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.     

Peak suppression in ESEEM spectra of multinuclear spin systems

We have observed a disturbing suppression effect in three-pulse ESEEM and HYSCORE spectra of systems with more than one nucleus coupled to the electron spin. For such systems, the ESEEM signal contains internuclear combination peaks of varying intensity. At the same time, the peaks at the basic ESEEM frequencies are reduced in intensity, up to the point of complete cancellation. For both three-pulse ESEEM and HYSCORE, the amplitude of a peak of a given nucleus depends not only on its modulation depth parameter k and the tau-dependent blind-spot term b, but also on k and b of all other nuclei. Peaks of nuclei with shallow modulations can be strongly suppressed by nuclei with deep modulations. This cross-suppression effect explains the observation that HYSCORE (1)H peaks are often very weak or even undetectable in the presence of strong (14)N peaks. Due to this distortion of intensities, ESEEM spectra have to be analysed very carefully. We present a theoretical analysis of this effect based on the product rules, numerical computations, and illustrative experimental data on Cu(gly)(2). In experiments, the impact of this cross suppression can be alleviated by a proper choice of tau values, remote echo detection, and matched pulses.     

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.     

Shuttling through reversible covalent chemistry

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

A new approach to the statistical treatment of 2D-maps in proteomics using fuzzy logic

A new approach to the statistical treatment of 2D-maps has been developed. This method is based on the use of fuzzy logic and allows to take into consideration the typical low reproducibility of 2D-maps. In this approach the signal corresponding to the presence of proteins on the 2D-maps is substituted with probability functions, centred on the signal itself. The standard deviation of the bidimensional gaussian probability function employed to blur the signal allows to assign different uncertainties to the two electrophoretic dimensions. The effect of changing the standard deviation and the digitalisation resolution are investigated.     

Solving Nonconvex Planar Location Problems by Finite Dominating Sets

It is well-known that some of the classical location problems with polyhedral gauges can be solved in polynomial time by finding a finite dominating set, i.e. a finite set of candidates guaranteed to contain at least one optimal location.In this paper it is first established that this result holds for a much larger class of problems than currently considered in the literature. The model for which this result can be proven includes, for instance, location problems with attraction and repulsion, and location-allocation problems.Next, it is shown that the approximation of general gauges by polyhedral ones in the objective function of our general model can be analyzed with regard to the subsequent error in the optimal objective value. For the approximation problem two different approaches are described, the sandwich procedure and the greedy algorithm. Both of these approaches lead - for fixed - to polynomial approximation algorithms with accuracy for solving the general model considered in this paper.