Theoretical study of the smiles rearrangement in the activation mechanism of proton pump inhibitors

This work describes the conformational behavior and the activation mechanism of timoprazole and substituted prazoles from the most stable conformation to the sulphenic acid. The stability of the conformers can be explained by the presence of hydrogen bonds, stereoelectronic effect because of the lone pair of sulfur atom and the N^…C and N^…S interactions. The first step of the Smile rearrangement is a nucleophilic addition to benzimidazole by pyridine moiety, which depends on the difference of the electron population of the atoms involved in the attack. The second step produces sulphenic acid by a concerted reaction where breaking of the S–C bond goes along with a proton migration, and is determined by the electron population of the sulfur atom. Copyright © 2011 John Wiley & Sons, Ltd.     

Exploring the origin of tip‐enhanced Raman scattering; preparation of efficient TERS probes with high yield

Tip‐enhanced Raman scattering (TERS) spectroscopy is a promising technique for nanoscale chemical analysis. However, there are several challenges preventing widespread application of this technology, including reproducible fabrication of efficient TERS probes. These problems reflect a lack of clear understanding of the origins of, and the parameters influencing TERS. It is believed that the coating characteristics at the apex of the tip have a major effect on the near‐field optical enhancement and thus the TERS activity of a metalized probe. Here we show that the aspect ratio of the tip can play a significant role in the efficiency of TERS probes. We argue that the electrostatic field arising from the lightning‐rod effect has a substantial role in the observed TERS effect. This argument is supported by ‘edge‐enhanced Raman scattering’ which is shown for a noble metal film. Furthermore, it is reported that an associated tip‐surface‐enhanced Raman scattering effect can be achieved by using a TERS‐inactive metalized probe on a surface‐enhanced Raman spectroscopy‐inactive roughened surface. This observation can be explained by an interparticle enhancement of the electromagnetic field. Copyright © 2011 John Wiley & Sons, Ltd.     

Femtosecond laser-induced microstructure in Foturan glass

We report on the microstructure formation in Foturan glass, induced by 1~kHz, 120 femtosecond laser irradiation. It is found that the line-shaped filamentation, not void array tends to be formed in this glass. This is different from our previous experimental results in fused silica and BK7 glasses. A possible mechanism Ag$^+$ captures the free electrons generated by laser, is proposed to explain the observed phenomena.     

Enhanced mechanism of catalytic ozonation by ultrasound with orthogonal dual frequencies for the degradation of nitrobenzene in aqueous solution

The experiments have been performed with a semi-continuous batch reactor to investigate the degradation efficiency of nitrobenzene in aqueous solution by ultrasound with the different orthogonal dual frequencies catalytic ozonation. The introduction of ultrasound can enhance the degradation efficiency of nitrobenzene compared to the results obtained from the processes of ozonation alone and ultrasound alone. The degradation of nitrobenzene is found to be zero-order in the two systems of ultrasound alone, and the reactions follow the pseudo-first-order kinetic model in the processes of ozone alone and ozone/ultrasound. The investigation confirms that the degradation of nitrobenzene follows the mechanism of hydroxyl radical (^•OH) oxidation, and the enhancement function is even more pronounced in the presence of ultrasound with the greater difference between the orthogonal dual frequencies due to the obvious synergetic effect between ozone and ultrasound, which increases the utilization efficiency of ozone, and accelerates the initiation of ^•OH and the formation of H₂O₂, resulting in the rapid formation of an increasing diversity of byproducts and the advancement degree of mineralization of total organic carbon (TOC). The oxidative byproducts have been, respectively identified in the different processes selected, including o, p, m-nitrophenols, phenol, malonic acid, 4-nitrocatechol, nitrate ion, maleic acid, oxalic acid, hydroquinone, p-quinone, 1,2,3-trihydroxy-5-nitrobenzene and acetic acid.     

Characterization of different-Al-content AlGaN/GaN heterostructures on sapphire

Al x Ga 1-x N/GaN high-electron-mobility transistor (HEMT) structures with Al composition ranging from x = 0.13 to 0.36 are grown on sapphire substrates by low-pressure metalorganic chemical vapor deposition (LP-MOCVD). The effects of Al content on crystal quality, surface morphology, optical and electrical characteristics of the AlGaN/GaN heterostructures have been analyzed. Although high Al-content (36%) heterostructure exhibits a distinguished photoluminescence peak related to recombination between the two-dimensional electron gas and photoexcited holes (2DEG-h), its crystal quality and rough surface morphology are poor. 2DEG mobility increases with the Al content up to 26% and then it apparently decreases for high Al-content (36%) AlGaN/GaN heterostructure. The increase of sheet carrier density with the increase of Al content has been observed. A high mobility at room temperature of 2105 cm 2 /V s with a sheet carrier density of n s = 1.10 × 10 13 cm -2 , for a 26% Al-content AlGaN/GaN heterostructure has been obtained, which is approaching state-of-the-art for HEMT grown on SiC. Sheet resistance as low as 274 Ω/□ has also been achieved.     

Structural and physical properties of ZnO:Al films grown on glass by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on glass substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and grow with a c-axis orientation in the film growth direction. The films grow mainly with columnar grains perpendicular to the substrate and some granular grains also exist in the films. The film deposited at 673 K and 0.4 Pa has the largest grains whereas that prepared at 300 K and 0.4 Pa consists of the smallest grains and is porous. The films exhibit an n-type semiconducting behavior at room temperature. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity (3.40 × 10⁻³ Ω cm), the highest free electron concentration (4.63 × 10²⁰ cm⁻³) and a moderate Hall mobility (4.0 cm² V⁻¹ s⁻¹). The film deposited at 300 K and 0.4 Pa has the highest resistivity and the lowest free electron concentration and Hall mobility. A temperature dependence of the resistivity reveals that the carrier transport mechanism is Mott’s variable range hopping in the temperature region below 100 K and thermally activated band conduction above 215 K. The activation energy for the film deposited at 300 K and 0.4 Pa is 41 meV and that for the other films is about 35 meV. All the films have an average optical transmittance of over 85% in the visible wavelength range. The absorption edge of the film deposited at 300 K and 0.4 Pa shifts to the longer wavelength (redshift) relative to the films prepared under the other conditions.     

Manufacturing of Volumetric Glass–Based Composites with Single‐ and Double‐QD Doping

Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels.     

Time-reversal symmetry-breaking in two-band superconductors

Competition between an interband Josephson interaction and a biquadratic interband interaction can break time-reversal symmetry when the interband interactions are very weak compared with the intraband interaction. We demonstrate this using the phenomenological Ginzburg–Landau free energy, taking into account terms essential for this phenomenon. This time-reversal symmetry-breaking state peels away a sheet of an interband phase difference soliton wall. This sheet is the domain wall between two different chiral states. The peeling reduces the formation energy of the domain wall. The domain wall can simultaneously erase the Meissner effect and the specific heat jump when the entropy invokes many domain walls, and its life time is prolonged by a pinning owing to an inhomogeneity such as surface roughness.     

Multiparameter kinetic analysis of alkaline hydrolysis of a series of aryl diphenylphosphinothioates: models for P=S neurotoxins

Alkaline hydrolysis of a series of X‐substituted‐phenyl diphenylphosphinothioates ( 2a‐i ) in 80 mol%/20 mol% DMSO at 25.0 ± 0.1°C has been studied kinetically and assessed through a multiparameter approach. Substrates 2a to 2i are approximately 12 to 22 times less reactive than their P=O analogues 1a to 1i (ie, the thio effect). The Brønsted‐type plot for the reactions of 2a to 2i is linear with β_lg = ?0.43, consistent with a concerted mechanism. Hammett plots correlated with σ^o and σ^? constants also support a concerted mechanism; the Yukawa‐Tsuno plot results in an excellent linear correlation with ρ_X = 1.26 and r = 0.30, indicating that expulsion of the leaving group occurs in the rate‐determining step (RDS). The ΔH^? value increases from 10.5 to 11.7 and 13.9 kcal/mol as substituent X in the leaving group changes from 3,4‐(NO₂)₂ to 4‐NO₂ and H, in turn, while TΔS^? remains constant at ?6.0 kcal/mol. The strong dependence of ΔH^? on the electronic nature of substituent X also indicates that the leaving group departs in the RDS. The reaction mechanism and origin of the thio effect are discussed by comparison of the current kinetic results with those reported for the reactions of 1a to 1i . The results suggest that for useful OP neurotoxins the mechanism of abiotic hydrolysis is concerted (with varying degrees of asynchronicity) when the substrate bears good leaving groups.