Self-Assembled and One-Step Synthesis of Interconnected 3D Network of Fe3O4/Reduced Graphene Oxide Nanosheets Hybrid for High-Performance Supercapacitor Electrode.

In the present work, we have synthesized three-dimensional (3D) reduced graphene oxide nanosheets (rGO NSs) containing iron oxide nanoparticles (Fe3O4 NPs) hybrids (3D Fe3O4/rGO) by one-pot microwave approach. Structural and morphological studies reveal that the as-synthesized Fe3O4/rGO hybrids were composed of faceted Fe3O4 NPs induced into the interconnected network of rGO NSs. The morphologies and structures of the 3D hybrids have been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectrometer (XPS). The electrochemical studies were analyzed by cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy, which demonstrate superior electrochemical performance as supercapacitors electrode application. The specific capacitances of 3D hybrid materials was 455 F g-1 at the scan rate of 8 mV s-1, which is superior to that of bare Fe3O4 NPs. Additionally, the 3D hybrid shows good cycling stability with a retention ratio of 91.4 after starting from ∼190 cycles up to 9600 cycles. These attractive results suggest that this 3D Fe3O4/rGO hybrid shows better performance as an electrode material for high-performance supercapacitors.

Protein corona acts as a protective shield against Fe3O4-PEG inflammation and ROS-induced toxicity in human macrophages.

Protein corona (PC) is the main biological entity of initial cell interaction and can define the toxicological response to Fe3O4 nanoparticles (IONP). Polymer coating to IONP, polyethilenglycol (PEG) and polyvinylpyrrolidone (PVP), is a widely accepted strategy to prevent toxicity and avoid excessive protein binding. The aim of this study was to assess the role of PC as a potential protector for ROS-induced cytotoxicity and pro-inflammatory response in THP-1 macrophages (exposed to three different IONP: bare, PVP or PEG coated). Cells were exposed to either IONP in RPMI-1640 media or IONP with a preformed human PC. All three IONP showed cytotoxic effects, which in the presence of PC was abolished. IONP-PEG exposure significantly increased ROS, mitochondrial dysfunction and pro-inflammatory cytokines release (IL-1ß and TNF-α). PC presence on IONP-PEG promoted a decrease in ROS and prevented cytokine secretion. Also, presence of PC reduced cell uptake for IONP-bare, but had no influence on IONP-PVP or IONP-PEG. Hence, the reduction in IONP-PEG cytotoxicity can be attributed to PC shielding against ROS generation and pro-inflammatory response and not a differential uptake in THP-1 macrophages. The presence of the PC as a structural element of NP biological entity provides in vivo-relevant conditions for nanosafety testing.