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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18

Dysregulation of Macrophage Activation Profiles by Engineered Nanoparticles

Although the potential human health impacts from exposure to engineered nanoparticles (ENPs) are uncertain, past epidemiological studies have established correlations between exposure to ambient air pollution particulates and the incidence of pneumonia and lung infections. Using amorphous silica and superparamagnetic iron oxide (SPIO) as model high production volume ENPs, we examined how macrophage activation by bacterial lipopolysaccharide (LPS) or the lung pathogen Streptococcus pneumoniae is altered by ENP pretreatment. Neither silica nor SPIO treatment elicited direct cytotoxic or pro-inflammatory effects in bone marrow-derived macrophages. However, pretreatment of macrophages with SPIO caused extensive reprogramming of nearly 500 genes regulated in response to LPS challenge, hallmarked by exaggerated activation of oxidative stress response pathways and suppressed activation of both pro- and anti-inflammatory pathways. Silica pretreatment altered regulation of only 67 genes, but there was strong correlation with gene sets affected by SPIO. Macrophages exposed to SPIO displayed a phenotype suggesting an impaired ability to transition from an M1 to M2-like activation state, characterized by suppressed IL-10 induction, enhanced TNFα production, and diminished phagocytic activity toward S. pneumoniae. Studies in macrophages deficient in scavenger receptor A (SR-A) showed SR-A participates in cell uptake of both the ENPs and S. pneumonia and co-regulates the anti-inflammatory IL-10 pathway. Thus, mechanisms for dysregulation of innate immunity exist by virtue that common receptor recognition pathways are used by some ENPs and pathogenic bacteria, although the extent of transcriptional reprogramming of macrophage function depends on the physicochemical properties of the ENP after internalization. Our results also illustrate that biological effects of ENPs may be indirectly manifested only after challenging normal cell function. Finally, nanotoxicology screening strategies should therefore consider how exposure to these materials alters susceptibility to other environmental exposures.

Kodali, Vamsi↗

Structural and magnetic properties of cobalt iron disulfide (Co x Fe 1-x S 2 ) nanocrystals

We report on synthesis and investigation of nanocrystalline cobalt-iron-pyrites with an emphasis on nanocrystal structure, morphology and magnetic behavior. The nanocrystals (NCs) were 5–25 nm in diameter as characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). With an increase in Fe fraction, X-ray diffraction and small-angle-X-ray scattering (SAXS) showed a systematic decrease in lattice constant, primary grain/NC size (15 to 7 nm), and nanoparticle (NP) size (70 to 20 nm), respectively. The temperature dependence of the DC magnetization and AC susceptibility versus frequency revealed a number of magnetic phases in Co x Fe 1-x S 2 . Samples with x = 1 and x = 0.875–0.625 showed evidence of superspin glass (SSG) behavior with embedded ferromagnetic (FM) clusters of NPs. For x = 0.5, samples retained their mixed phases, but showed superparamagnetic (SPM) behavior with antiferromagnetic clusters suppressing magnetic dipolar interactions. Below x = 0.5, the pyrites show increasing paramagnetic character. We construct a phase diagram, which can be understood in terms of competition between the various dipolar, exchange, inter- and intracluster interactions. Our results suggest that NC size and shape can be tuned to engineer spin-polarized ferromagnetism of n-doped iron pyrite.

36 MATERIALS SCIENCE↗

Oxygen vacancies controlled multiple magnetic phases in epitaxial single crystal Co 0.5 (Mg 0.55 Zn 0.45 ) 0.5 O 1-v thin films

High quality single-crystal fcc-Co x (Mg y Zn 1-y ) 1-x O 1-v epitaxial thin films with high Co concentration up to x = 0.5 have been fabricated by molecular beam epitaxy. Systematic magnetic property characterization and soft X-ray absorption spectroscopy analysis indicate that the coexistence of ferromagnetic regions, superparamagnetic clusters, and non-magnetic boundaries in the as-prepared Co x (Mg y Zn 1-y ) 1-x O 1-v films is a consequence of the intrinsic inhomogeneous distribution of oxygen vacancies. Furthermore, the relative strength of multiple phases could be modulated by controlling the oxygen partial pressure during sample preparation. Armed with both controllable magnetic properties and tunable band-gap, Co x (Mg y Zn 1-y ) 1-x O 1-v films may have promising applications in future spintronics.

36 MATERIALS SCIENCE↗

The reaction mechanism of FeSb 2 as anode for sodium-ion batteries

The electrochemical reaction of FeSb 2 with Na is reported for the first time. The first discharge (sodiation) potential profile of FeSb 2 is characterized by a gentle slope centered at 0.25 V. During charge (Na removal) and the subsequent discharge, the main reaction takes place near 0.7 V and 0.4 V, respectively. The reversible storage capacity amounts to 360 mA h g -1 , which is smaller than the theoretical value of 537 mA h g -1 . The reaction, studied by ex situ and in situ X-ray diffraction, is found to proceed by the consumption of crystalline FeSb 2 to form an amorphous phase. Upon further sodiation, the formation of nanocrystalline Na3Sb domains is evidenced. During desodiation, Na 3 Sb domains convert into an amorphous phase. The chemical environment of Fe, probed by 57 Fe Mo ssbauer spectroscopy, undergoes significant changes during the reaction. During sodiation, the well-resolved doublet of FeSb2 with an isomer shift around 0.45 mm s -1 and a quadrupole splitting of 1.26 mm s -1 is gradually converted into a doublet line centered at about 0.15 mm s1 along with a singlet line around 0 mm s -1 . The former signal results from the formation of a Fe-rich FexSb alloy with an estimated composition of Fe4Sb while the latter signal corresponds to superparamagnetic Fe due to the formation of nanosized pure Fe domains. Interestingly the signal of Fe4Sb remains unaltered during desodiation. This mechanism is substantially different than that observed during the reaction with Li. The irreversible formation of a Fe-rich Fe 4 Sb alloy and the absence of full desodiation of Sb domains explain the lower than theoretical practical storage capacity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic/NIR-responsive drug carrier, multicolor cell imaging, and enhanced photothermal therapy of gold capped magnetite-fluorescent carbon hybrid nanoparticles

In our paper reports a type of multifunctional hybrid nanoparticle (NP) composed of gold nanocrystals coated on and/or embedded in a magnetite-fluorescent porous carbon core-shell NP template (Fe 3 O 4 @PC-CDs-Au) for biomedical applications, including magnetic/NIR-responsive drug release, multicolor cell imaging, and enhanced photothermal therapy. The synthesis of the Fe 3 O 4 @PC-CDs-Au NPs firstly involves the preparation of core-shell template NPs with magnetite nanocrystals clustered in the cores and fluorescent carbon dots (CDs) embedded in a porous carbon shell, followed by an in situ reduction of silver ions (Ag + ) loaded in the porous carbon shell and a subsequent replacement of Ag NPs with Au NPs through a galvanic replacement reaction using HAuCl 4 as a precursor. Moreover, the Fe 3 O 4 @PC-CDsAu NPs can enter the intracellular region and light up mouse melanoma B16F10 cells in multicolor mode. The porous carbon shell, anchored with hydrophilic hydroxyl/carboxyl groups, endows the Fe 3 O 4 @PC-CDs-Au NPs with excellent stability in the aqueous phase and a high loading capacity (719 mg g -1 ) for the anti-cancer drug doxorubicin (DOX). The superparamagnetic Fe 3 O 4 @PC-CDs-Au NPs with a saturation magnetization of 23.26 emu g -1 produce localized heat under an alternating magnetic field, which triggers the release of the loaded drug. The combined photothermal effects of the Au nanocrystals and the CDs on/in the carbon shell can not only regulate the release rate of the loaded drug, but also efficiently kill tumor cells under NIR irradiation. Finally, in benefitting from their excellent optical properties, their magnetic field and NIR light-responsive drug release capabilities and their enhanced photothermal effect, such nanostructured Fe 3 O 4 @PC-CDs-Au hybrid NPs are very promising for simultaneous imaging diagnostics and high efficacy therapy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

We present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting properties. Monodisperse superparamagnetic iron oxide nanoparticles were synthesized by thermal decomposition of three different iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) in organic solvents under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution. In particular, large quantities of excess surfactant (up to 25:1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase is also critical for establishing magnetic properties. As an example, we show the importance of obtaining the required iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled.

Environmental Molecular Sciences Laboratory↗

Tuning the structure and habit of iron oxide mesocrystals

A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.

36 MATERIALS SCIENCE↗

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commercially available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface-optimized core–shell nanocomposites (Fe 3 O 4 @Mn x Fe y O 4 ) for ultra-high uranium sorption and low-field separation in water

Multifunctional manganese ferrite-coated superparamagnetic magnetite (core–shell) nanocrystals, surface stabilized by a (organic) phosphate functionalized bilayer, have been simultaneously optimized here for ultra-high uranium sorption capacity, colloidal stability under elevated ionic strengths, and susceptibility to low magnetic fields, which are critical for subsequent separation processes.

36 MATERIALS SCIENCE↗

DNA-caged nanoparticles via electrostatic self-assembly

DNA-modified nanoparticles enable DNA sensing and therapeutics in nanomedicine and are also crucial for nanoparticle self-assembly with DNA-based materials. However, methods to conjugate DNA to nanoparticle surfaces are limited, inefficient, and lack control. Inspired by DNA tile nanotechnology, we demonstrate a new approach to nanoparticle modification based on electrostatic attraction between negatively charged DNA tiles and positively charged nanoparticles. This approach does not disrupt nanoparticle surfaces and leverages the programmability of DNA nanotechnology to control DNA presentation. We demonstrated this approach using a variety of nanoparticles, including polymeric micelles, polystyrene beads, gold nanoparticles, and superparamagnetic iron oxide nanoparticles with sizes ranging from 5–20 nm in diameter. DNA cage formation was confirmed through transmission electron microscopy (TEM), neutralization of zeta potential, and a series of fluorescence experiments. DNA cages present “handle” sequences that can be used for reversible target attachment or self-assembly. Handle functionality was verified in solution, at the solid–liquid interface, and inside fixed cells, corresponding to applications in biosensing, DNA microarrays, and erasable immunocytochemistry. Finally, these experiments demonstrate the versatility of the electrostatic DNA caging approach and provide a new pathway to nanoparticle modification with DNA that will empower further applications of these materials in medicine and materials science.

60 APPLIED LIFE SCIENCES↗

Resilience of the Aurivillius structure upon La and Cr doping in a Bi 5 Ti 3 FeO 15 multiferroic

Here, combining the experimental techniques of high-resolution X-ray diffraction, magnetometry, specific heat measurement, and X-ray photoelectron, Raman and dielectric spectroscopy techniques, we have studied the influence of La and Cr doping on the crystal structure and magnetism of the room temperature Aurivillius multiferroic Bi 5 Ti 3 FeO 15 by investigating the physical properties of (Bi 4 La)Ti 3 FeO 15 and Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 . The parent (Bi 5 Ti 3 FeO 15 ) and the doped ((Bi 4 La)Ti 3 FeO 15 and Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 ) compounds crystallize in the A2 1 am space group, which is confirmed through our analysis of high-resolution synchrotron X-ray diffraction data obtained on phase-pure polycrystalline powders. We determined the oxidation states of the metal atoms in the studied compounds as Fe 3+ , Ti 4+ , Cr 3+ , and La 3+ through the analysis of X-ray photoelectron spectroscopy data. The magnetic susceptibilities of the three compounds are marked by the absence of a long-range ordered ground state, but dominated by superparamagnetic clusters with dominant antiferromagnetic interactions. This signature of short-range magnetism is also seen in specific heat as a low temperature enhancement which is suppressed upon the application of external magnetic fields up to 8 T. Our dielectric spectroscopy experiments showed that the three studied compounds display similar features in the dielectric constant measured as a function of frequency. However, upon doping La at the Bi site, the width of the ferroelectric hysteresis loop increases for (Bi 4 La)Ti 3 FeO 15 compared to that of the parent compound Bi 5 Ti 3 FeO 15 , and with Cr doping, Bi 5 Ti 3 (Fe 0.5 Cr 0.5 )O 15 becomes a leaky dielectric. The resilience of the Aurivillius crystal structure towards doping of La at the Bi site and Cr at the Fe site is clearly seen in the bulk properties of magnetic susceptibility, specific heat and the average crystal structure. The relevance of changes in the local structure is evident from our Raman spectroscopy and X-ray pair distribution function studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced magnetic anisotropy in cobalt-carbide nanoparticles

An outstanding problem in nano-magnetism is to stabilize the magnetic order in nanoparticles at room temperatures. For ordinary ferromagnetic materials, reduction in size leads to a decrease in the magnetic anisotropy resulting in superparamagnetic relaxations at nanoscopic sizes. In this work, we demonstrate that using wet chemical synthesis, it is possible to stabilize cobalt carbide nanoparticles which have blocking temperatures exceeding 570 K even for particles with magnetic domains of 8 nm. First principles theoretical investigations show that the observed behavior is rooted in the giant magnetocrystalline anisotropies due to controlled mixing between C p- and Co d-states. (C) 2014 AIP Publishing LLC.

El-Gendy, AA↗

Magnetic tweezers with high permeability electromagnets for fast actuation of magnetic beads

As a powerful and versatile scientific instrument, magnetic tweezers have been widely used in biophysical research areas, such as mechanical cell properties and single molecule manipulation. If one wants to steer bead position, the nonlinearity of magnetic properties and the strong position dependence of the magnetic field in most magnetic tweezers lead to quite a challenge in their control. In this article, we report multi-pole electromagnetic tweezers with high permeability cores yielding high force output, good maneuverability, and flexible design. For modeling, we adopted a piece-wise linear dependence of magnetization on field to characterize the magnetic beads. We implemented a bi-linear interpolation of magnetic field in the work space, based on a lookup table obtained from finite element simulation. The electronics and software were custom-made to achieve high performance. In addition, the effects of dimension and defect on structure of magnetic tips also were inspected. In a workspace with size of 0.1 × 0.1 mm{sup 2}, a force of up to 400 pN can be applied on a 2.8 μm superparamagnetic bead in any direction within the plane. Because the magnetic particle is always pulled towards a tip, the pulling forces from the pole tips have to be well balanced in order to achieve control of the particle’s position. Active video tracking based feedback control is implemented, which is able to work at a speed of up to 1 kHz, yielding good maneuverability of the magnetic beads.

36 MATERIALS SCIENCE↗

Surface magnetism and proximity effects in hexaboride thin films

Here, the unexpected ferromagnetism in alkaline hexaborides has attracted extensive research efforts. The exceptionally high Curie temperature sustained by very low density of magnetic moments is yet to be clearly understood. Here, we report the magnetic properties studied in CaB 6 and SrB 6 thin films and their heterostructures with SmB 6 grown by pulsed laser deposition. A coexistence of ferromagnetic and superparamagnetic orders with 2D-type magnetic anisotropy was observed in CaB 6 and SrB 6 . Boron deficiency and closely correlated local oxidization were found at the film surface that contacts air and its interface with the oxide substrate. These results suggest that the magnetism observed is likely generated by two thin surface/interface layers with high concentration of boron vacancies which are energetically stabled by oxygen cation. Additionally, clear suppression of the superconductivity proximity effect in SmB 6 film was observed when SmB 6 was grown on top of the magnetic CaB 6 . Such results demonstrate the interesting perspective of engineering multifunctional heterostructures by coupling the surface magnetic layer with the diversity of other hexaboride materials.

36 MATERIALS SCIENCE↗

Thermocouple-tip-exposing temperature assessment technique for evaluating photothermal conversion efficiency of plasmonic nanoparticles at low laser power density

A new thermocouple (TC) tip-exposing temperature assessment technique that combines experimental temperature measurements with a numerical model of the photothermal conversion efficiency η is presented. The proposed technique is designed to evaluate η for a gold-coated superparamagnetic iron oxide nanoparticle (SPIO-Au NP) solution (26 nm, 12–70 ppm) at low continuous wave laser power (103 mW, 532 nm) irradiation in a convenient manner under ambient conditions. The TC tip temperature is measured during the first 30 s of the laser exposure, and the results are combined with a finite element model to simulate the temperature rise of the NP solution for a given concentration. The value of η is adjusted in the model until the model agrees with the measured transient TC temperature rise. Values of η = 1.00 were observed for all concentrations. Theoretical predictions of η derived by Mie theory confirmed the near unity conversion efficiency of the as-synthesized SPIO-Au NPs. Advantages of the current technique include co-locating the TC tip in the geometric center of the laser-heated region, rather than outside of this region. In addition, the technique can be done under ambient room conditions using unmodified commercially available hardware.

Numerical methods↗

Structural and magnetic properties of Co-V nanoparticles

We have investigated the structural and magnetic properties of Co 1-x V x nanoparticles (NPs) with composition x = 0.25 (stoichiometric) and 0.29 (under-stoichiometric) prepared by the cluster-beam deposition (CBD) technique. Our data shows that the as-made Co 1-x V x NPs are a mixture of the high-temperature phase (HTP) and the low-temperature phase (LTP) of Co 3 V and the particles are superparamagnetic at room temperature (RT) with blocking temperatures (T B ) of 90 and 137 K for x = 0.25 and 0.29, respectively. This behavior contrasts with the bulk which are paramagnetic down to 4.2 K. When the Co 75 V 25 NPs are annealed at 573 K, they undergo a phase separation into a mixture of phases and become ferromagnetic at room temperature with Curie temperature (T c ) of 515 K.

36 MATERIALS SCIENCE↗