Analysis of the Tautomeric Properties of 2-Formylcyclopentane-1,3-Dione Using the Data of IR Spectroscopy and Nonempirical (ab initio and DFT) Quantum-Chemical Calculations

The tautomerism, spectral properties, and properties of intramolecular hydrogen bonds in 2-formylcyclopentane-1,3-dione (FCPD) have been investigated by the methods of nonempirical quantum chemistry (calculations by the ab initio and DFT methods) and IR and ¹³C NMR spectroscopy. It is shown that FCPD in a crystalline form, as also does malonic dialdehyde, exists as self-associated enolized molecules with an open chelate ring. It is found that in solutions in CCl₄ the compound investigated exists as an equilibrium mixture of its exo- and endoenolic forms, with predominance of the former. The IR spectra of the solutions of FCPD in CCl₄ fix the presence of small amounts of the associate formed from the anionic and protonated forms of the substance. For the first time, the energies of the intramolecular H bonds of the endo- and exoenolic tautomeric forms in FCPD have been estimated theoretically. They appeared to be equal to 3.69 and 4.91 kcal·mole^–1, respectively. The possible mechanisms of enol-enolic interconversions of FCPD have been discussed.     

IR Spectra of Derivatives of Immunotropic 8-Azasteroids

By the method of IR Fourier spectroscopy with the use of numerical differentiation of spectral line profiles we have studied the spectra of some structural and functional derivatives of immunotropic 8-azasteroids in the region of C=O and C=C bonds (1800–1400 cm^–1). We have established the dependence of vibration frequencies of the C=O and C=C groups on the size of the ring D, the presence of heteroatoms (O, S) in the ring D, transformations in the -acyl--aminovinylcarbonyl fragment and in its adjacent positions of the heterosteroid skeleton, and the composite character of the absorption bands that are due to the vibrations of the C=O and C=C groups. The role of the structural and stereoelectronic factors in the observed group frequencies of 8-azasteroids is discussed.     

Manifestation of Intermolecular Interactions in the IR Spectra of 8-Azasteroids

We have investigated the intermolecular interactions of 8-aza-D-homogona-1,3,5(10),13-tetrane-12,17a-dione and 2,3-dimethoxy-8-azagone-1,3,5(10),13-tetran-12,17-dione with CHCl₃, binary solvents CHCl₃–CH₃OH, CCl₄–CHCl₃, and CCl₄–CH₃OH and also in the solid phase, which manifest themselves in the IR spectra. When the C=O groups of the studied 8-azasteroids form hydrogen bonding with the OH groups of alcohol, the frequencies (C=O) change insignificantly. We have found that they are higher than the corresponding frequencies in the IR absorption spectra of solid-phase samples, which is attributable not only to the effect of the medium but also to the possible shortened contacts of the C=O groups with the CH₃ and CH₂ groups of the molecules under study.     

Lifetimes of proton unstable states in 113I measured by the particle-X-ray coincidence technique

The -delayed proton decay of ¹¹³Xe was investigated by means of a total absorption -ray spectrometer and a telescope for particle detection. The energy window available for the -delayed proton decay of ¹¹³Xe and the relative branching ratios for proton transitions to the ¹¹²Te states were remeasured. The lifetimes of proton unstable ¹¹³I states populated in the electron capture decay of ¹¹³Xe were determined by means of the particle-X-ray coincidence technique. The results of the lifetime measurements are compared with statistical-model calculations.     

Specific Fluorescence Properties and Picosecond Transient Absorption of 8-Azasteroids

The specific fluorescence properties as well as picosecond transient absorption features have been studied for two 8-azasteroids. It is shown that at various excitation wavelengths the essentially different final excited electronic states are realized. Because of the multicenter character of 8-azasteroids the spectroscopic data obtained may be analyzed on a basis of the mesomeric tautomerism model taking into account the dynamic combination of cis- and trans-configurations. The dependence of fluorescence spectral characteristics on the solvent nature is a manifestation of intermolecular H-bond interactions.     

Total absorption spectroscopy of the β-delayed proton emitter 117Ba

The very neutron-deficient ¹¹⁷Ba nuclei were produced in ⁵⁸Ni-induced reactions on a ⁶³Cu target and selected for spectroscopic studies by using BaF⁺ molecules formed in the ion source of the GSI on-line mass separator. The -decay of ¹¹⁷Ba was investigated by means of the total absorption -ray spectrometer and a telescope for -delayed particle detection. In the analysis combining the -delayed -ray and proton data the energy window available for -delayed proton emission, the branching ratios for proton transitions to the ¹¹⁶Xe levels and the -feeding of the -ray and proton-emitting ¹¹⁷Cs states were determined. The -strength function for ¹¹⁷Ba derived from the measured -feeding distribution revealed the existence of a broad resonance structure at ¹¹⁷Cs excitation energy of about 4-5 MeV. The results of the -delayed proton studies and -strength measurements are confronted with theoretical predictions.     

Synthesis of peptidomimetics using a polymer-bound Boc-linker

Boc-resin-bound -hydroxy--amino-aldehydes are accessible starting from N-terminally bound amino acidesters by using Dondoni's C₁-homologationreaction sequence. The conversion of these synthons totwo different peptide mimetics – 2-hydroxy-1,3-ethyl-diamines and -hydroxy--amino-vinyl sulfones – hasbeen investigated. The successful transfer of thecomplex -amino acid homologation reactionsequence into solid-phase chemistry demonstrates thepotentials of the Boc-resin for synthesis of peptidomimetics.     

Space Videophotometric System for Recording Optical Radiations in the Earth Atmosphere

This paper describes the VFS-3M videophotometric system designed for automatic remote recording of images and parameters of optical radiations following lightning discharges from aboard the Russian segment of the International space station. The characteristics of the system and the possibilities of recording such types of radiation as Red Sprites and Blue Jets are given.     

Precision measurement of the half-life and the decay branches of 62Ga

In an experiment performed at the Accelerator Laboratory of the University of Jyväskylä, the -decay half-life of ⁶²Ga has been studied with high precision using the IGISOL technique. A half-life of T_1/2 = 116.09(17) ms was measured. Using - coincidences, the intensity of the 954 keV transition and an upper limit of the -decay feeding of the 0⁺₂ state have been extracted. The present experimental results are compared to previous measurements and their impact on our understanding of the weak interaction is discussed.     

The Impact of the Phenyl Spacer on the Electronic Structure and Spectra of Porphyrin Dimers

Quantum-chemical investigation of the electronic structure and properties of the excited states of porphyrin dimers, in which monomeric subunits are linked by the phenyl spacer, is performed by semiempirical methods. The molecular orbitals of the monomeric subunits are shown to interact with each other via molecular orbitals of the phenyl ring. Comparison of the experimental absorption data and quantum-chemical calculations of electronic absorption spectra for different conformations of Zn-tetraphenylporphyrin dimer is performed and the main conformation of the dimer in a solution at 295 K, in which the planes of tetrapyrrole macrocycles are located at an angle of about 60°, is substantiated.     

Influence of Close‐Range Dipole‐Dipole Interactions on the Real Part of the Susceptibility of a Dense Resonance Medium

Based on a solution of the stationary modified Bloch equations, an investigation is made of the influence of the effect of internal optical bistability (IOB) on the behavior of the refractive index of a dense resonance medium as a function of the constant b of closerange dipoledipole interactions, frequency detuning, and the intensity of optical radiation. The conditions of existence of the IOB effect of the system dense resonance medium + optical radiation are found and the dynamics of the loop width of the hysteresis dependence of the population difference of the resonance levels of the medium on the characteristics of the system is traced. The domains of the parameters are determined in which the effects of selffocusing and selfdefocusing of the radiation propagating in a dense resonance medium can take place.     

Electron Energy Loss Spectra of the Organic Complexes of Europium

In the electron energy loss spectra (EELS) of the organic europium complexes Eu³⁺ (BTFA)₃TPPO and Eu³⁺(BrBTFA)₃TPPO in a gas phase obtained on excitation by monokinetic beams of electrons of different energies in the range 12–50 eV, we have identified the bands associated with the electron transitions S ₀–S ₁, S ₀–S ₂, and S ₀–S ₃. The connection of these transitions with the structural groups of the complexes is established. The addition of the bromine atom to the phenyl ring of diketonate leads to the rise in the relative intensity of the S ₀–S ₂ band. The singlettriplet transitions manifest themselves in the region 2.5–3.2 eV and contribute to the S ₀–S ₂ band of the electron energy loss spectra.     

Calculation of the Tautomeric Properties of 3‐Formyl‐Tetrinic Acid by the ab initio and DFT Methods

We have carried out a nonempirical quantumchemical calculation with full optimization of the geometry of all theoretically possible tautomeric forms of 3formyltetrinic acid (FTRA) according to the Møller–Plesset secondorder perturbation theory with the use of a 6–31G(d) double zeta basis set. The correlation corrections to the total energy of molecules for optimized geometric configurations were calculated in the 631G(d,p) basis. All the possible tautomeric forms of FTRA and the harmonic vibrational frequencies were also calculated within the density functional theory (DFT) with the use of the Perdew–Burke–Ernzerhof (PBE) functional in a threeexponent basis. It is shown that FTRA in vapors (in the perfect gas approximation) exists in the form of a mixture of three enol forms, among which two exoforms predominate. The frequencies and forms of normal vibrations for each cisenol tautomer in the region of vibrations of ketogroups and double bonds differ widely, which permits identification of the tautomers present in the mixture. The possible mechanisms of enolenol transformations of 3acyltetrinic acids are discussed.     

Beta-decay studies of neutron-rich Sc- Cr nuclei

The neutron-rich nuclei ₂₁^{57, 58}Sc, ₂₂^58-60Ti, ₂₃^60-63V, ₂₄^62-66Cr have been produced at Ganil via interactions of a 61.8A MeV ⁷⁶Ge beam with a ⁵⁸Ni target. Beta-decay studies have been performed using combined - and -ray spectroscopy. Half-lives have been determined and -decay schemes are proposed for ⁵⁸Ti, ⁶¹V and ⁶²Cr. From these studies, new hints for the existence of -decaying isomers in ⁶⁰V and in ⁶²Mn are provided. These results are compared to shell model calculations. The role of the f_7/2- f_5/2 proton-neutron interaction is examined through its influence on the lifetime values.     

Modeling and Simulation of Saturation Gain of IR Integrated Photonic Amplifiers

IR integrated photonic amplifiers at 1.55m operation will have good foreground in optical phasedarray radars for splitters and signal processing. The saturation gain characteristics of IR integrated photonic waveguide amplifiers (taken Er³⁺Yb³⁺ co-doped phosphate glass waveguide amplifiers as an example) are studied theoretically. For the homemade laser glass materials the calculated saturation intensities are 2.22kw /cm² for signal and 10.15kw/cm² for pump. The effects of absorption saturation of signal and pump lights on the gain of amplifiers are discussed.     

Luminescence of Trivalent Thulium Ions in Complexes with β-Diketones

It is established that a fairly intense luminescence of thulium can be observed in solutions (suspensions of residues) of different-ligand complexes that include -diketone and an organic base. The luminescence characteristics of Tm compounds are determined in the series of acetyl acetone derivatives with different substituents, including fluorinated ones, of different length and structure. A relationship is found between I, , and of the Tm complexes and the character of the substituents in a -diketone molecule.     

Gravitational Waves in Matter

The theory of gravitational waves in matter is given. This covers the questions of constitutive relation, number of independent polarizations, index of refraction, reflection and refraction at an interface, etc. The theory parallels the familiar optics of electromagnetic waves in material media, but there are some striking differences. The use of the Campbell-Morgan formalism in which the gauge-invariant tidal force dyads E and B rather than the gauge-dependent metric perturbations are the unknowns is essential. The main justification of the theory at the moment is as a theoretical exercise worth doing. The assumption: size L of the medium gravitational wave length (infinite medium) rules out application to the already well-understood detection problem, but there may be an application to gravitational wave propagation through molecular gas clouds of galactic or inter-galactic size.     

Linear Theory of the Beam-Wave Interaction in the Arbitrary Cylindrical Cerenkov Device

The hot dispersion equation in Cerenkov devices has been derived and analyzed numerically using the self-consistent linear theory. In principle, the linear analysis can be applied to efficiently calculating all kinds of beam-wave interaction in various Cerenkov devices composed of axisymmetric slow-wave structures (SWS) with arbitrary periodic profile. Then the results for Cerenkov devices with three typical SWS profiles are presented.     

Absorption Spectra of Pentamers of Tetrapyrrole Compounds in Aqueous Solutions

Pentamers of two types have been obtained in aqueous solutions containing mixtures of two tetrapyrrole compounds, in whose molecules there are positively or negatively charged peripheral groups. The pentamers of one type include one molecule of mesotetra(4Nmethylpyridyl) porphin (TMPP) and four molecules of the complex of mesomono(nsulfophenyl)etioporphyrin II with palladium (PdSPhEP), and the pentamers of the other type include one molecule of sulfonated phthalocyanine (PCS) and four molecules of TMPP. The absorption bands of the pentamers are broadened and shifted toward longer wavelengths in comparison with the bands obtained as a result of the addition of the spectra of the monomers. It seems that the changes in the absorption spectra are first of all due to the change in the interaction of the molecules of the pigments with the molecules of the surrounding in formation of associates and due to the influence of the resonance dipoledipole interaction between the molecules in the associates. The influence of the intermolecular photoinduced charge transfer is also possible (it is most probable for the associates with PCS). We have revealed an effective quenching of the fluorescence of PCS and TMPP solutions upon heteroassociation.     

The maximum entropy principle as a consequence of the principle of Laplace

The maximum entropy principle states that the probability distribution which best represents our information is the one which maximizes the entropy with the given evidence as constraints. We prove that this principle is implied from the Laplace principle of equiprobabilities applied to the setS of allN-term sequences of results which are compatible with the given evidence. We generalize to the information gain method of Kullback.