Synthesis of 13c-labelled [s]-proline and its conformational analysis by nuclear magnetic resonance

In order to analyze completely the ring conformation of [S]-Proline (l-thiazolidine-4-carboxylic acid) this compound has been synthesized with its C_δ atom enriched at 90% in ¹³C. The ¹H-¹H, ¹³C-¹H, ¹³C-¹³C vicinal coupling constants measured at several pH values describe well the geometry of the thiazolidine ring. The results suggest that the ring has an average planar conformation only in a narrow range of pH close to the pK of the amine group. Above and below this pH the ring tends to adopt preferentially the S_γendo and S_γexo puckered conformations respectively. It is concluded that a good correlation exists between the value of the dihedral angle ø and the character S_γendo or S_γexo of the ring.     

Photocatalytic activity of nanostructured TiO2 films produced by supersonic cluster beam deposition

The photocatalytic activity of thin, nanostructured films of titanium dioxide, synthesized by supersonic cluster beam deposition (SCBD) from the gas phase, has been investigated employing the photodegradation of salicylic acid as test reaction. Because of the low deposition energy, the so-deposited highly porous TiO₂ films are composed of nanoparticles maintaining their original properties in the film, which can be fully controlled by tuning the deposition and post-deposition treatment conditions. A systematic investigation on the evolution of light absorption properties and photoactivity of the films in relation to their morphology, determined by AFM analysis, and phase composition, determined by Raman spectroscopy, has been performed. The absorption and photocatalytic activity of the nanostructured films in the visible region could be enhanced either through post-deposition annealing treatment in ammonia containing atmosphere or employing mild oxidation conditions, followed by annealing in N₂ at 600 °C.     

New insights on testing the efficiency of methods of pricing and hedging American options

With reference to the evaluation of the speed–precision efficiency of pricing and hedging of American Put options, we present and discuss numerical results obtained on the basis of four different large enough random samples according to the relevance of the American quality (relative importance of the early exercise opportunity) of the options. Here we provide a comparison of the best methods (lattice based numerical methods and an approximation of the American Premium analytical procedure) known in literature along with some key methodological remarks.     

A numerical methodology for thermo-fluid dynamic modelling of tyre inner chamber: towards real time applications

Meccanica - The characterization and reproduction of tyre behaviour for vehicle modelling is a topic of particular interest both for real-time driver in the loop simulations and for offline...     

Bis-furyl alditols via SnCl4- or ZnCl2-catalysed reaction of furans with sugars

Alditols have been obtained in very high yield using an excess of electron-rich furans with respect to the protected sugars. The scope and limitation of the reaction have been explored.     

Claisen Rearrangement of Hydroxynaphthoquinones: Selectivity toward Naphthofuran or α‐Xiloidone Using Copper Salts and Iodine

α‐xiloidone is an interesting chromene that are structurally related to lapachones; in this work, we selectively synthesized α‐xiloidone from the reaction of lawsone 1 with 3,3‐chloro‐3‐methylbut‐1‐yne under copper/I₂ catalysis via propargyl Claisen rearrangement.     

The Effect of Ligand Denticity in Size‐Selective Synthesis of Calix[n]arene‐Stabilized Gold Nanoparticles: A Multitechnique Approach

A series of gold nanoparticles (AuNPs) stabilized by monodentate, bidentate, and tridentate thiolate calix[n]arene ligands 1 – 3 was prepared by using the Brust–Schiffrin two‐phase direct synthesis and characterized with NMR spectroscopy, elemental analysis, transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). The experimental data show that the particular multidentate structure of calix[n]arene derivatives 2 and 3 introduces a control element in the preparation of the gold nanoparticles that allows, in the particular experimental conditions here reported, to obtain very small (≈1 nm) AuNPs. These are the first experimental findings that identify a role of ligand “denticity” in the determination of the nuclearity of nanoparticles.     

Effect of peptide ligand dipole moments on the redox potentials of Au38 and Au140 nanoparticles

Phenylethanethiolate monolayer-protected Au38 and Au140 nanoclusters were modified by ligand place exchange with a series of thiolated peptides. The peptides were homooligomers based on the alpha-aminoisobutyiric acid unit. The effects of changing the peptide concentration and the peptide length in the capping monolayer were studied by differential pulse voltammetry. The results showed that the redox behavior of the nanoparticles can be affected very significantly by such modifications. For example, the first oxidation peak of Au38, a cluster displaying molecule-like behavior, could be shifted positively by as much as 0.7-0.8 V. Detectable redox shifts were noted even when one single oriented peptide was in the Au140 monolayer. These effects were attributed to the molecular dipole moments of the peptide ligands.