Shock waves in gas flows with nanoparticles

Journal of Thermal Analysis and Calorimetry - The paper focuses on the analytical analysis of the propagation of a normal shock wave in an adiabatic gas flow with nanoparticles. A modified...     

Scattering of electromagnetic waves by a perfectly conducting body with a chiral coating

We propose a numerical method for solving problems of electromagnetic scattering in the resonance spectrum of frequencies by a 3D ideally conducting arbitrary-shaped body covered by a homogeneous chiral coating. A program package for calculating the characteristics of the scattered field and checking the accuracy of the obtained solution based on the above method is described briefly. Some results of numerical calculations are given, which are useful for a study of the influence of “chirality” on the scattering properties of absorbing coatings. Siberian Physical-and-Technical Institute at Tomsk State University, Tomsk, Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 41, No. 4, pp. 495–506, April, 1998.     

Chemical behavior of the biradicaloid (HO...ONO) singlet states of peroxynitrous acid. The oxidation of hydrocarbons, sulfides, and selenides

Various high levels of theory have been applied to the characterization of two higher lying biradicaloid metastable singlet states of peroxynitrous acid. A singlet minimum (cis-2) was located that had an elongated O-O distance (2.17 A) and was only 12.2 kcal/mol [UB3LYP/6-311+G(3df,2p)+ZPVE] higher in energy than its ground-state precursor. A trans-metastable singlet (trans-2) was 10.9 kcal/mol higher in energy than ground-state HO-ONO. CASSCF(12,10)/6-311+G(d,p) calculations predict the optimized geometries of these cis- and trans-metastable singlets to be close to those obtained with DFT. Optimization of cis- and trans-2 within the COSMO solvent model suggests that both exist as energy minima in polar media. Both cis- and trans-2 exist as hydrogen bonded complexes with several water molecules. These collective data suggest that solvated forms of cis-2.3H(2)O and trans-2.3H(2)O represent the elusive higher lying biradicaloid minima that were recently (J. Am. Chem. Soc. 2003, 125, 16204) advocated as the metastable forms of peroxynitrous acid (HOONO). The involvement of metastable trans-2 in the gas phase oxidation of methane and isobutane is firmly established to take place on the unrestricted [UB3LYP/6-311+G(d,p)] potential energy surface (PES) with classical activations barriers for the hydrogen abstraction step that are 15.7 and 5.9 kcal/mol lower than the corresponding activation energies for producing products methanol and tert-butyl alcohol formed on the restricted PES. The oxidation of dimethyl sulfide and dimethyl selenide, two-electron oxidations, proceeds by an S(N)2-like attack of the heteroatom lone pair on the O-O bond of ground-state peroxynitrous acid. No involvement of metastable forms of HO-ONO was discernible.     

Relative reactivity of peracids versus dioxiranes (DMDO and TFDO) in the epoxidation of alkenes. A combined experimental and theoretical analysis

Comparative analysis of the calculated gas-phase activation barriers (DeltaE++) for the epoxidation of ethylene with dimethyldioxirane (DMDO) and peroxyformic acid (PFA) [15.2 and 16.4 kcal/mol at QCISD(T)// QCISD/6-31+G(d,p)] and E-2-butene [14.3 and 13.2 kcal/mol at QCISD(T)/6-31G(d)//B3LYP/6-311+G(3df,2p)] suggests similar oxygen atom donor capacities for both oxidants. Competition experiments in CH(2)Cl(2) solvent reveal that DMDO reacts with cyclohexene much faster than peracetic acid/acetic acid under scrupulously dried conditions. The rate of DMDO epoxidation is catalyzed by acetic acid with a reduction in the classical activation barrier of 8 kcal/mol. In many cases, the observed increase in the rate for DMDO epoxidation in solution may be attributed to well-established solvent and hydrogen-bonding effects. This predicted epoxidative reactivity for DMDO is not consistent with what has generally been presumed for a highly strained cyclic peroxide. The strain energy (SE) of DMDO has been reassessed and its moderated value (about 11 kcal/mol) is now more consistent with its inherent gas-phase reactivity toward alkenes in the epoxidation reaction. The unusual thermodynamic stability of DMDO is largely a consequence of the combined geminal dimethyl- and dioxa-substitution effects and unusually strong C-H and C-CH(3) bonds. Methyl(trifluoromethyl)dioxirane (TFDO) exhibits much lower calculated activation barriers than DMDO in the epoxidation reaction (the average DeltaDeltaE++ values are about 7.5 kcal/mol). The rate increase relative to DMDO of approximately 10(5), while consistent with the higher strain energy for TFDO (SE approximately 19 kcal/mol) is attributed largely to the inductive effect of the CF(3) group. We have also examined the effect of alkene strain on the rate of epoxidation with PFA. The epoxidation barriers are only slightly higher for the strained alkenes cyclopropene (DeltaE++ = 14.5 kcal/mol) and cyclobutene (DeltaE++ = 13.7 kcal/mol) than for cyclopentene (DeltaE++ = 12.1 kcal/mol), reflecting the fact there is little relief of strain in the transition state. Alkenes strained by twist or pi-bond torsion do exhibit much lower activation barriers.     

Reactivity of alkyl versus silyl peroxides. The consequences of 1, 2-silicon bridging on the epoxidation of alkenes with silyl hydroperoxides and bis(trialkylsilyl)peroxides

The bond dissociation energies for a series of silyl peroxides have been calculated at the G2 and CBS-Q levels of theory. A comparison is made with the O-O BDE of the corresponding dialkyl peroxides, and the effect of the O-O bond strength on the activation barrier for oxygen atom transfer is discussed. The O-O bond dissociation enthalpies (DeltaH(298)) for bis (trimethylsilyl) peroxide (1) and trimethylsilyl hydroperoxide (2) are 54.8 and 53.1 kcal/mol, respectively at the G2 (MP2) and CBS-Q levels of theory. The O-O bond dissociation energies computed at G2 and G2(MP2) levels for bis(tert-butyl) peroxide and tert-butyl hydroperoxide are 45.2 and 48.3 kcal/mol, respectively. The barrier height for 1,2-methyl migration from silicon to oxygen in trimethylsilyl hydroperoxide is 47.9 kcal/mol (MP4//MP2/6-31G). The activation energy for the oxidation of trimethylamine to its N-oxide by bis(trimethylsilyl) peroxide is 28.2 kcal/mol (B3LYP/6-311+G(3df,2p)// B3LYP/6-31G(d)). 1,2-Silicon bridging in the transition state for oxygen atom transfer to a nucleophilic amine results in a significant reduction in the barrier height. The barrier for the epoxidation of E-2-butene with bis(dimethyl(trifluoromethyl))silyl peroxide is 25.8 kcal/mol; a reduction of 7.5 kcal/mol relative to epoxidation with 1. The activation energy calculated for the epoxidation of E-2-butene with F(3)SiOOSiF(3) is reduced to only 2.2 kcal/mol reflecting the inductive effect of the electronegative fluorine atoms.     

Simulation of the xenon gamma spectrometer for analyzing radioactive materials

The results of the calculation of the detection efficiency of gamma-rays for the xenon gamma spectrometer (XGS) obtained using the GEANT4 Monte Carlo simulation are presented. The gamma spectra of the set of basic standard gamma-sources (OSGI) are analyzed for a real detector, and the calculated and actual detection efficiencies are compared. The XGS spectra are analyzed to determine the minimum concentration of the ¹⁵²Eu radio nuclide in the ¹³⁷Cs and ⁶⁰Co mixture. It is shown that the xenon gamma spectrometer is capable of detecting the isotope at concentrations above 40% in the mixture.     

xMAP-based analysis of three most prevalent staphylococcal toxins in Staphylococcus aureus cultures

Detection of staphylococcal toxins presents a great interest for medical diagnostics. Screening of clinical samples for the presence of several types of staphylococcal toxins using traditional methods—biological tests on animals or cell cultures as well as ELISA—is laborious. Multiplex detection methods would simplify testing. We have designed an xMAP-based assay to detect three staphylococcal toxins—enterotoxins A and B (SEA and SEB) and toxic shock syndrome toxin (TSST)—in cultural supernatants obtained from different strains of Staphylococcus aureus. The limits of detection of SEA, SEB, and TSST multiplex detection in S. aureus growth medium were 10, 1,000, and 5 pg/mL, respectively. Fifty-nine samples of S. aureus cultural supernatants were tested with the xMAP assay. The developed assay has proved highly effective detection of the natural toxins in the samples obtained due to bacterial cells cultivation. In prospect, the developed test system can be used in clinical diagnostics and in monitoring of foodstuffs and environmental objects.     

Structure and magnetic properties of Cu-Fe fiber composites obtained using packet hydrostatic extrusion

The structure and magnetic properties of Cu-Fe fiber composites prepared by packet hydrostatic extrusion are studied. The number of armco-iron fibers in the copper matrix attained n ∼ 8 × 10¹⁰, and rated diameter d of fibers varied from 2 mm to 3 nm. A correlation is observed between the magnetization hysteresis curves and low-frequency magnetic susceptibility obtained on samples with various values of d. It is shown that the magnetic properties of composites in the submicrometer range of d values are satisfactorily described in the magnetization reversal theory for small ferromagnetic particles.