雾化热分解-氧化五羰基铁制备磁性氧化铁纳米粒子

通过雾化热分解-氧化五羰基铁(Fe(CO)5),在雾化液中添加三乙二醇(TREG)和三正辛基氧膦(TOPO),及在收集液中添加羧基化单甲醚聚乙二醇(MPEG—COOH)等有机修饰剂合成γ-Fe2O3纳米粒子。研究两段加热和单段加热对合成γ-Fe2O3纳米粒子的形貌、粒径、分散性的影响,同时分析温度对γ-Fe2O3纳米粒子结晶性、形貌及磁性能的影响。结果表明:合成的γ-Fe2O3纳米粒子结晶度随温度的升高而增加;MPEG—COOH已经修饰在γ-Fe2O3纳米粒子表面;在单段加热模式下温度为360,390,420℃和450℃时合成的γ-Fe2O3纳米粒子在300K下都具有超顺磁性,饱和磁化强度分别为30,37,41,71A·m2·kg-1;单段加热模式较两段加热模式合成的γ-Fe2O3纳米粒子分散性更好。     

P(AA-co-MPC)修饰超顺磁性Fe3O4纳米粒子的制备与表征

以丙烯酸(AA)和2-甲基丙烯酰氧乙基磷酰胆碱(MPC)为单体,采用RAFT聚合合成系列共聚物(P(AA-co-MPC)),并通过化学共沉淀法制备P(AA-co-MPC)表面修饰的磁性Fe3O4纳米粒子。利用1H NMR,FTIR,GPC,TG,TEM,XRD,Zeta电位及粒度分析仪和Squid-VSM磁性测量系统等手段对共聚物和纳米粒子进行表征。结果表明:采用RAFT聚合成功合成了窄分子量分布的P(AA-co-MPC),磁性Fe3O4纳米粒子表面含有修饰基团;单体摩尔比(AA∶MPC)为1∶1时合成的共聚物修饰磁性Fe3O4纳米粒子的分散性最好,具有最小的水合粒径(36.54±4.00)nm和最窄的粒径分布,最高的Zeta电位(-30.98±1.25)mV,饱和磁化强度为65.57A·m^2·kg^-1,剩磁和矫顽力均为零,具有超顺磁性。     

亲油性金纳米粒子的合成

利用相转移法成功地合成了粒径在2～7nm的硫醇表面修饰Au纳米粒子.采用透射电子显微镜、纳米粒度分布仪、红外光谱分析仪等现代测试技术对所合成的Au纳米粒子进行了表征.结果表明,表面为硫醇所修饰的Au纳米粒子,在有机溶剂中具有很好的分散性,表面修饰层的存在不仅有效地阻止Au纳米粒子的团聚,而且使得纳米粒子粒径分布窄,粒径可控.     

亲油性LaF3纳米粒子的制备及表征

在醇-水混合溶剂中合成了表面为油酸修饰的LaF3纳米粒子,并用透射电子显微镜、红外光谱和X射线粉末衍射仪对修饰LaF3纳米粒子进行了表征.结果表明:所制备的修饰LaF3纳米粒子大小均匀,粒径约为8nm;其纳米核为六方结构的LaF3;由于表面修饰剂油酸与LaF3纳米粒子表面之间发生化学键合作用,使得油酸修饰LaF3纳米粒子在苯及润滑油中的分散性明显提高.     

交联β-环糊精聚合物/Fe3O4核壳结构复合纳米颗粒的制备和性能研究

以羧甲基-β-环糊精为表面修饰剂对Fe3O4纳米粒子进行包覆修饰,以环氧氯丙烷为交联剂,在β-环糊精的碱性溶液中通过Fe3O4纳米粒子表面进行的交联反应制备了交联β-环糊精聚合物/Fe3O4复合纳米颗粒.利用FTIR、XRD、TEM和TGA分剐对复合纳米颗粒的结构、形貌和尺寸进行了表征.结果表明,制备的复合纳米颗粒为近球形、核壳结构,粒径约为10～20nm,环糊精聚合物含量为29%,在水中的分散性良好.磁性能测试和包合性能测试表明,复合纳米颗粒为超顺磁性,对特定分子具有一定的包合能力,可用于靶向给药系统和特定物质分离的载体.     

单分散纳米TiO2的合成及表征

以钛酸四丁酯为原料和三乙醇胺为形态控制剂,采用溶胶-凝胶-水热法可以简单快速地合成单分散的TiO2纳米粒子.研究了反应物料配比、凝胶形成温度、水热处理温度等反应条件对粒子粒径及分散性的影响.采用XRD和TEM等手段对粒子的结构与形貌进行了表征.结果表明,三乙醇胺与钛酸四丁酯物质的量配比为2:1,凝胶形成温度为100℃,水热处理温度为140℃时,所合成的TiO2粒子分散性最好.     

氨基修饰磁性氧化铁纳米粒子的制备

以聚乙二醇(PEG)为溶剂,高温热分解乙酰丙酮铁(Fe(acac)3)合成了磁性氧化铁纳米粒子。为改善氧化铁纳米粒子表面性能和生物应用潜能,分别用N,N二甲基甲酰胺和聚酰胺-胺(PAMAM)进行表面修饰,在氧化铁纳米粒子表面接枝-NH2活性官能团。分别采用X射线衍射仪(XRD)、透射电镜(TEM)、红外光谱(FT-IR)、动态光散射(DSL)对样品进行了表征测试。XRD和TEM结果表明高温热分解法合成的纳米粒子平均粒径为10nm,具有较好的结晶性和单分散性;FT-IR、DSL粒径和表面电位测试结果表明氨基官能团成功修饰在氧化铁纳米粒子表面,同时使氧化铁纳米粒子在水溶液中的稳定性增强。     

MPEG修饰的纳米氧化铁粒子的合成及清洗工艺

以MPEG为溶剂、还原剂及修饰剂,Fe(acac)3为铁源,通过高温热分解法制备了超顺磁性氧化铁纳米粒子(SPIONs).采用饱和食盐水清洗方法对合成的粒子进行收集,经透析除去其表面残留的NaCl.采用XRD,TEM,HRTEM,SQUID,ICP MS,TGA,FT IR,纳米粒度与Zeta电位分析仪对样品进行表征.结果表明:经透析处理后氧化铁的质量分数为NaCl的6.9×104倍,制备的SPIONs具有高的结晶度及单分散性,在300K下,具有超顺磁性,饱和磁化强度为53.7A· m2·kg-1;具有惰性端基的MPEG修饰于SPIONs表面,为其提供了良好的水分散性.采用盐桥法萃取清洗工艺可清除过量的MPEG,有利于SPIONs更好的应用在生物医学领域.     

多肽或转铁蛋白接枝的氧化铁纳米粒子的制备及表征

以聚乙二醇(PEG)为还原剂、溶剂和修饰剂,将乙酰丙酮铁(Fe(acac)_3)高温热分解合成超顺磁性氧化铁纳米粒子(Superparamagnetic iron oxide nanoparticles,SPIONs)。透射电镜(TEM)结果显示:纳米粒子形状规则,分布均匀,平均粒径为7.5±1.0 nm。XRD结果表明样品主相为结晶良好的Fe_3O_4。通过将SPIONs表面修饰的PEG与马来酸酐(Mal)结合,再借助EDC-NHS的方法,分别与多肽(angiopep-2,ANG)或转铁蛋白(transferrin,Tf)接枝。结果表明:修饰ANG的SPIONs的水合动力学粒径为42 nm,zeta电位为-9.9 mV,ANG的修饰量为19 wt%,饱和磁化强度为58emu/g;修饰Tf的SPIONs的水合动力学粒径为96 nm,zeta电位为2.3 mV,Tf的修饰量为10 wt%,饱和磁化强度为43 emu/g。红外分析表明ANG或Tf分别共同修饰在SPIONs表面。修饰物使纳米粒子具有良好了水分散性。本工作为SPIONs应用于生物医学研究建立了材料基础。     

原位表面修饰纳米CdS粒子的表面结构和光学性能

采用微乳液法合成了纳米尺度硫化镉粒子,并用硫醇和咪唑对粒子进行了原位表面修饰.对纳米硫化镉粒子的形貌与表面结构进行了表征,证实了表面修饰剂与粒子间的键合.电镜观察和紫外-可见吸收光谱的测定发现,表面修饰明显地提高了纳米粒子在溶剂中的分散性,改变了纳米粒子的表面结构,消除了粒子表面导致无辐射弛豫的缺陷,因而提高了纳米粒子分散于溶剂体系的荧光性能.修饰剂与溶剂间的相互作用决定了表面修饰粒子在溶剂中的分散性,对纳米粒子的光学性能也有一定的影响.     

Multifunctional iron and iron oxide nanoparticles in silica

Iron and iron oxide nanoparticles in silica layers deposited by sol–gel techniques on Si wafers were formed and studied. It was shown that multifunctional nanoparticles of different iron oxides possessing various physical properties can be fabricated by means of post-growth annealing of (SiO₂:Fe)/SiO₂/Si samples in various atmospheres. The hematite, maghemite, and iron nanoparticles were found to be dominant upon annealing the samples in air, argon, and hydrogen atmosphere, respectively. The physical properties of produced hybrid structures were studied by Raman and FT-IR spectroscopy, spectroscopic ellipsometry, AFM, and magnetic measurements. The sol–gel technique with subsequent annealing procedure is demonstrated to be an effective method for the formation of multifunctional hybrid structures composed of iron or iron oxide nanoparticles in silica matrix.     

Synthesis of ordered iron oxide nanoparticle arrays in planar DNA complexes

The formation of iron oxide nanoparticles in planar DNA complexes immobilized on substrates has been studied in reactions involving only biogenic reagents (ferritin and ascorbic acid) in aqueous solutions under normal conditions. Using transmission electron microscopy, we revealed ordered quasi-linear arrays of iron oxide nanoparticles 2–4 nm in diameter, which probably resulted from nanoparticle binding to linear DNA molecules. The electron diffraction patterns of the synthesized nanoparticles are characteristic of polycrystalline magnetic iron oxide (magnetite of maghemite) nanoparticles and point to good crystallinity of the nanoparticles. Our results demonstrate the feasibility of the synthesis of ordered arrays of iron oxide nanoparticles using DNA complexes and may have direct implications for the understanding of biomineralization processes and iron metabolism in living systems.     

One-pot size and shape controlled synthesis of DMSO capped iron oxide nanoparticles

We report here the capping of iron oxide nanoparticles with dimethyl sulfoxide (DMSO) to make chloroform soluble iron oxide nanoparticles. Size and shape of the capped iron oxide nanoparticles are well controlled by simply varying the reaction parameters. The synthesized nanocrystallites were characterized by thermal analysis (TG-DTA), powder X-ray diffraction (XRD), transmission electron microscopy (TEM) for evaluating phase, structure and morphology. ¹H NMR spectra of the synthesized samples confirm DMSO, and the capping of DMSO on the ferrite samples. Shift of the S=O stretching frequency in Fourier transformed infra-red (FTIR) spectra indicates that the bonding between DMSO and ferrite is through an oxygen moiety. The magnetic measurements of all the synthesized samples were investigated with a SQUID magnetometer which shows that the magnetic properties are strongly dependent on the size as well as shape of the iron oxide.     

A Review on Iron Oxide Nanoparticles and Their Biomedical Applications

The iron oxide nanoparticles have a great attraction in biomedical applications due to their non-toxic role in the biological systems. The iron oxide nanoparticles have both magnetic behaviour and semiconductor property which lead to multifunctional biomedical applications. The iron oxide nanoparticles used in biomedical fields such as antibacterial, antifungal and anticancer were reviewed. The uses of hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) nanoparticles, for an inhibition time in biological activities, are listed in this work. Also, this review explains the use of iron oxide nanoparticles in the biomedical fields with particular attention to the application of hematite and superparamagnetic iron oxide nanoparticles. In this review, analysis reveals that the role of iron oxide in biological activity is good due to its biocompatibility, biodegradability, ease of synthesis and different magnetic behaviours. The change of properties of iron oxide nanoparticles such as particle size, morphology, surface, agglomeration and electronic properties has specific impact in biomedical application. The review mainly focused in and discussed about antibacterial, anticancer, bone marrow and cell labelling activities. From this review work, the iron oxide nanoparticle may be specialised in particular bacterial and cancer treatments. Also discussed are the iron oxide nanoparticle-specific biomedical applications like human placenta, insulin and retinal locus treatments.     

Preparation of nanocomposites resin from seed Pterodon emarginatus doped maghemite nanoparticles

Electrical characterization and magnetic nanocomposite resin seeds Pterodon emarginatus (PE) doped with nanoparticles of maghemite and treated by different chemical processes is reported in this paper. The pure PE resin showed semiconducting characteristics probably the presence of natural iron oxide in its molecular structure. The analysis of M?ssbauer spectra pure resin showed two magnetic sites presented on measurements made at temperature of 300 K. Six "LEDs" to have been doped maghemite nanoparticles forming concentrations of 2.6 x 10(15) to 1.56 x 10(16) particles/cm2 forming the LED-PEMN. In the presence of the applied current versus voltage (0 to 0.9 V) LED-PEMN shown semiconducting properties. In the presence of frequency versus voltage sample of pure resin and LED features small decrease. While samples of LED-PEMN suffers loss frequency linearly with concentration and voltage. The pure PE resin shows high resistance to the applied voltage while the LED-PEMN is observed linear increase with the strength and concentration of nanoparticles of maghemite.     

Nanoparticles of pure and substituted maghemites (gamma-M(x)Fe(2_x)O3 where M = Al, Cr, Mn, Zn and 0 < or = x < or = 1.3): a comparative study

Magnetic nanoparticles of pure and substituted iron oxides are prepared by single step autocombustion or by wet chemical methods. The nanoparticles prepared by the first process had mixed phase of hematite and maghemite whereas the later essentially gives maghemite phase. XRD patterns and TEM micrographs of the pure and substituted maghemites samples suggest about their monophasic nature and inverse spinel structure. Further, the size of the particles for the above iron oxide samples was found to be in the range of 4 to 30 nm. Saturation magnetization value for the samples was observed to be varying with the type and the amount of substitution. For example, magnetization value initially increased and then decreased for Al- and Mn-substitutions but it continuously decreased for Cr- and Zn-substitutions. Contrary to the saturation magnetization value, the Curie temperature decreased continuously with increased substitutions irrespective of the type of substitutions. Due to higher magnetization value of Mn-substituted maghemite (for x = 0.2, 78 Am2/kg), it has higher heating ability and specific absorption rate compared to Al-substituted maghemite (for x = 0.07, 70 Am2/kg) and pure maghemite (62 Am2/kg).     

Capillary magnetic field flow fractionation and analysis of magnetic nanoparticles

This paper reports the purification and analysis of magnetic nanoparticles using capillary magnetic field flow fractionation, which utilizes an applied magnetic field oriented orthogonal to the capillary flow. To validate this approach as a separation method for nanometer-scale particles, samples of magnetic nanoparticles composed of either gamma-Fe2O3 (maghemite) or CoFe2O4 with average diameters ranging from 4 to 13 nm were prepared and characterized by transmission electron microscopy and SQUID magnetometry. Retention of the samples on the capillary was investigated as a function of solvent flow rate and the nanoparticle size and composition; the elution times of the nanoparticles are strongly dependent on their magnetic moments. We demonstrate the use of this method to separate a mixture of nanoparticles into size-monodisperse fractions. The magnetic moments of the particles are calculated based on analysis of the retention parameters and correlate with values obtained in separate SQUID magnetometry measurements.     

Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Core-shell iron-iron oxide nanoparticles synthesized by laser-induced pyrolysis

Passivated iron nanoparticles (10-30 nm) have been synthesized by laser pyrolysis of a mixture of iron pentacarbonyl and ethylene vapors followed by controlled oxidation. The nanoparticles show a well-constructed iron-iron oxide core-shell structure, in which the thickness and nature (structure similar to maghemite, gamma-Fe2O3) of the shell is found to be independent of the initial conditions. On the other hand, the composition of the core is found to change with the particle size from the alpha-Fe structure to a highly disordered Fe phase (probably containing C atoms in its structure). The dependence of the magnetic properties on the particle size, iron oxide fraction, and temperature was also investigated. In the case of smaller particles, the magnetic data indicate the existence at low temperature of a large exchange anisotropy field, the magnitude of which increases with decreasing temperature in correspondence with the freezing of magnetic moments in the oxide shell.     

Synthesis of silica-coated aqueous ferrofluids through ligand exchange with a new organosilica precursor

A new method for the production of aqueous dispersions of superparamagnetic iron oxide nanoparticles with applications in biomedicine is reported. The method is based on the use of a triethoxisilyl dodecanoic acid ligand that has been specially synthesized for this purpose. The nanoparticles were grown in organic medium using oleic acid as surfactant. Subsequently, oleic acid was exchanged for the alkoxysilane ligand, then hydrolysis was performed in a hydrocarbon solvent, and the nanoparticles were transferred into water. The organic and aqueous ferrofluids have been characterized and their magnetic properties have been determined. The resulting maghemite/silica nanoparticles were single core, and stable in aqueous suspension.