Acid-catalyzed decomposition of hydroperoxides in the presence of ketones

Ketones and aldehydes accelerate decomposition of hydroperoxides in acetonitrile solution in the presence of strong acids. An explanation of the effect, due to the formation of semiperketals (semiperacetals) which undergo rapid acid-catalytic decomposition, is proposed. The macrostage character of the reaction of acid-catalyzed decomposition of cyclohexyl hydroperoxide was demonstrated for the first time. The initially slow decomposition takes place homolytically and yields the product cyclohexanone, which accelerates decomposition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 278–285, February, 1990.     

Floating Electrode Dielectric Barrier Discharge Plasma in Air Promoting Apoptotic Behavior in Melanoma Skin Cancer Cell Lines

Initiation of apoptosis, or programmed cell death, is an important issue in cancer treatment as cancer cells frequently have acquired the ability to block apoptosis and thus are more resistant to chemotherapeutic drugs. Targeted and perhaps selective destruction of cancerous tissue is desirable for many reasons, ranging from the enhancement of or aid to current medical methods to problems currently lacking a solution, i.e., lung cancer. Demonstrated in this publication is the inactivation (killing) of human Melanoma skin cancer cell lines, in vitro, by Floating Electrode Dielectric Barrier Discharge (FE-DBD) plasma. Not only are these cells shown to be killed immediately by high doses of plasma treatment, but low doses are shown to promote apoptotic behavior as detected by TUNEL staining and subsequent flow cytometry. It is shown that plasma acts on the cells directly and not by “poisoning” the solution surrounding the cells, even through a layer of such solution. Potential mechanisms of interaction of plasma with cells are discussed and further steps are proposed to develop an understanding of such systems.     

Ueber die Einwirkung des Caro'schen Reagens auf Ketone

Ohne Zusammenfassung     

Fermentation of Fragrances: Biotransformation of β-Ionone by Lasiodiplodia theobromae

Pre-grown mycelia of Lasiodiplodia theobromae ATCC 28570 transform β-ionone (1) into a large variety of metabolites, by mainly degrading the side-chain of the β-ionone molecule by a C₂-unity. The enzyme system responsible for this degradation is proposed to be an oxygenase, which gives rise to the formation of the main product β-cyclo-homogeraniol (8) in analogy to a Baeyer- Villiger oxidation. Further enzymic actions of Lasiodiplodia such as hydrogenations and hydroxylations lead to an accumulation of several not yet described β-ionone metabolites.     

Proton distribution at low altitudes in near-equatorial latitudes according to satellite experiments: The dynamics of proton fluxes

The data obtained on the ACTIVE, SAMPEX, and TIROS-N satellites are used to study the dynamics of low-energy (from tens of keV to several MeV) proton fluxes in the region of the geomagnetic equator (L < 1.15) at low altitudes (up to 1000 km). The dependence of the fluxes on the local magnetic time is presented. A number of magnetic disturbances in November–December 1978 are analyzed to illustrate the dependence of the flux on the geomagnetic activity level. The results obtained allow the conclusion that the ring current is one of the main sources of protons at low altitudes in near-equatorial latitudes.     

Specific features of the distribution of protons at small altitudes in near-equatorial latitudes according to data of satellite experiments. I. Energy spectrum

The spectra of protons with energies from 10 keV to 1 MeV as measured in experiments conducted at satellites and the MIR orbital station are presented. These data were obtained in the area of the geomagnetic equator at L < 1.15 and at altitudes up to 1000 km. The proton spectrum was determined during periods of geomagnetic perturbations and quite periods. These spectra were approximated using a kappa-function. The proton spectra in the near-equatorial area and in the ring current are compared. The proton’s life time in the near-equatorial area is estimated, taking into account charge exchange and Coulomb scattering. It is confirmed that the ring current is a main source of protons in the near-equatorial area at low altitudes.     

Ultrasonic devulcanization of waste rubbers: Experimentation and modeling

Continuous ultrasonic devulcanization of ground tire rubber (GRT) and styrene-butadiene rubber (SBR) is considered. Experiments are performed under various processing conditions. Two recipes of SBR with different amounts of polysulfidic linkages are utilized. Gel fraction and crosslink density of devulcanized rubbers are measured and a unique relationship between them is established. Die characteristics with and without imposition of ultrasonic waves are determined. Devulcanized samples are revulcanized and mechanical properties are measured. In some cases, properties of revulcanized SBR samples exceeded those of virgin vulcanizates. This is explained based on the presence of a double network in the revulcanized rubber. A modification of acoustic cavitation and flow modeling of ultrasonic devulcanization of SBR and GRT is proposed using a concept of effective viscosity characterizing the flow of vulcanized particles before devulcanization combined with a shear rate, temperature and gel fraction-dependent viscosity of devulcanized rubber. Velocity, shear rate, pressure, and temperature field along with gel fraction, crosslink density and number of bonds broken are simulated. Predicted data on gel fraction, crosslink density, and pressure using the present modification of the model are found to be closer to experimental data then previously reported.Dedicated to the memory of Professor Tasos C. Papanastasiou     

Motion of a pair of bubbles in a liquid of low viscosity

Lagrange's equations are used to examine the long-range interaction of bubbles. The Lagrange function equals the kinetic energy of an ideal liquid flowing around a bubble. The generalized external forces include the upthrust and the viscous resistance to flow around each buble. The azimuthal angle is increased by the long-range interaction. The locus for the relative motion is calculated for: 1) the case in ~hieh the relative speed is fairly high, which allows one to neglect the effects of viscosity on the collision time. 2) low relative speed, where the viscous forces determine the motion. Estimates are given for the differential effective cross-section for elastic scattering and the coalescence cross-section.We are indebted to V. G. LevichandV. V. Tolmachev for discussions.     

Transfer of energy from an evaporating drop in a vapor medium

The article considers the temperature distribution around an evaporating drop in a vapor medium. The transfer of energy is effected by molecular thermal conductivity, convection, and radiation. The mean length of the free flight path of the radiation considerably exceeds the characteristic distance at which the temperature changes. The times required for relaxation of the temperature to a steady-state value are determined, as well as the characteristic distances at which the temperature distribution changes.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 1, pp. 74–78, January–February, 1972.The authors thank V. G. Levich for his evaluation of the results obtained.     

Surface plasmon polariton assisted optical pulling force

We demonstrate both analytically and numerically the existence of optical pulling forces acting on particles located near plasmonic interfaces. Two main factors contribute to the appearance of this negative recoil force. The interference between the incident and reflected waves induces a rotating dipole with an asymmetric scattering pattern, while the directional excitation of surface plasmon polaritons (SPPs) enhances the linear momentum of scattered light. The strongly asymmetric SPP excitation is determined by spin–orbit coupling of the rotating dipole and surface plasmon polariton. As a result of the total momentum conservation, the force acting on the particle points in a direction opposite to the incident wave propagation. We derive analytical expressions for the force acting on dipolar particles placed in the proximity of plasmonic surfaces. Analytical expressions for this pulling force are derived within the dipole approximation and are in excellent agreement with results of electromagnetic numerical calculations. The forces acting on larger particles are analyzed numerically, beyond the dipole approximation.