Method of identification of the spectra of multicomponent stochastic natural and technogenic mixtures

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 3, pp. 369–374, September, 1991.     

Solid-state NMR spectroscopy of paramagnetic metallocenes

The paramagnetic metallocenes and decamethylmetallocenes (C(5)H(5))(2)M and (C(5)Me(5))(2)M with M=V (S=3/2), Mn (S=5/2 or 1/2), Co (S=1/2), and Ni (S=1) were studied by (1)H and (13)C solid-state MAS NMR spectroscopy. Near room temperature spinning sideband manifolds cover ranges of up to 1100 and 3500 ppm, and isotropic signal shifts appear between -260 and 300 ppm and between -600 and 1640 ppm for (1)H and (13)C NMR spectra, respectively. The isotropic paramagnetic signal shifts, which are related to the spin densities in the s orbital of ligand atoms, were discussed. A Herzfeld--Berger spinning sideband analysis of the ring carbon signals yielded the principal values of the paramagnetic shift tensors, and for metallocenes with a small g-factor anisotropy the electron spin density in the ligand pi system was determined from the chemical shift anisotropy. The unusual features of the (1)H and (13)C solid-state NMR spectra of manganocene were related to its chain structure while temperature-dependent (1)H MAS NMR studies reflected antiferromagnetic interaction between the spin centers.     

The photoluminescence excitation spectra of multicomponent media

With no restrictions on the value of optical density, we derive an equation that describes the photoluminescence excitation spectra of separate components with overlapping absorption bands in a multicomponent medium. Based on the equation obtained, we propose methods for measuring the ratios of absorption optical densities of the components and quantum yields of their luminescence. The applicability of the proposed methods is demonstrated by measuring the characteristics of coumarin and porphyrin dissolved in different proportions in ethanol. We have also measured the quantum yield and luminescence decay time of the radiationinduced color centers F ₃ ⁺ in the lithium fluoride crystal and calculated probabilities of radiative and nonradiative transitions from the first excited singlet state of these centers.     

Mechano-chemistry; diffusion in multicomponent compressible mixtures

In the present work we derive the volume continuity equation and demonstrate its use to define the volume frame of reference in the multicomponent, compressible systems. The volume velocity (material velocity) is a unique frame of reference for all internal forces and processes, e.g., the mass diffusion, heat flow, etc. No basic changes are required in the foundations of linear irreversible thermodynamics except recognizing the need to add volume to the usual list of extensive physical properties undergoing transport in every continuum. The volume fixed frame of reference allows the translation of the Newton’s discrete mass-point molecular mechanics into continuum mechanics and the use of the Cauchy linear momentum equation of fluid mechanics and Navier-Lamé equation of mechanics of solids.Our proposed modifications of Navier-Lamé and energy conservation equations are self-consistent with the literature for solid-phase continua dating back to the classical interdiffusion experiments of Kirkendall and their subsequent interpretation by Darken in terms of diffuse volume transport. We do show that the local diffusion processes do not change the centre of mass of the system and that the stress and viscosity depend only on the local volume velocity.     

NMR spectra of alkylphenols

Journal of Applied Spectroscopy -     

Frontiers in 2D NMR of paramagnetic metalloproteins

The possibilities and the limitations of 2D NMR for the structural characterization of paramagnetic metalloproteins are reviewed. We survey the general strategies for 2D¹H NMR investigations of hyperfine shifted signals. Careful adaptation of classical 2D NMR experiments to fast relaxing systems results in the detection of previously not observed scalar and dipolar connectivities, thus leading to the specific assignment of selected resonances. The approach is of general applicability for paramagnetic metalloproteins. We report here on the application of the application of the method to an iron sulfur protein and a heme protein. In both cases specific assignment of several hyperfine shifted signals, corresponding to active site protons, were obtained; this allowed significant insight into the structure-function relationships of these metalloproteins.     

Evaluating virial coefficients for multicomponent mixtures: hard sphere mixtures and flexible chains

A new algorithm to compute the virial coefficients of multicomponent mixtures is proposed. The number of graphs that must be evaluated increases dramatically in a multicomponent mixture so that it becomes difficult to enumerate and compute all possible graphs. However, once all of them are known and evaluated, the virial coefficient of the mixture can be evaluated for any composition. If one is interested in the virial coefficient of a mixture of a certain composition, then a simpler approach can be followed. Starting from the graphs of a pure fluid, we assign a random chemical identity to each of the molecules of the graph. The probability of assigning a given chemical identity is taken from the composition of the mixture. In this way composition is treated as a random variable within the Monte Carlo procedure which determines the virial coefficient. The algorithm is checked by comparison with the virial coefficients of binary hard spheres mixtures which are well known. Good agreement is found. The procedure is then extended to multicomponent mixtures of hard spheres. Finally the procedure is applied to the determination of the virial coefficients of a flexible molecule. For flexible molecules the possible configurations of the molecules are treated as different components of the mixture. In this way we present what appears to be the first determination of the third and fourth virial coefficients of polymers in the continuum.     

New methodologies for computer simulation of paramagnetic resonance spectra

A new software package, SOPHE, for computer simulation of randomly oriented EPR spectra is described. A central feature of SOPHE is that all interactions associated with the electronic spins and major nuclear spins are treated equally through full matrix diagonalisation. In order to make this approach “workable”, several new methodologies have been developed, which include a novel partition scheme for partitioning the unit sphere, an interpolation scheme involving a combination of cubic spline and linear interpolations, and a segmentation method for handling multiple resonances between a given pair of energy levels. As a result, these new developments have led to a significant reduction in computational times. The SOPHE package can be used to simulate a variety of EPR spectra arising from isotropic organic radicals to complex coupled spin systems. It also incorporates the major linewidth models developed previously for the simulation of randomly oriented EPR spectra from magnetically isolated spin systems.     

Thermodynamic properties of multicomponent mixtures near the liquid-vapor critical point

A new method has been proposed to describe the physical properties of multicomponent mixtures near their critical points. The method is based on the transition from the experimental thermodynamic variables to scaling fields, is applicable to a mixture with any number of the components, and is, thus, universal. For the previously studied methane-propane-pentane mixture, it has been shown that the anomalies of the specific heat at a constant volume and derivative (?P/?T)_ρ,x can be quantitatively described in this approach in a wide vicinity of a critical point, including noncritical isochores.