Recent advances with π-conjugated salen systems

Schiff base ligands have long been successfully employed as ligands in combination with various metals to give catalysts capable of realizing a variety of synthetic transformations. One of the most widely used Schiff base ligands, the "salen" ligand, has been extensively researched. Recently, there has been increased interest in π-conjugated salen systems, known as "salphen" ligands, as a result of the differences in reactivity of the complexes in catalytic applications compared with the salen analogues. Complexes of salphen ligands display interesting photophysical and supramolecular properties which are not always observed with salen systems as a result of their π-conjugation. This tutorial review therefore describes the most significant advances recently made with salphen and related π-conjugated ligand systems.     

New phosphorylating reagents for deoxyribonucleosides and oligonucleotides

New phosphorylating reagents 1 and 2 were prepared in three steps from 4-hydroxybenzaldehyde. They showed good efficiency in the solid phase synthesis of 5′-phosphate monoester nucleosides. End-phosphate DNA sequence synthesis demonstrated the efficiency of the new reagents (1 and 2) according to the general procedure of automated DNA synthesis. The oxidation of P(III) to P(V) and the removal of benzyl protecting groups were achieved in a single step by treatment with a 0.02 M I₂/pyridine/H₂O solution. Due to this one-pot treatment, it is possible to use the phosphorylating reagents (1 and 2) for the synthesis of base-sensitive ODNs. The reagents 1 and 2 are unique among phosphorylating reagents.     

Modelling the soundscape quality of urban waterfronts by artificial neural networks

The renewal of the urban waterfronts has become a major focus of attention for politicians and decision makers in the city’s management programs. The recognition of the patterns that define the waterfronts’ identity is essential to select new strategies of intervention for the environmental recovery. In order to create adequate environments for everyday life within a sustainable development, new links between human senses, human perception and design need to be created. Within this wide approach, the landscape and the soundscape play a significant role and can become a key driving force in the implementation of the changes. New techniques have to be tested to identify the sonic and visual parameters capable to explain the specificity of a waterfront. With this purpose, an artificial neural network (ANN) was developed, and the relative importance of the input variables was evaluated. The collected database was also analysed by multiple linear regression (MLR) to compare the outcomes of both models. The urban waterfront of Naples (Italy) was chosen as case study. The results obtained show that the performance of the neural network is better than the one of the linear regression (rANN = 0.949, rMLR = 0.639). The interpretation of the relative importance method is also quite satisfactory in the ANN.     

Electronic structure of uracil-like nucleobases adsorbed on Si(001): uracil,thymine and 5-fluorouracil

We study the electronic properties of the Si(001):Uracil, Si(001):Thymine, andSi(001):5-Fluorouracil systems, focusing on the Si dimer-bridging configuration withadsorption governed by carbonyl groups. While the overall structural and electronicproperties are similar, with small differences due to chemical substitutions, much largereffects on the surface band dispersion and bandgap show up as a function of the molecularorientation with respect to the surface. An off-normal orientation of the molecular planesis favored, showing larger bandgap and lower total energy than the upright position. Wealso analyze the localization of gap-edge occupied and unoccupied surface states.     

Two-gap superconductivity in the Fe-1111 superconductor LaFeAsO1−x F x : A point-contact Andreev-reflection study

Point-contact Andreev-reflection (PCAR) experiments were performed in the Fe-1111 layered superconductor LaFeAsO_0.9F_0.1 with resistive T _c ^on ∼ 27 K. The observation of two pairs of peaks in the low-temperature Andreev-reflection spectra clearly indicates the presence of two order parameters. The behavior of the two gaps as a function of temperature, obtained by fitting the conductance curves by means of the generalized two-band Blonder-Tinkham-Klapwijk model, shows some anomalies. A theoretical analysis performed within the two-band Eliashberg theory with a generic electron-boson coupling can reproduce the low-temperature value of the two gaps but generally fails in giving a satisfactory fit of their overall temperature dependence, indicating the rich and complex physics of these newly discovered superconductors.      

Parallel two-photon photopolymerization of microgear patterns

We report parallel two-photon photopolymerization of microgear patterns by exposing a photoresist to holographically generated optical vortices. The optical vortices are created by imparting a helical pitch onto the incident light using a programmable lithographic phase mask realized with a computer addressable phase-only spatial light modulator. By varying the phase levels of the spatial light modulator, the truncated helical phase of an optical vortex results in output intensity patterns that typifies that of microgears instead of perfect doughnut beams. Our experiments and simulations are in good agreement implying a more efficient and highly parallel two-photon photopolymerization scheme that can be subsequently used for non-scanning fabrication of microgears.     

Nonrelativistic Geodesic Motion

We show that any second-order dynamic equationon a configuration space X R ofnonrelativistic time-dependent mechanics can be seen asa geodesic equation with respect to some (nonlinear)connection on the tangent bundle TX X of relativisticvelocities. We compare relativistic and nonrelativisticgeodesic equations, and study the Jacobi vector fieldsalong nonrelativistic geodesics.     

Stability and Morphodynamics

Linear and nonlinear aspects of the development of morphodynamical features of fluvial and coastal environments are reviewed. It is emphasized that, in spite of the as yet incomplete understanding of the mechanics of sediment transport, some essential mechanisms operating in morphodynamics have been recently clarified by employing classical tools of linear and weakly nonlinear stability theory.     

A comparison between the craig-cox and the kacker-okapuu methods of turbine performance prediction

Summary Two complete comprehensive loss correlations for estimating the efficienty of axial-flow turbines are examinated in this paper: the well-known Craig-Cox method, and the recent development of the Ainley-Mathieson method, presented by Kacker and Okapuu, which reproposes the validity of this approach.Firstly, a comparison is done by evaluating the losses in a number representative cascades, having various solidities, aspect ratios, Reynolds and Mach numbers. It is shown that the two methods are in good agreement for subsonic cascades having high flow coefficients, while significant differences are found in high deflection blades, especially for the secondary losses.In the second part, it is investigated how the choice of correlation affects the project of a turbine stage. A design procedure, automatically carried out by a computer program, was applied to a number of cases: the differences between the two solutions of the same project problem obtained by using the two correlations are discusses. Parameters like specific speed, expansion ratio and size parameter are used to generalize the results.

---

Sommario In questo articolo vengono considerati due metodi per la valutazione completa delle perdite fluidodinamiche in turbine assiali: il primo, ben noto, è quello proposto da Craig e Cox, mentre il secondo rappresenta il recente sviluppo del metodo di Ainley e Mathieson, operato da Kacker e Okapuu a conferma della validità dell'approccio originale.Un primo confronto è stato effettuato valutando le perdite in alcune schiere tipiche, con diversi numeri di Reynolds e di Mach. Viene mostrato che i due metodi sono in buon accordo per schiere subsoniche aventi elevati coefficienti di flusso, mentre si rilevano differenze significative in pale ad alta deflessione, specialmente per ciò che riguarda le perdite secondarie.Nella seconda parte si è voluto indagare come la scelta di una o dell'altra correlazione di perdite possa influenzare il progetto di stadi di turbine. Un certo numero di stadi tipici è stato ottimizzato mediante un codice automatico: vengono discusse le differenze tra le due soluzioni dello stesso problema progettuale risultate dall'uso di ambedue le correlazioni. I risultati sono presentati in funzione di parametri quali il numero di giri caratteristico, il rapporto di espansione e il coefficiente di «taglia», nell'intento di generalizzare i risultati.

---

     

Palladium(II) complexes with sulphonium ylides

Keto-stabilized sulphonium ylides displace styrene and benzonitrile from their adducts with PdCl₂ to give stable $\text{2}\text{1}$ ylidePdCl₂ complexes. Evidence is given for epimeric equilibrium between trans square-planar structures of these new complexes in solution.A $\text{1}\text{1}$ ylidePdI₂ complex, obtained from dimethylsulphonium methylide, is also described.