A Robust,Precious-Metal-Free Dye-Sensitized Photoanode for Water Oxidation: A Nanosecond-Long Excited-State Lifetime through a Prussian Blue Analogue

Herein, we establish a simple synthetic strategy affording a heterogeneous, precious metal-free, dye-sensitized photoelectrode for water oxidation, which incorporates a Prussian blue (PB) structure for the sensitization of TiO₂ and water oxidation catalysis. Our approach involves the use of a Fe(CN)₅ bridging group not only as a cyanide precursor for the formation of a PB-type structure but also as an electron shuttle between an organic chromophore and the catalytic center. The resulting hetero-functional PB-modified TiO₂ electrode demonstrates a low-cost and easy-to-construct photoanode, which exhibits favorable electron transfers with a remarkable excited state lifetime on the order of nanoseconds and an extended light absorption capacity of up to 500 nm. Our approach paves the way for a new family of precious metal-free robust dye-sensitized photoelectrodes for water oxidation, in which a variety of common organic chromophores can be employed in conjunction with CoFe PB structures.     

QSAR of genotoxic active benzazoles§

Previously synthesized 2,5-disubstituted benzoxazole and benzimidazole derivatives, were tested for their genotoxic activity in the Bacillus subtilis rec? assay. The results revealed that 5-methyl-2-(p-aminobenzyl)benzoxazole exhibited the highest genotoxic response, which was comparable to 4-nitroquinoline 1-oxide (4-NQO), the reference agent of classical positive mutagen. Among the other tested compounds, four showed a genotoxic activity. A QSAR study revealed that structural parameters IY_C2H4 and IY_CH2O, indicating the bridge elements between the phenyl moiety and the fused ring system at position 2 and the quantum chemical parameter (ΔE?), showing the difference between HOMO and LUMO energies, were found significant for enhancing the genotoxic activity in these compounds. In addition, the substituent effects on positions R and R₁ were found important for the activity as well as holding a substituent possessing a maximum length with a minimum width property on position R₁ like alkyl groups. On the other hand, substituting position R with an electron donating group instead of electron withdrawing group increased the genotoxic activity.     

Cyclic codes over $${{\mathbb{F}}_2+u{\mathbb{F}}_2+v{\mathbb{F}}_2+uv{\mathbb{F}}_2}$$

In this work, we focus on cyclic codes over the ring \mathbbF₂+u\mathbbF₂+v\mathbbF₂+uv\mathbbF₂{{{\mathbb{F}}_2+u{\mathbb{F}}_2+v{\mathbb{F}}_2+uv{\mathbb{F}}_2}} , which is not a finite chain ring. We use ideas from group rings and works of AbuAlrub et.al. in (Des Codes Crypt 42:273–287, 2007) to characterize the ring (\mathbbF₂+u\mathbbF₂+v\mathbbF₂+uv\mathbbF₂)/(xⁿ-1){({{\mathbb{F}}_2+u{\mathbb{F}}_2+v{\mathbb{F}}_2+uv{\mathbb{F}}_2})/(x^n-1)} and cyclic codes of odd length. Some good binary codes are obtained as the images of cyclic codes over \mathbbF₂+u\mathbbF₂+v\mathbbF₂+uv\mathbbF₂{{{\mathbb{F}}_2+u{\mathbb{F}}_2+v{\mathbb{F}}_2+uv{\mathbb{F}}_2}} under two Gray maps that are defined. We also characterize the binary images of cyclic codes over \mathbbF₂+u\mathbbF₂+v\mathbbF₂+uv\mathbbF₂{{{\mathbb{F}}_2+u{\mathbb{F}}_2+v{\mathbb{F}}_2+uv{\mathbb{F}}_2}} in general.     

Mechanism of void nucleation and growth in bcc Fe: atomistic simulations at experimental time scales

Evolution of small-vacancy clusters in bcc Fe is simulated using a multiscale approach coupling an atomistic activation-relaxation method for sampling transition-state pathways with environment-dependent reaction coordinate calculations and a kinetic Monte Carlo simulation to reach time scales on the order of ~10? s. Under vacancy-supersaturated condition, di- and trivacancy clusters form and grow by coalescence (Ostwald ripening). For cluster size greater than four we find a transition temperature of 150 °C for accelerated cluster growth, as observed in positron annihilation spectroscopy experiments. Implications for the mechanism of stage-IV radiation-damage-recovery kinetics are discussed.     

3D finite element analysis and mathematical modeling for estimation of material dissolution rate in the electrochemical machining processes

Journal of Solid State Electrochemistry - Electrochemical machining (ECM) operating with mechanism of electrochemical dissolution during an electrolysis process is one of the most crucial...     

Optimal ordering policies with convertible lead times

A firm receives orders that will be required at an uncertain time given by an Erlang distribution, and over time observes the associated independent exponential events. The firm, in turn, places orders at a linear cost from a supplier with fixed lead time l and has the option of converting (expediting) each order, at a cost, over a certain time interval after the order is originally placed. A converted order arrives l_e < l units of time after it is converted. We show that a threshold policy is optimal. Under such a policy the firm places an order after a certain number of exponential events have been observed. An order is converted the first time, if any, when the residual lead time exceeds a time threshold related to the number of exponential events realized since the order was placed.     

Fixed points in intuitionistic fuzzy metric spaces

The purpose of this paper, using the idea of intuitionistic fuzzy set due to Atanassov [Atanassov K. Intuitionistic fuzzy sets. Fuzzy Sets Syst 1986;20:87–96], we define the notion of intuitionistic fuzzy metric spaces due to Kramosil and Michalek [Kramosil O, Michalek J. Fuzzy metric and statistical metric spaces. Kybernetika 1975;11:326–34]. Further the well-known fixed point theorems of Banach and Edelstein are extended to intuitionistic fuzzy metric spaces with the help of Grabiec [Grabiec M. Fixed points in fuzzy metric spaces. Fuzzy Sets Syst 1988;27:385–9].     

A new soluble conducting polymer and its electrochromic devices

A new polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1‐(1‐phenylethyl)‐2,5‐di(2‐thienyl)‐1H‐pyrrole (PETPy). Of which the chemical method produces a polymer that is completely soluble in organic solvents. The structures of both the monomer and the soluble polymer were elucidated by nuclear magnetic resonance (¹H and ¹³C NMR) and Fourier transform infrared (FTIR) spectroscopy. The average molecular weight has been determined by gel permeation chromatography to be M_n = 3.29 × 10³ for the chemically synthesized polymer. Polymer of PETPy was synthesized via potentiostatic electrochemical polymerization in acetonitrile (AN)/NaClO₄/LiClO₄ (0.1 M) solvent–electrolyte couple. Characterizations of the resulting polymer were performed by cyclic voltammetry, FTIR, scanning electron microscopy, and UV–vis spectroscopy. Four‐probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the polymer films were investigated. In addition, dual‐type polymer electrochromic devices based on P(PETPy) with poly(3,4‐ethylenedioxythiophene) were constructed. Spectroelectrochemistry, electrochromic switching, and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts, and optical memories. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2215–2225, 2006     

Experimental and Computational Studies on the 1:1 Complex of Anthranilic Acid with P-Toluenesulfonic Acid

Abstract

The proton-transfer compound (3) was synthesized in good yields by the reaction of anthranilic acid with p-toluenesulfonic acid. It was characterized by elemental analysis, infrared spectroscopy, and X-ray single-crystal determination. The crystal structure analysis of 2-carboxyanilinium p-toulenesulfonate (3) has revealed a one-dimensional hydrogen-bonded network structure, involving the tosylate anion, the carboxyl group, and the ammonium group. The H(N)···O distances range from 1.97 to 2.23 Å. The molecular geometry and vibrational frequencies of 3 were calculated using the ab-initio method (HF) with the 6–31G(d) and 6–31+G(d,p) basis sets. The computed results indicate that the optimized geometry reproduces the crystal structure well, and the assignments of fundamental vibrations also agree well with the theoretical frequencies. The intermolecular proton transfer process between the ionic (3) and nonionic (4) structures was also investigated with the theoretical computations. The nonionic form (4) is energetically more stable than the ionic form (3) and TS(3→4) by 9.76 and 7.01 kcal/mol, respectively, including the zero-point vibrational energy correction at the HF/6–31+G(d,p) level. In addition, the atomic charges, the molecular electrostatic potentials, the nucleus-independent chemical shifts, and the frontier molecular orbitals of 3 were carried out at the HF/6–31+G(d,p) level of theory.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables     

Surface roughness and color characteristics of wood treated with preservatives after accelerated weathering test

Wood samples treated with ammonium copper quat (ACQ 1900 and ACQ 2200), chromated copper arsenate (CCA), Tanalith E 3491 and Wolmanit CX-8 have been studied in accelerated weathering experiments. The weathering experiment was performed by cycles of 2 h UV-light irradiation followed by water spray for 18 min. The changes on the surface of the weathered samples were characterized by roughness and color measurements on the samples with 0, 200, 400 and 600 h of total weathering.

The objective of this study was to investigate the changes created by weathering on impregnated wood with several different wood preservatives. This study was performed on the accelerated weathering test cycle, using UV irradiation and water spray in order to simulate natural weathering.

Surface roughness and color measurement was used to investigate the changes after several intervals (0–200–400–600 h) in artificial weathering of treated and untreated wood.