1H NMR study of self-association of actinomycin D in an aqueous solution

This paper presents the results of a proton magnetic resonance study (500 MHz) of self-association of actinomycin D (AMD) antibiotic in an aqueous solution. The equailibrium constants and thermo-dynamic parameters (ΔH, ΔS) of molecular association as well as the limiting values of proton chemical shifts of associate molecules were determined from the concentration and temperature dependences of¹H NMR chemical shifts of AMD. The results were analyzed using dimeric and infinite-dimensional cooperative models of molecular self-association. The value of the cooperativity parameter indicates that AMD self-association is anticooperative, i.e., formation of aggregates larger than dimers is energetically unfavorable. The values of induced proton chemical shifts were used to determine the most probable mutual orientation of chromophores in AMD structure. Sevastopol State Technical University. Berkbeck College, London University. Translated fromZhurnal Struktumoi Khimii, Vol. 36, No. 1, pp. 81–88, January–February, 1995. Translated by L. Smolina     

A new series of mesogenic derivatives of pyrimidine-substituted

Analogs of known mesogenic 2,5-diarylpyrimidines, 5-[p-alkyl(alkoxy)phenyl]-2-(o-hydroxy-p-alkoxyphenyl)pyrimidines (I), have been synthesized that have a wider mesogenic phase temperature range. Pyrimidines I show smectic C and A phases but not the nematic phase.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 377–381, March, 1992.     

Investigation of the influence of the substitutes on the intensity of the absorption band of some polymethine dyes

The dependence of the long-wave absorption-band intensity on the structural peculiarities of a number of polymethine dyes has been investigated using the PPP method. It has been shown that the analyzed dependence is caused by the electronic properties of the substitutes.     

Theoretical investigation of mechanism of antioxidant action of sterically hindered phenols

Heats of reaction describing the mechanism of antioxidant action of phenols in polyolefins have been calculated by the MNDO quantum-chemical method. It has been shown that reactions producing substituted quinones will proceed the most readily. The influence of substituents on the heat of reaction has been investigated.Vilnius University. Materials, Tambov. Translated from Teoreticheskaya i 8ksperimentaI'naya Khimiya, Vol. 27, No. 2, pp. 165–170, March–April, 1991. Original article submitted February 16, 1990.     

Nitro-substituted 2-phenyl- and 2-(2-tosylaminophenyl)-4H-3,1-benzoxazin-4-one

Nitro-substituted 2-phenyl- and 2-(2-tosylaminophenyl)-4H-3,1-benzoxazin-4-ones were synthesized. The UV, IR, and luminescence spectra were studied. The position of the nitro group affects the strength of the intramolecular hydrogen bond (IHB). The luminescence properties of nitro-substituted 2-(2-tosylaminophenyl)-4H-3,1-benzoxazin-4-ones are associated with the strength of the IHB. The luminescence maximum is shifted to the short-wave region as the IHB becomes stronger.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 616–621, May, 1972.     

Disparity between the transient hyperfine fields for Pt and Os in Fe; an electron vacancy sharing interpretation

Precessions of the 2 ₁ ⁺ states in¹⁹⁸Pt and¹⁹²Os have been measured in the enhanced transient hyperfine magnetic field acting on these nuclei as they recoiled through thin polarized cobalt foils. Two separate targets consisting of contiguous layers of¹⁹⁸Pt and¹⁹²Os electrodeposited on ～1 μm and ～4 μm Co foils were employed. The levels of interest were Coulomb excited by 80 MeV³²S and 220 MeV⁵⁸Ni beams and the precessions of the 2 ₁ ⁺ →0 ₁ ⁺ γ-ray angular distributions in both nuclides were measured simultaneously. The results of these studies are compared with recently reported similar studies in which ions of¹⁸⁸Os and¹⁹⁴Pt recoiled through thin polarized Fe foils. It is concluded that (i) the transient field acting on Pt in Fe is singularly anomalous, and (ii) the recent contention that the g-factors of the 2 ₁ ⁺ states in the event Pt isotopes may be substantially lower than had been reported in the literature cannot be sustained. This transient field discontinuity is examined in terms of possible molecular orbital electron vacancy sharing between Pt and Fe.     

Effect of membrane composition on the selectivity of electrodes selective for alkylammonium ions with different degrees of substitution

The effect of the nature of an ion exchanger and a plasticizer on the selectivity of ion-selective electrodes for cations of primary-tertiary amines and quaternary ammonium bases was studied. The increments of methylene and ionic groups in the logarithms of selectivity coefficients were calculated. It was demonstrated that the effect of the membrane composition on the selectivity coefficient was governed by changes in the increments of corresponding groups. The maximum change in selectivity, which may attain three orders of magnitude, was observed for pairs of primary-quaternary alkylammonium cations. It was shown that the effect of the nature of the cation exchanger on selectivity coefficients was comparable with that of the plasticizer nature.     

An expansion of Hartree-Fock and correlation energies,relativistic corrections and the dipole matrix element in the powers of of 1/Z

Feynman diagrammatic technique was used for the calculation of Hartree-Fock and correlation energies, relativistic corrections, dipole matrix element. The whole energy of atomic system was defined as a polen-electron Green function. Breit operator was used for the calculation of relativistic corrections. The Feynman diagrammatic technique was developed for 〈H_B>. Analytical expressions for the contributions from diagrams were received. The calculations were carried out for the terms of such configurations as 1s² 2sⁿ¹ 2pⁿ² (2 ≧n₁≧ 0, 6≧ n₂ ≧ 0). Numerical results are presented for the energies of the terms in the form $$E = E_0 Z^2 + \Delta {\rm E}_2 + \frac{1}{Z}\Delta {\rm E}_3 + \frac{{\alpha ^2 }}{4}(E_0^r + \Delta {\rm E}_1^r Z^3 )$$ and for fine structure of the terms in the form $$\begin{gathered} \left\langle {1s^2 2s^{n_1 } 2p^{n_2 } LSJ|H_B |1s^2 2s^{n_1 \prime } 2p^{n_2 \prime } L\prime S\prime J} \right\rangle = \hfill \\ = ( - 1)^{\alpha + S\prime + J} \left\{ {\begin{array}{*{20}c} {L S J} \\ {S\prime L\prime 1} \\ \end{array} } \right\}\frac{{\alpha ^2 }}{4}(Z - A)^3 [E^{(0)} (Z - B) + \varepsilon _{co} ] + \hfill \\ + ( - 1)^{L + S\prime + J} \left\{ {\begin{array}{*{20}c} {L S J} \\ {S\prime L\prime 2} \\ \end{array} } \right\}\frac{{\alpha ^2 }}{4}(Z - A)^3 \varepsilon _{cc} . \hfill \\ \end{gathered} $$ Dipole matrix elements are necessary for calculations of oscillator strengths and transition probabilities. For dipole matrix elements two members of expansion by 1/Z have been obtained. Numerical results were presented in the form P(a,a′) = a/Z(1+τ/Z).     

Polarization-luminescence studies of the structure and molecular dynamics of smectic and nematic mesophases

The liquid crystal 50B7A in the smectic A and nematic phases was studied by the method of polarization luminescence. The order parameters P₂ and P₄ were determined from the experimental values of the luminescence spectrum both neglecting and taking into account relaxation processes in the liquid crystal. The orientational distribution function of the molecules in the ground and excited states are constructed. The orientational relaxation time (10^–9 sec for the nematic and smectic A phases) is calculated. The results obtained are compared with calculation of the rotational relaxation time determined from the coefficient of diffusion for the related compound EBBA.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 39–43, August, 1987.     

Structure of aminonitrones and electronic effect of substituents on their acid-base properties

A series of para-substituted aromatic aminonitrones p-RC₆H₄C(NH₂)=N⁺(Me)O^– (R = NMe₂, H, Br, Cl, CF₃) have been prepared. Acidity constants of the conjugate acids RC₆H₄C(NH₂)N⁺(Me)OH at 25°C in a EtOH–H₂O mixture (5: 95) have been determined by potentiometric titration. A linear correlation between log (k_R/k_H) and σ_para values has been revealed, and a ρ²⁹⁸(σ_para) parameter has been determined as of 0.635.