Structure and function of a lignostilbene-α,β-dioxygenase orthologue from <Emphasis Type="Italic">Pseudomonas brassicacearum</Emphasis>

Background

Stilbene cleaving oxygenases (SCOs), also known as lignostilbene-α,β-dioxygenases (LSDs) mediate the oxidative cleavage of the olefinic double bonds of lignin-derived intermediate phenolic stilbenes, yielding small modified benzaldehyde compounds. SCOs represent one branch of the larger carotenoid cleavage oxygenases family. Here, we describe the structural and functional characterization of an SCO-like enzyme from the soil-born, bio-control agent Pseudomonas brassicacearum.

Methods

In vitro and in vivo assays relying on visual inspection, spectrophotometric quantification, as well as liquid-chormatographic and mass spectrometric characterization were applied for functional evaluation of the enzyme. X-ray crystallographic analyses and in silico modeling were applied for structural investigations.

Results

In vitro assays demonstrated preferential cleavage of resveratrol, while in vivo analyses detected putative cleavage of the straight chain carotenoid, lycopene. A high-resolution structure containing the seven-bladed β-propeller fold and conserved 4-His-Fe unit at the catalytic site, was obtained. Comparative structural alignments, as well as in silico modelling and docking, highlight potential molecular factors contributing to both the primary in vitro activity against resveratrol, as well as the putative subsidiary activities against carotenoids in vivo, for future validation.

Conclusions

The findings reported here provide validation of the SCO structure, and highlight enigmatic points with respect to the potential effect of the enzyme’s molecular environment on substrate specificities for future investigation.

     

A model of adsorption at liquid-solid interface involving association in the bulk phase

A model of monolayer adsorption of binary liquid mixtures on homogeneous and heterogeneous solid surfaces involving association of one component in the bulk phase is discussed. Suitable model calculations, illustrating association and heterogeneity effects, have been performed according to an equation derived for adsorption excess. This equation has been examined by using the experimental data of adsorption of alcohols from benzene andn-heptane on silica gel.

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Adsorptionsmodell für die Grenzfläche Feststoff-Flüssigkeit unter Berücksichtigung der Assoziation in der Flüssigkeitsphase

Zusammenfassung Es wird ein Adsorptionsmodell binärer, flüssiger Mischungen an homogenen und heterogenen Oberflächen von Feststoffen unter Beachtung der Assoziation eines der Bestandteile in der Flüssigkeitsphase diskutiert. Mit der aus dem Oberflächenüberschuß abgeleiteten Gleichung wurden entsprechende Modellberechnungen durchgeführt, die die mit Assoziation und Heterogenität verbundenen Effekte illustrieren. Die Gleichung wurde für die experimentellen Daten der Alkoholadsorption aus Benzol undn-Heptan an Kieselgel überprüft.

     

Photochemical ring opening of barbital

Photolysis of barbital yields derivatives of urea and biuret. The mechanism of ring opening involves an isocyanate intermediate.     

Hardy Spaces for Laguerre Expansions

Let be the standard Laguerre functions of type a. We denote . Let and be the semigroups associated with the orthonormal systems and . We say that a function f belongs to the Hardy space associated with one of the semigroups if the corresponding maximal function belongs to . We prove special atomic decompositions of the elements of the Hardy spaces.     

Stability problem for the Go?a?b-Schinzel type functional equations

Let X be a vector space over a field K of real or complex numbers, n∈N and λ∈K?{0}. We study the stability problem for the Go?a?b-Schinzel type functional equations

f(x+fn(x)y)=λf(x)f(y)     

Algebraic models of smooth manifolds

Research supported by the NSF Grant DMS-8602672     

Isosceles-orthogonality preserving property and its stability

For real normed spaces, we consider the class of linear operators, preserving approximately the relation of isosceles-orthogonality. We show some general properties of such mappings. Next, we examine whether an approximately orthogonality preserving mapping admits an approximation by an orthogonality preserving one. In regard to this, we generalize some results obtained earlier for inner product spaces with standard orthogonality relation.     

Dual Lukacs regressions for non-commutative variables

Dual Lukacs type characterizations of random variables in free probability are studied here. First, we develop a freeness property satisfied by Lukacs type transformations of free-Poisson and free-binomial non-commutative variables which are free. Second, we give a characterization of non-commutative free-Poisson and free-binomial variables by properties of first two conditional moments, which mimic Lukacs type assumptions known from classical probability. More precisely, our result is a non-commutative version of the following result known in classical probability: if U, V   are independent real random variables, such that E(V(1−U)|UV)$\mathbb{E}(V(1-U)|UV)$ and E(V²(1−U)²|UV)$\mathbb{E}(V^2{(1-U)}^2|UV)$ are non-random then V has a gamma distribution and U has a beta distribution.