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     

Racemization at C-2 of naringin in pummelo (Citrus grandis) with increasing maturity determined by chiral high-performance liquid chromatography

The relative content of (2S)- and (2R)-naringin in the albedo of pummelo during maturation in the entire season was determined by normal-phase HPLC using Chiralpak IB, a polysaccharide-derived chiral stationary phase, and n-hexane/ethanol doped with 0.5% TFA as mobile phase. A sigmoid curve was obtained showing variation from 95.3% of (2S)-naringin in very immature fruits to 53% in mature fruit samples (2.3 and 14.4 cm diameter, respectively). A comparison was made with previous results obtained for grapefruit and sour orange and a tentative explanation of the bitter taste of sour orange is proposed. The Chiralpak IB is much more efficient with respect to the Chiralcel OD used for the other two Citrus species and separation and resolution factors of 1.73 and 9.2, respectively, were achieved. Authentic samples of naringin and neohesperidin were also separated into their C-2 diastereomers with Chiralpak IB and isolation of the pure diastereomers of naringin was accomplished.     

Determination of elemental compositions by gas chromatography/time‐of‐flight mass spectrometry using chemical and electron ionization

Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under standard 70 eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam‐steering voltage of the ion source, the relative abundances of molecular ions at 70 eV EI were increased up to ten‐fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2‐fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high‐mass tuning. Thirty‐three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([M+H]⁺, [M–CH₃]⁺ for CI and [M]^{+ .} , [M–CH₃]^{+ .} for EI). On average, CI yielded 8‐fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8 ± 1.6 mm/z units and isotope ratio errors of 2.3 ± 2.0% (A+1/A ratio) and 1.7 ± 1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top‐3 hits in 80% of the cases. Copyright © 2010 John Wiley & Sons, Ltd.     

Localization of Bose-Einstein condensates in optical lattices

The dynamics of repulsive bosons condensed in an optical lattice is effectively described by the Bose-Hubbard model. The classical limit of this model, reproduces the dynamics of Bose-Einstein condensates, in a periodic potential, and in the superfluid regime. Such dynamics is governed by a discrete nonlinear Schrödinger equation. Several papers, addressing the study of the discrete nonlinear Schrödinger dynamics, have predicted the spontaneous generation of (classical) breathers in coupled condensates. In the present contribute, we shall focus on localized solutions (quantum breathers) of the full Bose-Hubbard model. We will show that solutions exponentially localized in space and periodic in time exist also in absence of randomness. Thus, this kind of states, reproduce a novel quantum localization phenomenon due to the interplay between bounded energy spectrum and non-linearity.     

Computational aspects of the integration of the von Mises linear hardening constitutive laws

The problem of the integration of the von Mises linear kinematic and isotropic hardening constitutive equations is considered. A new numerical integration algorithm, a generalised trapezoidal rule, is proposed and discussed in detail. It is shown how the structure of the elastic-plastic constitutive equations of the, well known, backward difference and midpoint rules, leading to a symmetric consistent tangent modulus, can be adopted for this trapezoidal rule. On this base a unified treatment of the backward difference, midpoint, and trapezoidal rules is presented. An accuracy analysis is conducted by means of detailed isoerror maps so as to provide a comparison between different integration algorithms.     

Nanocomposites by melt intercalation based on polycaprolactone and organoclay

Nanocomposites based on biodegradable polycaprolactone (PCL) and organically modified layered silicates (organoclay) were prepared by melt mixing. Their structures and properties were characterized by wide‐angle X‐ray diffraction, thermal analysis, and rheological measurements. The exfoliation of the organoclay was achieved via a melt mixing process in an internal mixer and showed a dependence on the type of organic modifier, the organoclay contents, and the processing temperature. The addition of the organoclay to PCL increased the crystallization temperature of PCL, but a high content of the organoclay could show an inverse effect. The PCL/organoclay nanocomposites showed a significant enhancement in their mechanical properties and thermal stability due to the exfoliation of the organoclay. The nanocomposites showed a much higher complex viscosity than the neat PCL and significant shear‐thinning behavior in the low frequency range. The shear storage modulus and loss modulus of the nanocomposites also exhibited less frequency dependence than the pure PCL in the low frequency range, and this was caused by the strong interactions between the organoclay layers and PCL molecules and by the good dispersion of exfoliated organoclay platelets in the PCL. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 670–678, 2003     

Design and electro-optical characterization of Si-based resonant cavity light emitting devices at 850 nm

We report on the fabrication and characterization of Si/SiO₂ Fabry-Perot microcavities. These structures are used to enhance the external quantum efficiency along the cavity axis and the spectral purity of emission from silicon rich oxide films that are used as active media to fabricate a Si based RCLED (resonant cavity light emitting devices). A new structure to electrically pump the active media in the resonant cavity has been designed. These structures are fabricated by chemical vapour deposition on a silicon substrate. The microcavities are tuned at 850 nm and present a quality factor ranging from 17 to 150 depending on the number of pairs constituting the dielectric mirrors. An enhancement of the electro and photoluminescence (PL) signal of 20 times is achieved for the selected emission wavelength. These cavities are characterized by TEM analysis to evaluate film uniformity, thicknesses and the densification after annealing processes for temperature ranging from 800 to 1100 °C. The electrical properties of the active media are analyzed. The electroluminescence spectral features are compared with PL spectra correlated with the quality factor of the cavities. The photometric diagram shows also a high directionality of the emitted light within a 30° cone from the sample normal.