Hydration water rotational motion as a source of configurational entropy driving protein dynamics. Crossovers at 150 and 220 K

The existence of a protein dynamic transition around 220 K is widely known and the central role of the protein hydration shell is now largely recognized as the driving force for this transition. In this paper, we propose a mechanism, at the molecular level, for the contribution of hydration water. In particular, we identify the key importance of rotational motion of the hydration water as a source of configurational entropy triggering (i) the 220 K protein dynamic crossover (the so-called dynamic transition) but also (ii) a much less intense and scarcely reported protein dynamic crossover, associated to a calorimetric glass transition, at 150 K.     

Boron oxide encapsulated Bridgman growth of high-purity high-resistivity cadmium telluride crystals

High-purity semi-insulating CdTe crystals have been successfully grown by encapsulated (B₂O₃) Bridgman technique. The procedure strongly limits component losses allowing the achievement of stoichiometry control material and keeps a low level of impurity contamination as shown by mass spectroscopy analysis data. When strictly stoichiometry-controlled and high-purity polycrystalline source material has been used, high-resistivity crystals have been obtained without any intentional doping. EPD values in the range of 1–3×10⁴ cm⁻² have been observed in a wide region of the crystals. Luminescence spectroscopy confirms the purity and good structural quality of the material. The proposed method avoids the technical problems posed by the High Pressure Bridgman technique and fits the requirements for CdTe/CdZnTe crystals large-scale production.     

Structural consequences of metal complexation of cyclo[Pro-Phe-Phe-Ala-Xaa]2 decapeptides

The conformational features of both free and Ca2+-complexed cyclo[Pro-Phe-Phe-Ala-Xaa]2 (with Xaa= Glu(OtBu), Lys(CIZ), Leu, and Ala) in solution have been determined by NMR spectroscopy and extensive distance-geometry calculations. The decapeptides are conformationally homogeneous in solution and show common structural features in their free and complexed forms. The structures of the free form contain only trans peptide bonds and are topologically similar to the structure of gramicidin-S, folded up in two antiparallel extended structures, stabilized by interstrand hydrogen bonds, and closed at both ends by two beta-turns. In contrast, the Ca2+-complexed peptides present two cis peptide bonds and are generally similar to those observed for the metal-complexed forms of antamanide and related analogues, folded into a saddle shape with two beta-turns. The Glu(OtBu)-, Leu-, and Lys(ClZ)-containing peptides examined here maintain the biological activity of the cyclolinopeptide A in their ability to competitively inhibit cholate uptake. The natural antamanide and cyclolinopeptide A are both able to inhibit the uptake of bile salts into hepatocytes. They share the same postulated active sequence Pro-Phe-Phe. Based on our structural results, we conclude that the ability to adopt a global conformation, characterized by a clear amphipathic separation of hydrophobic and hydrophilic surfaces, is an important feature for the functioning of this class of peptides.     

Direct stripping voltammetric determination of lead,cadmium and zinc dithizonates

A procedure is described in order to determine lead, cadmium and zinc dithizonates by stripping voltammetry. The polarographic analysis is performed in a medium of methanol and benzene (chloroform) in a ratio of 7:1 and in the presence of silver dithizonate. Sodium nitrate was used as a base electrolyte. By carrying out these analytic conditions it is possible to perform directly the stripping voltammetric analysis in benzene (chloroform) solution of extracted dithizonates, without further treatment. Silver nitrate in methanol is added to dithizonates in order to free lead, cadmium, and zinc from their complexes, to be determined polarographically.     

Vapour‐phase growth,purification and large‐area deposition of ZnO tetrapod nanostructures

Large‐yield zinc oxide (ZnO) nanosized tetrapods have been obtained by a standard vapour‐phase growth technique to which a few modifications have been added, such as the separation of the Zn source evaporation region from the Zn oxidation region inside the reactor setup. This modification allows to keep the growth conditions constant and continuous for a long time, thus favouring the obtainment of large amounts of ZnO tetrapod nanostructures. As some contaminations usually occur due to metallic Zn particles and/or different ZnO nanostructures, including not completely reacted ZnO_1‐x solid phases, they can be removed by a three‐step “purification” procedure as described in the article. Further to that, a deposition method from suitable liquid suspensions is also reported, which allows to produce homogeneous distributions of ZnO tetrapods on large substrate areas. The proposed procedures are expected to be particularly appropriate for a large production of samples for device use. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CC bond formation in diiron complexes

The growing effort to design new sustainable synthetic methodologies, based on readily available and environmentally friendly transition metals, has boosted research on iron complexes. This review article focuses on C?C-bond-forming reactions occurring at bridging ligands in diiron complexes, aimed at evidencing distinctive aspects and advantages associated with the presence of two adjacent iron centres. A number of diiron-mediated C?C-bond-forming reactions reported in the literature, including nucleophilic and electrophilic additions and insertion and cycloaddition reactions, have been accumulated over the years, which, together with more recent developments, indicate that diiron complexes might provide promising alternatives to precious metals in the challenging field of metal-promoted C?C bond formation.     

First measurement of the partial widths of 209Bi decay to the ground and to the first excited states

209Bi alpha decay to the ground and to the first excited state have been recently observed for the first time with a large BGO scintillating bolometer. The half-life of 209Bi is determined to be τ(1/2)=(2.01±0.08)×10(19) yr while the branching ratio for the ground-state to ground-state transition is (98.8±0.3)%.     

Nanometric confinement: Toward new physical properties and technological developments

In numerous real life situations, molecular systems are not found in bulk but instead trapped in limited volumes of nanometric size: this is nanometric confinement. The complex interplay of the confinement topology, dimensionality (3D to 1D) and surface/volume ratio significantly affects the physical properties of the confined material. After decades of intense fundamental research, we are now entering a time when the unusual properties of fluids under confinement may be tuned to target specific technological objectives. In this paper, we highlight few situations, all related to the fields of energy production or storage, where diverse neutron scattering techniques (imaging, small angle scattering, diffraction, inelastic and quasi-elastic scattering) may help to bridge basic science and applied research.