Flexible Polymer–Organic Solar Cells Based on P3HT:PCBM Bulk Heterojunction Active Layer Constructed under Environmental Conditions

In this study, some crucial parameters were determined of flexible polymer–organic solar cells prepared from an active layer blend of poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) mixed in 1:1 mass ratio and deposited from chlorobenzene solution by spin-coating on poly(ethylene terephthalate) (PET)/ITO substrates. Additionally, the positive effect of an electron transport layer (ETL) prepared from zinc oxide nanoparticles (ZnO np) on flexible photovoltaic elements’ performance and stability was investigated. Test devices with above normal architecture and silver back electrodes deposed by magnetron sputtering were constructed under environmental conditions. They were characterized by current-voltage (I–V) measurements, quantum efficiency, impedance spectroscopy, surface morphology, and time–degradation experiments. The control over morphology of active layer thin film was achieved by post-deposition thermal treatment at temperatures of 110–120 °C, which led to optimization of device morphology and electrical parameters. The impedance spectroscopy results of flexible photovoltaic elements were fitted using two R||CPE circuits in series. Polymer–organic solar cells prepared on plastic substrates showed comparable current–voltage characteristics and structural properties but need further device stability improvement according to traditionally constructed cells on glass substrates.     

Defect Formation,T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling

We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively.     

Subsurface Carbon: A General Feature of Noble Metals

Carbon moieties on late transition metals are regarded as poisoning agents in heterogeneous catalysis. Recent studies show the promoting catalytic role of subsurface C atoms in Pd surfaces and their existence in Ni and Pt surfaces. Here energetic and kinetic evidence obtained by accurate simulations on surface and nanoparticle models shows that such subsurface C species are a general issue to consider even in coinage noble‐metal systems. Subsurface C is the most stable situation in densely packed (111) surfaces of Cu and Ag, with sinking barriers low enough to be overcome at catalytic working temperatures. Low‐coordinated sites at nanoparticle edges and corners further stabilize them, even in Au, with negligible subsurface sinking barriers. The malleability of low‐coordinated sites is key in the subsurface C accommodation. The incorporation of C species decreases the electron density of the surrounding metal atoms, thus affecting their chemical and catalytic activity.     

Synthesis and Structural Determination of the Disordered Bixbyite Cu3‐xSb1+xO5.5+3x/2 with Spin‐Glass Behaviour

The ternary copper antimony oxide Cu_3‐xSb_1+xO_5.5+3x/2 (x=0.23) has been synthesized under 0.8–1.3 MPa pO₂ at 1022–1082 °C. Rietveld refinements of X‐ray and neutron powder diffraction patterns concluded that the oxide adopts a bixbyite type structure, crystallising in the cubic space group Ia‐3 with the unit cell parameter a=9.61164(4) Å at room temperature from powder neutron diffraction data. The cationic 8b and 24d sites were found to be occupationally disordered where both Cu and Sb could be found on both sites. This is supported by X‐ray absorption spectroscopy experiments showing more than one possible Cu environment. There was a significant net deficiency of oxygen in the compound which was first inferred from observations of a thermochromic‐like phenomena and also seen from in situ high temperature neutron diffraction experiments. Magnetic susceptibility and magnetization measurements show paramagnetic behaviour with spin‐glass like transition below 6 K.     

Mechanism of direct oxidation of cyclohexene to cyclohexanone with nitrous oxide. Theoretical analysis by DFT method

New very effective results on the liquid-phase oxidation of cyclohexene to cyclohexanone by nitrous oxide are analyzed using the B3LYP/6-31G* approximation to predict a two-step reaction mechanism correlated with the experimental data.     

Spectroscopy vs. Electrochemistry: Catalyst Layer Thickness Effects on Operando/In Situ Measurements

In recent years, operando/in situ X-ray absorption spectroscopy (XAS) has become an important tool in the electrocatalysis community. However, the high catalyst loadings often required to acquire XA-spectra with a satisfactory signal-to-noise ratio frequently imply the use of thick catalyst layers (CLs) with large ion- and mass-transport limitations. To shed light on the impact of this variable on the spectro-electrochemical results, in this study we investigate Pd-hydride formation in carbon-supported Pd-nanoparticles (Pd/C) and an unsupported Pd-aerogel with similar Pd surface areas but drastically different morphologies and electrode packing densities. Our in situ XAS and rotating disk electrode (RDE) measurements with different loadings unveil that the CL-thickness largely determines the hydride formation trends inferred from spectro-electrochemical experiments, therewith calling for the minimization of the CL-thickness in such experiments and the use of complementary thin-film control measurements.     

Correction to: Lithium ion conductivity of solid solutions based on Li8ZrO6

Journal of Solid State Electrochemistry - Lithium ion conductivity of lithium hexaoxozirconate Li8ZrO6 doped by Mg2+, Sr2+, Nb5+, V5+, and Ce4+ cations was studied using impedance spectroscopy. The...     

Halogen–Aromatic π Interactions Modulate Inhibitor Residence Times

Prolonged drug residence times may result in longer‐lasting drug efficacy, improved pharmacodynamic properties, and “kinetic selectivity” over off‐targets with high drug dissociation rates. However, few strategies have been elaborated to rationally modulate drug residence time and thereby to integrate this key property into the drug development process. Herein, we show that the interaction between a halogen moiety on an inhibitor and an aromatic residue in the target protein can significantly increase inhibitor residence time. By using the interaction of the serine/threonine kinase haspin with 5‐iodotubercidin (5‐iTU) derivatives as a model for an archetypal active‐state (type I) kinase–inhibitor binding mode, we demonstrate that inhibitor residence times markedly increase with the size and polarizability of the halogen atom. The halogen–aromatic π interactions in the haspin–inhibitor complexes were characterized by means of kinetic, thermodynamic, and structural measurements along with binding‐energy calculations.     

A semiempirical and ab initio MO study of the tautomers ofN-unsubstituted pyrazolones [hydroxy pyrazoles]

Semiempirical (MNDOC, MINDO/3, AM1, and MNDO) and ab initio (STO-3G and 4-31G basis sets) calculations on the relative stabilities, structures, and dipole moments of the 8 theoretically possible tautomeric forms of pyrazolone are reported. It is shown that MNDO + CI and MINDO/3 predict that 5-hydroxy pyrazole, 3-hydroxy pyrazole, and 2-pyrazolin-5-on are the most stable. These results correspond to the known experimental data. Of all used quantum chemical methods, the MINDO/3 results for the dipole moments of the investigated tautomers are in best agreement with the known experimental data. The electronic excitation energies were calculated using the CNDO/S-CI method. The results are in good agreement with the experimental UV spectra.     

Comparison theorems forL-monosplines of minimal norm

Summary LetLM _N be the set of allL-monosplines withN free knots, prescribed by a pair (x;E) of pointsx = {x _i } ₁ ⁿ ,a <x ₁ < ... <x _n <b and an incidence matrixE = (e _ij ) _i=1 ⁿ , _r-1 ^j=0 with Denote byLM _N ^O the subset ofLM _N consisting of theL-monosplines withN simple knots (n=N). We prove that theL-monosplines of minimalL _p-norms inLM _N belong toLM _N ^O .The results are reformulated as comparison theorems for quadrature formulae.