Novel polycarbonate-based polyurethane elastomers: Composition–property relationship

Novel all-aliphatic polycarbonate-based polyurethane (PC-PU) elastomers, as well as PC-PU nanocomposites filled with organic-modified clays were synthesized, characterized and studied. It was found that they have very attractive mechanical properties (e.g., elongation at break between 600% and 800%). The prepared PC-PUs possess a distinctly segmented structure, which is the key prerequisite for their behavior as strong physical rubbery networks. All synthesized materials melt at elevated temperatures (between 110 and 200 °C) and hence can be processed like normal thermoplastics. The dispersion of the clay nanofiller was achieved by its one day swelling in the alcohol and a brief successive stirring. This procedure is very successful and leads to a partial exfoliation of the clay (documented by X-ray diffraction and TEM). The best nanocomposites with very good tensile properties, particularly with significantly increased moduli were obtained using the bentonite nanofiller. The study shows that the nanofiller interacts strongly with the hard domains and influences their melting temperature (DMTA and DSC), but it does not affect the glass transition temperature of soft domains. While Cloisite 15A was found to interact preferentially with the hard domains, the organic modified bentonite shows a strong interaction with both soft and hard segments, behaving as a blending agent. Hard domains in neat matrices, formed by hydrogen bonding of hard segments, were practically invisible by X-ray or TEM, but were successfully detected by AFM. Besides excellent mechanical properties, the prepared elastomers and their nanocomposites showed an interesting phase behavior (which was studied by combining DMTA and modulated DSC).     

Anomalous thermodynamics of Coulomb-interacting massless Dirac fermions in two spatial dimensions

It is argued that the specific heat of N massless Dirac fermions in two spatial dimensions interacting with 1/r Coulomb interactions is suppressed logarithmically relative to its noninteracting counterpart. The (dimensionless) coefficient of the logarithm is calculated in a closed form in the leading order in large N expansion, but to all orders in the effective fine structure constant, alpha(F), a procedure which takes into account finite temperature screening. This effect is expected to occur in a single-layer graphene embedded in a dielectric medium. Its dependence on the dielectric constant is calculated analytically.     

Quantum Mechanical Calculations of Redox Potentials of the Metal Clusters in Nitrogenase

We have calculated redox potentials of the two metal clusters in Mo-nitrogenase with quantum mechanical (QM) calculations. We employ an approach calibrated for iron–sulfur clusters with 1–4 Fe ions, involving QM-cluster calculations in continuum solvent and large QM systems (400–500 atoms), based on structures from combined QM and molecular mechanics (QM/MM) geometry optimisations. Calculations on the P-cluster show that we can reproduce the experimental redox potentials within 0.33 V. This is similar to the accuracy obtained for the smaller clusters, although two of the redox reactions involve also proton transfer. The calculated P¹⁺/P^N redox potential is nearly the same independently of whether P¹⁺ is protonated or deprotonated, explaining why redox titrations do not show any pH dependence. For the FeMo cluster, the calculations clearly show that the formal oxidation state of the cluster in the resting E₀ state is MoIIIFe3IIFe4III , in agreement with previous experimental studies and QM calculations. Moreover, the redox potentials of the first five E₀–E₄ states are nearly constant, as is expected if the electrons are delivered by the same site (the P-cluster). However, the redox potentials are insensitive to the formal oxidation states of the Fe ion (i.e., whether the added protons bind to sulfide or Fe ions). Finally, we show that the later (E₄–E₈) states of the reaction mechanism have redox potential that are more positive (i.e., more exothermic) than that of the E₀/E₁ couple.     

Über die Reduktion und die Darstellungen positiver quaternärer quadratischer Formen

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