Low-Platinum-Content Exchange-Coupled CoPt Nanoalloys with Enhanced Magnetic Properties.

Bimetallic colloidal CoPt nanoalloys with low platinum content were successfully synthesized following a modified polyol approach. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) studies were performed to estimate the crystal structure, morphology, and surface functionalization of the colloids, respectively, while the room-temperature magnetic properties were measured using a vibrating sample magnetometer (VSM). The particles exhibit excellent uniformity, with a narrow size distribution, and display strong room-temperature hysteretic ferromagnetic behavior even in the as-made form. Upon annealing at elevated temperatures, progressive formation and co-existence of exchange coupled, of both chemically ordered and disordered phases significantly enhanced the room-temperature coercivity.

LAPONITE® nanodisk-"decorated" Fe3O4 nanoparticles: a biocompatible nano-hybrid with ultrafast magnetic hyperthermia and MRI contrast agent ability.

Magnetic Fe3O4 nanoparticles "decorated" by LAPONITE® nanodisks have been materialized utilizing the Schikorr reaction following a facile approach and tested as mediators of heat for localized magnetic hyperthermia (MH) and as magnetic resonance imaging (MRI) agents. The synthetic protocol involves the interaction between two layered inorganic compounds, ferrous hydroxide, Fe(OH)2, and the synthetic smectite LAPONITE® clay Na0.7+[(Si8Mg5.5Li0.3)O20(OH)4]0.7-, towards the formation of superparamagnetic Fe3O4 nanoparticles, which are well decorated by the diamagnetic clay nanodisks. The latter imparts high negative ζ-potential values (up to -34.1 mV) to the particles, which provide stability against flocculation and precipitation, resulting in stable water dispersions. The obtained LAPONITE®-"decorated" Fe3O4 nanohybrids were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Mössbauer spectroscopy, dynamic light scattering (DLS) and vibrating sample magnetometry (VSM) at room temperature, revealing superior magnetic hyperthermia performance with specific absorption rate (SAR) values reaching 540 W gFe-1 (28 kA m-1, 150 kHz) for the hybrid material with a magnetic loading of 50 wt% Fe3O4/LAPONITE®. Toxicity studies were also performed with human glioblastoma (GBM) cells and human foreskin fibroblasts (HFF), which show negligible to no toxicity. Furthermore, T2-weighted MR imaging of rodent brain shows that the LAPONITE®-"decorated" Fe3O4 nanohybrids predominantly affected the transverse T2 relaxation time of tissue water, which resulted in a signal drop on the MRI T2-weighted imaging, allowing for imaging of the magnetic nanoparticles.

Chemically synthesized nanoparticles of iron and iron-carbides.

In this paper, we report a one-pot chemical synthesis technique for the preparation of iron and iron-carbide nanoparticles. Mössbauer spectroscopy, X-ray diffraction and magnetometry were used as the main tools to identify the different phases of Fe-C present. The influence of experimental parameters on the structural and compositional properties of nanoparticles was investigated in detail. These particles show ferromagnetic behavior with room temperature coercivity higher than 300 Oe. The X-ray diffraction was complemented by Mössbauer spectroscopy and thermo-magnetic analysis. Remarkably, the carbon content in iron-carbide nanoparticles (carbon rich or carbon poor iron-carbides) can be modulated simply by varying the experimental conditions, like the reaction time, temperature and iron precursor concentration. Magnetic properties can be tailored based upon crystallographic structure and particles composition.

Photocatalysis as an advanced reduction process (ARP): The reduction of 4-nitrophenol using titania nanotubes-ferrite nanocomposites.

TiO2 photocatalysis is an advanced process, employed worldwide for the oxidation of organic compounds, that leads to significant technological applications in the fields of health and environment. The use of the photocatalytic approach in reduction reactions seems very promising and can open new horizons for green chemistry synthesis. For this purpose, titanium dioxide nanotubes (TNTs) were developed in autoclave conditions using TiO2 P25 as a precursor material. Based on these nanotubular substrates, TiO2/CoFe2O4 (TCF) nanocomposites were further obtained by wet impregnation method. The materials were thoroughly characterized and their structural, textural, vibrational, optoelectronic and magnetic properties were determined. The composite materials combine absorbance in the visible optical range and high BET surface area values (˜100 m2/g), showing extremely high yield in the photocatalytic reduction of 4-nitrophenol (4-NP), exceeding 94% within short illumination time (only 35 min). The developed nanocomposites were successfully reused in consecutive photocatalytic experiments and were easily removed from the reaction medium using magnets. Both remarkable recycling ability and high-performance stability in the photocatalytic reduction of nitrophenol were observed, thus justifying the significant economic potential and industrial perspectives for this advanced reduction process.

Iron carbide nanoplatelets: colloidal synthesis and characterization.

Iron carbide nanoplatelets with an orthorhombic Fe3C structure were synthesized following a simple liquid chemical approach. The formation of the carbide phases was shown to depend on the presence of a long chain diol and the reaction temperature. Confirmation of the iron carbide phases and structural characterization was made by X-ray diffraction (XRD) and Mössbauer spectroscopy. Particle morphology was characterized by transmission electron microscopy (TEM) and HR-TEM and the magnetic properties were measured with magnetometry (VSM). The sample with the Fe3C phase shows a ferromagnetic behavior with a magnetization of 139 emu g-1 under a 30 kOe applied field. The simple methodology presented here for producing iron carbide nanoplatelets has promising application in the biomedical and catalyst industries.

Enrichment and oral bioaccessibility of selected trace elements in fly ash-derived magnetic components.

The mineralogy, morphology, and chemical composition of magnetic fractions separated from fly ashes (FAs) originating from Greek lignite-burning power plants was investigated. The oral bioaccessibility of potentially harmful elements (PHEs) from the fly ash magnetic fractions (FAMFs) was also assessed using in vitro gastrointestinal extraction (BARGE Unified Bioaccessibility Method, UBM). The FAMFs isolated were in the range 4.6-18.4%, and their mass specific magnetic susceptibility ranged from 1138 × 10-8 to 1682 × 10-8 m3/kg. XRD analysis and Mossbauer spectroscopy indicated that the dominant iron species were Fe-rich aluminosilicate glass along with magnetite, hematite, and maghemite (in decreasing order). The raw FAs exhibited differences in their chemical composition, indicating the particularity of every lignite basin. The elemental contents of FAMFs presented trends with fly ash type; thus, the FAMFs of high-Ca FAs were enriched in siderophile (Cr, Co, Ni) and lithophile (Cs, Li, Rb) elements and those separated from low-Ca FAs were presented depleted in chalcophile elements. Based on UBM extraction tests, the PHEs were more bioaccessible from the non-magnetic components of the FAs compared to the magnetic ones; however, the bioaccessible fractions estimated for the FAMFs were exceeding 40 % in many cases. Arsenic was found to be significantly bioaccessible (median ~ 80 %) from FAMFs despite the lower As contents in the magnetic fraction.

Biotechnological promises of Fe-filled CNTs for cell shepherding and magnetic fluid hyperthermia applications.

Fe-filled carbon nanotubes (Fe@CNTs) recently emerged as an effective class of hybrid nanoparticles for biotechnological applications, such as magnetic cell sorting and magnetic fluid hyperthermia. Aiming at studying the effects of both the Fe loading and the magnetocrystalline characteristics in these applications, we describe herein the preparation of Fe@CNTs containing different Fe phases that, upon functionalization with the antibody Cetuximab (Ctxb), allow the targeting of cancer cells. Our experimental findings reveal that an optimal Ctxb/Fe weight ratio of 1.2 is needed for efficient magnetic cell shepherding, whereas enhanced MFH-induced mortality (70 vs. 15%) can be reached with hybrids enriched in the coercive Fe(3)C phase. These results suggest that a synergistic effect between the Ab loading and the Fe distribution in each nanotube exists, for which the maximum shepherding and hyperthermia effects are observed when higher densities of Fe@CNTs featuring the more coercive phase are interfaced with the cells.

New mononuclear Cu(II) complexes and 1D chains with 4-amino-4H-1,2,4-triazole.

The crystal structures of two mononuclear Cu(II) NH2trz complexes [Cu(NH2trz)4(H2O)](AsF6)2 (I) and [Cu(NH2trz)4(H2O)](PF6)2 (II) as well as two coordination polymers [Cu(µ2-NH2trz)2Cl]Cl∙H2O (III) and [Cu(µ2-NH2trz)2Cl] (SiF6)0.5∙1.5H2O (IV) are presented. Cationic 1D chains with bridging bis-monodentate µ2-coordinated NH2trz and bridging µ2-coordinated chloride ligands are present in III and IV. In these coordination polymers, the Cu(II) ions are strongly antiferromagnetically coupled with J=-128.4 cm(-1) for III and J=-143 cm(-1) for IV (H=-JΣSiSi+1), due to the nature of the bridges between spin centers. Inter-chain interactions present in the crystal structures were taken into consideration, as well as g factors, which were determined experimentally, for the quantitative modeling of their magnetic properties.

First structurally characterized self-assembly of bipodal N-thiophosphorylated bis-thiourea with Co(II): magnetic properties and thermal decomposition.

Reaction of piperazine with isothiocyanate (iPrO)2P(S)NCS leads to N-thiophosphorylated bis-thiourea (iPrO)2P(S)NHC(S)NC4H8NC(S)NHP(S)(OiPr)2 (H2L). Recrystallization of H2L from DMSO leads to the formation of the new ligand (iPrO)2P(S)NC4H8NP(S)(OiPr)2 (1). Reaction of doubly deprotonated L with Co(II) leads to the [Co2L2] complex. The thermal properties of [Co2L2] in an air atmosphere were studied by means of TGA with the observed final residue corresponding to [CoPS3]2. The crystal structure of [Co2L2] was elucidated by single crystal X-ray diffraction. Two metal cations are in a tetrahedral 1,5-S2S'2 environment formed by the C=S and P=S sulfur atoms. Investigation of the temperature dependence of the magnetic susceptibility is consistent with two effectively non-interacting Co(II) S = 3/2 ions.

Experimental and theoretical Mössbauer study of an extended family of [Fe8(µ4-O)4(µ-4-R-px)12X4] clusters.

Six [Fe(8)(µ(4)-O)(4)(µ-4-R-pyrazolato)(12)X(4)] complexes containing an identical Fe(8)(µ(4)-O)(4) core have been structurally characterized and studied by Mössbauer spectroscopy. In each case, an inner µ(4)-O bridged Fe(III) cubane core is surrounded by four trigonal bipyramidal iron centers, the two distinct sites occurring in a 1:1 ratio. The Mössbauer spectrum of each of the clusters consists of two quadrupole doublets, which, with one exception (X = NCS, R = H), overlap to give three absorption lines. The systematic variation of X and R causes significant changes in the Mössbauer spectra. A comparison with values for the same clusters computed using density functional theory allows us to establish an unequivocal assignment of these peaks in terms of a nested model for the overlapping doublets. The changes in Mössbauer parameters (both experimental and computed) for the 1-electron reduced species [Fe(8)(µ(4)-O)(4)(µ-4-Cl-pyrazolato)(12)Cl(4)](-) are consistent with a redox event that is localized within the cubane core.

Magnetically modified single and turbostratic stacked graphenes from tris(2,2'-bipyridyl) iron(II) ion-exchanged graphite oxide.

Loading of graphite oxide (GO) with tris(2,2'-bipyridyl) iron(II) ions and subsequent calcination affords a novel graphene-based composite with magnetic and electrically conductive properties. The pH of the starting aqueous suspension and the washing procedure play a crucial role in the successful immobilization of the iron precursor, which is mainly governed by ion exchange. The complex is intercalated between the graphene oxide layers, where it adopts a distorted conformation. Rapid heating of this solid results in the deflagration of GO and the formation of ultrafine ( d = 2-14 nm) Fe2O3 particles with maghemite as the dominant phase. The superparamagnetic maghemite crystals are dispersed uniformly in the high-surface-area diamagnetic matrix built up from single or turbostratic stacked graphenes.

No aging phenomena in ferrofluids: the influence of coating on interparticle interactions of maghemite nanoparticles.

The influence of coating on interparticle interactions in ferrofluids has been investigated using various techniques such as Mossbauer spectroscopy, magnetometry, transmission electron microscopy, photon correlation spectroscopy, X-ray diffraction, X-ray photoelectron, and resonance micro-Raman spectroscopy. Aging and spin-glass-like behavior was investigated in frozen ferrofluids of various concentrations from dense, initial value of 40 mg of coated nanoparticles per 1 mL of water, to dilute 1:10 (4 mg/mL). The as-prepared nanoparticles, core size 7-8 nm, were subsequently coated with a gummic acid corona of 20 nm thickness, which was observed to prevent agglomeration and to delay aggregation even in dense ferrofluids. The resulting separation of magnetic cores due to the coating eliminated all magnetic interparticle interaction mechanisms, such as exchange and dipoledipole, thus ensuring no aging effects of the magnetic particle system, as manifested in particle agglomeration and precipitation.