Cl nuclear quadrupole resonance studies of molecular motions of ClO3 and water diffusion in Ca(ClO3)2·2H2O

A ³⁵Cl nuclear quadrupole resonance (³⁵Cl-NQR) investigation of polycrystalline Ca(ClO₃)₂·2H₂O is described. The ³⁵Cl-NQR frequencies (ν_Q) for two resonance lines (ν_Q1 and ν_Q2), the spin lattice relaxation time (T_1Q) for ν_Q2 only and the line width δν_Q2 were measured in the temperature range 292–345 K, except for the frequency measured up to 455 K. The observed decrease in the resonance frequencies with increasing temperature permitted the determination of the frequencies of librations of the ClO₃⁻ ion about two axes perpendicular to the three-fold axis of the ion mainly responsible for this effect. The temperature dependence of the relaxation time T_1Q proved the occurrence of water diffusion and hindered rotation of ClO₃⁻ ions. The activation energies of these two molecular motions were determined, and their effect on the electric field gradient at the site of a chlorine nucleus was discussed. Temperature measurements of the line width δν_Q2 confirmed the conclusions drawn from the analysis of T_1Q(T).     

Dielectric study of dipolar association in dilute solutions of nitrobenzene in benzene

The correlation factors R_p and R_s are determined for the dielectric polarization and the non-linear dielectric effect in dilute solutions of nitrobenzene in benzene. Assuming dipole association of the nitrobenzene molecules to be restricted to dimerization, we determined the concentration x₂ of dimers, their dipole moment μ_dim, and the equilibrium constant K_x and Gibbs energy ΔG of the dimerization process.     

Consequence of hydrogen atom abstraction from 5’-hydroxyl group of 2’-deoxyadenosine. Theoretical quantum mechanics study

Reactive oxygen species (ROS) may generate different nucleoside/nucleotide radicals in a cell environment. In this study, the possibility of cyclic-2’-deoxyadenosines formation by a rearrangement of their free radicals was investigated. It seems that for cyclic-nucleosides formation, adoption of an O4’-exo conformation by the sugar moiety is necessary. However, this is the energetically unfavoured form of the 2-deoxyribose ring. Moreover, the creation of a O5’, C8 bond in purine deoxy-nucleosides/nucleotides leads to the termination of the DNA elongation process.      

Electronic structure and biological activity of chosen DDT-type insecticides studied by 35Cl-NQR

A correlation between the electronic structure and biological activity of chosen dichlorodiphenyltrichloroethane (DDT)-type insecticides: 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane, 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene, 2,2-bis(4-chlorophenyl)ethanoic acid and 4,4'-dichlorobenzophenone (used in agriculture) has been analysed on the basis of the (35)Cl-nuclear quadrupole resonance (NQR) spectroscopy. The (35)Cl-NQR resonance frequencies measured at 77 K have been correlated with the lethal dose (LD(50)) parameter that characterises the biological activity of these insecticides.     

Optimality of Euler-integral information for solving a scalar autonomous ode

We study the minimum error of algorithms for solving a scalar autonomous ODE. Information is defined asn evaluations of functionals of the right hand sidef. These functionals can be linear or nonlinear and continuous. Euler-integral information is defined and its optimality is proved in a class of regularf.     

Generalization of two theorems of M. I. Kadets concerning the indefinite integral of abstract almost periodic functions

Conditions are obtained for the almost periodicity (or almost automorphy) of an abstract functionf (t) on a group G satisfying the difference equationsf (t)–f(t)=g(t), where, for each G, the function (t) is almost periodic (or almost automorphic) (the difference problem). The investigation of the almost periodicity of the integral of an almost periodic function (t) on the real line R is reduced to a study of the difference problem.Translated from Matematicheskie Zametki, Vol. 9, No. 3, pp. 311–321, March, 1971.In conclusion I wish to thank V. V. Zhikov for suggesting this problem, and B. M. Levitan and E. A. Gorin for their discussion of the work.     

Fluorescence quenching of polystyrene by oxygen

The fluorescence quenching of polystyrene by oxygen at room temperature was investigated. The diffusion coefficient of oxygen in polystyrene films was taken as 3.1 × 10^?7 cm²/sec; the energy migration coefficient of polystyrene in the excited singlet state was estimated as 6 × 10^?6 cm²/sec.     

Brownian dynamics simulation of protein association

Summary The Brownian Dynamics (BD) method is applied to study the diffusive dynamics and interaction of two proteins, cytochrome c (CYTC) and cytochrome c peroxidase (CYP). We examine the role of protein electrostatic charge distribution in the facilitation of protein-protein docking prior to the electron transfer step, assessing the influence of individual charged amino acid residues. Accurate interaction potentials are computed by iterating the linearized Poisson-Boltzmann (PB) equation around the larger protein CYP. The low dielectric constant inside proteins, electrolyte screening effects and irregular protein surface topography are taken into account. We observe a large ensemble of electrostatically stable encounter complexes seemingly with acceptable geometric requirements for electron transfer rather than a single dominant complex. Stabilities of the large variety of docking complexes are rationalized in terms of generalized charged residue complementarities. However, it is found that the electrostatic interactions giving rise to complex stabilities are somewhat nonspecific in nature. A large series of additional simulations are performed in which individual charged residues on CYTC have been chemically modified. Resulting perturbations of the association rate are significant and qualitatively similar to results observed in comparable kinetics experiments. We therefore demonstrate the potential of the Brownian dynamics method to estimate the effects of site-directed mutagenesis on protein-protein and protein-ligand diffusional association rates.     

Optimal adaptive solution of initial-value problems with unknown singularities

The optimal solution of initial-value problems in ODEs is well studied for smooth right-hand side functions. Much less is known about the optimality of algorithms for singular problems. In this paper, we study the (worst case) solution of scalar problems with a right-hand side function having r   continuous bounded derivatives in R$\mathbf{R}$, except for an unknown singular point. We establish the minimal worst case error for such problems (which depends on r similarly as in the smooth case), and define optimal adaptive algorithms. The crucial point is locating an unknown singularity of the solution by properly adapting the grid. We also study lower bounds on the error of an algorithm for classes of singular problems. In the case of a single singularity with nonadaptive information, or in the case of two or more singularities, the error of any algorithm is shown to be independent of r.     

An Efficient Synthesis of Racemic and Optically Active Telluromethionine

A direct and efficient route for the construction of racemic and optically active L-telluromethionine (L-Te-Met) starting from the readily available hydrochloride salt of α-amino-γ-butyrolactone and lithium methyltellurolate is described. The reaction has been successfully scaled up to afford gram quantities of L-Te-Met in 75–80% yield.