Wettability of Magnetite Nanoparticles Guides Growth from Stabilized Amorphous Ferrihydrite.
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ABSTRACT: Crystal formation via amorphous precursors is a long-sought-after gateway to engineer nanoparticles with well-controlled size and morphology. Biomineralizing organisms, like magnetotactic bacteria, follow such a nonclassical crystallization pathway to produce magnetite nanoparticles with sophistication unmatched by synthetic efforts at ambient conditions. Here, using in situ small-angle X-ray scattering, we demonstrate how the addition of poly(arginine) in the synthetic formation of magnetite nanoparticles induces a biomineralization-reminiscent pathway. The addition of poly(arginine) stabilizes an amorphous ferrihydrite precursor, shifting the magnetite formation pathway from thermodynamic to kinetic control. Altering the energetic landscape of magnetite formation by catalyzing the pH-dependent precursor attachment, we tune magnetite nanoparticle size continuously, exceeding sizes observed in magnetotactic bacteria. This mechanistic shift we uncover here further allows for crystal morphology control by adjusting the pH-dependent interfacial interaction between liquidlike ferrihydrite and nascent magnetite nanoparticles, establishing a new strategy to control nanoparticle morphology. Synthesizing compact single crystals at wetting conditions and unique semicontinuous single-crystalline nanoparticles at dewetting conditions in combination with an improved control over magnetite crystallite size, we demonstrate the versatility of bio-inspired, kinetically controlled nanoparticle formation pathways.
Project description:A Transcriptomics Approach to Study the Biocompatibility and Finding out the Potential Applications of Magnetite (Fe3O4) Nanoparticles Here in this study, we examine the molecular effects of uptake of Fe3O4 nanoparticles using a whole genome microarray study in human epithelial cancer cell line. 38 genes (55%) out of 69 downregulated genes were found to be associated with TGF-beta or BMP signaling including six genes, Id1, Id2, Id3, Caspase-9, Smad6 and SMAD7, important negative regulators of these signaling pathways involved in development and tumorigenesis.
Project description:We report the seeded synthesis of gold nanoparticles (GNPs) via the reduction of HAuCl4 by (L31 and F68) triblock copolymer (TBP) mixtures. In the present study, we focused on [TBP]/[Au(III)] ratios of 1-5 (?1 mM HAuCl4) and seed sizes ~20 nm. Under these conditions, the GNP growth rate is dominated by both the TBP and seed concentrations. With seeding, the final GNP size distributions are bimodal. Increasing the seed concentration (up to ~0.1 nM) decreases the mean particle sizes 10-fold, from ~1000 to 100 nm. The particles in the bimodal distribution are formed by the competitive direct growth in solution and the aggregative growth on the seeds. By monitoring kinetics of GNP growth, we propose that (1) the surface of the GNP seeds embedded in the TBP cavities form catalytic centers for GNP growth and (2) large GNPs are formed by the aggregation of GNP seeds in an autocatalytic growth process.
Project description:Density functional theory (DFT) calculations were performed on a model of a ferrihydrite nanoparticle interacting with chromate ([Formula: see text]) in water. Two configurations each of monodentate and bidentate adsorbed chromate as well as an outer-sphere and a dissolved bichromate ([Formula: see text]) were simulated. In addition to the 3-D periodic planewave DFT models, molecular clusters were extracted from the energy-minimized structures. Calculated interatomic distances from the periodic and cluster models compare favorably with Extended X-ray Absorption Fine Structure spectroscopy values, with larger discrepancies seen for the clusters due to over-relaxation of the model substrate. Relative potential energies were derived from the periodic models and Gibbs free energies from the cluster models. A key result is that the bidentate binuclear configuration is the lowest in potential energy in the periodic models followed by the outer-sphere complex. This result is consistent with observations of the predominance of bidentate chromate adsorption on ferrihydrite under conditions of high surface coverage (Johnston Environ Sci Technol 46:5851-5858, 2012). Cluster models were also used to perform frequency analyses for comparison with observed ATR FTIR spectra. Calculated frequencies on monodentate, bidentate binuclear, and outer-sphere complexes each have infrared (IR)-active modes consistent with experiment. Inconsistencies between the thermodynamic predictions and the IR-frequency analysis suggest that the 3-D periodic models are not capturing key components of the system that influence the adsorption equilibria under varying conditions of pH, ionic strength and electrolyte composition. Model equilibration via molecular dynamics (MD) simulations is necessary to escape metastable states created during DFT energy minimizations based on the initial classical force field MD-derived starting configurations.
Project description:Supported platinum nanoparticles are currently the most functional catalysts applied in commercial chemical processes. Although investigations have been performed to improve the dispersion and thermal stability of Pt particles, it is challenging to apply amorphous silica supports to these systems owing to various Pt species derived from the non-uniform surface structure of the amorphous support. Herein, we report the synthesis and characterization of amorphous silica-supported Pt nanoparticles from (cod)Pt-disilicate complex (cod = 1,5-cyclooctadiene), which forms bis-grafted surface Pt species regardless of surface heterogeneity. The synthesized Pt nanoparticles were highly dispersible and had higher hydrogenation activity than those prepared by the impregnation method, irrespective of the calcination and reduction temperatures. The high catalytic activity of the catalyst prepared at low temperatures (such as 150 °C) was attributed to the formation of Pt nanoparticles triggered by the reduction of cod ligands under H2 conditions, whereas that of the catalyst prepared at high temperatures (up to 450 °C) was due to the modification of the SiO2 surface by grafting of the (cod)Pt-disilicate complex.
Project description:Cobalt-doped magnetite (CoxFe3 -xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe(2+) site with Co(2+), with up to 17 per cent Co substituted into tetrahedral sites.
Project description:Knowledge of how arsenic (As) partitions among various phases in Fe-rich sulfidic environments is critical for understanding the fate and mobility of As in such environments. We studied the reaction of arsenite and arsenate sorbed on ferrihydrite nanoparticle surfaces with dissolved sulfide at varying S/Fe ratios (0.1-2.0) to understand the fate and transformation mechanism of As during sulfidation of ferrihydrite. By using aqueous As speciation analysis by IC-ICP-MS and solid-phase As speciation analysis by synchrotron-based X-ray absorption spectroscopy (XAS), we were able to discern the mechanism and pathways of As partitioning and thio-arsenic species formation. Our results provide a mechanistic understanding of the fate and transformation of arsenic during the codiagenesis of As, Fe, and S in reducing environments. Our aqueous-phase As speciation data, combined with solid-phase speciation data, indicate that sulfidation of As-sorbed ferrihydrite nanoparticles results in their transformation to trithioarsenate and arsenite, independent of the initial arsenic species used. The nature and extent of transformation and the thioarsenate species formed were controlled by S/Fe ratios in our experiments. However, arsenate was reduced to arsenite before transformation to trithioarsenate.
Project description:Magnetite nanoparticles have size- and shape-dependent magnetic properties. In addition, assemblies of magnetite nanoparticles forming one-dimensional nanostructures have magnetic properties distinct from zero-dimensional or non-organized materials due to strong uniaxial shape anisotropy. However, assemblies of free-standing magnetic nanoparticles tend to collapse and form closed-ring structures rather than chains in order to minimize their energy. Magnetotactic bacteria, ubiquitous microorganisms, have the capability to mineralize magnetite nanoparticles, the so-called magnetosomes, and to direct their assembly in stable chains via biological macromolecules. In this contribution, the synthesis and assembly of biological magnetite to obtain functional magnetic dipoles in magnetotactic bacteria are presented, with a focus on the assembly. We present tomographic reconstructions based on cryo-FIB sectioning and SEM imaging of a magnetotactic bacterium to exemplify that the magnetosome chain is indeed a paradigm of a 1D magnetic nanostructure, based on the assembly of several individual particles. We show that the biological forces are a major player in the formation of the magnetosome chain. Finally, we demonstrate by super resolution fluorescence microscopy that MamK, a protein of the actin family necessary to form the chain backbone in the bacteria, forms a bundle of filaments that are not only found in the vicinity of the magnetosome chain but are widespread within the cytoplasm, illustrating the dynamic localization of the protein within the cells. These very simple microorganisms have thus much to teach us with regards to controlling the design of functional 1D magnetic nanoassembly.
Project description:Magnetite nanoparticles exhibit magnetic properties that are size and organization dependent and, for applications that rely on their magnetic state, they usually have to be monodisperse. Forming such particles, however, has remained a challenge. Here, we synthesize 40 nm particles of magnetite in the presence of polyarginine and show that they are composed of 10 nm building blocks, yet diffract like single crystals. We use both bulk magnetic measurements and magnetic induction maps recorded from individual particles using off-axis electron holography to show that each 40 nm particle typically contains a single magnetic domain. The magnetic state is therefore determined primarily by the size of the superstructure and not by the sizes of the constituent sub-units. Our results fundamentally demonstrate the structure - property relationship in a magnetic mesoparticle.
Project description:A magnetic nanocomposite, consisting of Fe3O4 nanoparticles embedded into a Mg/Al layered double hydroxide (LDH) matrix, was developed for cancer multimodal therapy, based on the combination of local magnetic hyperthermia and thermally induced drug delivery. The synthesis procedure involves the sequential hydrolysis of iron salts (Fe2+, Fe3+) and Mg2+/Al3+ nitrates in a carbonate-rich mild alkaline environment followed by the loading of 5-fluorouracil, an anionic anticancer drug, in the interlayer LDH space. Magnetite nanoparticles with a diameter around 30 nm, dispersed in water, constitute the hyperthermia-active phase able to generate a specific loss of power of around 500 W/g-Fe in an alternating current (AC) magnetic field of 24 kA/m and 300 kHz as determined by AC magnetometry and calorimetric measurements. Heat transfer was found to trigger a very rapid release of drug which reached 80% of the loaded mass within 10 min exposure to the applied field. The potential of the Fe3O4/LDH nanocomposites as cancer treatment agents with minimum side-effects, owing to the exclusive presence of inorganic phases, was validated by cell internalization and toxicity assays.
Project description:Magnetic nanomaterials record information as fast as picoseconds in computer memories but retain it for millions of years in ancient rocks. This exceedingly broad range of times is covered by hopping over a potential energy barrier through temperature, ultrafast optical excitation, mechanical stress, or microwaves. As switching depends on nanoparticle size, shape, orientation, and material properties, only single-nanoparticle studies can eliminate the ensemble heterogeneity. Here, we push the sensitivity of photothermal magnetic circular dichroism down to individual 20 nm magnetite nanoparticles. Single-particle magnetization curves display superparamagnetic to ferromagnetic behaviors, depending on the size, shape, and orientation. Some nanoparticles undergo thermally activated switching on time scales of milliseconds to minutes. Surprisingly, the switching barrier varies with time, leading to dynamical heterogeneity, a phenomenon familiar in protein dynamics and supercooled liquids. Our observations will help to identify the external parameters influencing magnetization switching and, eventually, to control it, an important step for many applications.