Morphology and deformation behaviour of SBS/PS blends: a combined microscopic and spectroscopic study

Correlation between morphology and micromechanical deformation behaviour of blends consisting of a lamellae-forming linear styrene/butadiene block copolymer and polystyrene homopolymer (hPS) was studied by different microscopic techniques (transmission electron microscopy and scanning electron microscopy) and rheo-optical Fourier transformed infrared spectroscopy. Attributable to a change in morphology from well-ordered lamellae to a distorted one, a transition in deformation mechanism from homogeneous plastic flow of the lamellae to formation of local craze-like deformation zones was observed on addition of hPS. The latter led to a drastic reduction in elongation at break. An abrupt depression in the degree of orientation of the polystyrene (PS) and the polybutadiene (PB) phases in the blends suggested that the failure occurs at the interface between the added hPS and PS blocks of the block copolymer.     

Anion recognition and sensing with Zn(II)-dipicolylamine complexes

This critical review covers the developments in anion recognition and sensing using Zn(II)-dipicolylamine functionalized receptors over the past decade with emphasis on recent rapid advances in the last five years.     

Amyloid formation from an α-helix peptide bundle is seeded by 3(10)-helix aggregates

Transformation of proteins and peptides to fibrillar aggregates rich in β sheets underlies many diseases, but mechanistic details of these structural transitions are poorly understood. To simulate aggregation, four equivalents of a water‐soluble, α‐helical (65 %) amphipathic peptide (AEQLLQEAEQLLQEL) were assembled in parallel on an oxazole‐containing macrocyclic scaffold. The resulting 4α‐helix bundle is monomeric and even more α helical (85 %), but it is also unstable at pH 4 and undergoes concentration‐dependent conversion to β‐sheet aggregates and amyloid fibrils. Fibrils twist and grow with time, remaining flexible like rope (>1 μm long, 5–50 nm wide) with multiple strings (2 nm), before ageing to matted fibers. At pH 7 the fibrils revert back to soluble monomeric 4α‐helix bundles. During α→β folding we were able to detect soluble 3₁₀ helices in solution by using 2D‐NMR, CD and FTIR spectroscopy. This intermediate satisfies the need for peptide elongation, from the compressed α helix to the fully extended β strand/sheet, and is driven here by 3₁₀‐helix aggregation triggered in this case by template‐promoted helical bundling and by hydrogen‐bonding glutamic acid side chains. A mechanism involving α?α₄?(3₁₀)₄?(3₁₀)_n?(β)_n?m(β)_n equilibria is plausible for this peptide and also for peptides lacking hydrogen‐bonding side chains, with unfavourable equilibria slowing the α→β conversion.     

Improving on Nature: Making a Cyclic Heptapeptide Orally Bioavailable

The use of peptides in medicine is limited by low membrane permeability, metabolic instability, high clearance, and negligible oral bioavailability. The prediction of oral bioavailability of drugs relies on physicochemical properties that favor passive permeability and oxidative metabolic stability, but these may not be useful for peptides. Here we investigate effects of heterocyclic constraints, intramolecular hydrogen bonds, and side chains on the oral bioavailability of cyclic heptapeptides. NMR‐derived structures, amide H–D exchange rates, and temperature‐dependent chemical shifts showed that the combination of rigidification, stronger hydrogen bonds, and solvent shielding by branched side chains enhances the oral bioavailability of cyclic heptapeptides in rats without the need for N‐methylation.     

Three-hole microstructured optical fiber for efficient fiber Bragg grating refractometer

We present a photosensitive three-hole microstructured optical fiber specifically designed to improve the refractive index sensitivity of a standard fiber Bragg grating (FBG) sensor photowritten in the suspended Ge-doped silica core. We describe the specific photowriting procedure used to realize gratings in such a fiber. We then determine their spectral sensitivity to the refractive index changes of material filling the holes surrounding the core. The sensitivity is compared with that of standard FBGs photowritten in a six-hole fiber with a larger core diameter. We demonstrate an improvement in the sensitivity by two orders of magnitude and reach a resolution of 3 x 10(-5) and 6 x 10(-6) around mean refractive index values of 1.33 and 1.40, respectively.     

Radioluminescent mechanism of Li2B4O7:Cu crystal

The structure of the radioluminescent (RL) spectrum of Li₂B₄O₇:Cu crystal is complex, having no normal Gauss peaks. The RL spectrum recorded showed one sharp and strong peak near 365 nm. For the purpose of explaining this phenomenon, we used the self-trapped exciton (STE) model to analyze experimental data of absorption spectrum, emission spectrum, radioluminescence spectrum and decay-time curves. We found a short lifetime component (of the order of ns) from phosphorous signals of Li₂B₄O₇:Cu. We realized that the short lifetime component related to inherent signal of host lattice and the d-p transitions of Cu⁺. This result is applicable in the detector system with high time resolution.     

Novel synthesis of highly ordered mesoporous Fe2O3/SiO2 nanocomposites for a room temperature VOC sensor

The controlled synthesis of mesoporous silica and metal oxide nanocomposites with a highly ordered porous structure and large specific surface area for specific applications has been an attractive topic in the field of porous materials. Herein, we introduce a novel method for the fabrication of highly ordered mesoporous structured and large specific surface area Fe₂O₃/SiO₂ nanocomposites, and consider their application in room temperature gas sensors. The mesoporous Fe₂O₃/SiO₂ nanocomposites were synthesised by a two-step method, which combines the hydrothermal growth of Fe₂O₃ nanoparticles and the microemulsion phase of Brij 56 (C₁₆EO₁₀) surfactant as templates in instantly direct-templating synthesis. This synthesis method enables the fabrication of mesoporous Fe₂O₃/SiO₂ nanocomposites without distortion of the ordered porous structure after calcination at high temperature. The synthesised materials were found to be efficient in a room temperature VOC sensor application, with good recovery.     

Mode locking of an erbium-doped fiber laser with intra-cavity polarization modulation

Erbium-doped fiber lasers are normally actively mode-locked through amplitude modulation or phase modulation. In this paper, we demonstrate that the laser can also be mode-locked by employing polarization modulation with a polarization-dependent cavity loss. We obtain a nearly transform-limited mode-locked pulse train at 10 GHz repetition rate with timing jitter as low as 164 fs. The timing jitter is only limited by the timing jitter of the driving signal.     

On an Iyengar-type inequality involving quadratures in n knots

In this short note, we give an Iyengar-type inequality involving quadratures in n knots, where n is an arbitrary natural number.     

Integral of the Clarke subdifferential mapping and a generalized Newton-Leibniz formula

In the theory of Lebesgue integration it has been proved that if f is a real Lipschitz function defined on a segment [a,b]⊂R, then the Newton-Leibniz formula (the fundamental theorem of calculus) holds. This paper extends the fact to the case where the Fréchet derivative f^′(⋅) (which is defined almost everywhere on [a,b] by the Rademacher theorem) and the Lebesgue integral are replaced, respectively, by the Clarke subdifferential mapping ∂_Cf(⋅) and the Aumann (set-valued) integral. Among other things, we show that and the equality is valid if and only if f is strictly Hadamard differentiable almost everywhere on [a,b]. The result is derived from a general representation formula, which we obtain herein for the integral of the Clarke subdifferential mapping of a Lipschitz function defined on a separable Banach space.