Variation–iteration method for one-dimensional two-electron systems

A quantum chemical study of the two low-lying quartet states of seven model compound I iron–porphyrin complexes with varying axial ligands has been carried out using the INDO method. The varying axial ligands included in this study are five that are models for those in the intact enzymes: imidazole and imidazolate (model peroxidase HRP and CCP), CH₃CONH₂ (Gln175 mutant of CCP), PhO^?1 (catalase), CH₃S^?1 (P450), and two that have been used in biomimetics of these enzymes: Cl^?1 (hemin) and PhS^?1 (model P450s). The purpose of these studies was to determine the role of the axial ligands in determining (i) the relative energies of the two nearly degenerate quartet electronic states of compound I, involved either as an a_1u or a_2u porphyrin π cation radical and (ii) the electron and spin distributions in the a_1u and a_2u radical cations of compound I. For most of the model complexes, including both HRP-I and CAT-I, a moderate effect of the axial ligand on the relative energy of these two states was observed and the a_1u radical cation was found to be the ground state. The energy order of these two radical cations, however, was reversed in the P450-I model complexes, indicating an association of the unique property of the Fe?O bond breaking with an a_2u radical cation. The symmetry-allowed overlap between the Fe?O and 3a_2u orbitals may lower the activation energy for the Fe?O bond cleavage in P450-I. However, the calculated electronic and spin properties, including the unpaired spin and net charge on the oxygen and the Fe?O bond overlap density, important determinants of the reactivity of this complex in the ligand–Fe?O region, are very similar for all complexes and in both cation states. © 1992 John Wiley & Sons, Inc.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Flavin-protein interaction in bound glucose oxidase

Glucose oxidase was bound to Sepharose, Sephadex, gelatin, and dextran, yielding immobilized soluble and insoluble derivatives of the enzyme. The soluble preparations possessed higher enzymic activity than the analogous insoluble ones. The reversible dissociation process of the bound enzyme into apoenzyme and flavin adenine dinucleotide (FAD) was studied with the soluble and insoluble glucose oxidase in relation to enzymic activity and conformational changes as measured by circular dichroism and fluorescence methods. Bound apoenzyme was found to be more stable than the apoenzyme obtained from the unmodified glucose oxidase. The binding constant of FAD in bound glucose oxidase (K_diss≈10^-8M) calculated from fluorescent studies was lower than that of FAD in the native enzyme (K_diss10^-10M). The circular dichroism measurements indicated that dextran-bound glucose oxidase has a conformation similar to that of the native enzyme.     

Convexity preserving interpolation by algebraic curves and surfaces

The problem of interpolation by a convex curve to the vertices of a convex polygon is considered. A natural 1-parameter family ofC algebraic curves solving this problem is presented. This is extended to a solution, of a general Hermite-type problem, in, which the curve also interpolates to one or two prescribedtangents at any desired vertices of the polygon. The construction of these curves is a generalization of well known methods for generatingconic sections. Several properties of this family of algebraic curves are discussed. In addition, the method is generalized to convexC interpolation of strictly convex data sets inR ³ by algebraicsurfaces.     

Magnetic field value in the weak energy release region of the solar corona

Spectrographic data from observations of the polarized weak steplike (with relatively sharp growth t 3 sec and slow decay t 10² sec) solar continuum radioemission are analyzed below. The main results are found using a sweeping spectrograph in the 8–12 GHz frequency range (sweep rate 1 sample per second and frequency resolution 120 MHz) and using the RT-22 radio telescope at the Crimean Astrophysical Observatory (angular resolution 4–6). In a series of events at the leading edge of the continuum a narrow-band frequency drifting emission termed blip-type is found. The degree of continuum circular polarization (p<10%) is low compared to that of the narrow-band component (p20%). Both components of the aforementioned events should be radiating on the second harmonic of the local plasma frequency in the context of a plasma generating mechanism. Based on the model proposed and using the observed degree of circular polarization of each component, we can estimate the strength of the magnetic field within the area of the source and the width of the angular spectrum from the radiating plasma turbulence. The results of analysis of the real microwave events are given below.Radiophysical Research Institute, Nizhnii Novgorod. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 37, No. 7, pp. 874–882, July, 1994.     

An approach to pancratistatins via ring-closing metathesis: efficient synthesis of novel 1-aryl-1-deoxyconduritols F. cv

Structurally novel cyclitols, 1-aryl-1-deoxyconduritols F, were efficiently prepared from d-xylose, utilizing RCM as a key step. Various aromatic residues were incorporated in the cyclitol skeleton with total stereochemical control, utilizing a diastereoselective aryl cuprate addition to a gamma-alkoxy enoate. The synthetic route establishes a firm foundation for a practical synthesis of the antitumor alkaloid pancratistatin and its aryl analogues. [structure: see text]