磁性Fe3O4纳米粒子用作靶向药物载体的制备及分析

Fe3O4 magnetic nanoparticles were prepared by the aqueous co-precipitation of FeCl3-6H2O and FeCl2-4H2O with addition of ammonium hydroxide. The conditions for the preparation of Fe3O4 magnetic nanoparticles were optimized, and Fe3O4 magnetic nanoparticles obtained were characterized systematically by means of transmission electron microscope （TEM）, dynamic laser scattering analyzer （DLS） and X-ray diffraction （XRD）. The results revealed that the magnetic nanoparticles were cubic shaped and dispersive, with narrow size distribution and average diameter of 11.4 nm. It was found that the homogeneous variation of pH value in the solution via the control on the dropping rate of aqueous ammonia played a critical role in size distribution. The magnetic response of the product in the magnetic field was also analyzed and evaluated carefully. A 32.6 mT magnetic field which is produced by four ferromagnets was found to be sufficient to excite the dipole moments of 0.05 g Fe3O4 powder 2 cm far away from the ferromagnets. In conclusion, the Fe3O4 magnetic nanoparticles with excellent properties were competent for the magnetic carders of targeted-drug in future application.     

超声辅助合成磁性四氧化三铁/氧化石墨烯复合物及其在染料去除中的应用（英文）

A simple ultrasound-assisted co-precipitation method was developed to prepare ferroferric oxide/graphene oxide magnetic nanoparticles (Fe3O4/GO MNPs). The hysteresis loop of Fe3O4/GO MNPs demonstrated that the sample was typical of superparamagnetic material. The samples were characterized by transmission electron microscope, and it is found that the particles are of small size. The Fe3O4/GO MNPs were further used as an adsorbent to remove Rhodamine B. The effects of initial pH of the solution, the dosage of adsorbent, temperature, contact time and the presence of interfering dyes on adsorption performance were investigated as well. The adsorption equilibrium and kinetics data were fitted well with the Freundlich isotherm and the pseudo-second-order kinetic model respectively. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption of Rhodamine B. And the adsorption process was endothermic in nature. Furthermore, the magnetic composite with a high adsorption capacity of Rhodamine B could be effectively and simply separated using an external magnetic field. And the used particles could be regenerated and recycled easily. The magnetic composite could find potential applications for the removal of dye pollutants.     

Effect of preparation methods on the structure and catalytic performance of Fe–Zn/K catalysts for CO_2 hydrogenation to light olefins

Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5~+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.     

Synthesis and Properties of Micron-size Magneic Polymer Spheres with Epoxy Groups

Micron-size superparamagnetic poly(styrene-divinylbenzene-glycidyl methacrylate) (PSt-DVB-GMA)spheres were prepared via a modified suspension copolymerization method. Oleic acid coated magnetite (Fe_3O_4)nanoparticles made by co-precipitation were first mixed with monomers of St, DVB, GMA, and benzoyl peroxide(BPO) to form oil in water suspension with the presence of poly(vinyl pyrrolidone) (PVP-K30) as a stabilizer.Then the temperature of mixture was increased at a controlled rate to obtain small and relatively uniform droplets.Finally, the copolymerization reaction was initiated by the decomposition of BPO. The morphology and propertiesof magnetic PSt-DVB-GMA microspheres were examined by SEM, TEM, VSM, XRD and FT-IR. The magneticmicrospheres obtained have very small size (about 4-7μm) in diameter with narrow size distribution and super-paramagnetic characteristics. Powder X-ray diffraction measurements show the inverse cubic spinel structure forthe magnetite dispersed in polymer microspheres. FT-IR     

Numerical study of homogeneous–heterogeneous reactions on stagnation point flow of ferrofluid with non-linear slip condition

This study deals with the stagnation point flow of ferrofluid over a flat plate with non-linear slip boundary condition in the presence of homogeneous-heterogeneous reactions.Three kinds of ferroparticles,namely,magnetite(Fe_3O_4),cobalt ferrite(CoFe_2O_4) and manganese zinc ferrite(Mn-ZnFe_2O_4) are taken into account with water and kerosene as conventional base fluids.The developed model of homogeneous-heterogeneous reactions in boundary layer flow with equal and unequal diffusivities for reactant and autocatalysis is considered.The governing partial differential equations are converted into system of non-linear ordinary differential equations by mean of similarity transformations.These ordinary differential equations are integrated numerically using shooting method.The effects of pertinent parameters on velocity and concentration profiles are presented graphically and discussed.We found that in the presence of Fe_3O_4-kerosene and CoFe_2O_4-kerosene,velocity profiles increase for large values of α and β whereas there is a decrement in concentration profiles with increasing values of if and K_s.Furthermore,the comparison between non-magnetic(A1_2O_3) and magnetic Fe_3O_4 nanoparticles is given in tabular form.     

Structure,characterization, and dynamic performance of a wet air oxidation catalyst Cu–Fe–La/γ-Al_2O_3

A Cu–Fe–La/γ-Al_2O_3(CFLA) catalyst was prepared by the excessive impregnation method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that the catalyst contained mostly Cu~(2+), Fe~(3+), and La~(3+)and a small amount of Cu~+, Fe~(2+), and La. The active components were uniformly distributed in the catalyst, and the particle size of the components was approximately 7.5 nm. The CFLA catalyst was used for the treatment of methyl orange(MO) solution by catalytic wet air oxidation(CWAO), and it exhibited a high catalytic activity. The catalytic reaction involved variable valence states of metals and free-radical reaction mechanism. The CWAO reaction of MO solution was fitted by a segmented first-order dynamic model, and the rapid reaction apparent activation energy was 13.9 k J·mol~(-1).     

离子液体修饰超顺磁性纳米颗粒用于青霉素G酰化酶固定化(英文)

Functionalized ionic liquids containing ethyoxyl groups were synthesized and immobilized on magnetic silica nanoparticles(MSNP) prepared by two steps,i.e.,Fe3O4 synthesis and silica shell growth on the surface.This magnetic nanoparticle supported ionic liquid(MNP-IL) were applied in the immobilization of penicillin G acylase(PGA).The MSNPs and MNP-ILs were characterized by the means of Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and vibrating sample magnetometer(VSM).The results showed that the average size of magnetic Fe3O4 nanoparticles and MSNPs were ~10 and ~90 nm,respectively.The saturation magnetizations of magnetic Fe3O4 nanoparticles and MNP-ILs were 63.7 and 26.9 A?m2?kg?1,respectively.The MNP-IL was successfully applied in the immobilization of PGA.The maximum amount of loaded enzyme was about 209 mg?g?1(based on carrier),and the highest enzyme activity of immobilized PGA(based on ImPGA) was 261 U?g?1.Both the amount of loaded enzyme and the activity of ImPGA are at the same level of or higher than that in previous reports.After 10 consecutive operations,ImPGA still main-tained 62% of its initial activity,indicating the good recovery property of ImPGA activity.The ionic liquid modified magnetic particles integrate the magnetic properties of Fe3O4 and the structure-tunable properties of ionic liquids,and have extensive potential uses in protein immobilization and magnetic bioseparation.This work may open up a novel strategy to immobilize proteins by ionic liquids.     

Catalytic ozonation of thymol in reverse osmosis concentrate with core/shell Fe3O4@SiO2@Yb2O3 catalyst:Parameter optimization and degradation pathway

In this work, a novel catalyst of Fe_3O_4@SiO_2@Yb_2O_3 was prepared and the degradation of thymol in reverse osmosis concentrate using ozonation was explored. The operational parameters, such as ozone dosage(8–48 mg·min~(-1)),initial thymol concentration(20–100 mg·L~(-1)), initial pH value(3–11), and catalyst Fe_3O_4@SiO_2@Yb_2O_3dosage(0.2–1.0 g), were studied focusing on the thymol degradation and COD removal. The results indicated that the increase in ozone dosage, initial p H value, and Fe_3O_4@SiO_2@Yb_2O_3dosage accelerated the thymol degradation and COD removal, while the increase in initial thymol concentration hampered the effect of ozonation. A pathway of thymol degradation by catalytic ozonation was proposed based on the intermediates detected by gas chromatography-mass spectrometer and ion chromatography. This paper can provide basic data and technical alternative for pollutant removal from reverse osmosis concentrate by ozonation.     

分散聚合法合成含有环氧基的无孔超顺磁性微球及其表征

Non-porous superparamagnetic polymer microspheres with epoxy groups were prepared by dispersion polymerization of glycidyl methacrylate (GMA) in the presence of magnetic iron oxide (Fe3O4) nanoparticles coated with oleic acid. The polymerization was carried out in the ethanol/water medium using polyvinylpyrrolidone (PVP) and 2,2'-azobisisobutyronitrile (AIBN) as stabilizer and initiator, respectively. The magnetic microspheres obtained were characterized with scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the magnetic microspheres had an average size of 1μm with superparamagnetic characteristics. The saturation magnetization was found to be 4.5emu·g-1. There was abundance of epoxy groups with density of 0.028 mmol·g-1 in microspheres. The magnetic PGMA microspheres have extensive potential uses in magnetic bioseparation and biotechnology.     

以类水滑石为前体的Ni催化剂及其催化甲烷水蒸气重整制氢:催化活性和动力学(英文)

Ni/Mg–Al catalysts derived from hydrotalcite-type precursors were prepared by a co-precipitation technique and applied to steam reforming of methane. By comparison with Ni/γ-Al2O3 and Ni/α-Al2O3 catalysts prepared by in-cipient wetness impregnation, the Ni/Mg–Al catalyst presented much higher activity as a result of higher specific surface area and better Ni dispersion. The Ni/Mg–Al catalyst with a Ni/Mg/Al molar ratio of 0.5:2.5:1 exhibited the highest activity for steam methane reforming and was selected for kinetic investigation. With external and inter-nal diffusion limitations eliminated, kinetic experiments were carried out at atmospheric pressure and over a temperature range of 823–973 K. The results demonstrated that the overal conversion of CH4 and the conversion of CH4 to CO2 were strongly influenced by reaction temperature, residence time of reactants as wel as molar ratio of steam to methane. A classical Langmuir–Hinshelwood kinetic model proposed by Xu and Froment (1989) fitted the experimental data with excellent agreement. The estimated adsorption parameters were consistent thermodynamical y.     

带环氧基的超顺磁性高分子微球的制备及其性能表征

Micron-size superparamagnetic poly(styrene-divinylbenzene-glycidyl methacrylate) (PSt-DVB-GMA)spheres were prepared via a modified suspension copolymerization method. Oleic acid coated magnetite (Fe3O4) nanoparticles made by co-precipitation were first mixed with monomers of St, DVB, GMA, and benzoyl peroxide (BPO) to form oil in water suspension with the presence of poly(vinyl pyrrolidone) (PVP-K30) as a stabilizer.Then the temperature of mixture was increased at a controlled rate to obtain small and relatively uniform droplets.Finally, the copolymerization reaction was initiated by the decomposition of BPO. The morphology and properties of magnetic PSt-DVB-GMA microspheres were examined by SEM, TEM, VSM, XRD and FT-IR. The magnetic microspheres obtained have very small size (about 4-7 μm) in diameter with narrow size distribution and superparamagnetic characteristics. Powder X-ray diffraction measurements show the inverse cubic spinel structure for the magnetite dispersed in polymer microspheres. FT-IR spectroscopy indicates extensive oxirane groups existed on the surface of magnetic PSt-DVB-GMA microspheres.     

Performance investigation of Fe3O4 blended poly (vinylidene fluoride) membrane on filtration and benzyl alcohol oxidation: Evaluation of sufficiency for catalytic reactors

Fe_3O_4-PVDF membranes were prepared by blending of magnetic Fe_3O_4 powders with polyvinylidene fluoride to investigate whether those were usable or not in catalytic membrane reactors. Filtration performances and catalytic activity of membranes in microwave conditions were measured in separate processes. Composite Fe_3O_4-PVDF membranes were characterized by TG-DTA, FTIR, XRD, SEM and contact angle techniques.Disappearing of α-phases at PVDF was observed with increasing amount of additives from XRD diffraction patterns. Decomposition of polymer fastened due to catalytic effect of Fe_3O_4. Finger-like structures and large number of small pores were observed at the SEM images. Those provided effective transportation of substrate among the active sites of catalyst. At the experiments conducted in batch reactor, 51%, 77%, 66% and 63% benzyl alcohol conversion were recorded for 2%, 4%, 6% and 8% Fe_3O_4-PVDF composite pieces respectively. Catalyst were separated magnetically and reused several times. On the other hand Fe_3O_4 blended PVDF membranes provided improved flux and BSA rejection compared with performance of bare PVDF membrane; 41.6% BSA rejection was obtained with 4% Fe_3O_4-PVDF whereas it was only 6.7% for PVDF. Fe_3O_4-PVDF composites performed high activity for the benzyl alcohol oxidation in batch reactor and also better filtration at filtration cell. These results promise to obtain practical and low cost membrane material for catalytic reactors usable in microwave support to get fast results.     

Kinetic and thermodynamic studies of acid scarlet 3R adsorption onto low-cost adsorbent developed from sludge and straw简

A low-cost adsorbent was prepared from sludge and straw by pyrolysis in a dried state with the surface area of the adsorbent of 829.49 ma. g-l, micropore volume of 0.176 cm2·g-1 and average pore radius of 5.0 nm. The kinetic, equilibrium isotherm and thermodynamic characteristics of trisodium 1-（1-naphthylazo）-2-hydroxynaphthalene- 4＇,6,8-trisulphonate （acid scarlet 3R） onto the adsorbent from sludge and straw were investigated. The results indicated that the pseudo second order adsorption was the predominant adsorption mechanism of acid scarlet 3R. Thus, the adsorption phenomenon was suggested as a chemical process. The adsorption data were fitted better with Langmuir model than Freundlich model, indicating that the adsorption of acid scarlet 3R belonged to the monolayer adsorption and mainly occurred in micropores.     

Hydrothermal and entropy generation specifications of a hybrid ferronanofluid in microchannel heat sink embedded in CPUs

The objective of this numerical work is to evaluate the first law and second law performances of a hybrid nanofluid flowing through a liquid-cooled microchannel heatsink.The water-based hybrid nanofluid includes the Fe_3O_4 and carbon nanotubes(CNTs) nanoparticles.The heatsink includes a microchannel configuration for the flow field to gain heat from a processor placed on the bottom of the heatsink.The effects of Fe_3O_4 concentration(φFe_3O_4),CNT concentration(φ_(CNT)) and Reynolds number(Re) on the convective heat transfer coefficient,CPU surface temperature,thermal resistance,pumping power,as well as the rate of entropy generation due to the heat transfer and fluid friction is examined.The results indicated higher values of convective heat transfer coefficient,pumping power,and frictional entropy generation rate for higher values of Re,φFe_3O_4 and φ_(CNT).By increasing Re,φFe_3O_4 and φ_(CNT),the CPU surface temperature and the thermal resistance decrease,and the temperature distribution at the CPU surface became more uniform.To achieve the maximum performance of the studied heatsink,applying the hybrid nanofluid with low φFe_3O_4 and φ_(CNT) was suggested,while the minimum entropy generation was achieved with the application of nanofluid with high φFe_3O_4 and φ_(CNT).     

铁酸镍负载TiO2的可磁分离光催化剂的制备及性能

A magnetically separable photocatalyst TiO2/SiO2/NiFe2O4 （TSN） with a typical ferromagnetic hysteresis was prepared by a liquid catalytic phase transfer method. When the intensity of applied magnetic field weakened to zero, the remnant magnetism of the prepared photocatalyst faded to zero. The photocatalytst can be separated from water when an external magnetic field is added and redispersed into aqueous solution after the external magnetic field is eliminated, that makes the photocatalysts promising for wastewater treatment. Transmission electron microscope （TEM） and X-ray diffractometer （XRD） were used to characterize the structure of the photocatalyst indicating that the magnetic SiOffNiFe204 （SN） particle was compactly enveloped by P-25 titania and Tit2 shell was formed. The magnetic composite showed high photocatalytic activity for the degradation of methyl orange in water. A thin SiO2 layer between NiFe2O4 and TiO2 shell prevented effectively the leakage of charges from TiO2 particles to NiFe2O4, which gave rise to the increase in photocatalytic activity. Moreover, the experiment on recycled use of TSN demonstrated a good repeatability of the photocatalytic activity.     

Influence of synthesis parameters on the properties of LiFePO4/C cathode material☆

The influence of sintering temperature,carbon content and dispersive agent in ball-milling was investigated on the properties of Li Fe PO_4/C prepared using Fe_2O_3,NH_4H_2PO_4,Li_2CO_3 and glucose via solid state reaction.X-ray powder diffraction,scanning electron microscopy and charge–discharge test were applied to the characterization of the Li Fe PO_4/C samples synthesized under different conditions.Sintering temperature affects the crystallite/particle size and degree of crystallinity of LiF eP O_4,formation of Fe_2 P and maintenance of carbon in LiF e PO_4/C.Carbon maintenance is favored by low sintering temperature,and 700 °C is optimum for synthesis of LiF eP O_4/C with superior electrochemical performance.A higher carbon content in the range of 4.48%–11.03% results in a better rate capability for Li Fe PO_4/C.The dispersive agent used in ball-milling impacts the existent state of carbon in the final product which subsequently determines its charge–discharge behavior.The sample prepared at700 °C by using acetone as the dispersive agent in ball-milling exhibits an excellent rate capability and capacity retention without any fade at 0.1C,1C and 2C,with corresponding average discharge capacities of 153.8,128.3and 121.0 m A·h·g~(-1),respectively,in the first 50 cycles.     

磁场对丙酮-水-三氯乙烷物系萃取过程的影响

In order to investigate the effect of magnetic field on the liquid-liquid extraction, the extraction in the acetone-water-trichloroethane system was studied under magnetic field with different magnetic induction intensity.The results showed that the effect of magnetic field was positive in the extraction process, and the partition coeffi-cient and the yield of acetone increased-with the increasing magnetic induction intensity by 5.16%-8.35% and 1.85%-5.70% respectively. The effect of magnetic field on the extraction was intensified when the temperature became, higher. The experimental data of the partition coefficient of acetone were correlated by the method of least square in terms of a power-law correlation.     

Fabrication of Poly（y-glutamic acid）-coated Fe3O4 Magnetic Nanoparticles and Their Application in Heavy Metal Removal

In this study, poly（y-glutamic acid）-coated Fe3O4 magnetic nanoparticles （y-PGA/Fe304 MNPs） were successfully fabricated using the co-precipitation method. Fe3O4 MNPs were also prepared for comparison. The av erage size and specific surface area results reveal that 7-PGA/Fe304 MNPs （52.4 nm, 88.41 m2.g-1） have smaller particle size and larger specific surface area_ than Fe3O4 MNPs （62.0 nm, 76.83 mLg-1）. The y-PGA/Fe3O4 MNPs     

TiN/Al_2O_3 Composite Material Synthesized by Aluminothermic Reduction Process in Coke Bed

TiN/Al_2O_3 composite material was prepared by aluminothermic reduction of TiO2 in coke bed. The phase composition, lattice parameter and microstructure of products treated at 1 300 ℃, 1 400 ℃, 1 500 ℃ for 3 h respectively were analyzed by XRD, SEM and TEM. The results showed that TiN/Al_2O_3 composite material can be prepared in coke bed via aluminothermic reduction method. However, the treatment temperatures affect the evolution of aluminothermic reaction and morphology of the materials obviously. The con...     

Syntheses of Fe-Ni Magnetic Nanoparticles and Their Applications on Biologic Labeling

In this study, we compared FeNi alloy magnetic nanoparticles (MNPs) prepared by either combustion or chemical precipitation methods. We found that the FeNi MNPs generated by combustion method have a rather high saturation magnetization Ms of～180 emu/g and a coercivity field Hc of near zero. However, the alloy nanoparticles are easily aggregated and are not well dispersive such that size distribution of the nanoparticle clusters is wide and clusters are rather big (around 50～700 nm). To prepare a better quality and well dispersed Fe-Ni MNPs, we also developed a thermal reflux chemical precipitation method to synthesize FeNi3 alloy MNPs. The precursor chemicals of Fe(acac)3 and Ni(acac)2 in a molecular ratio 1,2-hexadecandiol and tri-n-octylphosphine oxide (TOPO) were used as reducer and surfactant, respectively. The chemically precipitated FeNi3 MNPs are well dispersed and have well-controlled particle sizes around 10～20 nm with a very narrow size distribution (±1.2 nm). The highly monodispersive FeNi3 MNPs present good uniformity in particle shape and crystallinity on particle surfaces. The MNPs exhibit well soft magnetism with saturation magnetization of ～61 emu/g and Hc～0. The biomedically compatible FeNi MNPs which were coated with biocompatible polyethyleneimine (PEI) polymer were also synthesized. We demonstrated that the PEI coated FeNi MNPs can enter the mammalian cells in vitro and can be used as a magnetic resonance imagine (MRI) contrast agent. The results demonstrated that FeNi MNPs potentially could be applied in the biomedical field. The functionalized magnetic beads with biocompatible polymer coated on MNPs are also completed for biomedical applications.