Textural and catalytic properties of the FexOy/Fe-KClO4 system

Selected properties of commercial iron powders, standardised in the atmosphere of hydrogen, have been studied. The reactivity of iron oxides in the thermal decomposition of KClO₄ in the solid-state mechanical mixture of Fe and KClO₄ containing 9, 13, 17, 21 and 25 wt.% of KClO₄, respectively, has been tested by the differential thermal analysis (DTA) and thermogravimetric analysis (TG). It has been established that the Fe₃O₄ phase on the surface of the iron powder act as an effective catalysts in the thermal decomposition of KClO₄.     

High-pressure testing of heterogeneous charge transfer in a room-temperature ionic liquid: evidence for solvent dynamic control

We report the first application of a high-pressure electrochemical strategy to study heterogeneous charge transfer (CT) in a room-temperature ionic liquid, [BMIM][BTA]. High-pressure kinetic studies on electron exchange for two redox couples of different charge type, viz. [Fe(bipy)3]3+/2+ and [Fe(cp)2]+/0, at bare Au electrodes within the range of 0.1-150 MPa, revealed large positive volumes of activation that were found to be virtually the same for the two redox couples in terms of the CT rate constants and diffusion coefficients, despite the reactant's charge type. Independent viscosity (fluidity) studies at elevated pressure (up to 175 MPa), were also performed and revealed a pressure coefficient closely resembling the former ones. Complementary temperature-dependent kinetic studies within the range of 298-358 K also revealed the virtual similarity in activation enthalpies for the same kinetic and diffusion processes, as well as the viscosity of [BMIM][BTA]. A rigorous analysis of the complete variety of obtained results strongly indicates that dynamic (frictional) control of CT is operative by way of the full adiabatic mechanism. The contribution of the Franck-Condon term to the activation free energy of the kinetic process seems almost diminished because of the high value of electronic coupling and freezing out of the outer-sphere reorganization energy. Further analyses indicate that frictional control most probably takes place through slow translational modes (implying "minimal volume" cooperative dislocations) of constituent ions. This kind of motion seems further slowed down within the vicinity of the active site presumably located within the diffusive-like zone situated next to the compact (first) part of the metal/ionic liquid junction.     

Unusual fluorescence anisotropy spectra of three-component donor–mediator–acceptor systems in uniaxially stretched polymer films in the presence of energy transfer

Energy transfer was studied for donor–mediator–acceptor systems in uniaxially stretched polymer films. The systems differ in the ability of mediator transition moment to orientate in the matrix. It was found that acceptor fluorescence remains polarized in the stretched matrix irrespectively of mediator. This means that information on the orientation of electric vector of the exciting light was conserved after energy transfer. In disordered system sensibilized fluorescence of mediator and acceptor is strongly depolarized. The effect of transition moments correlation on κ² in the stretched matrix is presented using Monte-Carlo simulation.     

Thioperoxy derivative generated by UV-induced transformation of N-hydroxypyridine-2(1H)-thione isolated in low-temperature matrixes

Photochemical transformations of N-hydroxypyridine-2(1H)-thione and its deuterated isotopologue were studied using the matrix-isolation technique. Low-temperature Ar and N2 matrixes containing monomers of this compound were irradiated with continuous-wave near-UV light. Photogeneration of two products was observed in these experiments. The relative population of these photogenerated species was found to be dependent on the wavelength of the UV light used for irradiation. By comparison of the IR spectra of the photoproducts with the spectra simulated theoretically at the DFT(B3LYP)/6-311++G(d, p) level, the final and the intermediate products were identified as rotameric forms of 2-hydroxysulfanyl-pyridine. This is the first report on generation of this thioperoxy derivative of pyridine. The mechanism of photogeneration of 2-hydroxysulfanyl-pyridine involves a photoinduced cleavage of the N-O bond in N-hydroxypyridine-2(1H)-thione, generation of the .OH radical weakly bound with the remaining pyridylthiyl radical, and recombination of these two radicals by formation of the new -S-O- bond. A theoretical model supporting this interpretation was constructed on the basis of approximate coupled cluster (CC2) calculations of the potential energy surfaces of the ground and first excited singlet electronic states of the system. After electronic excitation of the monomeric N-hydroxypyridine-2(1H)-thione, the molecule evolves to the conical intersection with the potential energy surface of the ground state and then to the global minimum corresponding to 2-hydroxysulfanyl-pyridine.     

Adaption allows efficient integration of functions with unknown singularities

We study numerical integration for functions f with singularities. Nonadaptive methods are inefficient in this case, and we show that the problem can be efficiently solved by adaptive quadratures at cost similar to that for functions with no singularities. Consider first a class of functions whose derivatives of order up to r are continuous and uniformly bounded for any but one singular point. We propose adaptive quadratures Q*_n, each using at most n function values, whose worst case errors are proportional to n^−r. On the other hand, the worst case error of nonadaptive methods does not converge faster than n⁻¹. These worst case results do not extend to the case of functions with two or more singularities; however, adaption shows its power even for such functions in the asymptotic setting. That is, let F^∞_r be the class of r-smooth functions with arbitrary (but finite) number of singularities. Then a generalization of Q*_n yields adaptive quadratures Q**_n such that |I(f)−Q**_n(f)|=O(n^−r) for any f ∈ F^∞_r. In addition, we show that for any sequence of nonadaptive methods there are `many' functions in F^∞_r for which the errors converge no faster than n⁻¹. Results of numerical experiments are also presented. The authors were partially supported, respectively, by the State Committee for Scientific Research of Poland under Project 1 P03A 03928 and by the National Science Foundation under Grant CCR-0095709.     

X-ray structures of 1,3-dithiolo[4,5-c]quinoline and 2,3-dihydro-1,4-dithiino[5,6-c]quinoline

The title compound I (C₁₀H₇NS₂) is orthorhombic: Pbca,a=16.223(6),b=15.065(5),c=7.356(4) Å. The conformation of 1,3-dithiol ring is of an envelope-type. A very short intramolecular sulfur-sulfur distance of 2.94 Å was observed. The compoundII (C₁₁H₉NS₂) is monoclinic: P2₁/c,a=5.113(2),b=11.978(4),c=16.444(5) Å, =98.00(5) deg. The conformation of the 1,4-dithiin rings is a half-chair. As compared to other 3,4-quinolinediyl bis-sulfides an elongated intramolecular sulfur-sulfur distance of 3.437(4) Å in dihydrodithiinoquinolineII was observed.Part XXXI in the series of Azinyl Sulfides.     

Phosphorus (V) porphyrin diaxially substituted with Leu-enkephalin

Synthesis of the first phosphorus (V) porphyrin-peptide conjugate was successfully accomplished. A biologically active peptide, leucine enkephalin, was constructed on the phosphorus atom of the 5,10,15,20-meso-tetraphenylporphinato dichlorophosphorus (V) chloride. The method involved solution phase peptide synthesis. The first C-terminal amino acid in the sequence of the peptide was axially attached to the porphyrin through a linker, 3-aminopropanol, and the remainder of leucine enkephalin was synthesized by subsequent additions of amino acids. Leucine enkephalin-P(V) porphyrin conjugate represents a new group of compounds, and its synthesis broadens potential applications of P(V) porphyrine, e.g. in photodynamic therapy.     

Spin‐orbit ZORA and four‐component Dirac–Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble gas dimers

Hartree–Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange‐correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin‐orbit zeroth‐order regular approximation Hamiltonian in combination with the large Slater‐type basis set QZ4P as well as with the four‐component Dirac–Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles with noniterative triple excitations [CCSD(T)] calculations using the very large polarization‐consistent basis sets aug‐pcSseg‐4 for He, Ne and Ar, aug‐pcSseg‐3 for Kr, and the AQZP basis set for Xe. For the dimers also, zero‐point vibrational (ZPV) corrections are obtained at the CCSD(T) level with the same basis sets were added. Best estimates of the dimer chemical shifts are generated from these nuclear magnetic shieldings and the relative importance of electron correlation, ZPV, and relativistic corrections for the shieldings and chemical shifts is analyzed. © 2015 Wiley Periodicals, Inc.     

Applications of Hückel-Su-Schrieffer-Heeger method

Structural Chemistry - The equilibrium carbon-carbon (C-C) bond lengths in π-electron hydrocarbons are very sensitive to the electronic ground-state characteristic. In the recent two papers by...