表面巯基化修饰的磁性Fe3O4纳米粒子合成与表征

通过化学共沉淀法制备了粒径约30nm的磁性四氧化三铁(Fe3O4)纳米粒子,并采用3-巯丙基三乙氧基硅烷(MPTES)将Fe3O4纳米粒子表面修饰上巯基(-SH)官能团,获得了表面巯基化的磁性Fe3O4纳米粒子。利用X-射线粉末衍射仪(XRD),透射电子显微镜(TEM),带有能谱仪(EDS)的扫描电子显微镜(SEM),光电子能谱仪(XPS),以及磁学测量系统(MPMS)对粒子的结构和性能进行了表征和分析。结果表明:表面巯基化后的磁性粒子粒径略有增加,室温下磁化强度由原来的64emu/g变为62emu/g,较好地保留了原始磁性特征。研究结果对巯基化磁性纳米粒子实现生物分子结合、固定负载乃至生物传感的应用具有重要意义。     

Modification of Magnetite Cellulose Nanoparticles via Click Reaction for use in Controlled Drug Delivery

Superparamagnetic Fe₃O₄ nanoparticles (MNPs) were functionalized by modified cellulose. The modified cellulose was synthesized through bromoacetylation of cellulose (BACell) followed by the substitution of sodium azide to form BACell-N₃. The remaining methylene bromide groups on BACell-N₃ was further reacted with the MNPs to form Fe₃O₄/Cell-N₃. Then propargyl alcohol (PA) was immobilized on the azide-terminated Fe₃O₄ nanoparticles through copper (I)-catalyzed azide-alkyne cycloaddition (click reaction) to form Fe₃O₄/Cell/TAA nanoparticles. Doxorubicin (DOX) was loaded on prepared nanoparticles and release profiles of the DOX as a model drug from the Fe₃O₄/Cell/TAA nanoparticles and its loading capacity were determined by UV–Vis absorption at λ_max 483?nm.     

Synthesis of Magnetite Nanoparticles with PDLLA Corona

The ring-opening polymerization (ROP) of D,L-lactide (DLLA) initiated by tin(II) 2-ethylhexanoate (Sn(Oct)₂) on the surface-initiated magnetite (Fe₃O₄) nanoparticles was performed at 130 °C. Effects of the polymer molar mass and concentration on the amount of polymer on the surface were investigated. The number average molecular weights, M _n , that we obtained by both nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) methods fit well within the accuracy of the applied methods, and range from 1,100 g · mol⁻¹ to 4,040 g · mol⁻¹. The surface functionalization density for up to 3,900 initiation sites per particle was obtained. The composition of various particles with poly(D,L-lactide) (PDLLA) corona is by means of thermogravimetric analysis (TGA), and indicates magnetite (Fe₃O₄) content between 17 wt.% and 59 wt.%. An erratum to this article can be found at     

CTAB存在下纳米Pd粒子的超声诱导生长

在微量十六烷基三甲基溴化铵(CTAB)存在下,超声辐射PdCl2的乙醇水溶液,制得了纳米Pd粒子,用XRD、UV、TEM和HRTEM等进行了表征,探讨了超声诱导纳米Pd粒子的生长过程。结果表明,当超声辐射50min时,得到呈多边形的纳米Pd粒子,粒径分布较集中,大约为10nm。     

磁微粒子Fe3O4纯化CdS纳米晶的实验研究

以L-半胱氨酸、醋酸镉为原料,在磁微粒子Fe3O4存在下,通过水热法合成出CdS纳米晶与磁微粒子连接混合体,利用磁微粒子的磁性对合成的CdS纳米晶进行分离纯化,然后加入聚乙烯吡咯烷酮(PVP)、3-巯基丙酸使磁微粒子与硫化镉纳米晶分离。对产品进行了详尽的XRD、SEM、HRTEM及EDS能谱表征分析,并测试了纯化前后样品的荧光激发谱与荧光发射谱,荧光光谱显示获得预期的纯化效果。     

Modification of Magnetite Nanoparticles with Triazine-Based Dendrons and Their Application as Drug-Transporting Systems

The following research aims at the synthesis of magnetite nanoparticles functionalized with triazine-based dendrons and the application of the obtained materials as effective sorptive materials dedicated to acidic bioactive compounds. The adopted synthetic approach involved: (1) the synthesis of nanosized Fe₃O₄ particles via classic co-precipitation method, (2) the introduction of amine groups on their surface leading to materials’ precursor, and (3) the final synthesis of branched triazine-based dendrons on the support surface by an iterative reaction between cyanuric chloride (CC) and piperazine (p) or diethylenetriamine (DETA) via nucleophilic substitution. The characterized materials were tested for their adsorptive properties towards folic acid, 18β–glycyrrhetinic acid, and vancomycin, showing high adsorption capacities varying in the ranges of 53.33–401.61, 75.82–223.71, and 68.17–132.45 mg g⁻¹, respectively. The formed material–drug complexes were also characterized for the drug-delivery potential, performed as in vitro release studies at pH 2.0 and 7.4, which mimics the physiological conditions. The release profiles showed that the proposed materials are able to deliver up to 95.2% of the drugs within 48 h, which makes them efficient candidates for further biomedical applications.     

Synthesis of Environmentally Friendly Highly Dispersed Magnetite Nanoparticles Based on Rosin Cationic Surfactants as Thin Film Coatings of Steel

This work presents a new method to prepare monodisperse magnetite nanoparticles capping with new cationic surfactants based on rosin. Core/shell type magnetite nanoparticles were synthesized using bis-N-(3-levopimaric maleic acid adduct-2-hydroxy) propyl-triethyl ammonium chloride (LPMQA) as capping agent. Fourier transform infrared spectroscopy (FTIR) was employed to characterize the nanoparticles chemical structure. Transmittance electron microscopies (TEM) and X-ray powder diffraction (XRD) were used to examine the morphology of the modified magnetite nanoparticles. The magnetite dispersed aqueous acid solution was evaluated as an effective anticorrosion behavior of a hydrophobic surface on steel. The inhibition effect of magnetite nanoparticles on steel corrosion in 1 M HCl solution was investigated using potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Results obtained from both potentiodynamic polarisation and EIS measurements reveal that the magnetite nanoparticle is an effective inhibitor for the corrosion of steel in 1.0 M HCl solution. Polarization data show that magnetite nanoparticles behave as a mixed type inhibitor. The inhibition efficiencies obtained from potentiodynamic polarization and EIS methods are in good agreement.     

Different Storage Conditions Influence Biocompatibility and Physicochemical Properties of Iron Oxide Nanoparticles

Superparamagnetic iron oxide nanoparticles (SPIONs) have attracted increasing attention in many biomedical fields. In magnetic drug targeting SPIONs are injected into a tumour supplying artery and accumulated inside the tumour with a magnet. The effectiveness of this therapy is thus dependent on magnetic properties, stability and biocompatibility of the particles. A good knowledge of the effect of storage conditions on those parameters is of utmost importance for the translation of the therapy concept into the clinic and for reproducibility in preclinical studies. Here, core shell SPIONs with a hybrid coating consisting of lauric acid and albumin were stored at different temperatures from 4 to 45 °C over twelve weeks and periodically tested for their physicochemical properties over time. Surprisingly, even at the highest storage temperature we did not observe denaturation of the protein or colloidal instability. However, the saturation magnetisation decreased by maximally 28.8% with clear correlation to time and storage temperature. Furthermore, the biocompatibility was clearly affected, as cellular uptake of the SPIONs into human T-lymphoma cells was crucially dependent on the storage conditions. Taken together, the results show that the particle properties undergo significant changes over time depending on the way they are stored.     

Chemical and Colloidal Stability of Carboxylated Core-Shell Magnetite Nanoparticles Designed for Biomedical Applications

Despite the large efforts to prepare super paramagnetic iron oxide nanoparticles (MNPs) for biomedical applications, the number of FDA or EMA approved formulations is few. It is not known commonly that the approved formulations in many instances have already been withdrawn or discontinued by the producers; at present, hardly any approved formulations are produced and marketed. Literature survey reveals that there is a lack for a commonly accepted physicochemical practice in designing and qualifying formulations before they enter in vitro and in vivo biological testing. Such a standard procedure would exclude inadequate formulations from clinical trials thus improving their outcome. Here we present a straightforward route to assess eligibility of carboxylated MNPs for biomedical tests applied for a series of our core-shell products, i.e., citric acid, gallic acid, poly(acrylic acid) and poly(acrylic acid-co-maleic acid) coated MNPs. The discussion is based on physicochemical studies (carboxylate adsorption/desorption, FTIR-ATR, iron dissolution, zeta potential, particle size, coagulation kinetics and magnetization measurements) and involves in vitro and in vivo tests. Our procedure can serve as an example to construct adequate physico-chemical selection strategies for preparation of other types of core-shell nanoparticles as well.     

Probing of Interactions of Magnetite Nanoparticles Coated with Native and Aminated Starch with a DPPC Model Membrane

Understanding the mechanism of interactions between magnetite nanoparticles and phospholipids that form cellular membranes at the molecular level is of crucial importance for their safe and effective application in medicine (e.g., magnetic resonance imaging, targeted drug delivery, and hyperthermia-based anticancer therapy). In these interactions, their surface coating plays a crucial role because even a small modification to its structure can cause significant changes to the behaviour of the magnetite nanoparticles that come in contact with a biomembrane. In this work, the influence of the magnetite nanoparticles functionalized with native and aminated starch on the thermodynamics, morphology, and dilatational elasticity of the model cell membranes was studied. The model cell membranes constituted the Langmuir monolayers formed at the air–water interface of dipalmitoylphosphatidylcholine (DPPC). The surface of the aminated starch-coated nanoparticles was enriched in highly reactive amino groups, which allowed more effective binding of drugs and biomolecules suitable for specific nano–bio applications. The studies indicated that the presence of these groups also reduced to some extent the disruptive effect of the magnetite nanoparticles on the model membranes and improved their adsorption.     

Facile Fabrication of Ultrafine Copper Nanoparticles in Organic Solvent

A facile chemical reduction method has been developed to fabricate ultrafine copper nanoparticles whose sizes can be controlled down to ca. 1 nm by using poly(N-vinylpyrrolidone) (PVP) as the stabilizer and sodium borohyrdride as the reducing agent in an alkaline ethylene glycol (EG) solvent. Transmission electron microscopy (TEM) results and UV–vis absorption spectra demonstrated that the as-prepared particles were well monodispersed, mostly composed of pure metallic Cu nanocrystals and extremely stable over extended period of simply sealed storage.     

Study of the Surface Structure of Nickel Nanoparticles Catalyzing Filamentary Carbon Growth by EXAFS: Adsorption of Probe Molecules

This work is attempt to apply EXAFS technique using probe molecules for studying the surface of Ni catalysts for carbon production. It has been demonstrated that H₂Se is suitable for the probe molecule method. It was shown that (100) and (110) planes of the nanocrystals of nickel catalysts providing formation of filamentary carbon are mainly formed by one-layer height steps.     

表面活性剂PEG400存在下单质铜的微波固相合成

报道了在表面活性剂PEG400存在下通过前驱体的微波固相法快速合成单质铜纳米粒子,其直径在80~370nm之间,前驱体则通过一步室温固相反应制备。用X射线衍射仪(XRD)和透射电子显微镜(TEM)对产物的结构和形貌进行了表征。同时,对铜纳米粒子的紫外-可见光吸收性能(UV-vis)作了测试,结果表明在600nm处有一个明显的共振吸收峰。另外,通过对比实验研究了微波辐射时间对产物形成的影响。     

Simple Interpretation of the Verwey Transition in Magnetite

The Verwey transition in magnetite is rationalized in terms of an electronic model involving correlated electron occupancy of nearest-neighbor octahedral site pairs. This formalism can be restated in terms of order-disorder theory. The site pair representation of the lattice is analyzed in terms of possible occupation states that represent respectively the ground state of the system as a trapped electron, a first excited state in which an electron can resonate between the two constituents of a site pair, and a second excited state involving two electrons on neighboring sites. The free energy of this representative assembly is then minimized to obtain the equilibrium configuration. The Verwey transition is driven by the Coulomb repulsive interaction between electrons on neighboring sites. In certain limiting cases one obtains results equivalent to the phenomenological Strässler-Kittel model, which had been successfully used on an empirical basis to analyze both the first- and second-order Verwey transitions that have been experimentally encountered with increasing departures from the ideal 4/3 ratio of oxygen/iron in magnetite.     

Magnetite (Fe3O4) Nanoparticles‐Catalyzed Sonogashira– Hagihara Reactions in Ethylene Glycol under Ligand‐Free Conditions

A novel application of nanoparticles of paramagnetic magnetite (Fe₃O₄) as an efficient catalyst for carbon‐carbon bond formation via the Sonogashira–Hagihara reaction under heterogeneous ligand‐free conditions in ethylene glycol (EG) is described. By using this catalyst, arylalkynes are produced from the reaction of aryl iodides and activated heteroaryl bromides with alkynes. The results are reproducible using the catalyst, which was prepared from different sources. The catalyst is easily separated by an external magnetic field from the reaction mixture. The separated catalyst can be recycled for several consecutive runs without appreciable loss of its catalytic activity.     

New Magnetic Polymer Nanocomposites on the Basis of Isotactic Polypropylene and Magnetite Nanoparticles for Adsorption of Ultrahigh Frequency Electromagnetic Waves

In this study, we report about the preparation of magnetic polymer nanocomposites on the basis of isotactic polypropylene and magnetite Fe₃O₄ nanoparticles. The structure and composition of polymer nanocomposite materials have been studied by scanning electron microscopy, atomic force microscopy, and X-ray dispersive analysis. The magnetic properties of polymer nanocomposites based on PP+Fe₃O₄have been investigated. It is found that not significant adhesion and agglomeration of nanoparticles occur, by increasing the nanoparticle content in polymer matrix up to 40%, and therefore they act as single-domain nanoparticles. The samples of nanocomposites based on PP+Fe₃O₄, with up to 40% content of Fe₃O₄, exhibit superparamagnetic properties. It was also found out that the magnetic polymer nanocomposite material based on PP+Fe₃O₄ is able to absorb ultrahigh frequency electromagnetic waves in the frequencies range from 0.1 to 30?GHz. The increase in Fe₃O₄ concentration from 5 to 40% at the 400?µm thicknesses of the films leads to an increase in absorption of electromagnetic waves of high frequency from 15 to 22.7%.     

火焰法合成纳米TiO2颗粒生长过程

在新型火焰反应器生产纳米TiO2的过程中使用TEM微栅在不同火焰高度位置处进行原位取样分析,得到生长过程中纳米TiO2颗粒的粒径和形态. TiO2颗粒经历了成核、生长、聚并、烧结的过程. 调节反应物浓度为7.9×10-5~5.7×10-3 mol/L,研究了不同反应物浓度对纳米颗粒生长过程的影响,高前驱体浓度形成较高的单体浓度,使颗粒间碰撞几率增加,从而得到粒径较大的颗粒,产物粒径17~85 nm. 调节CH4和O2流量,改变温度场,研究温度对颗粒生长过程的影响,在相同反应物浓度条件下,较高的温度下形成分散性好、一次粒径为63 nm的颗粒,而在较低的温度下形成的颗粒一次粒径为35 nm,但颈部烧结严重;增加喷嘴气流速度减小了反应停留时间,颗粒粒径从63 nm减小到36 nm.     

钙钛矿含量对钒钛磁铁矿烧结性能的影响

通过烧结实验,并结合Fact Sage6.0热力学软件研究钒钛烧结矿中各液相和钙钛矿的生成情况与温度的关系.结果表明,钒钛烧结矿的转鼓指数为55.20%,低温还原粉化指数仅为25.92%.XRD和矿相结构分析表明,烧结矿冶金性能差的主要原因是钙钛矿的存在破坏了液相黏结作用,骸晶状结构和树枝状钙钛矿明显增加,严重加剧裂纹的扩散,造成烧结矿质量明显下降.热力学计算得出,低温有利铁酸钙和硅酸钙等液相物质的生成,高温有利于钙钛矿的生成,当温度超过800℃时,钙钛矿含量基本保持稳定,铁酸钙和硅酸钙含量明显降低.