Synthesis and characterization of sulfonated copolyethersulfones

The present article deals with the synthesis and characterization of some sulfonated copolyethersulfones. The synthetic approach differs from the post sulfonation approach traditionally reported in the literature. The synthetic procedure is based on the use of sulfonated monomers which are then reacted with previously synthesized telechelic hydoxy‐ended poly (ether sulpnone)s. Combining the MALDI‐TOF MS and ¹H NMR analyses, with SEC‐Viscometry and TGA measurements, we demonstrate a powerful tool for characterizing the chemical composition, end chains, degree of sulfonation (DS) and molecular mass distribution (MMD) of disulfonated poly(arylene ether‐sulfone) copolymers. The characterization techniques allowed to determine the exact nature of the copolymers synthesized and to reveal some interesting features about the reaction. DMA data show that the glass transition temperature of sulfonated copolymers with similar DS increase as raise their MMD. Copolymers with a DS of 10–11 mol % reach a T_g of 244–246 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3010–3023, 2010     

Entangled Porphyrins in Cyclodextrin Vesicles

The entanglement process between porphyrins and some amphiphiliccyclodextrins and the occurrence of different species have been proved by the combination of UV-Visabsorption, fluorescence anisotropy, resonance light scattering and ¹H NMR spectroscopy.     

Effects of the structure on the properties of new poly(arylene ether sulfone)s containing naphthalene units

A series of new poly(arylene ether sulfone)s has been obtained by solution condensation polymerisation starting from 1,5- and 2,6-bis-(4-fluorosulfonyl)naphthalene with various aromatic dihydroxy compounds. The polymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.68 dl g⁻¹, had good thermal stability (10% weight loss temperatures were above 405 and 420 °C respectively in nitrogen and air) and high glass transition temperatures (in the range 217-258 °C). They have been characterised by elemental and infrared analyses, GPC and wide-angle X-ray diffraction. The properties of these poly(arylene ether sulfone)s have been compared with those of the corresponding poly(arylene ether ketone)s.     

Semi-regular divisible designs and Frobenius groups

We study and characterize semi-regular (s, k, λ₁, λ₂)-divisible designs which admit a Frobenius group as their translation group. Moreover, we give a construction method for such designs by generalized admissible triads.     

Synthesis and structural characterization of syndiotactic trans‐1,2 and cis‐1,2 polyhexadienes

The (E) isomer in mixtures of (E) and (Z) 1,3‐hexadiene was polymerized with the system CoCl₂(PⁱPrPh₂)₂‐MAO, a highly active and stereospecific catalyst for the preparation of 1,2 syndiotactic polybutadiene. A new crystalline polymer with a melting point of 109 °C was obtained. The polymer was characterized by IR, NMR (¹³C, ¹H in solution and ¹³C in the solid‐state), X‐ray diffraction, DSC, GPC and it was found to have a trans‐1,2 syndiotactic structure with a 5.18 ± 0.04 Å fiber periodicity. Since only the (E) isomer was polymerized, at the end of the reaction we were able to separate the (Z) isomer, which was ultimately polymerized with CpTiCl₃‐MAO at low temperature, obtaining a low molecular weight, stereoregular polymer that, characterized by IR and NMR methods, was found to exhibit a cis‐1,2 syndiotactic structure, never reported before. Molecular mechanics calculations were carried out on the trans‐1,2 syndiotactic polymer and structural models consistent with the X‐ray diffraction data are proposed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5339–5353, 2007     

Torsion of Thin Tubes With Multicell Cross‐Section

It is known that the classical technical theories of Bredt and of sectorial areas are the variational limit of the SaintVenant torsion problem for hollow homogeneous isotropic cylinders with thin doubly connected crosssection when the wall thickness reaches zero. The main goal of this paper is to prove that the same result remains true for thin tubes with multicell crosssection.Sommario. E noto che le classiche teorie tecniche di Bredt e delle aree settoriali sono il limite variazionale del problema della torsione alla De SaintVenant per cilindri lunghi con sezione cava biconnessa quando lo spessore della parete tende a zero. In questo lavoro si estende il risultato alle sezioni multiconnesse con ordine di connessione qualsiasi.     

Similar Structural Dynamics for the Degradation of CH3NH3PbI3 in Air and in Vacuum

We investigate the degradation path of MAPbI₃ (MA=methylammonium) films over flat TiO₂ substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI₂. We describe how this degradation product is structurally coupled with the original MAPbI₃ lattice through the orientation of its constituent PbI₆ octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH₃NH₂ or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.     

A Combined Experimental and Theoretical Study on the Stereodynamics of Monoaza[5]helicenes: Solvent‐Induced Increase of the Enantiomerization Barrier in 1‐Aza‐[5]helicene

Helicenes and heterohelicenes are attractive compounds with great potential in materials sciences to be used in optoelectronics as ligand backbones in enantioselective catalysis and as chiral sensors. The properties of these materials are related to the stereodynamics of these helical chiral compounds. However, little is known about features controlling stereodynamics in helicenes; in particular, for heterohelicenes the position of the heteroatom could be relevant in this respect. Herein the complete stereodynamic characterization of monoaza[5]helicenes is shown by enantioselective dynamic HPLC and DFT calculations. At variance with previous theoretical calculations, 1‐aza[5]helicene shows a surprisingly high enantiomerization barrier, which is triggered by specific solvent interactions.     

Detecting Rigid Inclusions, or Cavities, in an Elastic Body

We prove upper and lower bounds on the size of unknown defects, like cavities or rigid inclusions, in an elastic body, from boundary measurements of traction and displacement. Such estimates might be useful in quality testing of materials.