Electrochemically deposited ZnO films: an XPS study on the evolution of their surface hydroxide and defect composition upon thermal annealing

Electrodeposition from ZnCl₂ aqueous solution was performed to grow ZnO thin films on the surface of polycrystalline copper plates. Electrochemical parameters for deposition were optimized by means of cyclic voltammetry (CV). The morphology of the deposits was studied via scanning electron microscopy (SEM), and their chemical composition was ascertained by means of X-ray photoelectron spectroscopy (XPS). The effects of changing the deposition bath temperature (T _bath) and the role played by post-deposition treatments, such as temperature and time of annealing in air, were studied. SEM images of freshly deposited vs. annealed samples have shown that in the former case the films display a rough morphology with mixed grain/hexagonal platelets structures and in the latter smaller but more uniformly dispersed cubic grains. T _bath is found to be the key parameter to induce the different morphology in the deposited films, which reflects in a different chemical reactivity of surface species, as found on the basis of the binding energies and relative quantitative ratios between Zn 2p and O 1s peaks. In fact, a higher T _bath favours a more efficient desorption of OH groups upon annealing, the O 1s peak resulting to much more drastically modified oxide/hydroxide intensity ratio with respect to the case of the sample deposited at lower T _bath.     

Preparation and Characterization of a π-Conjugated Donor–Acceptor System Containing the Strongly Electron-Accepting Tetraphenylborolyl Unit

A novel thiophene-bridged donor–acceptor system was synthesized with a carbazole as donor and a borole as acceptor unit. The borole group was successfully installed via the tin–boron exchange reaction of 1,1-dimethyl-2,3,4,5-tetraphenylstannole with 9-(5-(dibromoboryl)thiophen-2-yl)carbazole. The effect of the borole on the optoelectronic properties of the donor–acceptor system was explored by spectroscopic (UV/Vis and fluorescence spectroscopy), electrochemical (cyclic voltammetry) and theoretical (TD-DFT) methods as well as by modifying its structure. The corresponding donor–acceptor compound bearing the widely employed dimesitylboryl acceptor group was also synthesized for comparison.     

Cu–iminopyridine complexes as catalysts for carbene and nitrene transfer reactions

Copper complexes with chiral iminopyridine ligands were screened for their catalytic efficiency in carbene (cyclopropanation) and nitrene transfer reactions (aziridination, C? H amidation). Both pre‐formed and in situ formed complexes were considered. The results highlighted the poor catalytic efficiency of these complexes in cyclopropanation reactions employing methyl phenyldiazoacetate as the carbene source, whereas better results were obtained in nitrene transfer reactions, particularly in the amidation of C? H bonds, albeit the enantioselectivity of the reactions was negligible in nearly all cases. Finally, copper complexes were also found to promote an interesting oxidative functionalization of alkynes with PhI(OAc)₂ at room temperature. Copyright © 2014 John Wiley & Sons, Ltd.     

A novel statistical linearization solution for randomly excited coupled bending-torsional beams resting on non-linear supports

A novel statistical linearization technique is developed for computing stationary response statistics of randomly excited coupled bending-torsional beams resting on non-linear elastic supports. The key point of the proposed technique consists in representing the non-linear coupled response in terms of constrained linear modes. The resulting set of non-linear equations governing the modal amplitudes is then replaced by an equivalent linear one via a classical statistical error minimization procedure, which provides algebraic non-linear equations for the second-order statistics of the beam response, readily solved by a simple iterative scheme. Data from Monte Carlo simulations, generated by a pertinent boundary integral method in conjunction with a Newmark numerical integration scheme, are used as benchmark solutions to check accuracy and reliability of the proposed statistical linearization technique.

     

1,2‐Dimethoxyethane Degradation Thermodynamics in Li−O2 Redox Environments

The reaction thermodynamics of the 1,2‐dimethoxyethane (DME), a model solvent molecule commonly used in electrolytes for Li?O₂ rechargeable batteries, has been studied by first‐principles methods to predict its degradation processes in highly oxidizing environments. In particular, the reactivity of DME towards the superoxide anion O₂^? in oxygen‐poor or oxygen‐rich environments is studied by density functional calculations. Solvation effects are considered by employing a self‐consistent reaction field in a continuum solvation model. The degradation of DME occurs through competitive thermodynamically driven reaction paths that end with the formation of partially oxidized final products such as formaldehyde and methoxyethene in oxygen‐poor environments and methyl oxalate, methyl formate, 1‐formate methyl acetate, methoxy ethanoic methanoic anhydride, and ethylene glycol diformate in oxygen‐rich environments. This chemical reactivity indirectly behaves as an electroactive parasitic process and therefore wastes part of the charge exchanged in Li?O₂ cells upon discharge. This study is the first complete rationale to be reported about the degradation chemistry of DME due to direct interaction with O₂^?/O₂ molecules. These findings pave the way for a rational development of new solvent molecules for Li?O₂ electrolytes.     

Word problems and ceers

This note addresses the issue as to which ceers can be realized by word problems of computably enumerable (or, simply, c.e.) structures (such as c.e. semigroups, groups, and rings), where being realized means to fall in the same reducibility degree (under the notion of reducibility for equivalence relations usually called “computable reducibility”), or in the same isomorphism type (with the isomorphism induced by a computable function), or in the same strong isomorphism type (with the isomorphism induced by a computable permutation of the natural numbers). We observe, e.g., that every ceer is isomorphic to the word problem of some c.e. semigroup, but (answering a question of Gao and Gerdes) not every ceer is in the same reducibility degree of the word problem of some finitely presented semigroup, nor is it in the same reducibility degree of some non-periodic semigroup. We also show that the ceer provided by provable equivalence of Peano Arithmetic is in the same strong isomorphism type as the word problem of some non-commutative and non-Boolean c.e. ring.     

Production and extraction of astaxanthin from Phaffia rhodozyma and its biological effect on alcohol-induced renal hypoxia in Carassius auratus

The effect of astaxanthin (3,3′-dihydroxy-s-carotene-4,4′-dione) on alcohol-induced morphological changes in Carassius auratus, as an experimental model, was determined. The yeast Phaffia rhodozyma was used as a source of astaxanthin. The animals were divided into three groups for 30 days: one group was treated with ethanol at a dose of 1.5% mixed in water, the second one with EtOH 1.5% and food enriched with astaxanthin from P. rhodozyma, and the third was a control group. After a sufficient experimental period, the samples were processed using light microscopy and evaluated by histomorphological and histochemical staining, and the data were supported by immunohistochemical analysis, using a wide range of antibodies, such as calbindin, vimentin and alpha-smooth muscle actin. The results show that the alcoholic damage in the kidney led to hypoxia. In contrast, the group fed with astaxanthin from P. rhodozyma showed a normal morphological picture, with better glomeruli organisation and the presence of the area of filtration. Furthermore, the immunohistochemistry has confirmed these results.     

Effective Tuning of Ketocyanine Derivatives through Acceptor Substitution

A series of ketocyanine derivatives possessing bis(diarylamino)fluorenyl donors and variable acceptors installed at the bridging carbon atom were synthesized to investigate how the electronic structure of the dye can be systemically tuned through stabilization of the cyanine‐like character of the donor by increasing the acceptor strength. Analysis of the ¹H NMR spectra indicates that the “charge‐separated” species dominates in these dyes, given that carbons possessing a positive or negative charge in the resonance structures of this state purposefully shift downfield or upfield, respectively, depending on the strength of the acceptor moiety. In DAA‐Fl‐PI, the acceptor strength and the gain of acceptor aromaticity indicates a predisposition of the separated state, indicated by asymmetry in the ¹H NMR spectrum, as well as uneven distribution of the HOMO on the fluorenyl donor.     

Hardware-in-the-loop simulation of wave energy converters based on dielectric elastomer generators

Dielectric elastomer generators (DEGs) are soft electrostatic generators based on low-cost electroactive polymer materials. These devices have attracted the attention of the marine energy community as a promising solution to implement economically viable wave energy converters (WECs). This paper introduces a hardware-in-the-loop (HIL) simulation framework for a class of WECs that combines the concept of the oscillating water columns (OWCs) with the DEGs. The proposed HIL system replicates in a laboratory environment the realistic operating conditions of an OWC/DEG plant, while drastically reducing the experimental burden compared to wave tank or sea tests. The HIL simulator is driven by a closed-loop real-time hydrodynamic model that is based on a novel coupling criterion which allows rendering a realistic dynamic response for a diversity of scenarios, including large scale DEG plants, whose dimensions and topologies are largely different from those available in the HIL setup. A case study is also introduced, which simulates the application of DEGs on an OWC plant installed in a mild real sea laboratory test-site. Comparisons with available real sea-test data demonstrated the ability of the HIL setup to effectively replicate a realistic operating scenario. The insights gathered on the promising performance of the analysed OWC/DEG systems pave the way to pursue further sea trials in the future.