Molecular orbital study of the catalytic oxidation of propylene on silver

Analysis of the MINDO/2 reaction coordinates concerning the decomposition of the propylene perepoxide radical anion to propylene oxide and propylene peroxide makes it possible to explain the fundamental differences of ethylene and propylene oxidation on silver catalyst.

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Decomposition of methyl tert-butyl ether on zeolites

The H-forms of mordenite, ZSM-11 and ZSM-5 zeolites were employed for the decomposition of methyl tert-butyl ether to methanol and isobutene. It was found that even at low temperatures the zeolites exhibit an extremely high and relatively very stable activity and selectivity in this decomposition compared with the amorphous silica-based catalysts.

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Energetic analysis of 24 C20 isomers

Twenty-four individual geometric structures of the 20-carbon system are investigated using hybrid Hartree–Fock/density functional theory (DFT-B3LYP) in combination with the 6-31G and 6-311G* basis sets. These computations are carried out in order to evaluate the relative energies of the various C₂₀ isomers utilizing both geometry optimization and single-point energy calculations. The relative energies of the three most widely studied C₂₀ isomers (ring, bowl, and cage) are compared to the energies of other cyclic, bowl-like, and miscellaneous isomers. Although the ring and the bowl isomers are predicted to be the two most stable species, we have identified three to four additional cyclic structures that are predicted to be energetically competitive with the fullerene structure.     

On least squares estimation for long-memory lattice processes

A flexible class of anisotropic stationary lattice processes with long memory can be defined in terms of a two-way fractional ARIMA (FARIMA) representation. We consider parameter estimation based on minimizing an approximate residual sum of squares. The method can be applied to sampling areas that are not necessarily rectangular. A central limit theorem is derived under general conditions. The method is illustrated by an analysis of satellite data consisting of total column ozone amounts in Europe and the Atlantic respectively.     

Practical quantum mechanics-based fragment methods for predicting molecular crystal properties

Significant advances in fragment-based electronic structure methods have created a real alternative to force-field and density functional techniques in condensed-phase problems such as molecular crystals. This perspective article highlights some of the important challenges in modeling molecular crystals and discusses techniques for addressing them. First, we survey recent developments in fragment-based methods for molecular crystals. Second, we use examples from our own recent research on a fragment-based QM/MM method, the hybrid many-body interaction (HMBI) model, to analyze the physical requirements for a practical and effective molecular crystal model chemistry. We demonstrate that it is possible to predict molecular crystal lattice energies to within a couple kJ mol(-1) and lattice parameters to within a few percent in small-molecule crystals. Fragment methods provide a systematically improvable approach to making predictions in the condensed phase, which is critical to making robust predictions regarding the subtle energy differences found in molecular crystals.     

Thermodynamic, kinetic and solid-state study of divalent metal complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam) bearing two trans (1,8-)methylphosphonic acid pendant arms

Divalent metal complexes of macrocyclic ligand 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid)) (1,8-H4te2p, H4L) were investigated in solution and in the solid state. The majority of transition-metal ions form thermodynamically very stable complexes as a consequence of high affinity for the nitrogen atoms of the ring. On the other hand, complexes with Mn2+, Pb2+ and alkaline earth ions interacting mainly with phosphonate oxygen atoms are much weaker than those of transition-metal ions and are formed only at higher pH. The same tendency is seen in the solid state. Zinc(II) ion in the octahedral trans-O,O-[Zn(H2L)] complex is fully encapsulated within the macrocycle (N4O2 coordination mode with protonated phosphonate oxygen atoms). The polymeric {[Pb(H2L)(H2O)2].6H2O}n complex has double-protonated secondary amino groups and the central atom is bound only to the phosphonate oxygen atoms. The phosphonate moieties bridge lead atoms creating a 3D-polymeric network. The [{(H2O)5Mn}2(micro-H2L)](H2L).21H2O complex contains two pentaaquamanganese(II) moieties bridged by a ligand molecule protonated on two nitrogen atoms. In the complex cation, oxygen atoms of the phosphonate groups on the opposite sites of the ring occupy one coordination site of each metal ion. The second ligand molecule is diprotonated and balances the positive charge of the complex cation. Complexation of zinc(II) and cadmium(II) by the ligand shows large differences in reactivity of differently protonated ligand species similarly to other cyclam-like complexes. Acid-assisted dissociations of metal(II) complexes occur predominantly through triprotonated species [M(H3L)]+ and take place at pH < 5 (Zn2+) and pH < 6 (Cd2+).     

Nonparametric tests of independence between random vectors

A nonparametric test of the mutual independence between many numerical random vectors is proposed. This test is based on a characterization of mutual independence defined from probabilities of half-spaces in a combinatorial formula of Möbius. As such, it is a natural generalization of tests of independence between univariate random variables using the empirical distribution function. If the number of vectors is p and there are n observations, the test is defined from a collection of processes R_n,A, where A is a subset of {1,…,p} of cardinality |A|>1, which are asymptotically independent and Gaussian. Without the assumption that each vector is one-dimensional with a continuous cumulative distribution function, any test of independence cannot be distribution free. The critical values of the proposed test are thus computed with the bootstrap which is shown to be consistent. Another similar test, with the same asymptotic properties, for the serial independence of a multivariate stationary sequence is also proposed. The proposed test works when some or all of the marginal distributions are singular with respect to Lebesgue measure. Moreover, in singular cases described in Section 4, the test inherits useful invariance properties from the general affine invariance property.     

Propagation in one-dimensionally stratified time-independent scattering media

We calculate the probability density distributions of the power reflection coefficient, and of the various fluxes of the components of an erstwhile plane wave that propagates in a one-dimensionally stratified slab of a time-independent scattering medium. We determine the second- and fourth-order statistics of the power-fluxes, discuss the relevance of this problem to the localization phenomenon, examine the distribution of the emerging power-flux and the limitations on the assumption that it possesses a lognormal distribution, and finally discuss and rationalize the differences between the above and the corresponding characteristics of the radiation propagating in a time-dependent variant of this problem.     

Determination of oxygen radical absorbance capacity of black cumin (Nigella sativa) seed quinone compounds

In this study, the antioxidant capacities of main quinone constituents of Nigella sativa seeds, namely dithymoquinone (1), thymohydroquinone (2) and thymoquinone (3), were compared using DPPH and ORAC methods. The best scavenging activity was produced by 2, which showed a remarkable activity of 2.60 Trolox equivalents (TE) in a concentration range between 1.6 and 6.4 microg/mL and IC50 value of 2.4 microg/mL in ORAC and DPPH assays, respectively. Contrastingly, 3 possessed only weak DPPH scavenging efficacy (IC50 = 170 microg/mL) but significant antioxidative action of 1.91 TE in ORAC assay. No effect has been observed for 1. Additionally, modified protocol for synthesis of 2 has been developed with aim to enhance its availability for further studies as well as for its future potential use. Based on the results of this study, we conclude that 2 could be considered as a compound with prospective antioxidative properties.