Early stages in the oxidation of magnesium,aluminium and magnesium/aluminium alloys: I. Exoelectron emission and long wavelength photoemission

The initial stages in the oxidation of magnesium, aluminium and magnesium/aluminium alloys have been studied using a photoelectron spectrometer (XPS and exoelectron energy spectra) and the diode technique (surface potentials and volumetric adsorption of oxygen). This paper describes and characterises the exoelectron emission and the visible wavelength photoemission which occurs during oxidation. At low oxygen exposures (< 10 L), exoelectrons with a 4 eV energy spread are emitted in the dark from magnesium and magnesium/aluminium alloy. Aluminium shows no such emission. Another, dark pressure-dependent emission of exoelectrons occurs only on magnesium/aluminium alloy and aluminium at high oxygen exposures. The onset of this emission lies 3 eV higher and it again has a 4 eV spread. When the surface is illuminated, it is possible to distinguish photo/exoelectron emission, which occurs during oxygen uptake, and true photoemission which occurs in vacuo. Both these types of emission, which were only recorded on magnesium, show a resolved triplet. Photoelectric work functions as low as 0.3 eV were observed. A patchy surface evidently develops during oxidation. This process, which may correspond to the nucleation of oxide islands, is slower than the chemisorption of of oxygen. The nature of the low work function patches, which we associate with the electron emissions, is therefore very dependent on the oxygen ambient pressure. A tentative energy scheme is given for such “exopatches” which are neither metal nor oxide and contain a curious energy level that must be situated above the vacuum level of the patch, as well as above the metal Fermi level. The energy with which exoelectrons are emitted derives from the heat of adsorption.     

Spectroscopic studies of tautomeric systems—III : 2-arylhydrazones of 1,2,3-triketones

The IR and NMR spectra of a range of 2-arylhydrazones of 1,2,3-tricarbonyl compounds have been recorded. Compounds containing different end groups in the 1,2,3-tricarbonyl system can exist in two different tautomeric forms. The influence of electronic and steric factors on the structure of the preferred tautomer is discussed.     

Stability properties and the KMS condition

First we derive stability properties of KMS states and subsequently we derive the KMS condition from stability properties. New results include a convergent perturbation expansion for perturbed KMS states in terms of appropriate truncated functions and stability properties of ground states. Finally we extend the results of Haag, Kastler, Trych-Pohlmeyer by proving that stable states ofL ¹-asymptotically abelian systems which satisfy a weak three point cluster property are automatically KMS states. This last theorem gives an almost complete characterization of KMS states, ofL ¹-asymptotic abelian systems, by stability and cluster properties (a slight discrepancy can occur for infinite temperature states).Supported during this research by the Norwegian Research Council for Science and Humanities     

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.     

Triol protection with 6-benzoyl-3,4-dihydro-(2H)-pyran

6-Benzoyl-3,4-dihydro-(2H)-pyran will protect 1,2,3-triols such as glycerol as their corresponding spiro-[5-phenyl-3,6,8-trioxabicyclo[3.2.1]octane-4,2[prime or minute]-tetrahydropyran]s and 1,2,4-triols (less efficiently) as the corresponding trioxabicyclo[3.2.2]nonanes; the hexol mannitol is converted into the corresponding bis-protected product.     

Dynamical stability and pure thermodynamic phases

A notion of stability of dynamics under distant perturbations is introduced. It is demonstrated, for quasi-local systems, that the stability of an equilibrium state under the same perturbations implies the state is factorial, i.e. strongly clustering in space. We also characterize the set of perturbations necessary to ensure the equivalence of stability and factorialness.