Aggregation of magnetic chitosan based nanoparticles and their application in controlled drug release

Novel less than 100 nm sized magnetic Co_0.5Mn_0.5Fe₂O₄-chitosan nanoparticles advantageous in respect of excellent biodegradation and high level of controllability are successfully prepared. TEM and SEM images showed the cubic-shape magnetic Co_0.5Mn_0.5Fe₂O₄ particles were encapsulated by spherical chitosan nanoparticles. The release behavior of bovine serum albumin entrapped in the particles was of distinctly difference with the changes of pH value of loading medium. The release of bovine serum albumin in those two kinds of particles in the medium of pH=1.0 was much quicker in pH = 7.4 and 9.18. The amount of Bovine serum albumin (BSA) released from the particles at different time intervals was estimated using UV spectrophotomertic method at 279 nm. The dissolution profile and in vitro release kinetics showed that Co_0.5Mn_0.5Fe₂O₄-chitosan nanoparticles were promising for controlled delivery of the drug.     

New Synthesis and Magnetic Properties of NiFe2O4/SiO2 and Co0.5Zn0.5Fe2O4/SiO2 Nanocomposites Using Tetraglycolatosilane as Precursor

In this work the new synthesis and magnetic properties of NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites using a water‐soluble silica precursor, tetraglycolatosilane (THEOS), by the sol‐gel method were reported. Nanocomposite were obtained by the thermal decomposition of the organic part at different annealing temperatures varying from 400 to 900 °C. Studies carried out using XRD, FT‐IR, TEM, STA (TG‐DTG‐DTA) and VSM techniques. XRD patterns show that NiFe₂O₄ and Co_0.5Zn_0.5Fe₂O₄ have been formed in an amorphous silica matrix at annealing temperatures above 600 and 400 °C, respectively. It is found that when the annealing temperature is up to 900 °C NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ samples show almost superparamagnetic behavior with a magnetization 4.66 emu/g and ferromagnetic behavior with a magnetization 10.11 emu/g, respectively. The magnetization and coercivity values of nanocomposites using THEOS were considerably less than previous reports using TEOS. THEOS as a silica matrix network provides an ideal nucleation environment to disperse ferrite nanoparticles and thus to confine them to aggregate and coarsen. By using THEOS over the currently used TEOS and TMOS, organic solvents are not needed due to the entire solubility of THEOS in water. Synthesized nanocomposites with adjustable particle sizes and controllable magnetic properties make the applicability of ferrites even more versatile.     

Ultrasonic-assisted synthesis of PMMA/Ni0.5Zn0.5Fe2O4 nanocomposite in mixed surfactant system

PMMA/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite with superparamagnetic behavior was synthesized by in situ emulsion polymerization of methylmethacrylate (MMA) monomer in the presence of Ni_0.5Zn_0.5Fe₂O₄ colloidal suspension assisted by ultrasonic irradiation. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). XRD and FT-IR spectra confirmed the formation of PMMA/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite. TEM images showed that Ni_0.5Zn_0.5Fe₂O₄ nanoparticles with the particle sizes of about 12 nm were well dispersed in the polymer matrix. The nanocomposite at room temperature exhibited superparamagnetic behavior under applied magnetic field. The formation mechanism of PMMA/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite was proposed as well.     

Preparation and ferromagnetic properties of Ni0.5Zn0.5Fe2O4/polyaniline core–shell nanocomposites

Magnetic Ni_0.5Zn_0.5Fe₂O₄‐crosslinked polyaniline composites with a core–shell structure were prepared in the presence of Ni_0.5Zn_0.5Fe₂O₄ magnetic powder in a toluene solution containing iron chloride as a surfactant and dopant. Structural characterization by Fourier transform infrared, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy proved that Ni_0.5Zn_0.5Fe₂O₄ in the composites was responsible for the ferromagnetic behavior of the composites. The effects of the polyaniline and temperature on the magnetic properties of the Ni_0.5Zn_0.5Fe₂O₄/polyaniline composites were studied with electron paramagnetic resonance and superconducting quantum interference device techniques. A clear evolution from ferromagnetic resonance to electron paramagnetic resonance was observed as a function of temperature, which was related to the passage through the Curie point (～420 K). The magnetic properties of the resulting composites showed ferromagnetic behavior, such as high‐saturated magnetization (saturation magnetization = 35–39 emu/g), low coercive force (coercivity = 22–28 G), and low blocking temperatures (～23 K). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2657–2664, 2006     

Synthesis of the ZnO-Ni0.5Zn0.5Fe2O4-Fe2O3 magnetic catalyst in pilot-scale by combustion reaction and its application on the biodiesel production process from oil residual

A magnetic catalyst with composition ZnO-Ni_0.5Zn_0.5Fe₂O₄-Fe₂O₃ was synthesized by a combustion reaction on a pilot-scale and applied in the conversion of residual oil into biodiesel by simultaneous transesterification and esterification reactions (TES). For that, statistical analysis of the factors that influence the process (catalyst concentration, alcoholic route, and temperature) was evaluated by 2³ factorial experimental design. The ZnO-Ni_0.5Zn_0.5Fe₂O₄-Fe₂O₃ magnetic catalyst was characterized in terms of the structure, morphology, magnetic, TPD-NH₃ acidity analysis and catalytic properties. The results indicate the formation of a catalyst with a surface area of 52.9 m²g⁻¹, and density of the sample was 4.8 g/cm³ which is consisted of a mixture of the phases containing 55.87% Fe₂O₃, 36.96% Ni_0.5Zn_0.5Fe₂O₄, and 7.16% ZnO. The magnetic characterization indicated that the synthesized catalyst is ferromagnetic with magnetization 6.12 emu/g and coercive field of 5.3 G. In the TES reactions, the residual oil was active showing conversion to 96.16% ethyl esters and with a long useful life maintaining sustained activity after two consecutive reuse cycles with the conversion of 95.27%, 93.07% and 76.93%, respectively. The experimental design was significant and presented a 95% reliability level. The statistical analysis identified (+1) and (−1) as higher and lower level variables, respectively. The amount of catalyst used was equal to 5%, at 200 °C in methyl alcohol (alcoholic route). In summary, a new catalyst composed of a mixture of magnetically active phases was developed and successfully applied in biodiesel’s synthesis from residual oil. Undoubtedly these results have a positive and significant impact on the environment and to society as a whole.     

Interactions Magnetiques dans quelques Ferrites Oxyfluores a Structure Spinelle de Formule ZnxMFe2−xO4–xFx (M ? Fe,Co, Ni)

Magnetic interactions in some oxyfluoroferrites of spinel structure with the formula Zn_xMe_2?xO_4?xFx (M = Fe, Co, Ni) Whereas the ferromagnetic spin arrangement of the B-cations is not modified by the Zn²⁺?Fe³⁺ substitution in the ZnFe[Fe₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,50) spinel, this same substitution leads to a spin canting in the ZnFe[Co₂₊Fe³⁺]O_4?xF_x and ZnFe[Ni₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,80) simples. The difference in the magnetic behaviors with regard to the AB and BB interactions can be explained on the basis of the magnetic exchange theory.     

Influence of iron ions on the structural properties of Zn-borosilicate glasses

The effects of iron on the structural properties of Zn-borosilicate glasses have been studied using X-ray diffraction, IR spectroscopy and⁵⁷Fe Mössbauer spectroscopy. Zn-borosilicate glasses were doped with α?Fe₂O₃. In the systems Na₂O?ZnO?B₂O₃?SiO₂?Fe₂O₃ the presence of only one crystalline phase, ZnFe₂O₄, was detected. X-ray diffraction showed that crystallization is more pronounced in the systems ZnO?B₂O₃?SiO₂?Fe₂O₃. In these systems the presence of different crystalline phases, such as ZnO, γ?Fe₂O₃, Fe₃O₄, ZnFe₂O₄ and Fe₃BO₅, was detected. The crystallization of α?Zn₂SiO₄ in the system ZnO?B₂O₃?SiO₂ was confirmed by X-ray diffraction and IR spectroscopy. The valence state and coordination of iron in Zn-borosilicate glasses were determined by⁵⁷Fe Mössbauer spectroscopy.     

A highly coercive carbon nanotube coated with Ni0.5Zn0.5Fe2O4 nanocrystals synthesized by chemical precipitation-hydrothermal process

Novel magnetic composites (Ni_0.5Zn_0.5Fe₂O₄-MWCNTs) of multi-walled carbon nanotubes (MWCNTs) coated with Ni_0.5Zn_0.5Fe₂O₄ nanocrystals were synthesized by chemical precipitation-hydrothermal process. The composites were characterized by X-ray powder diffractometer (XRD), X-ray photoelectron spectrometer (XPS), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy (MS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED), etc. A temperature of about 200 °C was identified to be an appropriate hydrothermal condition to obtain Ni_0.5Zn_0.5Fe₂O₄-MWCNTs, being lower than the synthesis temperature of a single-phase Ni_0.5Zn_0.5Fe₂O₄ nanocrystals. The sizes of Ni_0.5Zn_0.5Fe₂O₄ in the composites were smaller than those of Ni_0.5Zn_0.5Fe₂O₄ nanocrystals in single phase. The composites exhibited more superparamagnetic than Ni_0.5Zn_0.5Fe₂O₄ nanocrystals in their relaxation behaviors. The magnetic properties measured by a vibrating sample magnetometer showed that the composites had a high coercive field of 386.0 Oe at room temperature, higher than those of MWCNT and Ni_0.5Zn_0.5Fe₂O₄ nanocrystals.     

Co3O4/SiO2 nanocomposites for supercapacitor application

In this study, Co₃O₄/SiO₂ nanocomposites have been successfully synthesized by citrate–gel method by utilizing SiO₂ matrix for Co₃O₄ embedment. Spectroscopy analyses confirm the formation of high crystalline Co₃O₄ nanoparticles; meanwhile, microscopy findings reveal that the Co₃O₄ nanoparticles are embedded in SiO₂ matrix. Electrochemical properties of the Co₃O₄/SiO₂ nanocomposites were carried out using cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) in 5 M KOH electrolyte. The findings show that the charge storage of Co₃O₄/SiO₂ nanocomposites is mainly due to the reversible redox reaction (pseudocapacitance). The highest specific capacitance of 1,143 F g ^?1 could be achieved at a scan rate of 2.5 mV s^?1 in the potential region between 0 and 0.6 V. Furthermore, high-capacitance retention (>92 %) after 900 continuous charge–discharge tests reveals the excellent stability of the nanocomposites. It is worth noting from the EIS measurements that the nanocomposites have low ESR value of 0.33 Ω. The results manifest that Co₃O₄/SiO₂ nanocomposites are the promising electrode material for supercapacitor application.     

纳米Fe_3O_4及钴离子掺杂Fe_3O_4:有机碱共沉淀制备和磁性质

以有机碱四甲基氢氧化铵(TMAH)为沉淀剂合成了纳米Fe3O4和Co2+掺杂的纳米Fe3O4粒子。分别讨论了碱用量,铁盐溶液浓度,反应温度,有机碱及PEG-4000的分散性等因素对纳米Fe3O4的形貌影响。结果表明,所合成的纳米Fe3O4为30nm左右的反尖晶石型面心立方结构,有机碱除了起沉淀剂作用,还能够提高纳米Fe3O4的分散性。本文还讨论了不同Co2+掺入量的纳米Fe3O4粒子的磁性质,结果表明Co2+掺杂的纳米Fe3O4粒子的矫顽力在不同掺入量的下有较大的改变。当Co2+掺入量为10.0%时,纳米Fe3O4的矫顽力达到最大值,为1628Oe。     

Preparation and optical properties of TiO2?xNx/Ni0.5Zn0.5Fe2O4 core–shell nanocatalyst from sol–gel-hydrothermal process

A nitrogen doped TiO₂/Ni_0.5Zn_0.5Fe₂O₄ core–shell structure nanoparticles was prepared by low temperature sol–gel-hydrothermal process. The characterizations of the catalyst indicate that the Ni_0.5Zn_0.5Fe₂O₄ nanocrystals of about 25 nm are well-coated with crystalline N-doped titania. The absorption edges in the diffusion reflectance spectra of TiO_0.98N_1.02 and TiO_1.37N_0.63/Ni_0.5Zn_0.5Fe₂O₄ shift to visible light region. The core–shell nanocatalysts can effectively photodegrade organic pollutants in the dispersion system and can be recycled easily by an external magnetic field.     

Critical Enhancements of MRI Contrast and Hyperthermic Effects by Dopant‐Controlled Magnetic Nanoparticles

Doped up : The incorporation of Zn²⁺ dopants in tetrahedral sites leads to the successful magnetism tuning of spinel metal ferrite nanoparticles (see picture). (Zn_0.4Mn_0.6)Fe₂O₄ nanoparticles exhibit the highest magnetization value among the metal ferrite nanoparticles. Such high magnetism results in the largest MRI contrast effects (r2=860 mm^?1 s^?1) reported to date and also huge hyperthermic effects.

     

Synthesis and characterization of La0.8Sr1.2Co0.5M0.5O4−δ (M=Fe, Mn)

The M⁴⁺-containing K₂NiF₄-type phases La_0.8Sr_1.2Co_0.5Fe_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O₄ have been synthesized by a sol–gel procedure and characterized by X-ray powder diffraction, thermal analysis, neutron powder diffraction and Mössbauer spectroscopy. Oxide ion vacancies are created in these materials via reduction of M⁴⁺ to M³⁺ and of Co³⁺ to Co²⁺. The vacancies are confined to the equatorial planes of the K₂NiF₄-type structure. A partial reduction of Mn³⁺ to Mn²⁺ also occurs to achieve the oxygen stoichiometry in La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6. La_0.8Sr_1.2Co_0.5Fe_0.5O_3.65 contains Co²⁺ and Fe³⁺ ions which interact antiferromagnetically and result in noncollinear magnetic order consistent with the tetragonal symmetry. Competing ferromagnetic and antiferromagnetic interactions in La_0.8Sr_1.2Co_0.5Fe_0.5O₄, La_0.8Sr_1.2Co_0.5Mn_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6 induce spin glass properties in these phases.     

Impact of Gd3+ and Nd3+ ions substitution on structural and magnetic properties of Co0.5Ni0.5Fe2O4 ferrite system

Co_0.5Ni_0.5(Gd/Nd)_xFe_2-xO₄ (x ?= ?0.0 and 0.06) ferrites were prepared by the solid-state reaction method. These materials were characterized by XRD, FT-IR spectroscopy, and VSM techniques. The XRD analysis revealed the phase formation of all samples and their cubic spinel structure with the Fd-3m space group. Lattice constant was found to increase due to Gd and Nd ions substitution. However, the crystallite size was observed to decrease by the substitution effect. The FT-IR spectra showed the two vibrational frequency bands of the tetrahedral and octahedral sites. From the magnetic properties study, it was identified that the pure and Gd substituted Co_0.5Ni_0.5Fe₂O₄ ferrite showed a ferromagnetic behaviour. While the Nd substituted Co_0.5Ni_0.5Fe₂O₄ ferrite delivered a superparamagnetic behaviour. The substitution of Gd and Nd changed the values of the magnetic parameters of Co_0.5Ni_0.5Fe₂O₄ ferrite. An increase in the saturation magnetization (M_s) value was observed due to substitution of Gd and Nd in Co_0.5Ni_0.5Fe₂O₄ ferrite, indicating that Gd and Nd substitution strengthen the supermagnetic interactions in Co_0.5Ni_0.5Fe₂O₄ ferrite. The highest value of M_s was observed in Gd doped sample.     

Preparation of MnxNi0.5-xZn0.5Fe2O4 Nanorods by the Co-precipitation Method

Mn_xNi_0:5-xZn_0:5Fe₂O₄ nanorods were successfully synthesized by the thermal treatment of rod-like precursors that were fabricated by the co-precipitation of Mn²⁺, Ni²⁺, and Fe²⁺ in the lye. The phase, morphology, and particle diameter were examined by the X-ray diffrac-tion and transmission electron microscopy. The magnetic properties of the samples were stud-ied using a vibrating sample magnetometer. The results indicated that pure Ni_0:5Zn_0:5Fe₂O₄ nanorods with a diameter of 35 nm and an aspect ratio of 15 were prepared. It was found that the diameter of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ (0≤x≤0.5) samples increased, the length and the aspect ratio decreased, with an increase in x value. When x=0.5, the diameter and the aspect ratio of the sample reached up to 50 nm and 7～8, respectively. The coercivity of the samples first increased and then decreased with the increase in the x value. The coer-civity of the samples again increased when the x value was higher than 0.4. When x=0.5,the coercivity of the Mn_xNi_0:5-xZn_0:5Fe₂O₄ sample reached the maximal value (134.3 Oe)at the calcination temperature of 600 oC. The saturation magnetization of the samples first increased and then decreased with the increase in the x value. When x=0.2, the satura-tion magnetization of the sample reached the maximal value (68.5 emu/g) at the calcination temperature of 800 oC.     

Preparation and adsorption of magnetic Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>-chitosan nanoparticles

In this paper, magnetic chitosan microspheres were prepared by the emulsification cross-linking technique, with glutaraldehyde as the cross-linking agent, liquid paraffin as the dispersant, and the Span-80 as emulsifier. The time of cross-linking and the ratio of Co_0.5Ni_0.5Fe₂O₄/chitosan were investigated. The morphology was studied by different instruments. The adsorption performance was investigated and the effects of initial concentration of methyl orange, the time of cross-linking, and the amount of adsorbent were discussed. It is found that the product has uniform morphology when the ratio of magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan is 1 : 2 and the time of cross-linking is 5 h; At room temperature, magnetic Co_0.5Ni_0.5Fe₂O₄–chitosan has a good adsorption toward methyl orange when the magnetic Co_0.5Ni_0.5Fe₂O₄/chitosan dosage is 20 mg.     

单分散NixZn1-xFe2O4纳米颗粒的制备及其磁热效应

以乙酰丙酮金属盐为前驱体,三乙二醇为溶剂,采用多元醇法制备了镍锌不同配比的Ni_xZn_(1-x)Fe_2O_4(x=0,0.3,0.5,0.7和1.0)铁氧体,并通过X射线衍射仪(XRD),透射电子显微镜(TEM)和振动样品磁强计(VSM)等对样品的结构、形貌、磁性能和磁热性能进行了表征。结果表明:Ni_xZn_(1-x)Fe_2O_4铁氧体分散性较好,尺寸均一,形状近似球形,平均粒径为4~5 nm。Ni_xZn_(1-x)Fe_2O_4纳米颗粒在室温下表现出亚铁磁性,饱和磁化强度随着镍含量的增加先增大后减小,当x=0.5时达到最大值29.38 emu·g~(-1)。在382k Hz交变磁场作用下,Ni_(0.5)Zn_(0.5)Fe_2O_4铁氧体温度可升温至313 K,表现出较好的磁热性能。     

Cetyltrimethylammonium-coated magnetic nanoparticles for the extraction of bromate,followed by its spectrophotometric determination

We report on a combination of magnetic solid-phase extraction and spectrophotometric determination of bromate. Cetyltrimethylammonium ion was adsorbed on the surface of phenyl-functionalized silica-coated Fe₃O₄ nanoparticles (Ph-SiO₂@Fe₃O₄), and these materials served as the sorbent. The effects of surfactant and amount of sorbent, the composition of the desorption solution, the extraction time and temperature were optimized. Under optimized conditions, an enrichment factor of 12 was achieved, and the relative standard deviation is 2.9 % (for n?=?5). The calibration plot covers the 1–50 ng mL^?1 range with reasonable linearity (r ²?>?0.998); and the limit of detection is 0.5 ng mL^?1. The method is not interfered by ionic compounds commonly found in environmental water samples. It was successfully applied to the determination of bromate in spiked water samples.

Fabrication and properties of Mn0.5Zn0.5Fe2O4 nanofibers

Zn-doped α-FeOOH nanofiber was synthesized by coprecipitation method. Then the α-FeOOH was enwraped by the complex of the Mn²⁺ and citric acid. The morphology of α-FeOOH did not transform after the calcination process and Mn_0.5Zn_0.5Fe₂O₄ nanofiber was successfully prepared. The phase, morphology, particle diameter and the magnetic properties of samples were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The results indicated that Mn_0.5Zn_0.5Fe₂O₄ nanofibers with an aspect ratio over 40 and a diameter of 20 nm were prepared. Compared with the amorphous Mn_0.5Zn_0.5Fe₂O₄, the anisotropy of the Mn_0.5Zn_0.5Fe₂O₄ nanofiber increased, resulting in the higher coercivity and magnetization of the obtained sample. With an increase in the calcination temperature, the diameter and the saturation magnetization of the sample increased, while the aspect ratio and coercivity decreased. The coercivity of the sample obtained at 700 °C was maximal (up to 185.4 Oe). The saturation magnetization of the sample obtained at 900 °C was maximal (up to 65.3 emu/g). The use of citric acid method prevented the presence of Mn(OH)₂, resulting in the decrease of the calcination temperature.     

Radar Absorption Properties of Ni0.5Zn0.5Fe2O4/PANI/epoxy Nanocomposites

A nitrate? citrate gel was prepared from metallic nitrates and citric acid by sol? gel process and was further used to synthesize Ni_0.5Zn_0.5Fe₂O₄ nanocrystalline powder by auto‐combustion. Then, two novel 15 and 35% (w/w) magnetic Ni_0.5Zn_0.5Fe₂O₄ containing polyaniline nanocomposites, named as PANI‐Ni15 and PANI‐Ni35, respectively, were prepared via in‐situ polymerization of aniline in an aqueous solution containing proper amount of Ni_0.5Zn_0.5Fe₂O₄ magnetic powder. The incorporation of the nanopowders to PANI matrix was confirmed by X‐ray diffraction (XRD), IR and SEM. Synthesized PANI‐NiZn ferrite composite particles were subsequently added to an epoxy resin matrix to produce related nanocomposites. The morphological properties of these nanocomposite materials were investigated by SEM and TEM. The electromagnetic‐absorbing properties were studied by measuring the reflection loss in the frequency range of 8.0 to 12.0 GHz. Results showed the reflection loss of the PANI‐Ni35 composite is higher than pure polyaniline and PANI‐Ni15. The good reflection loss of the nanocomposites suggests their potential applicability as radar absorber.