Simultaneous Determination of Major,Minor, and Trace Elements in Agricultural and Biological Samples by Inductively Coupled Argon Plasma Spectrometry

Three techniques for biological and agricultural sample preparation are compared. Commercially available inductively coupled argon plasma (ICAP) direct-reading spectrometers have been used to determine 29 major, minor, and trace elements in biological or agricultural samples following a nitric-perchloric acid digestion. At levels below the detection limit of the instrument, 21 other elements were found. The hydride generation-ICAP technique was employed for the determination of As, Bi, Sb, and Se in the same sample types.     

CP MAS 13C spectral editing and relative quantitation of a soil sample

A hydrofluoric acid (HF)-treated soil sample was studied by 13C NMR spectroscopy. Cross polarization (CP) Magic Angle Spinning (MAS) 13C spectral editing and relative CP peak quantitation, obtained through variable-contact-time experiments, were used to aid the interpretation of the spectrum. The combination of these two types of experiment allowed to obtain a higher degree of detail on the composition of the sample with respect to a standard CP MAS experiment.     

Structure factors in granular experiments with homogeneous fluidization

Velocity and density structure factors are measured over a hydrodynamic range of scales in a horizontal quasi-2D fluidized granular experiment, with packing fractions φ ∈ [10%, 40%]. The fluidization is realized by vertically vibrating a rough plate, on top of which particles perform a Brownian-like horizontal motion in addition to inelastic collisions. On one hand, the density structure factor is equal to that of elastic hard spheres, except in the limit of large length-scales, as it occurs in the presence of an effective interaction. On the other hand, the velocity field shows a more complex structure which is a genuine expression of a non-equilibrium steady state and which can be compared to a recent fluctuating hydrodynamic theory with non-equilibrium noise. The temporal decay of velocity modes autocorrelations is compatible with linear hydrodynamic equations with rates dictated by viscous momentum diffusion, corrected by a typical interaction time with the thermostat. Equal-time velocity structure factors display a peculiar shape with a plateau at large length-scales and another one at small scales, marking two different temperatures: the "bath" temperature T(b), depending on shaking parameters, and the "granular" temperature T(g) < T(b), which is affected by collisions. The two ranges of scales are separated by a correlation length which grows with φ, after proper rescaling with the mean free path.     

Iron speciation in ancient Attic pottery pigments: a non‐destructive SR‐XAS investigation

The present work reports a detailed investigation on the speciation of iron in the pigments of decorated pottery fragments of cultural heritage relevance. The fragments come from the Gioiosa Guardia archaeological site in the area of the `Strait of Messina' (Sicily, Southern Italy), and date back to VI–V century BC. The purpose of this study is to characterize the main pigmenting agents responsible for the dark‐red coloration of the specimens using non‐destructive analytical techniques such as synchrotron radiation X‐ray absorption spectroscopy (SR‐XAS), a well established technique for cultural heritage and environmental subjects. Absorption spectra were collected at the Fe K‐edge on the Italian beamline for absorption and diffraction (BM8‐GILDA) at the European Synchrotron Radiation Facility in Grenoble (France). In order to determine the speciation of Fe in the samples, principal component analysis and least‐squares fitting procedures were applied to the near‐edge part of the absorption spectra (XANES). Details on the local structure around the Fe sites were obtained by analyzing the extended part of the spectra (EXAFS). Furthermore, an accurate determination of the average Fe oxidation state was carried out through analysis of the pre‐edge peaks of the absorption spectra. Samples resulted composed of an admixture of Fe₂O₃ (hematite or maghemite) and magnetite (Fe₃O₄), occurring in different relative abundance in the dark‐ and light‐colored areas of the specimens. The results obtained are complementary to information previously obtained by means of instrumental neutron activation analysis, Fourier transform infrared absorbance and time‐of‐flight neutron diffraction.     

Uncovering Intramolecular π‐Type Hydrogen Bonds in Solution by NMR Spectroscopy and DFT Calculations

Reaction between the phosphinito bridged diplatinum species [(PHCy₂)Pt(μ‐PCy₂){κ²P,O‐μ‐P(O)Cy₂}Pt(PHCy₂)](Pt–Pt) ( 1 ), and (trimethylsilyl)acetylene at 273 K affords the σ‐acetylide complex [(PHCy₂)(η¹‐Me₃SiC≡C)Pt(μ‐PCy₂)Pt(PHCy₂){κP‐P(OH)Cy₂}](Pt–Pt) ( 2 ) featuring an intramolecular π‐type hydrogen bond. Scalar and dipolar couplings involving the POH proton were detected by 2D NMR experiments. Relativistic DFT calculations of the geometry, relative energy, and NMR properties of model systems of 2 confirmed the structural assignment and allowed the energy of the π‐type hydrogen bond to be estimated (ca. 22 kJ mol^?1).     

Bioinspired,Size‐Tunable Self‐Assembly of Polymer–Lipid Bilayer Nanodiscs

Polymer‐based nanodiscs are valuable tools in biomedical research that can offer a detergent‐free solubilization of membrane proteins maintaining their native lipid environment. Herein, we introduce a novel ca. 1.6 kDa SMA‐based polymer with styrene:maleic acid moieties that can form nanodiscs containing a planar lipid bilayer which are useful to reconstitute membrane proteins for structural and functional studies. The physicochemical properties and the mechanism of formation of polymer‐based nanodiscs are characterized by light scattering, NMR, FT‐IR, and TEM. A remarkable feature is that nanodiscs of different sizes, from nanometer to sub‐micrometer diameter, can be produced by varying the lipid‐to‐polymer ratio. The small‐size nanodiscs (up to ca. 30 nm diameter) can be used for solution NMR spectroscopy studies whereas the magnetic‐alignment of macro‐nanodiscs (diameter of > ca. 40 nm) can be exploited for solid‐state NMR studies on membrane proteins.