Exploring the synthesis and impact of end‐functional poly(3‐hexylthiophene)

In recent years, end‐functional poly(3‐hexylthiophene) (P3HT) has proven to be instrumental in the continued development and innovation within the broad conjugated polymer arena, enabling a variety of applications, particularly in organic electronics. The availability of P3HT with controlled molecular weights, low polydispersity, and importantly, a wide range of reactive end‐groups not only serves as a key building block for the preparation of conjugated block copolymers but also facilitates the development of hybrid nanocomposite materials via inorganic surface modification strategies. This Highlight focuses on the synthetic approaches to end‐functional P3HT and the impact of these systems in emerging technologies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 831–841     

Synthesis,crystal structures,spectral, electrochemical and magnetic properties of di-µ-phenoxido-bridged dinuclear copper(II) complexes with N-salicylidene-2-hydroxybenzylamine derivatives: axial coordination effect of dimethyl sulphoxide molecule

The template reaction of salicylaldehyde and its substituted derivatives and 2-hydroxy-5-bromobenzylamine or 2-hydroxy-5-chlorobenzylamine with copper(II) acetate in dimethyl sulphoxide (dmso) afforded eight dinuclear Cu(II) complexes, [Cu₂(L)₂(dmso)₂] (H₂ L = N-salicylidene-2-hydroxy-5-bromobenzylamine, N-salicylidene-2-hydroxy-5-chlorobenzylamine and their 5-bromo, 5-nitro and 5-methyl-substituted salicylidene derivatives). These Cu(II) complexes were characterised by IR and UV-VIS-NIR spectroscopy, electric conductivity, cyclic voltammetry, and temperature dependence of magnetic susceptibilities (4.5–300 K). In the THF solution, the complexes are nonelectrolytes and exhibit a characteristic CT band due to phenoxido-bridging at 360–384 nm. In the cyclic voltammograms, an irreversible reduction process was observed at ?1.18–1.54 V vs Fc/Fc⁺. Single-crystal X-ray crystallography revealed that two Cu(II) ions were bridged by the two phenoxido-oxygen atoms of the two Schiff-base ligands with axial coordination of dmso molecules forming a square pyramid with a Cu-Cu distance of 3.0628(8)–3.0931(6) °A. In accordance with the crystal structures, the magnetic interaction between the two Cu(II) ions is relatively anti-ferromagnetic with ?2J value of 386–575 cm^?1. The axial coordination effect of the dmso molecule was discussed in relation to the correlation between the Cu-O-Cu angle and the ?2J value.     

Proposal of FEM implemented with particle discretization for analysis of failure phenomena

A new method for numerical simulation of failure behavior, namely, FEM-β, is proposed. For a continuum model of a deformable body, FEM-β solves a boundary value problem by applying particle discretization to a displacement field; the domain is decomposed into a set of Voronoi blocks and the non-overlapping characteristic functions for the Voronoi blocks are used to discretize the displacement function. By computing average strain and average strain energy, FEM-β obtains a numerical solution of the variational problem that is transformed from the boundary value problem. In a rigorous form, FEM-β is formulated for a variational problem of displacement and stress with different particle discretization, i.e., the non-overlapping characteristic function of the Voronoi blocks and the conjugate Delaunay tessellations, respectively, are used to discretize the displacement and stress functions. While a displacement field is discretized with non-smooth functions, it is shown that a solution of FEM-β has the same accuracy as that of ordinary FEM with triangular elements. The key point of FEM-β is the ease of expressing failure as separation of two adjacent Voronoi blocks owing to the particle discretization that uses non-overlapping characteristic functions. This paper explains these features of FEM-β with results of numerical simulation of several example problems.     

Formation of multiple shocklets in a transonic diffuser flow

Multiple shocklets are frequently generated in transonic diffuser flows. The present paper investigates the formation of these shocklets with a high-speed CCD camera combined with the schlieren method. It is observed that compression waves steepen while propagating upstream, and eventually become new shock waves. The ordinary shock wave is found to move upstream beyond the nozzle throat or to disappear while moving downstream depending on the pressure ratio across the nozzle. This phenomenon is also analyzed with the one-dimensional Euler equations by assuming a pressure disturbance given by the sine function at the channel exit. The calculated results are found to reproduce quite well the experimental behavior of the shocklets. The effect of the frequency of disturbance is also studied numerically, and it is shown that the multiple shocklet pattern appears when the amplitude of disturbance is not large and the diverging part of the channel downstream of the ordinary shock wave is long. Received 26 June 1998 / Accepted 15 March 1999     

The mechanism of formation of N-formylkynurenine by heme dioxygenases

Heme dioxygenases catalyze the oxidation of L-tryptophan to N-formylkynurenine (NFK), the first and rate-limiting step in tryptophan catabolism. Although recent progress has been made on early stages in the mechanism, there is currently no experimental data on the mechanism of product (NFK) formation. In this work, we have used mass spectrometry to examine product formation in a number of dioxygenases. In addition to NFK formation (m/z = 237), the data identify a species (m/z = 221) that is consistent with insertion of a single atom of oxygen into the substrate during O(2)-driven turnover. The fragmentation pattern for this m/z = 221 species is consistent with a cyclic amino acetal structure; independent chemical synthesis of the 3a-hydroxypyrroloindole-2-carboxylic acid compound is in agreement with this assignment. Labeling experiments with (18)O(2) confirm the origin of the oxygen atom as arising from O(2)-dependent turnover. These data suggest that the dioxygenases use a ring-opening mechanism during NFK formation, rather than Criegee or dioxetane mechanisms as previously proposed.     

Fluorescence detection with an immersed flow cell in capillary electrophoresis

An immersed flowcell has been developed for fluorescence detection in capillary electrophoresis (CE) by modifying an ordinary HPLC spectrofluorimetric detector flowcell. The minimum detectability obtained for riboflavine was about 4 fmol. The use of the flowcell to measure a fluorescence spectrum by the stopped-flow method of shutting down the DC high voltage during a wavelength scan, has also been achieved successfully.     

On (<Emphasis Type="Italic">m</Emphasis>, <Emphasis Type="Italic">C</Emphasis>)-Isometric Operators

In this paper we study the spectral properties of (m, C)-isometric operators. In particular, if \(T\in \mathcal{{L(H)}}\) is (m, C)-isometric operators, then the power of (m, C)-isometric operators is also (m, C)-isometric operators. Moreover, if \(T^{*}\) has the single-valued extension property, then T has the single-valued extension property. Finally, we investigate conditions for (m, C)-isometric operators to be (1, C)-isometric operators.