Elasticity of flexible and semiflexible polymers with extensible bonds in the Gibbs and Helmholtz ensembles

Stretching experiments on single molecules of arbitrary length opened the way for studying the statistical mechanics of small systems. In many cases in which the thermodynamic limit is not satisfied, different macroscopic boundary conditions, corresponding to different statistical mechanics ensembles, yield different force-displacement curves. We formulate analytical expressions and develop Monte Carlo simulations to quantitatively evaluate the difference between the Helmholtz and the Gibbs ensembles for a wide range of polymer models of biological relevance. We consider generalizations of the freely jointed chain and of the worm-like chain models with extensible bonds. In all cases we show that the convergence to the thermodynamic limit upon increasing contour length is described by a suitable power law and a specific scaling exponent, characteristic of each model.     

Effect of the segmental mobility restriction on the thermoset chemical kinetics

The cure kinetics of an epoxy–amine commercial thermoset system have been investigated with the isothermal differential scanning calorimetry technique. In particular, a kinetic study has been performed in the glass–transition zone, in which diffusion phenomena compete with the chemical transformations and the overall reaction rate is partially slowed by the reduced segmental chain mobility. A generalized form of the Vogel equation has been formulated to account for the effect of the increasing glass–transition temperature on the chain mobility and, therefore, on the overall reaction rate. The kinetic model has been expressed with two factors representing the chemical reaction rate and the segmental mobility reduction. As the main result, the activation energy relative to the diffusion phenomena has been found to be very low, having a value of 42.5 K ≈ 0.356 kJ/mol, which is compatible only with the small‐angle rotation of the reactive unit. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3757–3770, 2002     

Cyclopentene-regioselective palladium-catalyzed cycloisomerization under neutral and bis-cationic reaction conditions

A series of 1,6-dienes is cyclized to cyclopentene derivatives under neutral conditions with palladium chloride in ethanol or with in situ generated LPd²⁺ in acetonitrile.     

On the reduction of NiO forms in magnesia supported catalysts

Reducibility of Ni/MgO catalysts has been studied by the temperature-programmed reduction (TPR) technique in the temperature range of 373–1273 K. The profile of reduction reveals the presence of various forms of NiO. The effects of nickel loading and treatment temperature on catalyst reducibility have been evaluated. The formation of NiO–MgO solid solution controls the whole reduction of Ni/MgO system.

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Ni/MgO 373–1273 . NiO. . Ni/MgO NiO–MgO.

     

Charge transfers at metal/oxide interfaces: a DFT study of formation of K delta+ and Au delta- species on MgO/Ag(100) ultra-thin films from deposition of neutral atoms

Ultra-thin oxide films grown on a metal substrate and of thickness smaller than 1 nm may exhibit unusual properties with respect to thicker films or single crystal oxide surfaces. In a previous study [G. Pacchioni, L. Giordano and M. Baistrocchi, Phys. Rev. Lett., 2005, 94, 226104] we have suggested that a Au atom adsorbed on a MgO/Mo(100) thin film becomes negatively charged by direct electron tunneling from the Mo metal and that this is related to the low MgO/Mo(100) work function. Here we show, based on periodic DFT supercell calculations, that charge transfer can occur also in the opposite direction by adsorption of electropositive K atoms on MgO/Ag(100) films. We predict the occurrence of a charge transfer also for Au on MgO/Ag(100) films despite the fact that here the work function is 1 eV larger than in MgO/Mo(100). The formation of a layer of adsorbed negative (Au delta-/MgO/Ag) or positive (K delta+/MgO/Ag) adsorbates results in an increase or decrease, respectively, of the MgO/Ag(100) work function as predicted by the classical Gurney model for ionic adsorbates on metal surfaces.     

Metamagnetism

This is a review of the physical properties of metamagnets. These are antiferromagnets which, upon the application of a magnetic field, can undergo first-order magnetic phase transitions to a state with a relatively large magnetic moment. The treatments of mean field theory describing these materials are reviewed, as are the treatments of more modern theories. The experimental properties of the known metamagnets are discussed, with emphasis on the variety of means by which the metamagnetic transitions have been observed and studied. For some materials, there have been studies of the tricritical behaviour, and a discussion of the experimental results of these studies is given, along with a comparison of the results with the present theory.     

Ultra-stable microwave generation with a diode-pumped solid-state laser in the 1.5-μm range

We demonstrate the first ultra-stable microwave generation based on a 1.5-μm diode-pumped solid-state laser (DPSSL) frequency comb. Our system relies on optical-to-microwave frequency division from a planar-waveguide external cavity laser referenced to an ultra-stable Fabry–Perot cavity. The evaluation of the microwave signal at ~10 GHz uses the transportable ultra-low-instability signal source ULISS^®, which employs a cryo-cooled sapphire oscillator. With the DPSSL comb, we measured ?125 dBc/Hz phase noise at 1 kHz offset frequency, likely limited by the photo-detection shot-noise or by the noise floor of the reference cryo-cooled sapphire oscillator. For comparison, we also generated low-noise microwave using a commercial Er:fiber comb stabilized in similar conditions and observed >20 dB lower phase noise in the microwave generated from the DPSSL comb. Our results confirm the high potential of the DPSSL technology for low-noise comb applications.     

Calcium polyphosphate coacervates: effects of thermal treatment

The addition of calcium chloride eletrolyte to sodium polyphosphate solutions lead to Calcium polyphosphate coacervates. The effects of a thermal treatment were investigated with the objective to increase the relative stability of the obtained material. Thermogravimetry analysis indicates that coacervates became less hydrophilic and more thermally stable after the thermal treatment. Crystallization was identified through differential scanning calorimetry and X-ray diffraction. Morphological changes were observed after the thermal treatment by scanning electron microscopy. N₂ adsorption?Cdesorption isotherms suggest that both materials, thermally treated or not, display type IV isotherms, low superficial area and mesoporous structure. Stability experiments in solutions at different pH values show that the thermally treated calcium polyphosphate is relatively more stable than the non-treated coacervate.     

Reverse roughening transition in carbon dioxide

We report the observation of a roughening transition in carbon dioxide along the melting line of phase I, which we call reverse as faceting appears with increasing temperature. The characteristics of the transition are discussed in light of modern theories of roughening and the causes of its reverse behavior investigated. We propose that high temperature faceting is related to a pressure-induced increase of the surface stiffness.