Analia L. Soldati

Amorphous calcium carbonate in the shells of adult Unionoida

Shells of adult individuals from two different bivalve families, Hyriopsis cumingii and Diplodon chilensis patagonicus, were studied by Micro-Raman spectroscopy and Focussed Ion Beam-assisted TEM. The shells contain amorphous calcium carbonate in a zone at the interface between the periostracum and the prismatic layer. In this area, the initial prism structures protrude from the inner periostracum layer and it is demonstrated that these structures systematically consist of highly disordered and amorphous calcium carbonate. Within this zone, ordered and disordered areas are intermingled discounting the existence of a crystallization front and favouring models of domainal crystallization processes via so-called mesocrystals. These observations are the first documentation of the use of amorphous calcium carbonate as a precursor phase by adult mollusc species and lend further support to hypotheses postulating widespread use of amorphous phases as building material of skeletal tissue in biology.

Structural characterization and chemical composition of aragonite and vaterite in freshwater cultured pearls

Abstract Vaterite and aragonite polymorphs in freshwater cultured pearls from mussels of the genus Hyriopsis (Unionidae) were structurally and compositionally characterized by Raman spectroscopy, Micro computer tomography, high resolution field emission scanning electron microscopy, electron microprobe analysis and laser ablation inductively coupled plasma mass spectrometry. The appearance of vaterite in pearls is related to the initial stages of biomineralization, although we demonstrate that vaterite can not be a precursor to aragonite. It is not related to a particular crystal habit and therefore does not have a structural functionality in the pearls. Larger contents of elements typically bound to organic molecules, such as P and S in vaterite, as well as larger total organic contents in vaterite as opposed to aragonite in conjunction with larger concentrations of Mn2+ and Mg2+, imply a stabilizing role of organic macromolecules and X2+ ions for biological vaterite. Distribution coefficients between aragonite and vaterite for provenance-independent elements, such as Mn and Mg (0.27 and 0.04, respectively) agree very well with those observed in fish otoliths.

Bio-vaterite formation by glycoproteins from freshwater pearls

A 48 kDa acidic and putative calcium-binding glycoprotein was isolated from pearls of the freshwater mussel Hyriopsis cumingii. This protein was compared with a related 46 kDa polypeptide, obtained from the nacreous shell of the same species. Separation by two-dimensional gel electrophoresis revealed that the difference in molecular weight is due to the higher extent of glycosylation of the 48 kDa protein existing in pearls. Evidence is presented that the sugar moieties of the protein contribute to crystal growth, starting with the nucleation step. In in vitro precipitation experiments, the 48 kDa glycoprotein of pearls directed the formation of round-shaped vaterite crystals while the 46 kDa glycoprotein of shells promoted formation of small irregular calcite particles. Furthermore, both proteins, 48 kDa/46 kDa, comprised carbonic anhydrase activity that has been implicated in CaCO(3) formation. Thus, a function of the isolated glycoproteins in biomineralization is proposed together with the mechanism by which they can stabilize different calcium carbonate polymorphs.

Element substitution by living organisms: the case of manganese in mollusc shell aragonite.

Determining the manganese concentration in shells of freshwater bivalves provides a unique way to obtain information about climate and environmental changes during time-intervals that pre-date instrumental data records. This approach, however, relies on a thorough understanding of how manganese is incorporated into the shell material –a point that remained controversial so far. Here we clarify this issue, using state-of-the-art X-ray absorption and X-ray emission spectroscopy in combination with band structure calculations. We verify that in the shells of all studied species manganese is incorporated as high-spin Mn2+, i.e. manganese always has the same valence as calcium. More importantly, the unique chemical sensitivity of valence-to-core X-ray emission enables us to show that manganese is always coordinated by a CO3-octahedron. This, firstly, provides firm experimental evidence for manganese being primarily located in the inorganic carbonate. Secondly, it indicates that the structure of the aragonitic host is locally altered such that manganese attains an octahedral, calcitic coordination. This modification at the atomic level enables the bivalve to accommodate many orders of magnitude more manganese in its aragonitic shell than found in any non-biogenic aragonite. This outstanding feature is most likely facilitated through the non-classical crystallization pathway of bivalve shells.

Manganese speciation in Diplodon chilensis patagonicus shells : a XANES study

X-ray absorption near-edge spectroscopy (XANES) at the Mn K-edge was used to investigate the environment of Mn in situ within the growth increments of the long-lived freshwater bivalve species Diplodon chilensis patagonicus. Single XANES spectra and Mn Kalpha fluorescence distributions were acquired at submillimetre resolution (up to 100 microm x 50 microm), at Mn concentrations below the weight percent range (100-1000 microg g(-1)) in a high Ca matrix. The position and intensity of the pre-edge feature in the shell spectrum resembles best that of the Mn(II)-bearing reference compounds, suggesting that this is the oxidation state of Mn in the bivalve shells. By comparison with the XANES spectra of selected standard compounds, hypotheses about Mn speciation in the shell are also reported. In particular, different factors, such as provenance, ontogenetic age, variable Mn-concentrations or seasonal shell deposition seem not to influence the speciation of the metal in this bivalve species.

Preparation and characterization of a supported system of Ni2P/Ni12P5 nanoparticles and their use as the active phase in chemoselective hydrogenation of acetophenone

Ni2P/Ni12P5 nanoparticles were obtained by thermal decomposition of nickel organometallic salt at low temperature. The use of different characterization techniques allowed us to determine that this process produced a mixture of two nickel phosphide phases: Ni2P and Ni12P5. These nickel phosphides nanoparticles, supported on mesoporous silica, showed activity and high selectivity for producing the hydrogenation of the acetophenone carbonyl group to obtain 1-phenylethanol. This is a first report that demonstrates the ability of supported Ni2P/Ni12P5 nanoparticles to produce the chemoselective hydrogenation of acetophenone. We attribute these special catalytic properties to the particular geometry of the Ni-P sites on the surface of the nanoparticles. This is an interesting result because the nickel phosphides have a wide composition range (from Ni3P to NiP3), with different crystallographic structures, therefore we think that different phases could be active and selective to hydrogenate many important molecules with more than one functional group.

Rapid preparation of block copolymer templated mesoporous Zr1−xCexO2 thin films

A scalable, simple, robust and reproducible method is presented for the preparation of chemically homogeneous and ordered nanocrystalline and mesoporous Zr1−xCexO2 thin films. The method utilizes widely available commercial block copolymers as templates. We show how the preparation conditions, film compositions and thermal treatments determine the mesoporous and crystalline structure. Through the scanning of the synthetic process, it was possible to arrive at an optimized and very reproducible method which allows the preparation of high quality, transparent, nanocrystalline and ordered Zr1−xCexO2 mesoporous thin films with different compositions.

Review on Ceramic Interphases by Transmission and Scanning Electron Microscopy

Abstract The Focused Ion Beam (FIB) technique was used to prepare site-specific samples from interfacial regions of different solid oxide fuel cells assemblies. Transmission and Scanning Electron Microscopy on the FIB foils combined with Electrochemical Impedance Spectroscopy (EIS) allowed the characterization of the electrode/electrolyte interphases and the determination of its influence on the cell performance after long-term operation conditions. This work reviews two cases: on one hand, Ln2NiO4+d (Ln= La, Nd) cathodes deposited on both Y0.08Zr0.92O1.96 and Ce0.9Gd0.1O1.95 electrolytes, that react at 900 °C during the adhesion treatment and at temperatures higher than 650 °C during the EIS measurements. These samples present a reaction layer of 10 nm thickness, which contains elements of both phases and was found responsible of the cell performance degradation. On the other hand, La0.4Sr0.6Co0.8Fe0.2O3-δ cathodes showed excelent performance on Ceria electrolytes, even after 1 000 h at operation conditions. In that case, the microscopic analyses of FIB foils showed a semi-coherent interphase growth.

Monitoring the ecotoxicity of γ-Al2O3 and Ni/γ-Al2O3 nanomaterials by means of a battery of bioassays

The increasing application of nanoparticles (NPs) to a variety of new technologies has become a matter of concern due to the potential toxicity of these materials. Many questions about the fate of NPs in the environment and the subsequent impact on ecosystems need to be answered. The aim of this work was to evaluate the ecotoxicity of two alumina-based nanoceramics, γ-Al2O3 (NC) and Ni/ γ-Al2O3 (NiNC) by means of three different standardized tests: Biochemical Oxygen Demand (BOD5), bioassay with luminescent bacteria (Vibrio fischeri; Microtox), and bioassay on amphibian larvae (Rhinella arenarum) (AMPHITOX). BOD5 values of a very biodegradable mixture (glucose/glutamic acid) decreased with the addition of NiNC(43.8%) and NC (31.6%) with respect to control samples (52.9%). Microtox test results indicated that NiNC presents higher toxicity than NC, with EC50s values of 16.1% and 29.9% respectively; a reduced toxicity was observed, however, in presence of organic matter, thus obtaining EC50s of 37.8% and 19.4%. The results of AMPHITOX test showed a significant increase in the toxicity of both substances over time, the NiNC toxicity being greater than that of NC. The values of 96h-LC50 and 504h-LC50 determined for NiNC were 1.58 and 0.83mg/L, respectively, and 14.5 and 10.5mg/L for NC samples. Amphibian larvae exhibited collapsed cavities, edema, axial flexures, and behavioral alterations as hyperkinesia and reduced movements. These results evidence the vulnerability of wildlife to xenobiotics and the need to develop specific standardized ecotoxicity tests in order to help environmental sustainability and natural species conservation.

Metal oxides: crystallographic characterizations for high-temperature electrochemistry applications

The strong relationship between the crystallographic structure and defects with the electronic and transport properties of a certain material is a key figure in most of the research conducted in materials science. The properties of an oxide in particular (transport, electrochemical, thermal, etc.) can be affected by several factors including the synthesis method and environmental conditions such as pressure, temperature, atmosphere, electrical current and field, magnetic field, etc. Therefore, it is important to go beyond the limited information obtained through the traditional ex-situ characterization techniques toward the more exhaustive ones provided by the in-situ or in-operando experiments, where it is possible the study of a device under nonambient working conditions.