Calculation of Normal Vibrations of Chlorin by the Method of Density Functionals

Using the DFT/B3LYP method with a 6-31G(d) basis set, the structure, normal vibration frequencies, and the absolute band intensities in the IR spectra of the chlorin molecule and its four symmetric isotopomers have been calculated. Scaling of the force field by the Pulay method in independent and natural coordinates has been carried out. A method for obtaining effective force fields without using experimental data on the fundamental vibration frequencies is proposed. By comparing the vibration modes and constructing special matrices, complete assignment of the fundamental frequencies of porphin and chlorin has been carried out. It has been shown that the majority of porphin macroring vibrations upon pyrrolenine ring hydrogenation are frequency-characteristic and only 12 vibrations change considerably. A frequency correlation with regard for the mode transition between chlorin and all its isotopomers under consideration has been established. Comparative analysis of the force fields of porphin and chlorin in dependent natural coordinates has revealed the unique nonlocal character of the change in force constants of the macroring upon hydrogenation of one pyrrolenine ring. Modeling of the IR spectra of chlorin and its isotopomers has been performed. Assignment and interpretation of the normal vibrations of the molecules under consideration have been carried out.     

Density-Functional Theory Calculations of Normal Modes and Raman Intensities for Tetraazaporphin

The structure, harmonic frequencies, and nonresonance Raman intensities for porphin, tetraazaporphin (TAP), and three of its isotopomers are calculated by the density-functional theory of B3LYP/6-31G(d). Scaling of force constants for porphin in nonredundant natural coordinates is performed. The scaling factors obtained were used to predict the force field and normal modes of TAP and three of its isotopomers. Two alternative methods are used to carry out reliable assignment of the TAP frequencies: wavenumber-linear scaling method and frequency-shift method. There is good agreement between the frequencies predicted within the framework of the three methods used. The conservativeness of the out-of-plane B _2g - and B _3g -modes for porphin and TAP is examined. The Raman spectrum for TAP is simulated. A refinement of the assignment of the experimental frequencies for TAP of even symmetry types on the basis of the calculations performed is made.     

Experimental and theoretical study of the IR spectrum of 4-amyloxy-4′-cyanobiphenyl

The IR absorption spectrum of polycrystalline 4-amyloxy-4′-cyanobiphenyl (5OCB) is measured in a KBr pellet over the range 400–4000 cm^?1. The structure of the molecule and the frequencies and intensities of the bands in the spectrum are calculated in the approximation of the B3LYP hybrid density functional with the 6-31G(d) and 6-31+G(d) basis sets. With the method of linear scaling of frequencies, 39 bands of the experimental IR spectrum are assigned. On the basis of calculations for related compounds, the vibrations belonging to the substituents and the biphenyl fragment are ascertained. It is shown that the IR absorption spectra of polycrystalline 4-hydroxypropyl-4′-cyanobiphenyl and 5OCB are almost identical and differ by the occurrence of three bands associated with vibrations localized on the oxyamyl radical.     

Mutual coupling of elements in finite microstrip antennas

The mutual coupling of the radiating elements in microstrip antennas is studied using a rigorous electrodynamic approach in which the field singularities at the radiator edges are taken into account with analytic accuracy. A spectral method is employed in combination with a method of semi-inversion by extraction of the Green-function singularity. The degree of interaction of the elements of microstrip structures at the fundamental and higher current harmonicsis determined, and the applicability of various approximations is assessed.Radio-Astronomy Institute, Academy of Sciences of Ukraine. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 35, No. 8, pp. 688–701, August, 1992.     

Dynamics of a polymer chain in an array of obstacles

On the basis of the model “polymer chain in an array of obstacles” the influence of the topology effects on the dynamics of concentrated polymer systems is investigated theoretically. The 1/z-expansion (where z is the coordinational number of the lattice of obstacles) is proposed for this problem. By means of this expansion the diffusion coefficient of a linear unclosed polymer chain is calculated. The equilibrium properties of linear closed chain (i.e. ring) unentangled with either of the edges of the lattice are investigated in detail. In particular, it is shown that the diffusion coefficient D of the center of mass of closed chain consisting of N links is proportional to N^−5/2.     

Vibrational spectra and force field of azacyclic compounds. I. Pyrrole

For the molecules of pyrrole and its symmetric deuterated derivatives, vibrational spectra have been analyzed, and the force field has been defined in natural coordinates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 29, No. 5, pp. 651–655, May, 1993.     

Intracavity laser polarization spectrometer for biomolecule traces

A polarization variant of an intracavity laser spectrometer based on the competition of beams in an argon ion laser, radiating a number of narrow lines in the 275 to 529 nm spectral range, is proposed and described for the spectral analysis of liquid samples, having broad absorption bands, mainly biomolecules in solutions. By careful optimization of the operating conditions, a procedure has been established that results in a minimal measurable absorbance decreased up to 10(-5) units of optical density. The examined spectrometer provides a wide dynamic range of analysis. A determination of trace contents of amino acids in methanol were carried out.     

Luminescence of the pyrene/N,N-diethylaniline triplet exciplex in methanol at room temperature

Fluorescence, whose spectral and magnetic properties permit its assignment to the luminescence of a triplex exciplex, has been discovered at times 3 sec after photoexcitation in the luminescence spectrum of the pyrene+N,N-diethylaniline system in methanol at 600 nm by the method of nanosecond stroboscopic fluorometry.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 25, No. 5, pp. 623–626, September–October, 1989.     

Protein and Dye Adsorption on Poly(ethylene terephthalate) Nucleopore Membranes Modified with Polymers

Adsorption of basic, neutral, and acidic proteins on poly(ethylene terephthalate) nucleopore membranes was studied as a function of solution pH. Higher adsorption values were observed for basic and neutral proteins and lower, for acidic proteins. The value of pH corresponding to maximal adsorption was somewhat lower than the isoelectric points of proteins, thus suggesting that the adsorption was governed by a combination of ionic and hydrophobic interactions between proteins and the membrane surface. Proteins were adsorbed in an associated form. Membrane surface was modified with poly(ethylene imine) and poly(ethylene glycol). Combined modification of the membranes with these polymers was found to substantially decrease the adsorption of basic and neutral proteins, as well as basic dye and to slightly increase the adsorption of acidic proteins. The modifying coating had a high hydrolytic stability.