Experimental evidence for a kinetic transition in reversible reactions

We provide a first experimental verification of a theoretical prediction of a kinetic transition in a reversible binding reaction, AB right harpoon over left harpoon A+B, driven by the difference in effective lifetimes of the bound and the unbound states. We consider the kinetics of excited-state proton transfer to solvent from a photoacid whose conjugate anionic base possesses an extremely short unbound anion lifetime. Its solvent variation relative to the overall dissociation rate coefficient induces a transition in the kinetics, from power law to exponential.     

Nanoporous silicon doped by Cu for gas-sensing applications

The effect of hydrogen sulphide on the current–voltage characteristics of metal–insulator–semiconductor (MIS) structures based on nanoporous silicon (Si_nanopor) under copper doping has been investigated. Scanning electron (SEM), atomic force (AFM) and optic microscopes and/or secondary ion mass spectroscopy (SIMS) were used to obtain detailed characterisation of copper cluster distribution present at the surface and pores, respectively. SIMS spectra reveal that finite gradient in copper distribution along the pores and oxidation of nanoporous silicon simultaneously can be obtained successfully under electroless deposition process. It was also shown that the doping of nanoporous silicon by Cu leads to enhanced hydrogen sulphide sensitivity of MIS structures even without catalytic active top electrodes (for example, Pd) at room temperature. Furthermore, for different types of familiar MIS structures based on nanoporous silicon, e.g., MIS structures doped or undoped by copper and by using Pd metal electrodes, the hydrogen sulphide detection at room temperature mainly depends on the modification in the height of barrier of hetero- (Al–Cu–Si_nanopor–c-Si) or Schottky-like (Pd–Cu–Si_nanopor–c-Si) structures resulting the chemical interaction of molecular H₂S gas with copper clusters at the surface and in the pores. It is demonstrated that MIS structures based on the nanoporous silicon with copper doping are more sensitive to H₂S action at room temperature. In addition, the physical mechanism explaining the observed phenomena is also discussed.     

Study of heat transfer in the separation zones formed in front of supersonic jets in a subsonic carrier flow

The heat transfer taking place between the gas and the surface of the plate in the zone of three-dimensional separation of the turbulent boundary layer in front of a set of supersonic jets injected perpendicularly to a subsonic carrier flow is considered. The aim of this investigation is to establish the main physical characteristics of heat transfer in the separation zones in front of jet obstacles and to obtain the distributions of the local heat-transfer coefficients and the temperature of the thermally insulating wall as functions of the parameters of the carrier flow and the injected jets. Analysis of the experimental results yields certain approximating relationships for the distribution of the local heat-transfer coefficients as functions of the Mach number of the carrier flow M, the Mach number of the jet M_j, the relative boundary-layer displacement thickness _s= _s ^* /d, and the degree of jet superheating T_ojT_o relative to the separation zones in front of supersonic jet obstacles.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 68–72, July–August, 1975.     

Novel Mechanism of Bioluminescence: Oxidative Decarboxylation of a Moiety Adjacent to the Light Emitter of Fridericia Luciferin

A novel luciferin from a bioluminescent Siberian earthworm Fridericia heliota was recently described. In this study, the Fridericia oxyluciferin was isolated and its structure elucidated. The results provide insight into a novel bioluminescence mechanism in nature. Oxidative decarboxylation of a lysine fragment of the luciferin supplies energy for light generation, while a fluorescent CompX moiety remains intact and serves as the light emitter.     

Flow in the zones of separation of a turbulent boundary layer in front of a subsonic jet injected through a circular nozzle

Flow taking place in the three-dimensional region of separation formed by the interaction of a subsonic stream with a single subsonic jet emerging from a circular hole in a plate perpendicular to the stream is considered. The aim of the investigation is to discover the physical characteristics of the flow in the three-dimensional separation zone in front of a subsonic jet obstacle and to determine the principal laws governing the geometrical and hydrodynamic characteristics of the flow as functions of the parameters of the driving stream and jet.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 34–41, May–June, 1973.