Atom Probe Tomographic Mapping Directly Reveals the Atomic Distribution of Phosphorus in Resin Embedded Ferritin.

Here we report the atomic-scale analysis of biological interfaces within the ferritin protein using atom probe tomography that is facilitated by an advanced specimen preparation approach. Embedding ferritin in an organic polymer resin lacking nitrogen provided chemical contrast to visualise atomic distributions and distinguish the inorganic-organic interface of the ferrihydrite mineral core and protein shell, as well as the organic-organic interface between the ferritin protein shell and embedding resin. In addition, we definitively show the atomic-scale distribution of phosphorus as being at the surface of the ferrihydrite mineral with the distribution of sodium mapped within the protein shell environment with an enhanced distribution at the mineral/protein interface. The sample preparation method is robust and can be directly extended to further enhance the study of biological, organic and inorganic nanomaterials relevant to health, energy or the environment.

Tantalum clusters supported on silica-alumina: influence of support composition and chemistry on cluster structure.

Small cationic tantalum clusters were prepared on the surfaces of SiO2, silica-aluminas, and gamma-Al2O3 supports by treating physisorbed pentabenzyltantalum at 523 K for 24 h in flowing H2. The rate of decomposition and the products formed in the decomposition of pentabenzyltantalum are dependent on the support composition. When the support was SiO2, the evolved products were mainly biphenyl and a small amount of toluene, indicating that the Ta-C bond in pentabenzyltantalum was activated. As the alumina content of the support increased, diphenylmethane, benzene, and ethylene were increasingly formed, and these products show that the activation of the C-C bonds linking the C atoms of methyl groups to the aromatic rings of the benzyl ligands was facilitated. Infrared spectra of the surface species and mass spectra of the effluents formed during the treatment show that the composition of the support had significant influence on the decomposition of pentabenzyltantalum, and the chemistry is inferred to be related to the electron-donor properties of the supports. Extended X-ray absorption fine structure (EXAFS) spectra recorded at the Ta LIII edge indicate the formation of clusters with a Ta-Ta first-shell coordination number of approximately 3, and images obtained by scanning transmission electron microscopy (STEM) confirm the presence of such small clusters. X-ray absorption near edge structure (XANES) data indicate that the formal oxidation state of the tantalum in the clusters decreased from approximately 3.0 to approximately 2.6 as the support was changed from SiO2 to silica-aluminas to gamma-Al2O3. The data suggest that the tantalum clusters were anchored to the supports via bridging O atoms. The EXAFS data show that the support composition had little influence on the cluster structure.