Investigation by EPR and ENDOR spectroscopy of the novel 4Fe ferredoxin fromPyrococcus furiosus

The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe₄S₄] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe₄S₄]⁺, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g₁ = 2.09, g₂ = 1.95, g₃ = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using¹³CN^? and C¹⁵N^? ligands.¹³C and¹⁵N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (a_iso(¹³C)～ ?3 MHz, a_iso(¹⁵N) ～ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the¹³C hyperfine coupling has a large isotropic component (a_iso(¹³C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as⁵⁷Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [⁵⁷FeFe₃S₄]⁺ and [Fe⁵⁷Fe₃S₄]⁺, show hyperfine coupling characteristic for [Fe₄S₄]⁺ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on¹³C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand.     

Calorimetric analysis of the ethanolysis of 1,2-epoxybutane

Polyethers, which are produced by alcoholysis of oxiranes, are often used as solvents in chemical plants. The spectra of the products can be influenced by the choice of the catalyst (acid or base). The results of the base-catalyzed ethanolysis of 1,2-epoxybutane are displayed. The reaction was investigated calorimetrically by varying the molar ratio between ethanol and 1,2-epoxybutane, the starting temperature and the concentration of the catalyst sodium hydroxide. Additionally, the influence of the used alcohol will be shown in one example. To determine the activation parameters, the experiments were evaluated by the nonlinear software package TA-kin v3.3.     

Dimeric stilbenes of the wood of Maackia amurensis

Dimeric stilbenes have been isolated from the wood of Amur maackia for the first time. Two of them have been identified as the known scirpusins A and B. The structure of a new dimeric stilbene with a dioxane linkage, which has been called maackinin, has been established. The PMR and¹³C NMR spectra of the substances isolated have been studied in detail.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 468–476, September–October, 1992.     

Problem of the Sand Production in a Producing Well

The problem of sand production (dilatant-plastic reservoir fragmentation) in the process of pumping-out fluid through an uncased borehole is considered. Taking the dilatant change in reservoir porosity into account makes it possible to find a relation between the fluid and solid mass flow rates. There is no steady-state solution if the elasto-plastic boundary does not coincide with the supply contour. In this case a self-similar problem of well start-up with a constant production rate is considered.     

Slow crack growth in blends of HDPE and model copolymers

The resistance to slow crack growth (SCG) was measured in binary blends of high density polyethylene (HDPE) and 5–10% concentrations of model ethylene-butene random copolymers by measuring the time to failure (t_f) under a constant stress intensity. An increase of t_f with the addition of the copolymer if the copolymer could crystallize and the increase was greater the higher branch density. The copolymer with 117 branches/1000C could not crystallize and therefore its blend had a t_f that was less than that of the HDPE. The fracture energies of the blends as determined by their resistance to SCG were compared with the energy by rapid fracture, J_c, as previously measured by Rhee and Crist. It is concluded that SCG is more sensitive to variations in the microstructure than is rapid fracture and that the differences in SCG behavior can be qualitatively explained in terms of the differences in microstructure of the blends. ©1995 John Wiley & Sons, Inc.     

Radioanalytical monitoring of the formation of barium sulfate in aqueous solutions

The formation of barium sulfate in aqueous media causes problems of insoluble scale formation. On the other hand, the coprecipitation of uranium and transuranium elements with barium sulfate has been suggested for the determination of these elements in environmental monitoring processes. Therefore, the study of barium sulfate crystal growth is required. The investigations done so far suffer from the low sensitivity of the analytical methods used. In the present work we have overcome this problem by using¹³¹Ba for the preparation of supersaturated solutions. Thus kinetics parameters such as induction time and precipitation rates were measured. The polynuclear mechanism was found to be operative at high and the spiral growth at low supersaturations.     

Paragrassmann differential calculus

This paper significantly extends and generalizes the paragrassmann calculus of our previous paper [1]. Here we discuss explicit general constructions for paragrassmann calculus with one and many variables. For one variable, nondegenerate differentiation algebras are identified and shown to be equivalent to the algebra of (p+1)×(p+1) complex matrices. If (p+1) is a prime integer, the algebra is nondegenerate and so unique. We then give a general construction of many-variable diffeentiation algebras. Some particular examples are related to multi-parametric quantum deformations of the harmonic oscillators.Dedication This paper is in memory of Mikhail Constantinovich Polivanov. One of the authors (A.T.F.) had a privilege to be a friend of him for many and many years. He was not only a distinguished scientist but a true Russian intellectual having deep roots in Russian culture. It is a deep sorrow that we can no more have a talk with him on science, poetry, religion ...Laboratory of Theoretical Physics, JINR, Dubna. SU-101 000 Moscow, Russia. Published in Teoreticheskaya i Matematicheskaya Fizika, Vol. 94, No. 2, pp. 213–231, February, 1993.