Mercury(II) dibromo-bis-(3-amino-5-mercapto-1,2,4-triazole): synthesis,crystal structure,and infrared characterization

The title compound C₄H₈N₈S₂HgBr₂ was prepared and characterized by means of X-ray crystallography, and i.r. measurements. The crystals are orthorhombic, space group Pbcn (no. 60) witha=9.707(2),b=8.609(1),c=16.128(2) Å, andZ=4. The compound exhibits discrete monometallic units with the 1,2,4-triazole molecule acting as a monodentate ligand. The structure consists of units in which the mercury atom is coordinated in a distorted tetrahedral geometry by two sulfur and two bromine atoms. The NH and NH₂ group of the 3-amino-5-mercapto-1,2,4-triazole unit are involved in intermolecular hydrogen bonds. Infrared bands are diagnostic of the coordination environment around the metal atoms.     

Preferential protonation and methylation at the nitrogen atoms of N,N-dimethylamino derivatives of pyridine

The relative reactivity toward protonation and methylation of the two nitrogen atoms in N,N-dimethylaminopyridines has been examined by ¹H NMR. The ring position of the dimethylamino group has no influence on protonation, which occurs in all the derivatives at the heterocyclic nitrogen. The N-methylation reaction does not follow a homogeneous behaviour, occurring at the exocyclic nitrogen in the 2-substituted dimethylamino derivative. The electronic characteristics of the molecules, determined by MO calculations at a semi-empirical level, indicate that both protonation and methylation should occur at the heterocyclic nitrogen; the calculated relative stabilites, however, of the N-protonated and N-methylated forms are in full agreement with the experimental results, and it appears that the anomalous behaviour of 2-dimethylaminopyridine in the N-methylation reaction is caused by steric factors.     

ZiCo: a peptide designed to switch folded state upon binding zinc

We describe a novel approach to the design of a metal-triggered conformational switch. Specifically, two distinct protein-folding motifs were merged into one polypeptide sequence. The target structures were an alpha-helical coiled-coil trimer and zinc-bound monomer. Solution-phase spectroscopic, sedimentation, and binding studies confirmed the key aspects of the design. Both forms of the peptide were cooperatively folded, and the switch between them was reversible. This design process potentially presents a novel route to peptide-based biosensors.     

Characterization of Al(III) complexes with hematein in artistic alum logwood inks

The complexes between Al(III) and hematein, the main coloring matter in alum logwood inks, were characterized by Raman and ²⁷Al NMR (nuclear magnetic resonance) spectroscopies. Raman spectra of the crystallized complexes and of the compounds applied on a paper substrate are presented and assigned based on published data for the parent compounds. These Raman spectra show that the coordination of the hematein to the Al(III) ions takes place in both cases through the carbonyl and hydroxyl groups in the molecule, and that the aromatic rings are also involved in the interaction. The Raman spectra of the pure hematein–Al(III) complexes were found to be consistent with those recorded for a logwood ink prepared following a late 19th century recipe, using logwood chips instead of pure hematein, and applied on a paper substrate. These spectra can be used as references for the noninvasive identification of the compounds in works of art. ²⁷Al solid‐state NMR showed that the coordination of the Al(III) atoms in the crystallized powder is predominantly octahedral, while when applied on a paper substrate the colorant is present mainly as a tetrahedral complex, with an octahedral coordination also present in a smaller proportion. The fact that the predominant coordinations for the complexes in the crystallized material and for the ones present on the paper substrate are different is relevant for the study of the lightfastness and thermal stability of works of art bearing these media. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopic characterization of a thiophene‐based active material for resistive organic nonvolatile memories

A combined theoretical and experimental Raman study is presented on a diphenyl bithiophene molecule known as a good candidate for the development of organic nonvolatile memory devices. Spectroscopic markers suitable to distinguish the different stable conformers of the molecule have been predicted and detected. The combined analysis of theoretical and experimental Raman spectra recorded in solution indicates that at room temperature a dynamical equilibrium, characterized by interconversion between the two more stable conformers (namely trans and cis), takes place and that the more populated species is the cis form. Referring to the solid phase instead, Raman spectra of single‐crystal samples show the presence of the only trans conformer, as confirmed by X‐ray measurements. Finally, Raman spectra of thin films, as those used for the memory device, were collected; samples just deposited from solution and after few hours from the deposition were analyzed. Following the evolution of selective spectroscopic Raman markers, an isomerization process from the abundant cis (as‐deposited) to the totally trans (after few hours) conformer in the solid phase was detected. These results open the way to the identification of the molecular isomers present in the thin film of the memory cell and finally of the active molecular species involved in the switching mechanism of the operating device. Copyright © 2009 John Wiley & Sons, Ltd.     

Electronic properties of the surface of perylene tetracarboxylic acid dianhydride film upon deposition of the ultrathin conjugated layers of Pyronine B

Ultrathin conjugated layers of Pyronine B were thermally deposited in UHV on the surface of perylene tetracarboxylic acid dianhydride (PTCDA) film. The structure of unoccupied electron states located 5-20 eV above the Fermi level (E_F) and the surface potential were monitored during the Pyronine B overlayer deposition, using an incident beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. Electronic work function of the PTCDA surface changed from 4.9 ± 0.1 eV, during the Pyronine B deposition due to the change of the contents of the surface layer, until it reached a stable value 4.6 ± 0.1 eV at the Pyronine B film thickness 8-10 nm. The interface dipole corresponds to electron transfer from the Pyronine B overlayer to the PTCDA surface and the polarization in the Pyronine B overlayer was found confined within approximately 1 nm near the interfaces. The edges of major bands of density of unoccupied electronic states (DOUS) of PTCDA substrate and of the Pyronine B overlayer were unaffected by the process of the interface formation. The major TCS spectral features of the Pyronine B film corresponding to the DOUS band edges were identified and the assignment of the π^*, σ^*(C-C) and σ^*(CC) character was suggested.     

A phase field approach to solidification and solute separation in water solutions

We propose a phase field model for the solid–liquid phase transition in a water-salt (sodium chloride) solution in the absence of macroscopic motion, under possibly non-isothermal conditions. A thermodynamic approach based on a free energy functional is assumed. The model consists of three evolution equations: a time-dependent Ginzburg–Landau equation for the solid–liquid phase change, a diffusion equation of the Cahn–Hilliard kind for the solute dynamics and the heat equation for the temperature change. The proposed system is aimed to contribute to the modelling of the brine channels formation in the ice of the polar seas.     

Structural investigation of an amorphous Si24Nb76 alloy produced by mechanical alloying using reverse Monte Carlo simulations

The atomic structure of an amorphous Si₂₄Nb₇₆ alloy produced by mechanical alloying was investigated by using one X-ray total structure factor S(K) as input data for reverse Monte Carlo (RMC) simulations. The partial S_Si–Si(K), S_Si–Nb(K), S_Nb–Nb(K) structure factors and G_Si–Si(r), G_Si–Nb(r), G_Nb–Nb(r) pair probability functions were obtained from the RMC simulations. The structural parameters (interatomic distances and co-ordination numbers) for the first neighbors were extracted and compared with those found in the Nb₃Si compound. It was observed some resemblance between these phases.