Nonstoichiometric spinel ferrites obtained from alpha-NaFeO2 via molten media reactions

Different solid/liquid "exchange" reactions involving divalent cations, protons, or ammonium ions have been performed at low/moderate temperatures (between 80 and 500 degrees C) on alpha-NaFeO2 dipped in molten salts (or acid) media. Several ferrites have been obtained which are nonstoichiometric with partially inverse spinel structures. When sodium is replaced by divalent cations (Mg2+, Co2+, Ni2+, and Zn2+), the obtained ferrites are hyperstoichiometric (cation/oxygen ratio higher than 3/4) whereas proton or ammonium reactions result in hypostoichiometric materials (cation/oxygen lower than 3/4). All these ferrites present a platelet-like morphology and show ferrimagnetic, soft magnet behavior.     

Photoelectrochemical study of Zn cytochrome-c immobilised on a nanoporous metal oxide electrode

Transient optical spectroscopies and photocurrent action spectra are used to demonstrate photoinduced charge separation between zinc-substituted cytochrome c and a nanocrystalline TiO2 electrode.     

Stereochemical memory in the temperature-dependent photodenitrogenation of bridgehead-substituted DBH-type azoalkanes: inhibition of inverted-housane formation in the diazenyl diradical through the mass effect (inertia) and steric hindrance

The photochemical denitrogenation of the cyclopentene-annelated DBH-type azoalkanes 1 has been examined in solution as a function of bridgehead substitution and temperature. For all derivatives, namely, the unsubstituted 1a(H/H), monomethyl 1b(Me/H) dimethyl 1c(Me/Me), monophenyl 1d(Ph/H), and diphenyl 1e(Ph/Ph), the temperature-dependent ratio of syn and anti housanes 2 provides experimental support for a competition between the singlet (high temperature) and triplet (low temperature) reaction channels in the direct photolysis. The syn/anti ratio of the housanes 2 depends on the extent and type of bridgehead substitution; the amount of the anti diastereomer (retention) follows the order Ph > Me > H, and double substitution is more effective than single. This stereochemical memory is interpreted in terms of the mass effect (inertia) of the substituents and steric interaction (size) between the substituents at the bridgehead and the methylene bridge during the deazetation step of the transient diazenyl diradical conformations (1)DZ (exo-ax) and (1)DZ (exo-eq). These conformers are impulsively generated upon decay of the (1)(n,pi)-excited azoalkane, a trajectory assessed through computational work. The new mechanistic feature disclosed by the unprecedented anti stereoselectivity (retention) is the intervention of a puckered 1,3-cyclopentanediyl singlet diradical (1)DR as product bifurcation step, whose conformational relaxation to the planar species (loss of stereochemical memory) is encumbered by bridgehead substitution.     

Laguerre geometry of surfaces with plane lines of curvature

We study surfaces with plane lines of curvature in the framework of Laguerre geometry and provide explicit representation formulae for these surfaces in terms of a potential function. As an application, we explicitly integrate allL- minimal surfaces with plane curvature lines. Partially supported by MURST 40.     

A representation formula of sum rules for zeros of polynomials

A representation formula in terms of Lucas polynomials of the second kind in several variables (see formula (4.3)), for the sum rulesJ _s ⁽ⁱ⁾ introduced by K.M. Case [1] and studied by J.S. Dehesa et al. [2]–[3] in order to obtain informations about the zeros’ distribution of eigenfunctions of a class of ordinary polynomial differential operator, is derived. Lavoro eseguito nell’ambito del G.N.I.M. del C.N.R.     

Graded Cluster Expansion for Lattice Systems

In this paper we develop a general theory which provides a unified treatment of two apparently different problems. The weak Gibbs property of measures arising from the application of Renormalization Group maps and the mixing properties of disordered lattice systems in the Griffiths’ phase. We suppose that the system satisfies a mixing condition in a subset of the lattice whose complement is sparse enough namely, large regions are widely separated. We then show how it is possible to construct a convergent multi-scale cluster expansion.The authors acknowledge the support of Cofinanziamento MIUR.     

A generic basis for some simple light-operated mechanical molecular machines

A novel type of mechanical switch is described in which light-induced translation of a macrocycle in a [2]rotaxane quenches anthracene fluorescence. Features of the system include the remarkable 200:1 difference in fluorescence intensity between the two positional states of the molecule ( approximately 85:1 between one isomer and the photostationary state). In principle the same concept could be used for mechanically switching virtually any property that can be influenced by functional group proximity effects.     

Relative importance of hydrogen bonding and coordinating groups in modulating the zinc-water acidity

The presence of second-sphere -NH(2) groups in the proximity of a zinc(ii)-bound water molecule enhances its acidity by ca. 2 pK(a) units.     

The affinity of phosphates to zinc(II) complexes can be increased with hydrogen bond donors

Amino H-bond donors adjacent to a zinc(II) centre increase the affinity of phosphates to the zinc(II) centre.     

Shuttling through reversible covalent chemistry

The first stimuli-responsive molecular shuttle that functions through reversible C-C bond formation is reported.