Study of the initial stage of manganese dioxide electrodeposition on a rotating ring-disk electrode

The initial stage of electrodeposition of manganese dioxide has been studied on the platinum disk electrode and on the ring-disk electrode. Two current maxima were observed on the anodic voltammograms. It has been shown that the first rise in the current is associated with the formation of manganese dioxide (MD) nuclei on the electrode surface, and the second with their growth at the border between MnO₂ and bare platinum due to an increase in the perimeter of the nuclei. Electrodeposition on bare platinum proceeds at a higher rate than on the surface of growing MD. This is explained by the difference in the reaction mechanisms on these substrates. The first stage of the process on the growing MD is the chemisorption of Mn(II) ions with the formation of Mn(III) ions, which are then electrochemically oxidized to MD. Chemisorption is the slowest step in the whole process.     

Pyrimidoquinazolinophenanthroline Opens Next Chapter in Design of Bridging Ligands for Artificial Photosynthesis**

The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)₃]²⁺ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD⁺ to NADH was achieved, highlighting the potential of this system for photocatalytic applications.     

CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology acco...     

New condensed indoline bis-spiropyrans

The synthesis of new condensed indoline bis-spiropyrans from isomeric hexamethyldihydroindolo-[4,5-e]-and -[7,6-g]indoles, and also from hexamethyldihydrobenzo[e]pyrrolo[3,2-g]indole in three stages has been generalized. By condensation of the isomeric bis-analogs of Fischer's bases obtained at the second stage with salicylic aldehydes, the following bis-spiro compounds have been synthesized: 6,6"-dinitro-, 6,6",8,8"-tetranitro-, 6,6",8,8"-tetrabromo-1',3',3',6',8',8'-hexamethyldispiro[chromene-2,2'-indolino[7,6-g]indoline-7',2"-chromenes], 6,6"-dinitro-, 6,6",8,8"-tetranitro-, 6,6",8,8"-tetrabromo-1',1',3',8',10',10'-hexamethyldispiro[chromene-2,2'-indolino[4,5-e]indoline-9',2"-chromenes], 6,6"-di-nitro-, 6,6"-dibromo-, and 6,6",8,8"-tetrabromo-1',1',8,8'-tetramethyl-1',4',5',8'-tetrahydrodispiro-[chromene-2,2'-dipyrrolo[1,2,3-d,e:3,2,1-i,j]benzo[g]quinoxaline-7',2"-chromenes].     

High pressure research using muons at the Paul Scherrer Institute

Pressure, together with temperature and magnetic field, is an important thermodynamical parameter in physics. Investigating the response of a compound or of a material to pressure allows to elucidate ground states, investigate their interplay and interactions and determine microscopic parameters. Pressure tuning is used to establish phase diagrams, study phase transitions and identify critical points. Muon spin rotation/relaxation (μSR) is now a standard technique making increasing significant contribution in condensed matter physics, material science research and other fields. In this review, we will discuss specific requirements and challenges to perform μSR experiments under pressure, introduce the high pressure muon facility at the Paul Scherrer Institute (PSI, Switzerland) and present selected results obtained by combining the sensitivity of the μSR technique with pressure.     

Relaxation of the shallow acceptor center in germanium

Polarized negative muons were used to study relaxation mechanisms of shallow acceptors in germanium. In p-type germanium at low temperatures relaxation of the muon spin was observed, indicating that the muonic atom (gallium-like acceptor center) formed via capture of the negative muon by a host atom is in the paramagnetic state and its magnetic moment is relaxing. The relaxation rate of the muon spin was found to depend on temperature and on concentration of gallium impurity. We conclude that to the relaxation of the magnetic moment of the Ga acceptor in Ge there contribute both scattering of phonons and quadrupole interaction between the acceptors. We estimate, for the first time, the hyperfine interaction constant for the gallium acceptor in germanium as 0.11 MHz.