One‐Pot Synthesis of Au25(SG)18 2‐ and 4‐nm Gold Nanoparticles and Comparison of Their Size‐Dependent Properties

A one‐pot synthesis of glutathione (denoted as ‐SG) capped gold nanoparticles, including Au₂₅(SG)₁₈ (ca. 1 nm in diameter) 2‐ and 4‐nm particles is reported. These nanoparticles are isolated by methanol‐induced precipitation with a controlled amount of added methanol. Except for their particle size, these nanoparticles have an identical chemical composition (i.e., gold and ‐SG content), synthetic history, and surface conditions, which allows for precise comparison of their size‐dependent properties, in particular the magnetic property as this could be attributed to contamination by trace iron impurities. Specifically, the structure, optical, and magnetic properties of these gold nanoparticles are compared. A trend from non‐fcc (fcc = face centered cubic) Au₂₅(SG)₁₈ nanoclusters (ca. 1 nm) to 2‐ and 4‐nm fcc‐crystalline Au nanocrystals is revealed. The Au₂₅(SG)₁₈ nanoparticles resemble molecules and exhibit multiple optical absorption peaks ascribed to one‐electron transitions, whereas the 4‐nm nanoparticles exhibit surface plasmon resonance at around 520 nm related to the collective excitation of conduction electrons upon optical excitation. The transition from the non‐fcc cluster state to the fcc crystalline state occurs at around 2 nm. Interestingly, both 2‐ and 4‐nm particles exhibit paramagnetism, whereas the Au₂₅(SG)₁₈ (anionic) clusters are diamagnetic. The information attained on the evolution of the properties of nanoparticles from nanoclusters to fcc‐structured nanocrystals is of major importance and provides insight into structure—property relationships.     

Synthesis of Monodisperse FeAu Nanoparticles with Tunable Magnetic and Optical Properties

Monodisperse FeAu nanoparticles can be synthesized via the reduction of gold acetate by 1,2‐hexadecanediol and the thermal decomposition of iron pentacarbonyl in the presence of the stabilizers oleic acid and oleylamine. The effects of composition, reaction time, and reaction temperature on their size, structure, and optical and magnetic properties are studied. It is found that the incorporation of Au into Fe nanoparticles leads to a structural change from body‐centered cubic (bcc) to face‐centered cubic (fcc). The size of the particles decreases with increasing reaction time and temperature because of atom rearrangement, and varies with the Au/Fe molar ratio as a result of the faster reduction rate of gold acetate compared with the decomposition rate of iron pentacarbonyl and the associated changes in nucleation and growth processes. The resultant FeAu nanoparticles possess the optical properties of Au nanoparticles and the magnetic properties of Fe nanoparticles. Their characteristic absorption bands, in the visible light range, become broader with decreasing Au/Fe molar ratio or increasing reaction time and temperature. Also, they are red‐shifted with decreasing the Au content and blue‐shifted with increasing reaction time. In addition, the particles are nearly superparamagnetic. With the increase in the Au/Fe molar ratio, their blocking temperature and coercivity increase while the saturation magnetization and remnant magnetization decrease. They can be self‐assembled into parallel stripes in the direction of an applied magnetic field.     

磁控溅射法制备Ag/FePt/C/FePt薄膜的结构和磁性能

采用磁控溅射法,在自然氧化的Si(001)基片上沉积了Ag/FePt/C/FePt纳米薄膜,并分别在400,450,500,600℃下对薄膜样品进行了1h的退火热处理。利用X射线衍射仪和振动样品磁强计,对薄膜样品的结构和磁性进行了分析。结果表明,当热处理温度为450℃时,Ag/FePt/C/FePt薄膜中已形成了具有有序面心四方结构的L10-FePt。随着热处理温度的升高,薄膜样品的有序化程度提高,矫顽力Hc增强,晶粒尺寸变大。当热处理温度为600℃时,薄膜样品的平行膜面Hc为905.8kA·m-1,晶粒尺寸为23nm。     

Freestanding Single Crystalline Fe–Pd Ferromagnetic Shape Memory Membranes – Role of Mechanical and Magnetic Constraints Across the Martensite Transition

Substrate‐attached and freestanding single crystalline Fe₇₀Pd₃₀ ferromagnetic shape memory alloy membranes, which were synthesized by molecular beam epitaxy on MgO (001) and later released from their substrates, are characterized with respect to their structural, thermal and magnetic properties. Residing in the two‐phase region of austenite and the correct martensite phase with face centered tetragonal (fct) structure at room temperature, they reveal martensite transition with little hysteresis at 326 K and 320 K, respectively. Comparing substrate‐attached with freestanding films, which show fundamentally different magnetic fingerprints, it is proposed that domain structure is capable of posing a bias on the austenite → fct‐martensite phase transition by favoring martensite variants with their easy axis aligned along the field – just as the substrate constitutes a mechanical constraint on the transition. If confirmed, this would suggest thermo‐magnetic actuation as an alternative where only moderate magnetic fields are feasible, but moderate temperature changes are possible.     

Graphite Coating of Iron Nanowires for Nanorobotic Applications: Synthesis,Characterization and Magnetic Wireless Manipulation

Wireless‐manipulated graphite coated nanomagnets are promising candidates for minimally invasive targeted drug delivery platforms. Iron nanowires coated with graphitic shells are synthesized by template‐assisted deposition. The use of porous aluminum oxide templates enables both the batch production of nanowires by electrodeposition and their subsequent conformal encapsulation in graphite using chemical vapor deposition (CVD). High quality graphitic shells are obtained when CVD conditions are optimized using acetylene as carbon feedstock at 740 °C. Interestingly, the iron nanowires transform into iron carbide during the CVD process leading to changes in magnetic properties. The graphite coated iron nanowires are precisely manipulated against a water flow (0.1 mm/s) using a magnetic field of 350 Oe and a gradient of 50 kOe m^?1 in a 5‐DOF magnetic manipulation system. Our approach opens new avenues for the design and synthesis of functional graphite coated nanowires that are promising for nanorobotics applications.     

Stability and Hydrogenation of “Bare” Gadolinium Nanoparticles

Gadolinium nanoparticles, deposited via an inert gas evaporation method, show improved stability towards oxidation and it is therefore possible to carry out an ex‐situ investigation on “bare” Gd nanoparticles, i.e., in the absence of a protective Pd layer, for the first time. A size‐induced structural transformation from hexagonal close packing to the higher‐symmetry face‐centered cubic structure is observed. The important observation of hydrogen–Gd‐nanoparticle interaction at room temperature and atmospheric pressure, without a Pd catalytic layer, makes Gd nanoparticles a potential candidate for hydrogen‐sensing, switching, and storage applications.     

Characterization and Growth Process of Copper Nanodisks

Copper nanocrystals with plate‐like morphologies and face‐centered cubic (fcc) structures have been synthesized in mixed reverse micelles with a large excess of reducing agent. High‐resolution transmission electron microscopy images and image simulations show the presence of multiple twin defects parallel to the (111) surface responsible for the forbidden reflections 1/3{422} of the fcc structure. A growth process related to the formation of twin defects is proposed to explain the existence of these morphologies.     

FePt纳米粒子有序膜结构的SPM研究

采用化学合成方法制备了单分散的FePt磁性纳米粒子，通过对纳米粒子的操纵与排布制得了磁性纳米粒子单层膜和多层膜，并利用扫描探针显微技术(SPM)和X射线粉末衍射(XRD)考察了磁性纳米粒子膜中FePt纳米粒子的形貌、粒度分布和表面聚集状态。研究结果表明在磁性纳米粒子单层膜中，磁性纳米粒子分布均匀、排列紧密，且多层膜在膜累加方向是具有周期结构的有序组合体。     

Facile Generation of L10‐FePt Nanodot Arrays from a Nanopatterned Metallopolymer Blend of Iron and Platinum Homopolymers

Hard ferromagnetic (L1₀ phase) FePt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are considered to be one of the most promising candidates for the next generation of ultrahigh‐density data storage system. The question of how to generate ordered patterns of L1₀‐FePt NPs and how to transform the technology for practical applications represents a key current challenge. Here the direct synthesis of L1₀ phase FePt NPs by pyrolysis of Fe‐containing and Pt‐containing metallopolymer blend without post‐annealing treatment is reported. Rapid single‐step fabrication of large‐area nanodot arrays (periodicity of 500 nm) of L1₀‐ordered FePt NPs can also be achieved by employing the metallopolymer blend, which possesses excellent solubility in most organic solvents and good solution processability, as the precursor through nanoimprint lithography (NIL). Magnetic force microscopy (MFM) imaging of the nanodot pattern indicates that the patterned L1₀ phase FePt NPs are capable of exhibiting decent magnetic response, which suggests a great potential to be utilized directly in the fabrication of bit patterned media (BPM) for the next generation of magnetic recording technology.     

Effect of Exchange Interactions on the Coercivity of SmCo5 Nanoparticles Made by Cluster Beam Deposition

Single crystal SmCo₅ nanoparticles with an average size of 3.5 nm are produced by cluster‐beam deposition. When deposited without matrix, the nanoparticles showed a super‐paramagnetic behavior with a blocking temperature of 145 K. Dispersion of the SmCo₅ nanoparticles in a carbon matrix results in an increase in both the coercivity and the blocking temperature. Room temperature coercivities as high as 12 kOe are obtained for the first time in mono‐layers of SmCo₅ nanoparticles dispersed in C matrix. δM plots show that the interactions in the samples are of exchange type, which can decrease the overall effective anisotropy and coercivity according to the random‐anisotropy model. Coercivity is found to be inversely proportional to the packing density of the particles. SmCo₅ nanoparticles with high coercivity are potential candidates for the next generation ultra high‐density magnetic recording media.     

Superparamagnetic Polymer Nanocomposites with Uniform Fe3O4 Nanoparticle Dispersions

Magnetic nanoparticles embedded in polymer matrices are good examples of functional nanostructures with excellent potential for applications such as electromagnetic interference shielding, magneto‐optical storage, biomedical sensing, flexible electronics, etc. Control over the dispersion of the nanoparticle phase embedded in a polymer matrix is critical and often challenging. To achieve excellent dispersion, competition between polymer–polymer and polymer–particle interactions have to be balanced to avoid clustering of particles in polymer nanocomposites. We report the first deposition of magnetic nanocomposite poly(methyl methacrylate)/polypyrrole bilayers from solution using spin‐coating. Fe₃O₄ nanoparticles have been synthesized using a chemical co‐precipitation route. Using a combination of dissolving the polymer and mixing fatty acid surfactant coated Fe₃O₄ nanoparticles, we have demonstrated the formation of nanocomposites with uniform nanoparticle dispersion. Cross‐sectional scanning electron microscopy, transmission electron microscopy, and magnetic measurements confirm the excellent dispersion and superparamagnetic response. Low‐frequency impedance measurements on these bilayers are also presented and analyzed.     

Biopolymer Networks for the Solid‐State Production of Porous Magnetic Beads and Wires

Aqueous solutions of sodium carboxymethyl cellulose are used for the morphosynthesis of spherical and wire‐shaped biopolymer networks, in which Fe³⁺ cations serve as a crosslinking and hardening agent. Their morphology remains intact upon drying, resulting in monolithic beads (1 mm) and wires (ca. 80 μm), which are exploited as reaction vessels to pre‐encapsulate poly(ethylene glycol) 400 (PEG 400) and cobalt cations. A solid‐state reaction in an inert atmosphere at 600 °C affords porous carbonaceous xerogels, macroscopically shaped as beads or wires and decorated with nanocrystalline magnetic iron oxide, metallic iron, or iron–cobalt alloy particles, thus imparting magnetic properties to the products. As such the reduction of Fe³⁺ species to α‐Fe nanoparticles can be achieved without H₂ treatment, since poly(ethylene glycol) serves as a reducing agent and the encapsulated Co²⁺ aids in the subsequent growth of the metallic iron particles. Particularly interesting are the magnetic properties of the carbon–α‐Fe composite, in which the size of the magnetic particles, estimated near the boundaries of the single magnetic domain, gives rise to increased coercivity compared with that of bulk iron.     

Intracellular Fate of Hydrophobic Nanocrystal Self‐Assemblies in Tumor Cells

Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water‐dispersible architectures of self‐assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self‐assemblies display increased cellular uptake by tumor cells compared to dispersions of the water‐soluble NC building blocks. Moreover, the self‐assembly structures increase the NCs density in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mechanical properties. Flexible and soft colloidosomes deform and spread along the biological membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mechanical and topological properties of the self‐assemblies direct their intracellular fate allowing the control intralysosomal density, ordering, and localization of NCs.     

C/FePt/Fe纳米薄膜的微结构和磁特性

利用超高真空磁控溅射方法制备了一系列不同C层厚度的C/FePt/Fe纳米薄膜,然后进行原位高温退火。应用X射线衍射仪(XRD)分析了样品的晶体结构,利用扫描探针显微镜(SPM)观测了表面形貌和磁畴结构,通过振动样品磁强计(VSM)测量了磁性。结果表明,薄膜的微结构和磁特性随C覆盖层厚度的变化有着非常显著的变化。C的加入使样品表面更加光滑,使10 nm厚的C覆盖层样品获得了0.3 nm的粗糙度和3.8 nm的颗粒尺寸。C覆盖层减弱了磁性颗粒间的磁偶极作用,同时减弱了磁性颗粒间的交换耦合作用,提高了L10织构的有序化程度,进而增大了样品的矫顽力,矫顽力达到了987 kA/m。     

Microwave Arcing Induced Formation and Growth Mechanisms of Core/Shell Metal/Carbon Nanoparticles in Organic Solutions

Well‐graphitized core/shell iron/carbon nanoparticles (Fe@CNPs) were formed in toluene solutions containing Fe(CO)₅‐C_60/70 via an novel microwave arcing process. High temperature γ‐Fe phase was found to be stable at room temperature when encapsulated inside graphene shells. In the absence of C_60/70, the structures of graphene shells are poor. Pre‐synthesized Co nanoparticles were used as templates for the growth of graphene shells in toluene‐C_60/70 solutions. Via acid etching and removal of the central core Co nanoparticles, hollow carbon nanoparticles could be obtained. Further thermal annealing by focused microwave irradiation leads to merging of small core/shell metal/carbon nanoparticles into large ones, as well as conversion of body centered cubic (bcc) α‐Fe to face centered cubic (fcc) γ‐Fe. The possible growth mechanisms of core/shell metal/carbon nanoparticles were discussed.     

FePt Magnetic Nanoparticles and Their Assembly for Future Magnetic Media

Magnetic nanoparticles with extremely high anisotropy such as chemically ordered $hbox{L}1_{0}$ phase FePt nanoparticles have been considered one of the best candidates for future magnetic recording media with areal density beyond 1 ${ hbox{Tbit/in}}^{2}$ for either the nanocomposite-film-type heat-assisted magnetic recording (HAMR) media or the self-organized-magnetic-array (SOMA)-type bit patterned media. However, current preparation methods via phase transformation must overcome many obstacles, including particle agglomeration, twinning, and difficulty of easy axis alignment. In this paper, the effort on and promise of the preparation of monodispersed magnetic nanoparticles with high anisotropy by a gas phase condensation method is reviewed and reported. The focus is to review recent progress on the fabrication of monodispersed highly ordered $ hbox{L}1_{0}$ phase FePt nanoparticles without phase transformation, successfully self-assembled and magnetically aligned magnetic nanoparticles for SOMA and HAMR media. The mechanisms for directly forming $hbox{L}1_{0}$ phase FePt nanoparticles during nucleation and growth processes and magnetically aligning these particles are analyzed.      

Magnetothermal Multiplexing for Selective Remote Control of Cell Signaling

Magnetic nanoparticles have garnered sustained research interest for their promise in biomedical applications including diagnostic imaging, triggered drug release, cancer hyperthermia, and neural stimulation. Many of these applications make use of heat dissipation by ferrite nanoparticles under alternating magnetic fields, with these fields acting as an externally administered stimulus that is either present or absent, toggling heat dissipation on and off. Here, an extension of this concept, magnetothermal multiplexing is demonstrated, in which exposure to alternating magnetic fields of differing amplitude and frequency can result in selective and independent heating of magnetic nanoparticle ensembles. The differing magnetic coercivity of these particles, empirically characterized by a custom high amplitude alternating current magnetometer, informs the systematic selection of a multiplexed material system. This work culminates in a demonstration of magnetothermal multiplexing for selective remote control of cellular signaling in vitro.     

Biosynthesis of Zinc Substituted Magnetite Nanoparticles with Enhanced Magnetic Properties

The magnetic moments of magnetite nanoparticles are dramatically enhanced through the addition of zinc in a microbiologically driven synthesis procedure. The particles are produced through the reduction of Fe(III)‐compounds containing Zn(II) by the iron reducing bacterium Geobacter sulfurreducens. Results indicate a significant increase in the saturation magnetization by over 50% compared to magnetite at both room and low temperatures for relatively minor quantities of zinc substitution. A maximum saturation magnetization of nearly 100 emu g^?1 of sample is measured at room temperature. Analysis of the cation site ordering reveals a complex dependence on the Zn content, with the combined effect of Zn substitution of Fe³⁺ ions on tetrahedral sites, together with Fe²⁺ cation oxidation, leading to the observed magnetization enhancement for low Zn doping levels. The improved magnetic properties give superior performance in MRI applications with an MRI contrast enhancement among the largest values reported, being more than 5 times larger than a commercial contrast agent (Feridex) measured under identical conditions. The synthesis technique applied here involves an environmentally benign route and offers the potential to tune the magnetic properties of magnetic nanoparticles, with increased overall magnetization desirable for many different commercial applications.     

Antibody‐Functionalized Hybrid Superparamagnetic Nanoparticles

Superparamagnetic hybrid nanoparticles (ca. 80 nm) are obtained. They consist of an inner iron oxide core coated by a silica shell, which is in turn functionalized with amine or carboxyl groups and covalently coupled to a monoclonal antibody (anti‐hCG; hCG = human chorionic gonadotropin). The prepared nanoparticles show a specific magnetic moment (per gram of iron) that is comparable to that measured for commercial superparamagnetic iron oxide preparations. The bioactivity of the antibody‐conjugated magnetic nanoparticles is verified by a standard bioassay. These results indicate the potential of the hybrid nanoparticles prepared for use as enhanced contrast agents in magnetic resonance imaging applications.     

Photoinduced Tuning of Optical Stop Bands in Azopolymer Based Inverse Opal Photonic Crystals

Photo‐tunable photonic crystals were prepared from three dimensional (3D) colloidal crystal templates using a photoresponsive azopolymer. For the preparation of azopolymer infiltrated photonic crystals, silica colloidal crystals were fabricated by gravity sedimentation, a self‐assembly technique. The interstitial voids between colloidal particles were filled with azopolymer and azopolymer inverse opals were produced by treatment with aqueous hydrofluoric acid. These photonic crystals exhibited stop bands in their transmission spectra measured in the normal incidence to the (111) plane of face centered cubic (fcc). The photonic bandgap of the azopolymer infiltrated opal and inverse opal could be controlled by the refractive index change due to the photoinduced orientation of azobenzene chromophores. When the azopolymer photonic crystals were irradiated with linearly polarized light, their bandgap positions were shifted to shorter wavelength regions with increasing irradiation time. This behavior experimentally produced a photoinduced orientation of the azobenzene groups in parallel with the incidence of the excitation light. Through such an out‐of‐plane orientation of azo chromophores, parallel to the [111] fcc crystallographic axis, the effective refractive index of the photonic crystal medium was decreased. Therefore, a blue‐shift in bandgap positions was consequently induced with 20–40 nm tuning ranges. The out‐of‐plane orientation was confirmed by angular resolved absorption spectral measurements.