Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines

An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999     

Ozone electrogeneration on Pt-TaO_y sol-gel film modified titanium electrode: Effect of electrode composition on the electrocatalytic activity

This work examines the ozone electrogeneration(OE) at a binary coating of different nominal compositions(Pt)x-(TaOy)(100-x), where x(percentage in the precursor solution) varied between 1% and 100%, coated on titanium substrate prepared by a sol-gel technique. TheOE is performed in an artificial tap water at room temperature(25C). The percentages of Pt and TaOy in the coating significantly affect the electrocatalytic activity towards oxygen evolution. The oxygen evolution was retarded to a different extent based on the electrode composition. The largest retardation was obtained at the(Pt)10-(TaOy)90 electrode(ca. 480 m V positive shift) as compared with the(Pt)100-(TaOy)0 electrode.This was reflected in a high current efficiency(CE) ofOE(ca. 19.3%) at the former electrode. This value is considered to be among the highest values reported forOE at 25C in neutral media. The composite electrodes were characterized by voltammetric and surface techniques. A plausible explanation for the change of the efficiency ofOE with the electrode composition is given based on the electrochemical results.     

Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Phosphorescent Ruthenium Complexes with a Nitroimidazole Unit that Image Oxygen Fluctuation in Tumor Tissue

Understanding oxygen fluctuation in a cancerous tumor is important for effective treatment, especially during radiotherapy. In this paper, ruthenium complexes bearing a nitroimidazole group are shown to report the oxygen status in tumor tissue directly. The nitroimidazole group was known to be accumulated in hypoxic tumor tissues. On the other hand, the ruthenium complex showed strong phosphorescence around 600 nm. The emission of ruthenium is quenched instantaneously by molecular oxygen due to energy transfer between triplet states of oxygen and ruthenium complex, but the emission is then recovered by the removal of oxygen. Thus, we could observe oxygen fluctuation in tumor tissue in a real‐time manner by monitoring the phosphorescence of the ruthenium complex. The versatility of the probe is demonstrated by monitoring oxygen fluctuation in living cells and tumor tissue planted in mice. The ruthenium complex promptly penetrated plasma membrane and accumulated in cells to emit its oxygen‐dependent phosphorescence. In vivo experiments revealed that the oxygen level in tumor tissue seems to fluctuate at the sub‐minute timescale.     

Water revealed as molecular mirror when measuring low concentrations of sugar with near infrared light

Near infrared spectroscopy is an overtone spectroscopy regarded as a quick and non-destructive method that provides analytical solutions for components that represent approximately 1% or more of the total mass of the investigated composite samples. Aquaphotomics offers the possibility for disentanglement of information remaining hidden in the spectra when conventional data evaluation methods are used, since this concept utilizes changes of the water structure induced by the measured solute as specific molecular vibrations at water bands. Here, near infrared technique and aquaphotomics are applied for non-destructive identification and quantification of mono- and di-saccharide solutes at 100–0.02 mM concentration that is accepted as unachievable with near infrared spectroscopy. The results presented in this study support the aquaphotomics' water molecular mirror concept that explores spectral changes related to water molecular rearrangements caused by minute changes of the solutes in the aqueous systems. The method provides quick and accurate alternative for classical analytical measurements of saccharides even at millimolar concentration levels.     

High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision)

We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers.     

Hydrogen bond network-stabilisation of blue phases by addition of a chiral N-(10-hydroxydecyl)succinimide derivative and alkane diols

Blue phases (BPs) obtained by doping a commercially available liquid crystalline compound (4-butyl-N-(4-ethoxybenzylidene)aniline (EBBA)) with (2R,3R)-2,3-bis(4-octyloxyphenylbenzoyloxy)-N-(hydroxydecyl)succinimide (1) were highly stabilised by the addition of a small amount of alkane diols. Especially, addition of only 0.5 mol% of octane-1,8-diol increased the BP–Iso transition temperature by 10 K and widened the BP temperature range up to 35 K. A model stabilisation mechanism based on the construction of a hydrogen bond network in each disclination zone in BPs was proposed.     

The elastic-plastic stress distribution near the flat surfaced notch with cycloidal tip in a work-hardening material

Summary Based on a deformation theory of plasticity, the stress distribution near an edge crack having finite root radius in strain-hardening material is given for the case of antiplane shear (Mode III). The approximate solution is derived in an analytical form by using Neuber's result and integral J by Rice.

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Übersicht Unter Zugrundelegung der Deformationstheorie der Plastizität wird die Spannungsverteilung in der Nähe eines Randrisses mit endlichem Radius für den Fall des nichtebenen Schubspannungszustandes (Mode III) und eines dehnungsverfestigenden Materials gegeben. Die angenäherte Lösung wird durch Verwendung der Ergebnisse von Neuber sowie dem J-Integral von Rice in analytischer Form erhalten.

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In honour of the 70th birthday of Professor H. Neuber.     

New Preparation of Cyclic Acyloxyphosphorane by Reaction of Glyoxylic Acid with Phosphorus(III) Compounds

We have recently found that the reaction of α-keto acids (1) with phosphorus (III) compounds (3) yielded cyclic acyloxyphosphoranes(C-AOPs, 4), a new class of pentacovalent phosphorus species having a P-OC(O) group.^{1, 2)} The present paper deals with a new reaction of glyoxylic acid (2) with 3 to give C-AOPs (5) having no substituent at the C-3 position. 1 is an α-keto acid whereas 2 can be taken as an α-formyl acid. Although it is well known in the field of organic chemistry that the formyl group often behaves differently from a keto group, the reaction of 2 with 3 provides an example in which both groups behave in a similar manner.     

Nonclassical Urea Oligomers. VII. Binding Specificity of Carbanilido-ethylenimine Oligomer: Absorption Behavior in Suspension

Polyester elastomers were prepared by block copolymerization of dimethyl terephthalate (DMT), butanediol (BDO), and polytetramethylene glycol (PTMG). Polyester from DMT and butanediol forms a high-melting hard segment in block copolyester to prevent undue chain slippage when fibers are stretched. High elongation was provided by soft segment which consisted of condensation product from DMT and PTMG.

Experiments were carried out to determine the effect of composition variables on the properties of these elastomers, such as glass transition temperature, elongation at break, tenacity, and elastic recovery. The study on molecular characteristics of the elastic polyester showed that a leather-like region exists between glassy and rubbery regions. These elastomers were melt-spun to give elastic fibers which are competitive with commercially available Spandex-type fibers.