Identification of collagen-based materials that are supports of cultural and historical objects

The TG, DTG, DTA methods were used for investigation of the thermal degradation in static air atmosphere of some collagen-based materials (some sorts of collagen, recent manufactured parchments and tanned leathers, patrimonial (historical) leathers). At the progressive heating, all investigated materials exhibit two main successive processes, associated with the dehydration and thermo-oxidative degradation. The patrimonial leathers were divided in two groups, namely: a group containing the majority of the analyzed materials, for which the rates of the thermo-oxidation process are substantially lower than those corresponding to the recent manufactured leathers, and a group for which the rates of thermo-oxidation process are closed to those corresponding to the recent manufactured leathers. Consequently, if by the thermal analysis in air atmosphere of a leather sample, a value of the rate of the thermo-oxidation process smaller than that corresponding to the recent manufactured leathers is obtained, then the analyzed leather is a patrimonial one. The reciprocal statement of this qualitative criterion for distinction between recent manufactured leather and patrimonial leather is not valid. The DSC analyses of collagen-based materials were performed in air (DSC(air)) and in water (DSC(water)). The denaturation process takes place at lower temperatures in water than in air. Unlike recent manufactured leathers and parchments, each patrimonial leather exhibits on DSC(water) plot 2-4 peaks. Consequently, the number of peaks from DSC(water) curve could be another qualitative criterion for distinction between a recently manufactured leather and a patrimonial leather. This revised version was published online in August 2006 with corrections to the Cover Date.     

129I-Mössbauer study of diffusion effects in the superionic conductor Ag3SI

The superionic conductor Ag₃SI was studied by¹²⁹I-Mössbauer spectroscopy in the rhombohedral γ-phase and in the cubic β-phase at temperatures between 4.2 K and 180 K. In the low-temperature γ-phase, one observes well below the γ-β phase transition at 157 K a motional-narrowing-like decrease of the electric-quadrupole interaction, roughly linear with temperature, which points to a diffusional motion of the Ag⁺ ions already in the γ-phase. Diffusional effects are also reflected by anomalous decrease of thef-factor in the same temperature region, which originates from a restricted short-range diffusional displacement of the iodide ions induced by the hopping Ag⁺ ions.     

Magnetic order observed in Er6Mn23H21 using the Mössbauer effect

The ferrimagnetic compound Er₆Mn₂₃ and its hydride Er₆Mn₂₃H₂₁ have been investigated using the ¹⁶⁶Er and ⁵⁷Fe (as dilute impurity) Mössbauer resonances. For the hydride a small ⁵⁷Fe magnetic hyperfine field is observed below 85 K indicating magnetic ordering. This observation is contrary to the previous assumption that the Mn sublattice must be non-magnetic. The ¹⁶⁶Er results demonstrate that the Er³⁺ magnetic moment is not “quenched” by crystal electric fields on hydrogenation.     

Shrinking droplets in electrospray ionization and their influence on chemical equilibria

We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was used to monitor droplet size and velocity, whereas LIF was used to monitor fluorescent analytes within the electrospray droplets. Using acetonitrile as solvent, we found an average initial droplet diameter of 10 microm in the electrospray. The PDA allowed us to follow the evolution of these droplets down to a size of 1 microm. Rhodamine B-sulfonylchloride was used as a fluorescent analyte within the electrospray. By spatially resolved LIF it was possible to probe the dimerization equilibrium of this dye. Measurements at different spray positions showed no influence of the decreasing droplet size on the monomer-dimer equilibrium. However, with the fluorescent dye pair DCM and oxazine 1 it was shown that a concentration increase does occur within electrosprayed droplets, using fluorescence resonance energy transfer as a probe for the average pair distance.     

Generic approach for the sensitive absolute quantification of large undigested peptides in plasma using a particular liquid chromatography-mass spectrometry setup

A generic LC-MS approach for the absolute quantification of undigested peptides in plasma at mid-picomolar levels is described. Nine human peptides namely, brain natriuretic peptide (BNP), substance P (SubP), parathyroid hormone 1-34 (PTH), C-peptide, orexines A and B (Orex-A and -B), oxytocin (Oxy), gonadoliberin-1 (gonadothropin releasing-hormone or luteinizing hormone-releasing hormone, LHRH) and α-melanotropin (α-MSH) were targeted. Plasma samples were extracted via a 2-step procedure: protein precipitation using 1vol of acetonitrile followed by ultrafiltration of supernatants on membranes with a MW cut-off of 30 kDa. By applying a specific LC-MS setup, large volumes of filtrates (e.g., 2×750 μL) were injected and the peptides were trapped on a 1mm i.d.×10 mm length C8 column using a 10× on-line dilution. Then, the peptides were back-flushed and a second on-line dilution (2×) was applied during the transfer step. The refocalized peptides were resolved on a 0.3mm i.d. C18 analytical column. Extraction recovery, matrix effect and limits of detection were evaluated. Our comprehensive protocol demonstrates a simple and efficient sample preparation procedure followed by the analysis of peptides with limits of detection in the mid-picomolar range. This generic approach can be applied for the determination of most therapeutic peptides and possibly for endogenous peptides with latest state-of-the-art instruments.     

Pressure-induced valence changes in EuS and SmTe

Abstract

X-ray absorption spectroscopy was applied to study the pressure-induced valence changes in EuS and SmTe, which are divalent semiconductors of NaCl-type structure at ambient pressure. In both systems the Eu-L_III and Sm-L_III thresholds exhibit the onset of intermediate valencies of the rare earth ions at 15 GPa and 4 GPa, respectively. In EuS, one observes only a small increase of the valency within the investigated pressure range (36 GPa), while in SmTe a full transition to trivalency is observed above 20 GPa. The transition to the CsCl-Type high-pressure phase has no significant influence on the valence in both systems.     

High-Pressure/High-Temperature NFS Study of Magnetism in LuFe 2 and ScFe 2

Using the new technique of nuclear forward scattering (NFS) of synchrotron radiation, we studied the magnetic hyperfine fields B hf and ordering temperatures T M of the Laves phases LuFe 2 (cubic C15) and ScFe 2 (hexagonal C14) at pressures up to 90 GPa and temperatures up to 700 K. For LuFe 2 we find for T M first an increase from 562 K at 0 GPa to 603 K at 10 GPa and then a decrease to 295 K around 75 GPa. The hyperfine fields B hf show at 295 K a continuous decrease with pressure, indicating a reduction of the Fe band moment. A similar behaviour of both T M and B hf was observed in ScFe 2.     

Phonon Spectroscopy of Oriented hcp Iron

High-pressure phonon spectroscopy was performed on iron in the bcc and hcp phase up to 40 GPa using the nuclear inelastic scattering (NIS) of synchrotron radiation (SR). In hcp iron we observe differences in the density of phonon states for spectra measured with different orientations of the diamond anvil cell (DAC) with respect to the SR beam. These differences are attributed to a preferred orientation of the hexagonal c -axis along the load axis of the DAC. These texture effects are used, in conjunction with theoretical calculations, to extract density of phonon states as seen parallel and perpendicular to the c -axis of hcp iron.     

High-pressure studies with nuclear scattering of synchrotron radiation

Hyperfine Interactions - The nuclear forward scattering (NFS) of synchrotron radiation is especially suited for probing magnetism at high pressure (h.p.), here in the Mbar range, by the nuclear...     

151Eu-Mössbauer study of pressure-induced valence transitions in EuM2Ge2 (M=Ni,Pd,Pt)

¹⁵¹Eu-Mössbauer spectroscopy is used to study the ternary intermetallics EuM₂Ge₂ (M=Ni, Pd, Pt), in which Eu is divalent, and EuNi₂Si₂ as a trivalent reference system in the pressure range 0–31 GPa. In EuNi₂Ge₂ and EuPd₂Ge₂, one observes a valence transition from Eu²⁺ to Eu³⁺ around 5 and 25 GPa, accompanied by a change in isomer shift of 9.3 and 10.1 mm/s, respectively. These are the largest pressure-driven changes in isomer shift for¹⁵¹Eu-spectroscopy observed up to now.