Facile Synthesis of Gd(OH)3‐Doped Fe3O4 Nanoparticles for Dual‐Mode T1‐ and T2‐Weighted Magnetic Resonance Imaging Applications

The facile hydrothermal synthesis of polyethyleneimine (PEI)‐coated iron oxide (Fe₃O₄) nanoparticles (NPs) doped with Gd(OH)₃ (Fe₃O₄‐Gd(OH)₃‐PEI NPs) for dual mode T₁‐ and T₂‐weighted magnetic resonance (MR) imaging applications is reported. In this approach, Fe₃O₄‐Gd(OH)₃‐PEI NPs are synthesized via a hydrothermal method in the presence of branched PEI and Gd(III) ions. The PEI coating onto the particle surfaces enables further modification of poly(ethylene glycol) (PEG) in order to render the particles with good water dispersibility and improved biocompatibility. The formed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs have a Gd/Fe molar ratio of 0.25:1 and a mean particle size of 14.4 nm and display a relatively high r₂ (151.37 × 10^?3m ^?1 s^?1) and r₁ (5.63 × 10^?3m ^?1 s^?1) relaxivity, affording their uses as a unique contrast agent for T₁‐ and T₂‐weighted MR imaging of rat livers after mesenteric vein injection of the particles and the mouse liver after intravenous injection of the particles, respectively. The developed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs may hold great promise to be used as a contrast agent for dual mode T₁‐ and T₂‐weighted self‐confirmation MR imaging of different biological systems.     

Multifunctional core–shell nanoparticles: superparamagnetic,mesoporous, and thermosensitive

Multifunctional core–shell composite nanoparticles (NPs) have been developed by the combination of three functionalities into one entity, which is composed of a single Fe₃O₄ NP as the magnetic core, mesoporous silica (mSiO₂) with cavities as the sandwiched layer, and thermosensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) copolymer as the outer shell. The mSiO₂-coated Fe₃O₄ NPs (Fe₃O₄@mSiO₂) are monodisperse and the particle sizes were varied from 25 to 95 nm by precisely controlling the thickness of mSiO₂-coating layer. The P(NIPAAm-co-AAm) were then grown onto surface-initiator-modified Fe₃O₄@mSiO₂ NPs through free radical polymerization. These core–shell composite NPs (designated as Fe₃O₄@mSiO₂@P(NIPAAm-co-AAm)) were found to be superparamagnetic with high r ₂ relaxivity. To manipulate the phase transition behavior of these thermosensitive polymer-coated NPs for future in vivo applications, the characteristic lower critical solution temperature (LCST) was subtly tuned by adjusting the composition of the monomers to be around the human body temperature (i.e. 37 °C), from ca. 34 to ca. 42 °C. The thermal response of the core–shell composite NPs to the external magnetic field was also demonstrated. Owing to their multiple functionality characteristics, these porous superparamagnetic and thermosensitive NPs may prove valuable for simultaneous magnetic resonance imaging (MRI), temperature-controlled drug release, and temperature-programed magnetic targeting and separation applications.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/functional exfoliation graphene on carbon paper nanocomposites for supercapacitor electrode

In this work, the commercial carbon paper was firstly peeled in K₂CO₃ solution and then was further treated in a KNO₃ solution to form functional exfoliation graphene (FEG) on the commercial carbon paper. The FEG/carbon paper was characterized by Raman spectra and scanning electron microscopy, confirming that some typical layered fold graphenes were successfully peeled off and stood on the carbon paper matrix. Then, Fe₃O₄ nanoparticles (NPs) were grown on the surface of FEG/carbon paper and the as-prepared Fe₃O₄ NPs/FEG/carbon paper was directly used as supercapacitor electrode. The specific capacitance of Fe₃O₄ NPs/FEG/carbon paper was about 316.07 F g^?1 at a current density of 1 A g^?1. Furthermore, the FEG/carbon papers were also functionalized by benzene carboxylic acid to form FFEG/carbon papers, and then the Fe₃O₄ NPs were grown on the surface of FFEG/carbon paper. The specific capacitance of Fe₃O₄ NPs/FFEG/carbon paper was 470 F g^?1 at a current density of 1 A g^?1, superior to some previous reported results. This work might provide a new strategy to prepare various nanostructures on FFEG/carbon papers for future applications.     

Multifunctional Plasmonic Co‐Doped Fe2O3@polydopamine‐Au for Adsorption,Photocatalysis, and SERS‐based Sensing

A new type of multifunctional plasmonic nanoparticles, cobalt‐doped Fe₂O₃@polydopamine‐Au (Co‐Fe₂O₃@PDA‐Au), is fabricated via coating PDA through self‐polymerization onto Co‐Fe₂O₃ and further loading gold nanoparticles by in situ reduction onto the surface of PDA shell. Benefiting from the universal adhesive ability of PDA and negative zeta potetntial of the composite, the Co‐Fe₂O₃@PDA‐Au shows strong adsorptivity for cationic dyes. The presence of gold nanoparticle with the diameter of 15 nm in the Co‐Fe₂O₃@PDA‐Au system promotes surface‐enhanced Raman scattering (SERS) activity with an impressive detection limit of 1 × 10^?6 m . Thanks to the synergistic effect of the light harvesting of PDA, the surface plasmon resonance of Au, and the electron conductibility of PDA and Au, the Co‐Fe₂O₃@PDA‐Au exhibits an enhanced photocatalytic activity comparing with unmodified Co‐Fe₂O₃. All the above‐mentioned functions enable Co‐Fe₂O₃@PDA‐Au to be a multifunctional material system for various applications toward environmental pollutants.     

Amplified Photoacoustic Imaging of Tumor through In Situ Cycloaddition

Photoacoustic (PA) imaging has received great attention in the field of biomedical applications due to the combination advantages of the high contrast of optical imaging and the high spatial resolution of ultrasound. The limited targeting property of PA contrast agents is restricted to elaborate its advantage. To overcome this point, a pretargeting strategy is developed to amplify the targeting property and PA imaging of a model dye in vivo. As a proof of concept, the dibenzyl cyclootyne (DBCO)‐modified Fe@Fe₃O₄ nanoparticles (NPs) (Fe@Fe₃O₄/DBCO) and azide‐modified Cy7.5 (Cy7.5‐N₃) are adopted as the pretargeting and PA contrast agents, respectively. Fe@Fe₃O₄/DBCO NPs are first targeted into tumors by the enhanced permeability and retention effect, and then Cy7.5‐N₃ is conjugated to the pretargeted Fe@Fe₃O₄/DBCO labeled tumor cells via strain‐promoted alkyne azide cycloaddition reaction after intravenous injection, which results in an obvious increase of the accumulated dose and PA signal of Cy7.5 in tumor, and simultaneously extends its residence time. This signal amplification strategy should have an important guiding significance for the clinical application in cancer theranostics.     

Amphiphilic Core–Shell Nanocomposite Particles for Enhanced Magnetic Resonance Imaging

A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe₂O₃ nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T₂ relaxivity of up to 364 mM_Fe^?1 s^?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T₂‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.     

Clean and reproducible SERS substrates for high sensitive detection by solid phase synthesis and fabrication of Ag‐coated Fe3O4 microspheres

The solid‐phase synthesis of Ag‐coated Fe₃O₄ microsphere was elaborated under argon atmosphere. This straightforward process utilized neither reducing agents nor electric current and involved the dry mixing of a precursor of CH₃COOAg with Fe₃O₄ microspheres followed by heating in an inert atmosphere. Ag nanoparticles with diameters of 30–50 nm were well‐decorated on the surfaces of Fe₃O₄ microspheres. The as‐synthesized Ag‐coated Fe₃O₄ microspheres were assembled into a surface‐enhanced Raman scattering (SERS) substrate holding clean and reproducible properties under an externally exerted magnetic force. Using these nanoprobes, analyte molecules can be easily captured, magnetically concentrated, and analyzed by SERS. This clean SERS substrate was used to detect 4‐aminothiophenol, even at a concentration as low as1.0 × 10^–12 M. In particular, the Ag‐coated Fe₃O₄ microspheres, acting as reproducible SERS substrates, were applied to detect methyl‐parathion and 4‐mercaptopyridine. Strong SERS signals were obtained with the analytes at a concentration of 1.0 × 10^–6 M. The unique, clean, and reproducible properties indicate a new route in eliminating the single‐use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants. Similarly, this work may provide a new model system to a series of metal–Fe₃O₄ decorating reactions for a reproducible utilization. Copyright © 2012 John Wiley & Sons, Ltd.     

Engineering the Internal Structure of Magnetic Silica Nanoparticles by Thermal Control

Calcination of hydrated iron salts in the pores of both spherical and rod‐shaped mesoporous silica nanoparticles (NPs) changes the internal structure from an ordered 2D hexagonal structure into a smaller number of large voids in the particles with sizes ranging from large hollow cores down to ten nanometer voids. The voids only form when the heating rate is rapid at a rate of 30 °C min^?1. The sizes of the voids are controlled reproducibly by the final calcination temperature; as the temperature is decreased the number of voids decreases as their size increases. The phase of the iron oxide NPs is α‐Fe₂O₃ when annealed at 500 °C, and Fe₃O₄ when annealed at lower temperatures. The water molecules in the hydrated iron (III) chloride precursor salts appear to play important roles by hydrolyzing Si? O? Si bonding, and the resulting silanol is mobile enough to affect the reconstruction into the framed hollow structures at high temperature. Along with hexahydrates, trivalent Fe³⁺ ions are assumed to contribute to the structure disruption of mesoporous silica by replacing tetrahedral Si⁴⁺ ions and making Fe? O? Si bonding. Volume fraction tomography images generated from transmission electron microscopy (TEM) images enable precise visualization of the structures. These results provide a controllable method of engineering the internal shapes in silica matrices containing superparamagnetic NPs.     

Optimization of ultrasonic-assisted approach for synthesizing a highly stable biocompatible bismuth-coated iron oxide nanoparticles using a face-centered central composite design

The incorporation of additional functional groups such as bismuth nanoparticles (Bi NPs) into magnetite nanoparticles (Fe₃O₄ NPs) is critical for their properties modification, stabilization, and multi-functionalization in biomedical applications. In this work, ultrasound has rapidly modified iron oxide (Fe₃O₄) NPs via incorporating their surface through coating with Bi NPs, creating unique Fe₃O₄@Bi composite NPs. The Fe₃O₄@Bi nanocomposites were synthesized and statistically optimized using an ultrasonic probe and response surface methodology (RSM). A face-centered central composite design (FCCD) investigated the effect of preparation settings on the stability, size, and size distribution of the nanocomposite. Based on the numerical desirability function, the optimized preparation parameters that influenced the responses were determined to be 40 ml, 5 ml, and 12 min for Bi concentration, sodium borohydride (SBH) concentration, and sonication time, respectively. It was found that the sonication time was the most influential factor in determining the responses. The predicted values for the zeta potential, hydrodynamic size, and polydispersity index (PDI) at the highest desirability solution (100%) were −45 mV, 122 nm, and 0.257, while their experimental values at the optimal preparation conditions were −47.1 mV, 125 nm, and 0.281, respectively. Dynamic light scattering (DLS) result shows that the ultrasound efficiently stabilized and functionalized Fe₃O₄NPs following modification to Fe₃O₄@Bi NPs, improved the zeta potential value from –33.5 to −47.1 mV, but increased the hydrodynamic size from 98 to 125 nm. Energy dispersive spectroscopy (EDX) validated the elemental compositions and Fourier transform infrared spectroscopy (FTIR) confirmed the presence of Sumac (Rhus coriaria) compounds in the composition of the nanocomposites. The stability and biocompatibility of Fe₃O₄@Bi NPs were improved by using the extract solution of the Sumac edible plant. Other physicochemical results revealed that Fe₃O₄NPs and Fe₃O₄@Bi NPs were crystalline, semi-spherical, and monodisperse with average particle sizes of 11.7 nm and 19.5 nm, while their saturation magnetization (Ms) values were found to be 132.33 emu/g and 92.192 emu/g, respectively. In vitro cytotoxicity of Fe₃O₄@Bi NPs on the HEK-293 cells was dose- and time-dependent. Based on our findings, the sonochemical approach efficiently produced (and RSM accurately optimized) an extremely stable, homogeneous, and biocompatible Fe₃O₄@Bi NPs with multifunctional potential for various biomedical applications.     

Nanostructured Materials with Conducting and Magnetic Properties: Preparation of Magnetite/Conducting Copolymer Hybrid Nanocomposites by Ultrasonic Irradiation

Conducting copolymer poly(aniline-co-p-phenylenediamine) [poly(Ani-co-pPD)] and surface-modified magnetite (Fe₃O₄) composites were synthesized by ultrasonically-assisted chemical oxidative polymerization. Fe₃O₄ nanoparticles were surface-modified with silane coupling agent methacryloxypropyltrimethoxysilane (MPTMS) in order that they would be well dispersed for the reaction process. It was also found that the aggregation of Fe₃O₄ nanoparticles could be reduced under ultrasonic irradiation. TEM analysis confirmed that the resulting poly(Ani-co-pPD)/Fe₃O₄ nanocomposite showed core–shell morphology, in which Fe₃O₄ nanoparticles were well dispersed. The incorporation of Fe₃O₄ in the nanocomposites was endorsed by FT-IR. The nanocomposites were also confirmed by UV-visible, TGA and XRD. Conductivity of the nanocomposites was found to be in the range of 7.02 × 10^?4–6.54 × 10^?6 S/cm. Higher saturated magnetization of 12 emu/g was observed for composite with 20% Fe₃O₄.     

Full Protection for Graphene‐Incorporated Micro‐/Nanocomposites Containing Ultra‐small Active Nanoparticles: the Best Li‐Storage Properties

In recent years, graphene‐incorporated micro‐/nanocomposites represent one of the hottest developing directions for the composite materials. However, a large number of active nanoparticles (NPs) are still in the unprotected state in most constructed graphene‐containing designs, which will seriously impair the effects of the graphene additives. Here, a fully protected Fe₃O₄‐based micro‐/nanocomposite (G/Fe₃O₄@C) is rationally developed by carbon‐boxing the common graphene/Fe₃O₄ microparticulates (G/Fe₃O₄). The processes and results of full protection are tracked in detail and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and nitrogen absorption–desorption isotherms, as well as scanning and transition electron microscopy. When used as the anode for lithium‐ion batteries, the fully protected G/Fe₃O₄@C exhibits the best lithium‐storage properties in terms of the highest rate capabilities and the longest cycle life compared to the common G/Fe₃O₄ composites and commercial Fe₃O₄ products. These much improved properties are mainly attributed to its novel structural features including complete protection of active Fe₃O₄ nanoparticles by the surface carbon box, a robust conductive network composed of nitrogen‐doped graphene nanosheets, ultra‐small Fe₃O₄ NPs of 4–5 nm, abundant mesopores to accommodate the volume variation during cycling, and micrometer‐sized secondary particles.     

Facile synthesis of multifunctional Ag/Fe3O4-CS nanocomposites for antibacterial and hyperthermic applications

Nanocomposites containing two or more functional constituents are attractive candidates for advanced nanomaterials. In this study, multifunctional Ag/Fe₃O₄-CS nanocomposites were successfully prepared, using chitosan as a stabilizing and cross-linking agent. The as-synthesized nanocomposites were characterized by Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), UV–visible spectrophotometer (UV–Vis) and vibrating sample magnetometer (VSM). The results demonstrated that Ag/Fe₃O₄-CS composite nanoparticles (NPs) were composed of parent components, Fe₃O₄ and Ag NPs, which were uniformly dispersed in the chitosan matrix. The hybrid NPs exhibited strong antibacterial property against Pseudomonas aeruginosa. With high magnetization value (67 emu/g), the synthesized Ag/Fe₃O₄-CS composite can be easily separated or recycled in potential biomedical applications. Furthermore, the results showed that the multicomponent hybrid nanostructures appeared to be the promising material for local hyperthermia, which can be used as thermoseeds for localized hyperthermia treatment of cancers.     

Gadolinium-doped carbon quantum dots loaded magnetite nanoparticles as a bimodal nanoprobe for both fluorescence and magnetic resonance imaging

Nowadays, it is highly desired to develop dual-modal fluorescence and magnetic resonance imaging (FI/MRI) probes in medical imaging because it unites the respective advantages of each imaging modality: high sensitivity of FI and superior spatial resolution of MRI. In this study, a facile strategy to fabricate a new bimodal imaging nanoprobe (Gd-CQDs@N-Fe₃O₄) was reported by integrating the fluorescence ability of carbon quantum dots (CQDs) and T₁ and T₂ contrast-enhancing functionality of Gd(III) ions and Fe₃O₄ nanoparticles into a single hybrid nanostructure. The hybrid composites were investigated by FT-IR, XRD, TEM, XPS, VSM, and so on, which confirmed that Gd-CQDs@N-Fe₃O₄ nanoparticles were successfully obtained and exhibited superparamagnetic property at room temperature. The derived nanoprobes presented an excitation wavelength-independent emission behavior. In addition, r₁ and r₂ relaxivities of the synthesized imaging nanoprobes were measured to be 5.16 and 115.6 mM⁻¹ s⁻¹, which nominated Gd-CQDs@N-Fe₃O₄ nanocomposites as a suitable T₁-T₂ contrast agent. The Gd-CQDs@N-Fe₃O₄ nanoparticles combining two synergetic imaging modalities showed great potential in FI/MRI dual-modal imaging for a more complementary and accurate detection.     

HoF3 and DyF3 Nanoparticles as Contrast Agents for High‐Field Magnetic Resonance Imaging

Clinical contrast agents (CAs) currently used in magnetic resonance imaging (MRI) at low fields are less effective at high magnetic fields. The development of new CAs is mandatory to improve diagnostic capabilities of the new generation of high field MRI scanners. The purpose of this study is to synthesize uniform, water dispersible LnF₃ (Ln = Ho, Dy) nanoparticles (NPs) and to evaluate their relaxivity at high magnetic field (9.4 T) as a function of size and composition. Two different types of HoF₃ NPs are obtained by homogeneous precipitation in ethylene glycol at 120 °C. The use of holmium acetate as holmium precursor leads to rhombus‐like nanoparticles, while smaller, ellipsoid‐like nanoparticles are obtained when nitrate is used as the holmium salt. To explain this behavior, the mechanism of formation of both kinds of particles is analyzed in detail. Likewise, rhombus‐like DyF₃ nanoparticles are prepared following the same method as for the rhombus‐like HoF₃ nanoparticles. We have found, to the best of knowledge, the highest transverse relaxivity values at 9.4 T described in the literature for this kind of CAs. Finally, the LnF₃ NPs have shown negligible cytotoxicity for C6 rat glioma cells for concentrations up to 0.1 mg mL^?1.     

具有介孔结构的MnSiO3@Fe3O4@C纳米粒子的制备以及作为pH响应的T1-T2*双模MRI造影剂的研究应用

本文通过一个简单的、温和的方案制备了平均尺寸为120 nm,介孔结构的纳米粒子MnSiO₃@Fe₃O₄@C. 粒子的细胞毒性微小,可以用作T₁-T₂^*双模MRI造影剂. 酸性条件下MnSiO₃@Fe₃O₄@C释放出大量的Mn²⁺缩短T₁弛豫时间,提高成像分辨率. 超顺磁性的Fe₃O₄可以增强T₂对比成像,检测病变组织. 类似于肿瘤微环境/细胞器的酸性PBS(pH=5.0)中Mn²⁺的释放率达到31.66%,约为中性条件(pH=7.4)下的7倍. 释放的Mn²⁺通过内吞作用被细胞摄取,经肾脏排出,细胞毒性实验表明,MnSiO₃@Fe₃O₄@C具有低的细胞毒性,即使高浓度的200 ppm MnSiO₃@Fe₃O₄@C对HeLa细胞的毒性也相对较小. 对荷瘤小鼠静脉注射定量MnSiO₃@Fe₃O₄@C后,可以观察到一个快速增强的对比成像,给药24 h后,T₁MRI信号显著增强,达到132%,而T₂信号则明显降低至53.8%,活体MR成像证明了MnSiO₃@Fe₃O₄@C可以同时作为阳性和阴性造影剂. 此外,得益于介孔MnSiO₃优秀的酸敏感性,MnSiO₃@Fe₃O₄@C可以作为一种潜在的药物载体,实现肿瘤的诊疗一体化.     

A Facile Strategy to Synthesize Cobalt‐Based Self‐Supported Material for Electrocatalytic Water Splitting

Designing and developing active, robust, and noble‐metal‐free catalysts with superior stability for electrocatalytic water splitting is of critical importance but remains a grand challenge. Here, a facile strategy is provided to synthesize a series of Co‐based self‐supported electrode materials by combining electrospinning and chemical vapor deposition (CVD) technologies. The Co, Co₃O₄, Co₉S₈ nanoparticles (NPs) are formed in situ simultaneously with the formation of carbon nanofibers (CNFs) during the CVD process, respectively. The Co‐based NPs are uniformly distributed through the CNFs and they can be directly used as the electrode materials for hydrogen evolution reaction (HER) in acid and oxygen evolution reaction (OER) in alkaline. The Co₉S₈/CNFs membrane exhibits the best HER activity with overpotential of 165 mV at j = 10 mA cm^?2 and Tafel slope of 83 mV dec^?1 and OER activity with overpotential of 230 mV at j = 10 mA cm^?2 and Tafel slope of 72 mV dec^?1. The onion‐like graphitic layers formed around the NPs not only improve the electrical conductivity of the electrode but also prevent the separation of the NPs from the carbon matrix as well as the aggregation.     

Dextran‐Coated Antiferromagnetic MnO Nanoparticles for a T1‐MRI Contrast Agent with High Colloidal Stability

A simple approach to synthesize carboxymethyl dextran‐coated MnO nanoparticles (CMDex‐MnONPs) with high colloidal stability in physiological saline solutions is described here for potential applications as a magnetic resonance imaging (MRI) T₁ contrast agent. The thermal decomposition methodology is used to produce uniform MnONPs with an average size of around 20 nm, and its hydrophobic surface is modified with CMDex molecules, conferring hydrophilic properties. After CMDex coating, the nanoparticle presents high colloidal stability in concentrations ranging from 10 to 50 μg mL^?1, average hydrodynamic size (Z‐average) of 130 nm, polydispersity degree of ≈12%, and negative surface charge in both simulated body fluid solutions and pure water with zeta‐potential of –20 and –40 mV, respectively. The CMDex‐MnONPs with 20 nm show antiferromagnetic behavior at room temperature, and the magnetic properties are found to be strongly dependent of the nanoparticle size, increasing the contribution of the ferromagnetic Mn₃O₄ phase with decreasing size for nanoparticles about 3 nm. Cytotoxicity evaluation in cancerous and noncancerous cells in the range of 5.0–50.0 μg mL^?1 shows low toxicity for cancerous cells and lack of the same for healthy cells lines. Related to the magnetic properties, CMDex‐MnONP presents significant r₁ relaxivity and low r₂/r₁ relaxivity ratio. The results suggest that these nanoparticles display characteristics for potential applications as an MRI T₁ contrast agent.     

Raman study of ultrathin Fe3O4 films on GaAs(001) substrate: stoichiometry,epitaxial orientation and strain

The growth and characterization of high‐quality ultrathin Fe₃O₄ films on semiconductor substrates is a key step for spintronic devices. A stable, single‐crystalline ultrathin Fe₃O₄ film on GaAs(001) substrate is obtained by post‐growth annealing of epitaxial Fe film with thicknesses of 5 and 12 nm in air. Raman spectroscopy shows a high ability to convincingly characterize the stoichiometry, epitaxial orientation and strain of such ultrathin Fe₃O₄ films. Polarized Raman spectroscopy confirms the unit cell of Fe₃O₄ films is rotated by 45° to match that of the Fe (001) layer on GaAs, which results in a built‐in strain of − 3.5% in Fe₃O₄ films. The phonon strain‐shift coefficient(−126 cm⁻¹) of the A_1g mode is proposed to probe strain effect and strain relaxation of thin Fe₃O₄ films on substrates. It can be used to identify whether the Fe layer is fully oxidized to Fe₃O₄ or not. Copyright © 2011 John Wiley & Sons, Ltd.