Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides

Direct palladium‐catalysed cross‐couplings between organolithium reagents and (hetero)aryl halides (Br, Cl) proceed fast, cleanly and selectively at room temperature in air, with water as the only reaction medium and in the presence of NaCl as a cheap additive. Under optimised reaction conditions, a water‐accelerated catalysis is responsible for furnishing C(sp³)–C(sp²), C(sp²)–C(sp²), and C(sp)–C(sp²) cross‐coupled products, in competition with protonolysis, within a reaction time of 20 s, in yields of up to 99 %, and in the absence of undesired dehalogenated/homocoupling side products even when challenging secondary organolithiums serve as the starting material. It is worth noting that the proposed protocol is scalable and the catalyst and water can easily and successfully be recycled up to 10 times, with an E‐factor as low as 7.35.     

Dyads of G-Quadruplex Ligands Triggering DNA Damage Response and Tumour Cell Growth Inhibition at Subnanomolar Concentration

Naphthalene diimide (NDI) dyads exhibiting a different substitution pattern and linker length have been synthesised and evaluated as G-quadruplex (G4) ligands, by investigating their cytotoxicity in selected cell lines. The dyads with the long C₇ linker exhibit extremely low IC₅₀ values, below 10 nm , on different cancer cell lines. Contrary, the dyads with the shorter C₄ linker were much less effective, with IC values increasing up to 1 μm . Among the three dyads with the longest linker, small differences in the IC₅₀ values emerge, suggesting that the linker length plays a more important role than the substitution pattern. We have further shown that the dyads are able to induce cellular DNA damage response, which is not limited to the telomeric regions and is likely the origin of their cytotoxicity. Both absorption titration and dynamic light scattering of the most cytotoxic dyads in the presence of hTel22 highlight their ability to induce effective G4 aggregation, acting as non-covalent cross-linking agents.     

Effects of cables damage on vertical and torsional eigenproperties of suspension bridges

This paper presents a continuum model for the nonlinear coupled vertical and torsional vibrations of suspension bridges with arbitrary damage in one main cable and, after pursuing a suitable linearization of the equations of motion, an investigation of damage effects on modal parameters. Damage is modeled as a diffused loss of cross-section representing the typical effect of fretting fatigue and it is introduced in the formulation by enforcing relevant literature results providing analytical solution for the static response of damaged suspended cables. The coupled nonlinear equations of motion of the damaged bridge, including the effects of shear deformation, rotary inertia and warping of the cross-section of the girder, are derived by application of Hamilton?s principle. In this way, the equations of motion available in the literature for undamaged suspension bridges are generalized to the presence of arbitrary damage in one main cable and the resulting eigenfrequencies and eigenfunctions are derived in an analytical fashion. An extensive parametric investigation is finally presented to discuss damage effects on eigenfunctions and eigenfrequencies under variation of practically meaningful parameters.     

Qualitative behavior of global solutions to some nonlinear fourth order differential equations

We study global solutions to a fourth order semilinear ordinary differential equation. We determine sufficient conditions on the nonlinearity that ensure global continuation of the solutions. Furthermore, we discuss their qualitative behaviors such as oscillations and boundedness.     

Effectiveness of measures of performance during speculative bubbles

Statistical analysis of financial data mostly focused on testing the validity of Brownian motion (Bm). Analyses performed on several time series have shown deviation from the Bm hypothesis, that is at the base of the evaluation of many financial derivatives. We analyze the behavior of performance measures based on maximum drawdown movements (MDD(T)), testing their stability when the underlying process deviates from the Bm hypothesis. In particular we consider the fractional Brownian motion (fBm), and fluctuations estimated empirically on raw market data. The case study of the rising part of speculative bubbles is reported.     

Three-electron auger process from beam-foil excited multiply charged ions

Electron emission from collisions of C3+ ions (22.7 A MeV) with carbon foils (21, 49 and 90 microg/cm(2)) was studied by the time-of-flight method. Two prominent emission patterns can be readily identified as "binary encounter" electrons and "cusp" electrons. With the thinnest target only, a third structure is visible at slightly lower time-of-flight (thus slightly higher energy) than the cusp electrons. The energy of these electrons would correspond to 647(+116)/(-104) eV if they were emitted from the projectile frame of reference. A possible explanation is a rare three-electron-Auger K(2)L(2)L(1) process.