A study on optical absorption and constants of doped poly(ethylene oxide)

Thin films of polymer electrolyte based on poly(ethylene oxide) doped with sodium iodide (NaI) were prepared using the solution cast method. The films obtained have average thickness of 70 μm and different NaI concentrations. Absorption and reflectance spectra of UV-radiation were studied in the wavelength range 300-800 nm. The optical results were analyzed in terms of absorption formula for non-crystalline materials.The optical energy gap and the basic optical constants, refractive index, and dielectric constants of the prepared films have been investigated and showed a clear dependence on the NaI concentration. The interpreted absorption mechanism is a direct electron transition.The observed optical energy gap for neat poly(ethylene oxide) is about 2.6 eV, and decreases to a value 2.36 eV for the film of 15 wt% NaI content. It was found that the calculated refractive index and the dielectric constants of the polymer electrolyte thin films increase with NaI content. Models were used to describe the dependences of the dielectric constant on the NaI concentration, and the refractive index on the incident photon energy.     

Disorder structure of free-flow and global jams in the extended BML model

The original BML model is extended by introducing extended sites, which can hold several vehicles at each time-step. Unexpectedly, the flow in the extended model sharply transits from free-flow to global jams, but the transition is not one-order in original BML model. And congestion in the extended model appears more easily. This can ascribe to the mixture of vehicles from different directions in one site, leading to the drop-off of the capacity of the site. Furthermore, the typical configuration of free flowing and global jams in the extended models is disorder, different from the regular structure in the original model.     

Mechanical properties of anion exchange membranes by combination of tensile stress–strain tests and dynamic mechanical analysis

The thermomechanical properties of anion exchange polymers based on polysulfone (PSU) quaternized with trimethylamine (TMA) or 1,4‐diazabicyclo[2.2.2]octane (DABCO) and containing hydroxide or chloride anions by tensile stress–strain tests and dynamic mechanical analysis (DMA) have been determined. The reported mechanical properties included the Young's modulus, tensile strength, and elongation at break from tensile tests and the storage and loss modulus and glass transition temperature from DMA. The anion exchange membranes behaved as stiff polymers with Young's modulus in the order of 1 GPa, relatively with high strength (about 30 MPa) and low elongation at break (around 10%) was observed. Tensile tests were also made with membranes exchanged with hydrogen‐carbonate and carbonate anions to control the absence of important carbonation of the OH form. The glass transition temperatures were of the order of 150 °C (PSU‐TMA) or 200 °C (PSU‐DABCO) for the hydroxide form, confirmed by differential scanning calorimetry; they increase further by about 50 K, when hydroxide ions are replaced by chloride. This result and the increase of the storage modulus could be interpreted by the higher hydration of hydroxide ions and the plasticizing effect of water, which reduced the Van der Waals interactions between the macromolecular chains. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1180–1187     

Bis-chelate Fe(III) complex of an azomethine at the focal point of a branched ester functionalized with cyclohexylbenzoic acid

A Fe(III) complex with Cl counter ion based on a branched Schiff base has been synthesized and studied. The compound was produced by the reaction of the Schiff base with FeCl₃ at room temperature in benzene–ethanol. The complex is symmetric, i.e., bis-chelate, with an octahedral coordination of Fe. The compound revealed phase transitions of the “solid–solid” type. The complex displayed a temperature-induced spin transition (S?=?1/2???5/2) which was detected by EPR.     

Ultrathin Co3S4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions

Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co₃S₄ under neutral conditions can be enhanced by exposed octahedral planes and self‐adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn–Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co³⁺ in the octahedral self‐adapt from low‐spin to high‐spin states. As a result, the synergistic effect endow the Co₃S₄ nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state‐of‐the‐art among inorganic non‐noble metal compounds.     

The Hard Rod Fluid in a Uniform Gravitational Field

Abstract

The system of hard rods in an external, uniform gravitational field is studied and exact expressions obtained for the partition functions, and the one- and two-particle distributions. In principle all higher order distributions can be exactly expressed as finite sums and the Laplace transforms of the one-particle density and pressure for a semi-infinite system are reducible to single integrals. Limiting cases of weak field and small rod diameters are examined. In the former case, these results agree with Percus and Lebowitz's local density expansion. In the latter case, corrections to the barometric pressure and density laws are obtained. Finally some mathematical difficulties involved in the calculation of the virial expansion and distribution of roots of the grand partition function are mentioned.     

Revealing sol-gel type main effects by exploring a molecular cluster behavior in model in-plane amphiphilic aggregations

In-plane (bio)matter aggregations of amphiphilic nature are modeled extensively by Monte Carlo simulation in their natural entropic contexts. The modeling starts by designing the aggregations at a molecular level, pointing to its well-known configuration vs conformation character. Then, the conformational behavior is distributed over the aggregations obtained, with the aim of revealing their main sol-gel type (viscoelastic) effects. The passage between the resulting sol and gel phases is not controlled by a scan in the temperature domain, on the contrary, the control parameter is selected to be the hydrophobic-interaction strength while the temperature remains unchanged. The distribution of ordered fringed micelles, and the overall crystalline inclusions of the gel phase, suggested a first-order phase change, reasonably conceivable in terms of Avrami-Kolmogorov formalism for such hydrophobic-force driven and percolation-in-nature systems. A phase transition diagram has been presented as a novel proposition to discern between sol vs gel phases. As specific results, also of high experimental value, a damped-oscillating cluster-involving effect on the resulting hydrophobic-polar matrices has been detected and analysed. Other additional intermolecular-sharing entropy-influenced effects on clustering, as seen in terms of chain-to-chain connectivities, have been addressed as being of sufficient relevance to the gelation mechanism described. The microcrystalline inclusions downgrade to some extent the overall picture of entropy-affected gelation, being all together suitable for experimental check-out.     

Structure of the even-even ~(78-84)Kr isotopes within SD-pair shell model

The collective properties in the even-even 78-84Kr isotopes have been studied within the framework of the SD-pair shell model.It is found that the collectivity of low-lying states in the even-even Kr isotopes can be described very well.     

Absorption and fluorescence emission spectroscopic characters of naphtho‐homologated yy‐DNA bases and effect of methanol solution and base pairing

A comprehensive theoretical study of electronic transitions of naphtho‐homologated base analogs, namely, yy‐T , yy‐C , yy‐A , and yy‐G , was performed. The nature of the low‐lying excited states is discussed, and the results are compared with those from experiment and also with those of y‐bases. Geometrical characteristics of the lowest excited singlet ππ* and nπ* states were explored using the CIS method, and the effects of methanol solution and paring with their complementary natural bases on the relevant absorption and emission spectra of these modified bases were examined. The calculated excitation and emission energies agree well with the measured data, where experimental results are available. In methanol solution, the fluorescence from yy‐A and yy‐G would be expected to occur around 539 and 562 nm, respectively, suggesting that yy‐A is a green‐colored fluorophore, whereas yy‐G is a yellow‐colored fluorophore. The methanol solution was found to red‐shift both the absorption and emission maxima of yy‐A , yy‐T , and yy‐C , but blue‐shift those for yy‐G . Generally, though base pairing has no significant effects on the absorption and fluorescence maxima of yy‐A , yy‐C , and yy‐T , it blue‐shifts those for yy‐G . © 2009 Wiley Periodicals, Inc. J Comput Chem 2010