Crystal and molecular structure of a 1:1 complex of a chiral α-d-glucosido-benzo-18-crown-6 and potassium thiocyanate

C₂₈H₃₆O₁₀. KSCN is monoclinic, space groupP2₁ withZ=2,a=10.390(3),b=8.959(7),c=16.377(7) Å, =92.49(5)°. FinalR=0.053 for 1437 reflections measured at room temperature. The K^– ion lies on the least-squares plane formed by the six oxygen atoms in the macrocyclic ring. The SCN^– ion was found on the same face of the macrocycle as the chiral glucopyranoside moiety.Methyl-4,6-O-benzylidene-2,3-O-(1,2-bis(ethoxyethoxy)benzenediyl)--d-glucopyranoside.     

Note on vertex degrees of planar graphs

In this note the second moment of the vertex degree sequence of planar graphs is considered. We prove that

• 1 If G is an outerplanar graph of order n ? 3 then

• 2 If G is a planar graph of order n ? 4 then

where d₁,…,d_n is the vertex degree sequence of G. We exhibit all graphs for which these upper bounds are attained.     

Application of the ellipsoid method in an interactive procedure for multicriteria linear programming

The research reported in this paper is concerned with an application of the ellipsoid algorithm in the interactive multicriteria linear programming step method (STEM) byBenayoun et al. [1971]. Due to this application we eliminate some drawbacks of the original version of STEM and, moreover, we avoid extra computations connected with sensitivity analysis in every iteration. Specifically, we use the ellipsoid algorithm to minimize the Euclidean norm in the criterion space instead of the Chebyshev norm, which ensures that every solution submitted to the decision maker is efficient. As follows from a computational experiment, in comparison with the application of the simplex method, the proposed modification of STEM shows a smaller increase of the computational effort when the number of criteria increases. However, the absolute computation time becomes worse for problems of larger size.

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Zusammenfassung In dieser Arbeit wird über eine Anwendungsmöglichkeit der Khachiyan-Shor-Algorithmus (Ellipsoid-Algorithmus) im Rahmen des STEM-Verfahrens zur interaktiven Lösung linearer Vektoroptimierungsmodelle berichtet. Auf diese Weise können einige spezifische Nachteile des STEM-Verfahrens in seiner Originalversion vermieden werden. Durch die Verwendung der Euklidischen Norm anstelle der beim STEM-Verfahren üblichen Tschebyscheff-Norm wird garantiert, daß dem Entscheidungsträger nur effiziente Lösungen vorgeschlagen werden. Die numerischen Erfahrungen zeigen, daß der Lösungsaufwand der hier vorgeschlagenen Modifikation des STEM-Verfahrens mit steigender Anzahl von Zielfunktionen weniger stark zunimmt als bei der üblichen Version. Dies gilt jedoch nicht hinsichtlich der allgemeinen Problemgröße.

     

Uniqueness and the global Markov property for Euclidean fields: The case of general exponential interaction

The uniqueness and the global Markov property for the regular Gibbs measure corresponding to the interaction $$U_\Lambda (\varphi ): = \lambda \int\limits_\Lambda {d_2 x\int {d\varrho (\alpha ):e^{\alpha \varphi } :_0 (x)} } $$ [forλ>0,d?(α) a probability measure with support in \(( - 2\sqrt {\pi ,} 2\sqrt \pi )\) ] is proved.     

Effect of the modification of silica on thermal properties and flammability of cross-linked butadiene-acrylonitrile rubbers

The paper presents the results of testing the thermal stability and flammability of butadiene-acrylonitrile rubber vulcanizates with different contents of combined acrylonitrile: Perbunan NT 1845 and Perbunan NT 3945 from Bayer, containing unmodified and bromine- or iodine-modified silica. The test results were obtained with the use of a derivatograph, measurements of flammability by the method of oxygen index, in air and also with the use of a cone calorimeter. The effect of the modification on the zeta potential was also examined. A considerable reduction in the flammability of nitrile rubber vulcanizates filled with silica can be obtained by the modification of filler with bromine or iodine. All the vulcanizates containing modified silica are self-extinguishing. An appropriate filling of NBR 39 vulcanizates with bromine-modified silica makes it possible to obtain non-flammable polymeric materials. They neither ignite nor glow under the action of a flame source for 30 s. The findings can be a rational basis for the synthesis of modified silica that can act as active filler and effective flame-retardant agent at the same time.     

Acid-catalysed hydrolysis of cis -[Cr(C2O4)(AaraNH2)(OH2)(OSO2)]? (where AaraNH2 denotes methyl 3-amino-2,3-dideoxy-α,d -arabino-hexopyranoside)

The synthesised complex cis-[Cr(C₂O₄)(AaraNH₂)(OH₂)(OSO₂)]⁻ anion with SO ₃ ²⁻ as a ligand in the inner coordination sphere, where AaraNH₂ denotes methyl 3-amino-2,3-dideoxy-α-d-arabino-hexopyranoside, was hydrolysed in the presence of acid at H⁺ concentrations from 0.01 to 2.7 m (HClO₄). The reaction kinetics was studied with the stopped-flow spectrophotometric (u.v.–vis.) technique at temperatures of 5, 10, 15, 18 and 20 °C. This hydrolysis turned out to be a single-step process. Determined for this reaction were the rate constant k ₁ for the removal of SO₂ from the coordination sphere of the cis-[Cr(C₂O₄)(AaraNH₂)(OH₂)(OSO₂)]⁻ ion and the constant pK ₁ of the protonation of this species in the reaction preceding the hydrolysis. The final product of this reaction – a new complex of Cr^III, cis-[Cr(C₂O₄)(AaraNH₂)(OH₂)₂]⁺, was obtained. A mechanism for the acid hydrolysis reaction is put forward based on the analysis of the rate constants obtained.     

Sr and stable strontium in bones of wild, herbivorous animals from Poland

Activity concentration of ⁹⁰ Sr and stable strontium concentration was analysed in 42 samples of animal (deer, roe-deer, elk and boar) bones, which mostly originated from north-eastern Poland. Strontium separation was performed by extraction chromatography. Determination of chemical yield was controlled by means of stable Sr determination using atomic spectrometry at the beginning and at the end of the separation procedure. Equilibrated ⁹⁰ Sr and ⁹⁰ Y activity was measured using a liquid scintillator spectrometer. Stable strontium range was from 55.4±1.7 ppm to 91.8±4.5 ppm, the mean was 71.84 ppm with a standard deviation (SD) of 9.31 ppm. The mean recovery of strontium was 26.7% with SD = 16.1%. The maximum activity of ⁹⁰ Sr, equal to 629±13 Bq/kg (ash) was found for a deer sample from Augustów Primeval Forest. In average, deer show the highest radiostrontium level, followed by roe-deer, elk and the lowest level were observed for boar. Differences between boar and deer or roe-deer are significant in terms of Kruskal-Wallis statistical test. Animal bones from north-eastern Poland showed about twice the mean concentration of ⁹⁰ Sr, compared to those of south-central Poland, but the difference was found not significant. Activities observed in roe-deer bones suggest the deposition of a concentration of 1.9 to 3.5 kBq/m² in the average of Chernobyl-origin ⁹⁰ Sr in 1986 in north-eastern Poland.     

Radiation-induced degradation and crosslinking of poly(ethylene oxide) in solid state

The effects of g-irradiation on solid poly(ethylene oxide) (PEO) of an initial weight-average molecular weight of 6.3^.10⁵ Da were investigated by gel permeation chromatography and viscometry. The parameters studied were changes in number- and weight-average molecular weight, molecular weight distribution and viscosity of PEO in aqueous solution. Irradiation of poly(ethylene oxide) powder in the presence of oxygen leads to the dominance of chain scission reactions. Their high radiation-chemical yield [G(scission) » 2.5^.10^-6 mol/J] indicates the occurrence of effective chain reactions. Upon irradiation in vacuum, crosslinking and scission occur side-by-side and the changes in molecular weight are less pronounced in the studied dose range (up to 20 kGy). Scission dominates for doses up to ca. 15 kGy, while for higher doses intermolecular crosslinking gains in importance. The competition between these processes seems to depend not only on the applied dose but also to be influenced by the inhomogenity of the material (molecular weight and/or possibly the crystallinity). Parallel occurrence of scission and crosslinking leads to the broadening of the molecular weight distribution.     

On the conformational stability and dimerization of phosphotransferase enzyme I from Escherichia coli

The activity of enzyme I (EI), the first protein in the bacterial PEP:sugar phosphotransferase system, is regulated by a monomer–dimer equilibrium where a Mg²⁺-dependent autophosphorylation by PEP requires the homodimer. Using inactive EI(H189A), in which alanine is substituted for the active-site His189, substrate binding effects can be separated from those of phosphorylation. Whereas 1 mM PEP (with 2 mM Mg²⁺) strongly promotes dimerization of EI(H189A) at pH 7.5 and 20 °C, 5 mM pyruvate (with 2 mM Mg²⁺) has the opposite effect. A correlation between the coupling of N- and C-terminal domain unfolding, measured by differential scanning calorimetry, and the dimerization constant for EI, determined by sedimentation equilibrium, is observed. That is, when the coupling between N- and C-terminal domain unfolding produced by 0.2 or 1.0 mM PEP and 2 mM Mg²⁺ is inhibited by 5 mM pyruvate, the dimerization constant for EI(H189A) decreases from >10⁸ to <5 × 10⁵ or 3 × 10⁷ M⁻¹, respectively. With 2 mM Mg²⁺ at 15–25 °C and pH 7.5, PEP has been found to bind to one site/monomer of EI(H189A) with K_A′10⁶ M⁻¹ (ΔG′=−33.7±0.2 kJ mol⁻¹ and ΔH=+16.3 kJ mol⁻¹ at 20 °C with ΔC_p=−1.4 kJ K⁻¹ mol⁻¹). The binding of PEP to EI(H189A) is synergistic with that of Mg²⁺. Thus, physiological concentrations of PEP and Mg²⁺ increase, whereas pyruvate and Mg²⁺ decrease the amount of dimeric, active, dephospho-enzyme I.     

Reactivity of iron(II) 5,10,15,20-tetraaryl-21-oxaporphyrin with arylmagnesium bromide: formation of paramagnetic six-coordinate complexes with two axial aryl groups

Coordination of sigma-aryl carbanions by chloroiron(II) 5,20-ditolyl-10,15-diphenyl-21-oxaporphyrin (ODTDPP)Fe(II)Cl has been followed by (1)H NMR spectroscopy. Addition of pentafluorophenyl Grignard reagent (C(6)F(5))MgBr to the toluene solution of (ODTDPP)Fe(II)Cl in the absence of dioxygen at 205 K resulted in the formation of the high-spin (ODTDPP)Fe(II)(C(6)F(5)). The titration of (ODTDPP)Fe(II)Cl with a solution of (C(6)H(5))MgBr carried at 205 K yields a rare six-coordinate species which binds two sigma-aryl ligands [(ODTDPP)Fe(II)(C(6)H(5))(2)](-). Warming of the [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) solution above 270 K results in the decomposition to mono-sigma-phenyliron species (ODTDPP)Fe(II)(C(6)H(5)). Controlled oxidation of [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) with Br(2) affords (ODTDPP)Fe(III)(C(6)H(5))Br, which demonstrates a typical (1)H NMR pattern of low-spin sigma-aryl iron(III) porphyrin. The considered oxidation mechanism involves the (ODTDPP)Fe(III)(C(6)H(5))(2) species, which is readily reduced to the iron(I) 21-oxaporphyrin, followed by oxidation with Br(2) and replacement of one bromide anion by aryl substituent. The (1)H NMR spectra of paramagnetic iron complexes have been examined in detail. Functional group assignments have been made with the use of selective deuteration. The peculiar (1)H NMR spectral features of [(ODTDPP)Fe(II)(p-CH(3)C(6)H(4))(2)](-) (sigma-p-tolyl: ortho, 30.8; meta, 53.6; para-CH(3), 42.1; furan: -16.0; beta-H pyrrole: -27.5, -34.3, -41.8 ppm, at 205 K) are without a parallel to any iron(II) porphyrin or heteroporphyrin and indicate a profound alteration of the electronic structure of iron(II) porphyrin upon the coordination of two sigma-aryls.