Helical Carbon and Graphite Films Prepared from Helical Poly(3,4‐ethylenedioxythiophene) Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals

Helical carbon and graphite films from helical poly(3,4‐ethylenedioxythiophene) (H‐PEDOT) films synthesized through electrochemical polymerization in a chiral nematic liquid‐crystal (N*‐LC) field are prepared. The microscope investigations showed that the H‐PEDOT film synthesized in the N*‐LC has large domains of one‐handed spiral morphology consisting of fibril bundles. The H‐PEDOT films exhibited distinct Cotton effects in circular dichroism spectra. The highly twisted N*‐LC with a helical pitch of smaller than 1 μm produced the H‐PEDOT film with a highly ordered morphology. The spiral morphologies with left‐ and right‐handed screws were observed for the carbon films prepared from the H‐PEDOT films at 800 °C and were well correlated with the textures and helical pitches of the N*‐LCs. The spiral morphologies of the precursors were also retained even in the graphite films prepared from the helical carbon films at 2600 °C.     

Aqueous‐Solution Route to Zinc Telluride Films for Application to CO2 Reduction

As a photocathode for CO₂ reduction, zinc‐blende zinc telluride (ZnTe) was directly formed on a Zn/ZnO nanowire substrate by a simple dissolution–recrystallization mechanism without any surfactant. With the most negative conduction‐band edge among p‐type semiconductors, this new photocatalyst showed efficient and stable CO formation in photoelectrochemical CO₂ reduction at ?0.2–?0.7 V versus RHE without a sacrificial reagent.     

Deterioration of ancient cellulose paper,Hanji: evaluation of paper permanence

Hanji paper, the paper material traditionally used in Korea, is in the focus of the present aging and mechanistic study. As raw materials and historic recipes for paper making are still available for Hanji today, specimen resembling historical material at the point of production can be prepared. While from that starting point, historical material had taken the path of natural aging, newly prepared samples—prepared according to both historic and current recipes—were artificially aged, and both aging modes can be compared. For the first time, an in-depth chemical and mathematical analysis of the aging processes for Hanji is presented. The aging of Hanji paper, resulting in hydrolysis and oxidation processes, was addressed by means of selective fluorescene labeling of oxidized groups in combination with gel permeation chromatography, providing profiles of carbonyl and carboxyl groups relative to the molar mass distribution. Starting Hanji showed the highest molecular weight (>1,400 kDa) ever reported for paper. We have defined two critical parameters for comparison of the paper samples: half-life DP (the time until every chain is split once on average) and life expectancy (the time until an average DP of failure is reached and no further mechanical stress can be tolerated). The two values were determined to be approximately 500 and 4,000 years, respectively, for the Hanji samples, provided there is no UV radiation. The rate of cellulose chain scission under accelerated aging (80 °C, RH 65 %), was about 600 times faster than under natural conditions. In addition, cellulose degradation of Hanji paper under accelerated aging condition was about 2–3 times slower than that of historical rag paper as those used in medieval Europe.     

Conformation‐Specific Circular Dichroism Spectroscopy of Cold,Isolated Chiral Molecules

The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations.     

A Bifunctional Perovskite Catalyst for Oxygen Reduction and Evolution

La_0.3(Ba_0.5Sr_0.5)_0.7Co_0.8Fe_0.2O_3?δ is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm‐scale rhombohedral LaCoO₃ cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A‐site cations with La³⁺ and local stress on Co‐site sub‐lattice with the cubic perovskite structure.     

Fabrication and sensing property for conducting polymer nanowire-based biosensor for detection of immunoglobulin G

Conducting polymers are excellent sensing materials in the design of bioanalytical sensors because of their electronic conductivity, low energy optical transitions, biocompatibility, and room temperature operation. Among them, Polypyrrole (Ppy) is one of the most extensively used conducting polymers because of a number of properties such as redox activity, rapid electron transfer, and ability to link a variety of biomolecules to pyrrole groups by chemical treatment. In this study, Ppy nanowires were synthesized by an electrospinning method. The nanowires were prepared from a solution mixture of Ppy and poly(ethylene oxide). The method of detection in such a device is based on the selective binding of antigen onto an antibody that is covalently attached to the nanowires. Thus, anti-IgG was immobilized on Ppy nanowires using an EDC {[N-(3-dimethyl aminopropyl)-N₂-ethylcarbodiimide hydrochloride]}-NHS(N-hydrosuccinimide) modified technique. Fluorescence images of BSA–FITC (fluorescein isothiocyanate labeling of bovine serum albumin) conjugation demonstrated that antibody was functionalized on the Ppy nanowires without non-specific binding and facilitated selective detection of antigen. Current–voltage (I–V) characterization was used to monitor the change in the conductivity of nanowires while the specific binding interaction occurred. These results of electrical properties enable Ppy nanowire-based biosensors to detect biomolecules in real-time.     

An efficient synthetic approach towards a single diastereomer of (2R,3R)-N2,N3-bis((S)-1-phenylethyl)butane-2,3-diamine via metalation and demetalation

Transition Metal Chemistry - A facile synthetic approach has been adopted towards the synthesis of (2R,3R)-N2,N3-bis((S)-1-phenylethyl)butane-2,3-diamine via demetalation of its dichloro Zn(II)...     

Vibro-impact analysis of two adjacent cantilever beams

Nonlinear Dynamics - This study analyzes the vibro-impact behavior of two adjacent cantilever beams subjected to vibration generated by applying harmonic excitation to their rigid base. For the...