J. Appl. Cryst.の発刊に際して

Elements Of X Ray Diffraction

Iron oxide nanoparticles (NPs) hold great promise for future biomedical applications because of their magnetic properties as well as other intrinsic properties such as low toxicity, colloidal stability, and surface engineering capability. Numerous related studies on iron oxide NPs have been conducted. Recent progress in nanochemistry has enabled fine control over the size, crystallinity, uniformity, and surface properties of iron oxide NPs. This review examines various synthetic approaches and surface engineering strategies for preparing naked and functional iron oxide NPs with different physicochemical properties. Growing interest in designed and surface-engineered iron oxide NPs with multifunctionalities was explored in in vitro/in vivo biomedical applications, focusing on their combined roles in bioseparation, as a biosensor, targeted-drug delivery, MR contrast agents, and magnetic fluid hyperthermia. This review outlines the limitations of extant surface engineering strategies and several developing strategies that may overcome these limitations. This study also details the promising future directions of this active research field.

Designed synthesis and surface engineering strategies of magnetic iron oxide nanoparticles for biomedical applications

Biogeochemical transformation (inclusive of dissolution) of iron (hydr)oxides resulting from dissimilatory reduction has a pronounced impact on the fate and transport of nutrients and contaminants in subsurface environments. Despite the reactivity noted for pristine (unreacted) minerals, iron (hydr)oxides within native environments will likely have a different reactivity owing in part to changes in surface composition. Accordingly, here we explore the impact of surface modifications induced by phosphate adsorption on ferrihydrite reduction by Shewanella putrefaciens under static and advective flow conditions. Alterations in surface reactivity induced by phosphate changes the extent, decreasing Fe(Ill) reduction nearly linearly with increasing P surface coverage, and pathway of iron biomineralization. Magnetite is the most appreciable mineralization product while minor amounts of vivianite and green rust-like phases are formed in systems having high aqueous concentrations of phosphate, ferrous iron, and bicarbonate. Goethite and lepidocrocite, characteristic biomineralization products at low ferrous-iron concentrations, are inhibited in the presence of adsorbed phosphate. Thus, deviations in iron (hydr)oxide reactivity with changes in surface composition, such as those noted here for phosphate, need to be considered within natural environments.

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Phosphate Imposed Limitations onBiological Reduction and Alterationof Ferrihydrite

Coccoliths are calcitic particles produced inside the cells of unicellular marine algae known as coccolithophores. They are abundant components of sea-floor carbonates, and the stoichiometry of calcium to other elements in fossil coccoliths is widely used to infer past environmental conditions. Here we study cryo-preserved cells of the dominant coccolithophore Emiliania huxleyi using state-of-the-art nanoscale imaging and spectroscopy. We identify a compartment, distinct from the coccolith-producing compartment, filled with high concentrations of a disordered form of calcium. Co-localized with calcium are high concentrations of phosphorus and minor concentrations of other cations. The amounts of calcium stored in this reservoir seem to be dynamic and at a certain stage the compartment is in direct contact with the coccolith-producing vesicle, suggesting an active role in coccolith formation. Our findings provide insights into calcium accumulation in this important calcifying organism.

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A vacuole-like compartment concentrates a disordered calcium phase in a key coccolithophorid alga

The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.

https://www.pnas.org/content/pnas/110/37/14883.full.pdf

Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates

One-dimensional magnetic nanostructures have magnetic properties superior to non-organized materials due to strong uniaxial shape anisotropy. Magnetosome chains in magnetotactic bacteria represent a biological paradigm of such magnet, where magnetite crystals synthesized in organelles called magnetosomes are arranged into linear chains. Two-dimensional synchrotron X-ray diffraction (XRD) is applied to cells of magnetotactic bacteria that are pre-aligned with a magnetic field to determine the crystallographic orientation of magnetosomes relative to the chain axis. The obtained pole figure patterns reveal a [111] fiber texture along the chain direction for magnetospirilla strains MSR-1 and AMB-1, whereas a [100] fiber texture is measured for Desulfovibrio magneticus strain RS-1. The [100] axis appears energetically unfavorable because it represents a magnetic hard axis in magnetite, but can be turned into an effective easy axis by particle elongation along [100] for aspect ratios higher than 1.25, consistent with aspect ratios in RS-1 magnetosomes determined earlier. The pronounced fiber textures can be explained either by a strain-specific biological control on crystal orientation at the chain level or by physical alignment effects due to intra-chain magnetic interactions. In this case, biological control of the axis of elongation would be sufficient to influence the crystallographic texture of the magnetosome chain.

/pdf/magnetite-crystal-orientation-in-magnetosome-chains-3nxj0dg7rr.pdf

Magnetite Crystal Orientation in Magnetosome Chains

Structure-function studies of the magnetite-biomineralizing magnetosome-associated protein MamC

Magnetotactic bacteria are aquatic microorganisms that intracellularly mineralize ferrimagnetic nanoparticles enabling the cells to align with the geomagnetic field. The bacteria produce a magnetic mineral of species-specific phase (magnetite Fe(II)Fe(III)2O4 or greigite Fe(II)Fe(III)2S4), size, morphology and particle assembly. Several species produce crystals of unusual elongated particle shapes, which break the symmetry of the thermodynamically favoured isometric morphology. Such morphologies are thought to affect domain size and orientation of the internal magnetization. Therefore, they are interesting study objects to develop new synthetic strategies for the morphological control of nanoparticles. We investigate the formation of such irregularly shaped nanomagnets in the species Desulfovibrio magneticus RS-1. In contrast to previously described organisms, this bacterium accumulates iron predominantly as Fe(II) rather than Fe(III) consistent with an alternative oxidative biomineralization route. Further, using high-resolution electron microscopy, we observe an epitaxial relationship between precursor and the final mineral phase supporting the notion of a solid-state transformation pathway. The precursor is likely a green rust previously thought to convert to magnetite only by dissolution and re-precipitation. Our findings represent a novel observation in the interconversion of iron (oxyhydr)oxide materials and suggest that solid-state growth processes could be required to produce irregularly shaped, elongated magnetite nanocrystals.

https://royalsocietypublishing.org/doi/pdf/10.1098/rsif.2016.0665

Teresa Perez Gonzalez

Papers

Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates

Magnetite Crystal Orientation in Magnetosome Chains

Structure-function studies of the magnetite-biomineralizing magnetosome-associated protein MamC

Elongated magnetite nanoparticle formation from a solid ferrous precursor in a magnetotactic bacterium.