Perthamides C-F, potent human antipsoriatic cyclopeptides

Two new cyclopeptides, perthamides E and F were isolated from the polar extracts of the sponge Theonella swinhoei. The new structures, featuring an unprecedented β-amino acid unit (AHMOA), were determined by interpretation of NMR and MS data. The absolute configuration of the AHMOA residue was proposed on the basis of quantum chemical calculation of NMR chemical shifts. Perthamides were proved to inhibit TNF-α and IL-8 release in primary human keratinocytes cells and therefore could represent potentially leads for the treatment of psoriasis.     

Thermal and microstructural analysis of Cu(II) 2,2′-dihydroxy azobenzene and thin films deposition by MAPLE technique

A newly synthesized copper-complex exhibiting nonlinear optical properties, crystalline nature, and generating interest as a material for non-linear optical applications was investigated. As thermal stability studies are indispensable before attempting any laser-assisted processing experiments, the thermal behavior of 2,2′-dihydroxy azobenzene with Cu²⁺ cations that are found to organize themselves as non-central symmetric crystallites, was investigated. The thin films were deposited on silicon substrates by matrix-assisted pulsed laser evaporation using a Nd:YAG laser working at 266 and 355 nm. Thermal analysis of the bulk compound indicates a higher thermal stability in argon flow when compared to the air atmosphere; as well, since, the adhesion of the compound onto the substrate enhances the bonding, the thermal stability of the Cu complex increases. Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, spectroscopic ellipsometry, and ultraviolet–visible spectroscopy investigations were also performed.     

The design of self-collapsed super-strong nanotube bundles

The study reported in this paper suggests that the influence of the surrounding nanotubes in a bundle is nearly identical to that of a liquid having surface tension equal to the surface energy of the nanotubes. This surprising behaviour is supported by the calculation of the polygonization and especially of the self-collapse diameters, and related dog-bone configurations, of nanotubes in a bundle, in agreement with atomistic simulations and nanoscale experiments. Accordingly, we have evaluated the strength of the nanotube bundle, with or without collapsed nanotubes, assuming a sliding failure: the self-collapse can increase the strength up to a value of about ∼30%, suggesting the design of self-collapsed super-strong nanotube bundles.Other systems, such as peapods and fullerites, can be similarly treated, including the effect of the presence of a liquid, as reported in the appendices.     

An overview on the processing of polymers growth rate data and on the methods to verify the accuracy of the input parameters in crystallization regime analysis

This work reviews criteria for the successful application of regime analysis to polymers and also discusses the influence of accuracy of input variables on the results. Despite that it has often been stated that the uncertainty in the input parameters remarkably affects the trustworthiness of the outcomes of the regime analysis, the literature offers on the subject only a fragmentary information and there is no paper looking over all the effects of accuracy of the input parameters. Here the influence of errors in input parameters has been investigated and methods to test the reliability of thermodynamic outcomes have been discussed. Mathematical ways to ascertain the accuracy of the input parameters consist in comparisons between the growth rates expressed by the Hoffman–Lauritzen equation and their derivatives generated by means of the output of the regime analysis. These comparisons, under the hypothesis of validity of the secondary nucleation theory, allow excluding the presence of remarkable errors in input values and variables.     

Mechanical properties of anion exchange membranes by combination of tensile stress–strain tests and dynamic mechanical analysis

The thermomechanical properties of anion exchange polymers based on polysulfone (PSU) quaternized with trimethylamine (TMA) or 1,4‐diazabicyclo[2.2.2]octane (DABCO) and containing hydroxide or chloride anions by tensile stress–strain tests and dynamic mechanical analysis (DMA) have been determined. The reported mechanical properties included the Young's modulus, tensile strength, and elongation at break from tensile tests and the storage and loss modulus and glass transition temperature from DMA. The anion exchange membranes behaved as stiff polymers with Young's modulus in the order of 1 GPa, relatively with high strength (about 30 MPa) and low elongation at break (around 10%) was observed. Tensile tests were also made with membranes exchanged with hydrogen‐carbonate and carbonate anions to control the absence of important carbonation of the OH form. The glass transition temperatures were of the order of 150 °C (PSU‐TMA) or 200 °C (PSU‐DABCO) for the hydroxide form, confirmed by differential scanning calorimetry; they increase further by about 50 K, when hydroxide ions are replaced by chloride. This result and the increase of the storage modulus could be interpreted by the higher hydration of hydroxide ions and the plasticizing effect of water, which reduced the Van der Waals interactions between the macromolecular chains. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1180–1187     

Enantioselective reduction and deracemisation using the non-conventional yeast Pichia glucozyma in water/organic solvent biphasic systems: preparation of (S)-1,2-diaryl-2-hydroxyethanones (benzoins)

Water/organic solvent two-liquid-phase systems have been successfully applied in the synthesis of enantiomerically pure (S)-benzoin through two different methodologies catalysed by whole cells from the non-conventional yeast Pichia glucozyma: the stereoselective monoreduction of benzil and the deracemisation of benzoin. The presence of the organic solvent influences the redox systems implied in the reactions, avoiding the formation of the corresponding diols, increasing the enantioselectivity and allowing the easy isolation of the products in high yields and excellent enantiomeric excesses. The use of both strategies has been extended to the preparation of different chiral benzoin derivatives.