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.     

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.     

Infrared Spectroscopic Study of N,N‐Dimethylthioformamide Complexes of the Hofmann Type

Four new Hofmanntype complexes, M(DMTF)₂Ni(CN)₄, (where DMTF is dimethylthioformamide, M=Mn, Cd, Co, or Ni) were synthesized and their structure was determined by an elemental analysis and infrared spectroscopy. The IR spectra of DMTF and its nickel tetracyanine complexes with Mn(II), Cd(II), Co(II), and Ni(II) have been investigated within the range 4000–400 cm^–1. The frequency shifts in the metal complexes agree with the assignment of the CS and CN frequencies. The complexes consist of infinite planar polymer layers of |MNi(CN)₄|. Ndimethylthioformamide is coordinated to this layer from above and below; it is a monodentate ligand and is Sbonded through the metal atom in these complexes.     

IR Spectra and Structure of Immunoactive 8–Azasteroids in Model Compounds

The IR spectra of biologically active molecules of 8-azasteroids and model compounds in the region of C=O, C=C, C--N, and C--H vibrations (1800–1400 cm^–1) have been studied in detail. The structure of compounds containing isostructural and isoelectronic --acyl----aminovinylcarbonyl and --acyl----alkoxyvinylcarbonyl fragments have been analyzed. Interpretation of the structure of the IR spectra and of the specificity of the manifestation of the vibrational modes under consideration in the molecules of a particular class of 8-azasteroids is given. The electronic structure of the molecules under investigation complies with the model of mesomeric tautomerism of the aminovinyldicarbonyl fragment.     

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.     

Analysis of the Tautomeric Properties of Substituted 3-Acryloyltetrahydrofuran-2,4-Dione According to the Data of IR Spectra and Ab Initio Quantum Chemical Calculations

The tautomerism and spectral properties of 3-[3-(4-methoxycarbonylphenyl-acryloyl]tetrahydrofuran-2,4-dione (MCPATD) have been investigated by the methods of nonempirical and semiempirical quantum chemistry (nonempirical calculations by the Möller–Plesset theory of 2nd-order perturbations, calculations by the AM1 and PM3 semiempirical methods), as well as by IR and ¹H NMR spectroscopy. It has been shown that the presence of an additional chain of conjugation in the side chain of MCPATD substantially changes its tautomeric composition and spectral properties as compared to 3-formyl- and 3-acetyltetrahydrofuran-2,4-diones. The frequencies and forms of normal vibrations calculated for each cis-enolic tautomer differ substantially within the region of vibrations of keto groups and double bonds, which makes it possible to identify the tautomers present in the mixture. It is found that in CHCl₃ solutions MCPATD exists as an equilibrium mixture of its exoenolic forms. The possible mechanisms underlying the enol-enolic conversions of MCPATD are discussed.     

The Dependence of the Luminescence Intensity of Lanthanide Complexes with β-Diketones on the Ligand Form

The influence of -diketone forms on the luminescence intensity of lanthanide compounds in a series of ligands, acetylacetone (trifluoroacetylacetone, benzoylacetone)—their unsaturated analogues (monomeric form)—copolymers of the latter with styrene (methylmethacrylate), was studied. Lanthanides in compounds with copolymers have been established to demonstrate the brightest luminescence. It was found that its intensity depends not only on the character of the substituent (CH₃, CF₃, C₆H₅) in the -diketone molecule, but also on the distance between the -diketone fragments in the copolymer. Reasons explaining the high intensity of luminescence in lanthanide–copolymer compounds are considered.     

Photometric and fluorimetric study of the acid-base behavior of 2,2′-diquinolyl and 2,2′,2″-terpyridyl

A photometric and fluorimetric study of the acid-base behavior of 2,2-diquinolyl and 2,2,2-terpyridyl was performed. In sulfuric acid medium, the doubly charged 2,2-diquinolynium ion undergoes the first dissociation atH ₀=0.20±0.09, as determined by fluorimetry (_ex=336 nm, _em=424 nm). Photometric titration is less accurate because of the overlapping of the absorption spectra. The second dissociation constant of 2,2-diquinolyl was determined by fluorimetric titration (_ex=336 nm, _em=420 nm), obtaining a value of 3.67±0.03. The triply charged 2,2,2-terpyridyl molecule was found to undergo the first dissociation atH ₀=–7.17±0.04, as determined by fluorimetric titration (_ex=316 nm, _em=350 nm), in aqueous sulfuric acid medium. Photometric titration (=335 nm) was performed in the presence of 6.5% ethanol because of the low solubility of the compound in water. In this ethanolicwater medium, a value of the dissociation constant atH ₀=–7.39±0.03 was calculated. The second dissociation constant was determined to be 2.81±0.12 by photometric titration at 285 nm, and values of 4.03±0.26 and 4.16±0.20 were found for the third dissociation constant by photometric titrations at 320 and 295 nm, in 10% ethanol, in close agreement with previously reported values. The fluorimetric titration profile obtained by exciting at 274 nm and measuring the fluorescence emission at 350 nm, in the zone betweenH ₀=–3 and pH=10, is complicated by the several equilibria involved.     

Specific Features of Light Scattering in [N(CH3)4]2CuCl4 Crystals with an Incommensurable Phase

We present the results of investigation of the optical birefringence and intensity of the main light beam that passed through an [N(CH₃)₄]₂CuCl₄ crystal under the conditions of viscous interaction of the incommensurable structure with defects. A nonmonotonic temperature dependence of the basic signal is revealed. The observed temperature dependence of the intensity (in the form of irregular steps) is related to different periods of the incommensurable structure. In transitions between adjacent metastable states the periodicity of the incommensurable structure changes. It is shown that in transition regions for the central beam one observes an anomalous decrease in the light intensity due to the appearance of a perturbation lattice with the wave vector q.     

Analysis of the Structure of the Bands in the IR Spectrum of β-D Glucose by the Regularized Method of Deconvolution

Deconvolution of the IR absorption spectrum of -D glucose in the spectral range 1500–450 cm^–1 has been carried out. The results of the deconvolution were compared with the IR and Raman spectra recorded at room and low temperatures and with the data obtained by theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. It is shown that deconvolution of the IR spectra recorded at room temperature makes it possible to separate the bands observed experimentally only at a very low temperature of the sample and a number of components that were not resolved earlier. The number of bands separated on deconvolution of the IR spectra of -D glucose in the spectral range 1500–450 cm^–1 is more than twice the number of visible absorption maxima in the usual spectrum. The results of deconvolution of the IR spectrum of -D glucose are in good agreement with the data of theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. The existence of the factor-group (Davydov) splitting of a number of frequencies of the nondegenerate fundamental vibrations of molecules in a crystal cell has been revealed in the IR spectrum of -D glucose. It was concluded that the model of an isolated molecule is insufficient for detailed theoretical interpretation of the vibrational spectra of carbohydrates.     

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.     

Shearing apparatus for neutron scattering studies on fluids: Preliminary results for colloidal suspensions

In this paper we study the transient diffusion-limited A+B0, A₀ = B₀ annihilation via deterministic reaction-diffusion equations and via simulation of the stochastic many-particle problem. We show that the two approaches are not equivalent and that the deterministic expressions capture only part of the picture. A lower bound is derived for the density decay which indicates that the overall density follows the power law t^–x with = mm(d/4, 1). Hierarchical oscillations superimposed on the power-law decay are observed for reactions on Sierpinski gaskets.This work is dedicated to Prof. George H. Weiss.     

Calculation of Out‐of‐Plane Vibrations of a Porphin Molecule

Using the DFT/B3LYP method with the base set 631G^**, we carried out calculation of the frequencies of the normal vibrations of porphin and of its five isotopic types. Scaling of force constants for outofplane vibrations has been performed in independent natural coordinates. The symmetry coordinates are introduced and a force field for outof plane vibrations of a porphin molecule in independent coordinates of symmetry is obtained. A new correlation of the frequencies of vibrations in the type of the symmetry B _1u for the isotopic type of the d ₂ porphin molecule is suggested on the basis of discrete analysis of the distribution of a potential energy.     

O(N) vector model with twisted boundary conditions

Prompted by a recent article of Chakravarty, we reexamine theO(N) vector model with twisted boundary conditions ind dimensions in the various frameworks of the =d–2 expansion, the =4–d expansion, and the large-N expansion. These continuum models describe the physics below the critical temperatureT _c and nearT _c of a latticeO(N) spin model. We determine the effect of the twisting on finite-size scaling functions, for various geometries.On leave from G. Nadjakov Institute of Solid State Physics, 1784 Sofia, Bulgaria.     

Frequency Measurements of Optically Pumped Laser Emissions from the CHD2OH Methanol Isotope

A threelaser heterodyne system was used to measure the frequencies of eleven optically pumped laser emissions from CHD₂OH in the farinfrared (FIR) region. These frequencies, reported with fractional uncertainties of the order ± 2 × 10^–7, are for emissions ranging from 102.9 to 212.4 m. To our knowledge, these measurements are the first reported FIR laser frequencies for the CHD₂OH methanol isotope when used as an optically pumped laser medium.     

Special Features of the Correlation between the Uranium–Oxygen Interatomic Distances and the Frequencies of the Valence Vibrations of the UO2 2+ Group in Complex Compounds of Uranyl

We considered the factors due to which the dependences between the uranium–oxygen distances R ₀ and the frequencies of valence vibrations _as for complex compounds of uranyl are described by two independent expressions generally represented by equations of the type R ₀ = a + b_as ^–2/3 (b > 0) with the coefficients a and b differing in the regions R ₀ < 0.178 nm and R ₀ > 0.178 nm. It is shown that the reason is that there is a mutual effect of the ligands in the uranyl complex responsible for different partial contributions of the uranium orbitals and of the atoms of the first coordination sphere to the chemical bonding.     

Preparation, Luminescence Properties, and Application of Scintillators Based on Lu3Al5O12:Ce Single‐Crystal Films

The possibility of obtaining scintillators with a high effective atomic number of the element Z _ef based on Lu₃Al₅O₁₂:Ce³⁺ singlecrystal films (SCF) on doping with La³⁺ and Sc³⁺ ions on Y₃Al₅O₁₂ substrates has been investigated. It is established that the SCF of (LuLaY)₃Al₅O₁₂:Ce³⁺ (Z _ef = 58.9 and = 6.67 g/cm²) does not rank below those of Y₃Al₅O₁₂:Ce³⁺ (Z _ef = 29 and = 4.52 g/cm²) in the conversion efficiency of radiation at the band with _max = 515 nm. This allows their use as screens of xray images with a space resolution of 0.75–1.00 m. It is suggested that in the SCF of Lu₃Al₅O₁₂ the isoelectronic impurities of lanthanum and scandium form radiative recombination centers of the type La_Lu, Sc_Lu, and ScAl as well as the centers Lu as a consequence of the effect of replacement of some Lu³⁺ ions by the La³⁺ ions to octanodes of the garnet lattice. The low efficiency of Ce³⁺ radiation in the SCF of (LuSc)₃(AlSc)₅O₁₂:Ce is explained by substantial losses due to excitation of the recombination luminescence in the UV region of the centers formed by the isoelectronic impurities of scandium and to the possible existence of the channel of energy excitation dissipation related to the transitions between extrema of the allowed energy bands and activator levels.