Synthesis and characterization of magnetic nanoparticles

Magnetic nanoparticles with average diameter in the range of 6.4-8.3 nni have been synthesized by a chemical co-precipitation of Fe(Ⅱ)and Fe(Ⅲ)salts in 1.5 M NH4OH solution.The size of the magnetic particles is dependent on both temperature and the ionic strength of the iron ion solutions.The magnetic particles formed at higher temperature or lower ionic strength were slightly larger than those formed at lower temperature or higher ionic strength respectively.In spite of the different reaction conditions,all the resultant nanoparticles are nearly spherical and have a similar crystalline structure.At 300 K,such prepared nanoparticles are superparam-agnetic.The saturation magnetizations for 7.8 and 6.4 nm particles are 71 and 63 emu/g respectively,which are only ~ 20-30% less than the saturation magnetization(90 emu/g)of bulk Fe3O4 Our results indicated that a control of the reaction conditions could be used to tailor the size of magnetic nanoparticles in free precipitation.     

Preparation and application of streptavidin magnetic particles

Two kinds of streptavidin magnetic particles,namely streptavidin GoldMag particles and streptavidin amino terminal particles were prepared by the methods of physical adsorption and covalent interaction respectively.The streptavidin coated on magnetic particle surface,crucial to many applications,was greatly influenced by the choice of the different buffer.Compared with DynalbeadsM-270 streptavidin, the binding capacity for biotin of different streptavidin magnetic particles was determined by enzyme inhibition method,and the coupling capacity and activity of biotinylated oligonucleotide on their sur- face were also analyzed.The results indicated that the streptavidin GoldMag particle prepared by physical adsorption was stable in STE(NaCl-Tris-EDTA)buffer that was frequently used in nucleic acid hybridization and detection.The streptavidin amino terminal particles prepared by covalent interaction could be used both in STE buffer and PBS(phosphate buffered saline)buffer.The biotin binding ca- pacity for 1 mg of streptavidin GoldMag particles and streptavidin amino terminal particles was 4950 and 5115 pmol respectively.The capacity of biotinylated oligonucleotide(24 bp)coupled on 1 mg of GoldMag and amino terminal magnetic particles was 2839 and 2978 pmol separately.These data were about 6-7 times higher than those of DynabeadsM-270 streptavidin.The hybridization results with FITC-labeled complementary probe on magnetic particle surface demonstrated that the oligonucleotide coupled on streptavidin magnetic particles had high biological activity.     

Iron–sulfur clusters and their electronic and magnetic properties

Iron–sulfur clusters of diverse nuclearities constitute the active sites of a large and prominent family of metalloproteins which play essential roles in all living organisms, such as in electron transfer chains, reduction catalysis, photosynthesis, the respiratory chain and nitrogen fixation. This review is devoted to the presentation of the current state of understanding of their electronic and magnetic properties, which is here derived from their Mössbauer, EPR and ENDOR spectroscopic properties. These techniques constitute fine tools for characterization and provide knowledge of the different oxidation states of these proteins, although our interest here will be mainly centered on the [4Fe–4S*]ⁿ⁺ clusters (with n=1–3). A qualitative physical model involving the competing magnetic interactions in these clusters is discussed. Moreover, this article contains new developments on two more specialized subjects:

• 1.some quantitative consequences of an already published theory of the g-tensors of [4Fe–4S*]ⁿ⁺ clusters (n=1,3) will be derived in Section 3;
• 2.a model permitting the rationalization, from very simple ingredients and formulae, of the redox potentials of a whole set of known synthetic redox clusters (with 1, 2, 3, 4 and 6 iron atoms) will be presented in the final Section 6.

     

Can large magnetic anisotropy and high spin really coexist?

This theoretical study discusses the interplay of the magnetic anisotropy and magnetic exchange interaction of two Mn6 complexes and suggests that large magnetic anisotropy is not favoured by a high spin state of the ground state.     

Synthesis and magnetic properties of an iminonitroxide-substituted phenolate–Cu complex

A new spin-chelate, iminonitroxide-substituted phenolate–copper complex (1), was designed and prepared. The structure of the complex 1 was considerably deviated from a square-planar geometry. The dihedral angle between the two planes defined by a set of copper, oxygen and nitrogen atoms was about 41°. The complex was found to have a relatively strong ferromagnetic interaction and a weaker antiferromagnetic interaction: J/k_B=+250 K and θ=−17 K using a three-spin model. The ferromagnetic interaction was assigned to the intramolecular interaction between the copper atom and the iminonitroxide. The antiferromagnetic interaction was assigned as an intermolecular interaction. These assignments were supported by susceptibility measurements for the diluted sample in polyvinyl chloride (PVC) film. The antiferromagnetic interaction was tentatively assigned due to the observed short intermolecular contacts between the C5 and O1 atoms or between the H5 and O1 atoms.     

Two isomorphous Mn(II) and Co(II) 5-amino-tetrazolate coordination polymers with magnetic Δ-chains: crystal structures and magnetic properties

Two Co(II) and Mn(II) coordination polymers, which have been synthesized under hydrothermal conditions, are isomorphous with magnetic Δ-chains containing trinuclear triangular [M(3)(μ(3)-OH)] clusters. The Δ-chains are bridged by isonicotinic spacers to generate a two-dimensional scalariform layer structure. Magnetic investigations indicate that Co(II) compound exhibits not only spin canting but also metamagnetic behaviors, while only spin-canted antiferromagnetic behaviors was observed in Mn(II) compound.     

Synthesis and characterization of amino-functionalized single magnetic core–silica shell composites

The thermal decomposition approach, reverse micro-emulsion system and surface modification technique had been successfully used to synthesis single magnetic core Fe₃O₄@Organic Layer@SiO₂–NH₂ complex microspheres. The magnetization of the magnetic microspheres core could be easily tuned between 28 and 56 emu/g by adjusting the amount of 2-mercaptobarbituric acid. It was found that the Organic Layer to some extent had a protective effect on avoiding Fe₃O₄ being oxidized into Fe₂O₃. Each Fe₃O₄@Organic Layer microsphere could be coated uniformly by about 30 nm of silica shell. The average diameter of the Fe₃O₄@Organic Layer@SiO₂ composites was about 538 nm. The saturation magnetization of the Fe₃O₄@Organic Layer@SiO₂ complex microspheres was 12.5% less than magnetic microspheres cores. The Fe₃O₄@Organic Layer@SiO₂–NH₂ composites possessed a huge application potentiality in specificity enriching and separating biological samples.     

Layered magnetite nanoparticles modification – synthesis,structure, and magnetic characterization

Core-shell and multilayered nanoparticles based on magnetite core with different metallic spacing and over-layers are prepared in one pot synthesis and characterized. The spacer layers were made from Au, Cu or Ag precursors. The nanoparticles were fabricated by a modified chemical seed based method. The obtained nanoparticles were examined by X-ray diffraction, Energy-dispersive X-ray spectroscopy, Transmission Electron Microscopy, Differential Scanning Calorimetry and Infrared spectroscopy. Magnetic properties of the nanoparticles were tested by Mössbauer spectroscopy and Magnetometry. Magnetization and Mössbauer measurements show that the presence of the metallic layers influences the magnetic state of the particles. XRD and EDX confirm layered structures of nanoparticles. Proposed synthesis allows for fabrication of layered particles with controlled morphology and register properties changes which are related to the nature of each subsequent layer.     

Synthesis and magnetic properties of μ-oxalato-bridged Cu2 IIFeIII-type heterotrinuclear complexes

Three new -oxalato-bridged heterotrinuclear copper(II)–iron(III)–copper(II) complexes have been synthesized and identified: [Cu₂Fe(ox)₃L₂]ClO₄ [L = 5-nitro-1,10-phenanthroline (NO₂phen); 2,9-dimethyl-1,10-phenanthroline (Me₂phen) or 2,2-bipyridine (bpy), respectively]; ox = the oxalato dianions. Based on elemental analyses, molar conductivity and magnetic moment (at room-temperature) measurements, i.r. and electronic spectral studies, extended ox-bridged structures consisting of two copper(II) and an iron(III) ions, in which the central iron(III) ion has an octahedral environment and the end-capped two copper(II) ions a square-planar environment, are proposed for these complexes. The [Cu₂Fe(ox)₃(Me₂phen)₂]ClO₄ (1) and [Cu₂Fe(ox)₃(bpy)₂]ClO₄ (2) complexes were characterized further by variable-temperature magnetic susceptibility (4.2–300 K) measurements and the observed data were simulated by the equation based on the spin Hamiltonian operator, = –2J₁ · ₂, giving the exchange integrals J = –12.85 cm^–1 for (1) and J = –11.28 cm^–1 for (2). The results indicate the presence of an antiferromagnetic spin-exchange interaction between the copper(II) and iron(III) ions through the oxalato-bridge in both complexes (1) and (2).     

Solvent-dependent structures of lanthanide–TCNQ coordination networks and their magnetic properties

Abstract

Lanthanide complexes were prepared with 2,6-diacetylpyridinebis(benzoylhydrazone) (DAPBH₂) and 7,7,8,8-tetracyano-p-quinodimethanide (TCNQ^??). The complexes adopted one of two structure types depending on the reaction solvent. The complexes were categorized as Type I (i.e. bis{[2,6-diacetylpyridinebis(benzoylhydrazone)] methanollanthanide(III)}bis(µ₂- 7,7,8,8-tetracyanoquinodimethanide(1?))bis(7,7,8,8-tetracyanoquinodimethanide(1?))bis(7,7,8,8-tetracyanoquinodimethanide(1?)) methanol disolvate, [Ln₂(DAPBH₂)₂ (µ₂-TCNQ^??)₂(TCNQ^??)₂(MeOH)₂](TCNQ^??)₂·2MeOH (Ln?=?Gd, Tb, or Dy) or Type-II (i.e. [Ln₂(DAPBH₂)₂(µ₂-TCNQ^??)₂(TCNQ^??)₂(EtOH)₂] (TCNQ^??)₂·solvent (Ln?=?Tb and Dy, solvent =4EtOH for the Tb and 2EtOH·2CH₂Cl₂ for the Dy complexes). These two complexes exhibit dramatically different molecular structures and packings. In all complexes, the strong intra- and intermolecular stacking interactions of the TCNQ^?? radicals lead to the formation of 1D TCNQ chains. Magnetic susceptibility measurements for Type I and Type II complexes reveal that they exhibit paramagnetic behavior and that their magnetic properties originate from the lanthanide ions alone, owing to the diamagnetic nature of the TCNQ^?? stacks.     

Synthesis and magnetic studies of phthalato-bridged oxovanadium(Ⅳ) binuclear complexes

Six new μ-phthalato binuclear oxovanadium(IV) complexes,namely [(VO)2(PHTH)-(L)2]SO4 (L denotes 2,2'-bipyridine (bpy);1,10-phenanthroline (phen);4,4'-dimethyl-2,2'-bipyridine (Me2bpy);5-nitro-1,10-phenanthroline (NO2-phen);5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-l,10-phenanthroline (CH3-phen),where PHTH is the phthalate dianion),have been synthesized and characterized by elemental analyses,IR,electronic spectra,magnetic moments at room temperature and molar conductivity measurements.The temperature dependence of the magnetic susceptibility of complexes [(VO)2(PHTH)(Phen)2]SO4 (1) and [(VO)2(PHTH)(CH3-phen)2]SO4 (2) was measured in 4-300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator,H--2JS1S2,giving the exchange integrals J=-12.8 cm-1 for 1 and J=-7.9 cm-1 for 2.This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.     

Estimation of σ- and π-donor properties of heterocyclic thioamides by spectroscopic and magnetic resonance methods

The charge-transfer complexes (CTC) of few thioamide: 1-methylimidazoline-2-thione (MMI), 3-methyl-1-ethoxycarbonilimidazoline-2-thione (Carb), 5-methylbenzimidazoline-2-thione (BIZ), benzothiazoline-2-thione (BTZ), benzoxazoline-2-thione (BOZ) as σ-donors and diiodine as σ-acceptor were studied by spectroscopic methods (UV/Vis, (1)H NMR). CTC formation constants of thioamides with diiodine were determined using the function of the average-iodine number. The charge-transfer complexes of thioamides as π-donors with tetracyanoethylene (TCNE) as π-electron acceptor, were studied by UV-spectroscopy in dichloromethane and chloroform solutions. The mechanism of interaction MMI and Carb with TCNE have been studied by EPR spectroscopy. Spectral characteristics and formation constants are discussed in the terms of electron donor affinity of thioamides and the nature of the organic solvent used. The ionization potentials of donors were estimated from the CT transition energies of their complexes. The photolytic equilibrium constants of five thioamides are determined using pH-metric titrations.     

Synthesis,structure, and magnetic properties of lanthanide ferrocenoylacetonates with nitrate and 2,2′-bipyridine ligands

Ferrocenoylacetonate complexes of several lanthanides, [Ln(fca)₂(NO₃)(bpy)]·nMeC₆H₅ (Ln = Sm (1), Dy (3), Er (4), Yb (5), n = 1; Eu (2), n = 0.5; fca = FcC(O)CHC(O)Me; bpy = 2,2′-bipyridine), were synthesized and characterized by X-ray single-crystal analysis. Complexes 1, 4, and 5 are isostructural; 2 has a similar molecular structure with cis-disposition of fca ligands. The molecular structure of 3 is different, with trans-disposition of the fca ligands. Crystal lattices of the complexes are stabilized by π-stacking interactions. The Ln³⁺ ions in the complexes are eight-coordinate. According to mass spectroscopic data, the complexes are unstable in the gas phase. Magnetic properties of 2 and 4 were studied in a DC field; for 4, AC studies were also carried out. The values of spin-orbital parameters obtained using two estimation methods for 2 are in satisfactory agreement. Slow relaxation of the magnetization was found for the Er complex.     

A new mixed valence VIV–V and Li phyllosilicate: swelling,magnetic and conductive properties

This paper presents the synthesis and characterisation of a new V–Li phyllosilicate, Li₂V_0.95Si₄O₁₀(OH)_1.24F_0.76, under hydrothermal conditions. Part of the alkali is located in the interlayer spacing while the rest occupies the octahedral layer together with V^IV and V^V. This silicate exhibits a mixed valence character and different properties, such as ferromagnetic order at low temperature, ionic conductivity and swelling upon exposure to moisture atmosphere. Thus, the basal spacing increases from 12.3 to 16.3 Å.     

Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis,structure, magnetic properties,and Mössbauer spectra

Russian Chemical Bulletin - Crystalline compounds (H3O)2(phz)3M2(C6O4Cl2)3·(CH3COCH3) n ·(H2O) n (n = 0?2, M = Mn (1), Fe (3)) were obtained in an acetone-water-tetrahydrofuran...     

Using silk-derived magnetic carbon nanocomposites as highly efficient Nanozymes and electromagnetic absorbing agents

Functional carbon nanomaterials have become the stars of many active research fields, such as electronics, energy, catalysis, imaging, sensing and biomedicine. Herein, a facile and one-pot strategy for generating ferromagnetic nanoparticles loaded on N-doped carbon nanosheets(Fe-N-CNS) is presented by salt-assisted high-temperature carbonization of natural silk proteins. Due to their graphitic structures,N-doping and ferromagnetic nanoparticles(FeN_x, FeO_y, FeC_z),...     

Structure and magnetic properties of Ho2Co17−xMx pseudobinary compounds

The homogeneity range of the pseudobinary system Ho₂Co_17−xM_x (M ≡; Ni, Fe, Mn, Cr, V, Ti, Cu, Al) and the dependence of the lattice constants and the Curie temperature on composition were studied. Although Ho₂Co₁₇, Ho₂Ni₁₇ and Ho₂Fe₁₇ have identical crystal structures and similar lattice constants, the homogeneity range for the Th₂Ni₁₇-type compound in the Ho₂Co_17−xNi_x and Ho₂Co_17−xFe_x systems is limited to x < 5. The curves of Curie temperature versus composition have maxima at x values of 1, 3 and 0.9 for the systems Ho₂Co_17−xNi_x, Ho₂Co_17−xFe_x and Ho₂Co_17−xCu_x respectively. This suggests that the effect of nickel, iron and copper on the Co-Co exchange interaction in the cobalt sublattice at low concentrations may be different from that at high concentrations.     

Preparation of magnetic modified chitosan and adsorption of Zn²⁺ from aqueous solutions

The performance of a cross-linked magnetic modified chitosan (CMMC), which has been coated with magnetic fluids and cross-linked with glutaraldehyde, has been investigated for the adsorption of Zn(2+) from aqueous solutions. The CMMC with a diameter range of 20-50 nm was prepared. The effects of pH and the contact time for the adsorption have been discussed, and the optimal adsorption conditions for the adsorption of Zn(2+) have been obtained. The research results showed that CMMC was highly efficient for fast adsorption of Zn(2+) within the first 25 min, and adsorption equilibrium could be achieved in 30 min. Equilibrium studies showed that the data of Zn(2+) adsorption followed the Langmuir model. The maximum adsorption capacity for Zn(2+) was estimated to be 32.16 mg/g with a Langmuir adsorption equilibrium constant of 0.01 L/mg at 298 K, which demonstrated that the CMMC had obvious efficient adsorption of Zn(2+). The CMMC was stable and easily recovered. Moreover, the adsorption rate was about 90% of the initial saturation adsorption capacity after being used five times.