Crystal Structures of Bacterial (6‐4) Photolyase Mutants with Impaired DNA Repair Activity

PhrB from Agrobacterium fabrum is the first prokaryotic photolyase which repairs (6‐4) UV DNA photoproducts. The protein harbors three cofactors: the enzymatically active FAD chromophore, a second chromophore, 6,7‐dimethyl‐8‐ribityllumazine (DMRL) and a cubane‐type Fe‐S cluster. Tyr424 of PhrB is part of the DNA‐binding site and could provide an electron link to the Fe‐S cluster. The PhrB_Y424F mutant showed reduced binding of lesion DNA and loss of DNA repair. The mutant PhrB_I51W is characterized by the loss of the DMRL chromophore, reduced photoreduction and reduced DNA repair capacity. We have determined the crystal structures of both mutants and found that both mutations only affect local protein environments, whereas the overall fold remained unchanged. The crystal structure of PhrB_Y424F revealed a water network extending to His366, which are part of the lesion‐binding site. The crystal structure of PhrB_I51W shows how the bulky Trp leads to structural rearrangements in the DMRL chromophore pocket. Spectral characterizations of PhrB_I51W suggest that DMRL serves as an antenna chromophore for photoreduction and DNA repair in the wild type. The energy transfer from DMRL to FAD could represent a phylogenetically ancient process.     

Synthesis of marine alkaloids leucettamines B and C by β-lactam ring rearrangement

A new method for the synthesis of marine alkaloids leucettamines B and C from Leucetta sp. sponges is described. The key step is the base-promoted rearrangement of β-lactam into imidazolone ring. Leucettamines B and C as well as their N-benzoyl derivatives were obtained in high yields. Single-crystal structures of both leucettamines B and C were determined by X-ray diffraction confirming Z-configuration of double bond at 4-position of imidazolone.     

Reaction of 3-chloroquinoline-2,4-diones with ethanolamine and rearrangement of the reaction products

The reaction of tertiary α-chloroketones with ethanolamine has not been hitherto described in the literature. Herein, we describe the reaction of tertiary 3-chloroquinoline-2,4-diones with ethanolamine to give novel 3-(2-hydroxyethylamino)quinoline-2,4-diones. These compounds provide 3-(2-oxooxazolidin-3-yl)quinoline-2,4(1H,3H)-diones and new compounds with dimeric character after reaction with triphosgene. Molecular rearrangement proceeds during the reaction of 3-(2-hydroxyethylamino)quinoline-2,4-diones with isocyanic acid. Three types of reaction products arise: 2-(2-hydroxyethyl)imidazo[1,5-c]quinazoline-3,5-diones, 3-(2-hydroxyethyl)-3,3a-dihydro-2H-imidazo[4,5-]quinoline-4(5H)diones and primarily 5-hydroxy-1-(hydroxyethyl)-1′H-spiro[imidazolidine-5,3′-indole]-2,2′-diones. The reaction mechanism and product stereochemistry are discussed. The ¹H, ¹³C and ¹⁵N NMR spectra of the prepared compounds were measured, and all resonances were assigned from appropriate two-dimensional experiments.     

Determination of vanadium in titanate-based ferroelectrics by INAA with discriminating gamma-ray spectrometry

Instrumental neutron activation analysis was used for determination of vanadium mass fraction in crystals of incipient ferroelectric strontium titanate and ferroelectric barium titanate. In order to improve vanadium limit of detection, discriminating gamma-ray spectrometry was used by inserting an absorption filter between the samples and an HPGe detector. The use of the absorption lead filter 6-mm thick yielded improvement of the vanadium limit of detection by a factor of two. The vanadium mass fraction determined in a quality control sample, which was NIST standard reference material SRM 1648 Urban Particulate Matter, was in close agreement with the certified value.

     

Determination of mechanical properties by instrumented indentation

The paper reviews the current state of the depth-sensing indentation (sometimes called nanoindentation), where the information on material behaviour and properties is obtained from the indenter load and depth, measured continuously during loading and unloading. It is shown how the contact parameters and principal characteristics are determined using pointed or spherical indenters. Indentation tests can be used for the measurement of hardness and elastic modulus, and also of the yield stress and for the construction of stress–strain diagrams, for the determination of the work of indentation and its components. Most devices use monotonic loading and unloading, but some also enable measurement under a small harmonic signal added to the basic monotonously increasing load. This makes possible continuous measurement of contact stiffness and the study of dynamic properties and the determination of properties of coatings. One section is devoted to the measurement on viscoelastic-plastic materials, where the delayed deforming must be considered during the measurement as well as in data evaluation. Instrumented indentation can also be used for the study of creep under high temperatures. The paper also discusses the errors arising in depth-sensing measurements and informs briefly about some other possibilities of the method.     

Inhomogeneous inverse problem in finite elasticity

For a class of materials for which the principal strain directions always coincide with the principal stress directions one can determine the stress field in an inhomogeneously deformed body from given boundary conditions and a known strain field without knowing the constitutive equations. Each point of the inhomogeneously deformed body contains information such as that derived from an individual homogeneous identification test. The practically important two-dimensional case leads to a problem of solving a linear hyperbolic system where two differential equations describe the principal stress components. The problem can be reduced to that of integration along characteristics.Under a certain globality condition the existence, uniqueness, and correctness of the solution are guaranteed in the whole test piece. It is shown that the globality condition is closely related to whether or not the test piece is isotropic and elastic. The influence of experimental error on the correctness of problem formulation is discussed.

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Abstrakte Für die Klasse der Materialen, für welche die Grundspannungsrichtungen und die Grundverformungsrichtungen gleich sind, kann man das Spannungsfeld in einem inhomogen deformierten Körper für gegebene Randbedingungen und einem bekannten Verformungsfeld ohne Kenntnis der detailierten Form der Dehnungs-Spannungsgleichung bestimmen. Jeder Punkt des inhomogen deformierten Körpers liefert dieselbe Information wie ein individueller homogener Test. Der praktisch wichtige zweidimensionale Fall führt zu einem Problem der Lösung eines linear hyperbolischen Systems von zwei Differentialgleichungen für die Grundspannungskomponenten. Das Problem kann auf die Integration entlang der Charakteristik des Systems reduziert werden.Unter einer Bedingung der Globalität das die Existent, Eindeutigkeit und Richtigkeit der Lösung in der ganzen Testprobe gewährleistet sind. Es wird gezeigt, dass diese Globalitätsbedingung damit zusammenhängt eng, ob die Testprobe isotrop und elastisch ist. Der Einfluss der experimentellen Fehler auf die Richtigkeit der Formulation des Problems wird auch analysiert.

     

A sharp condition for existence of an inertial manifold

It is shown that a perturbation argument that guarantees persistence of inertial (invariant and exponentially attracting) manifolds for linear perturbations of linear evolution equations applies also when the perturbation is nonlinear. This gives a simple but sharp condition for existence of inertial manifolds for semi-linear parabolic as well as for some nonlinear hyperbolic equations. Fourier transform of the explicitly given equation for the tracking solution together with the Plancherel's theorem for Banach valued functions are used.     

Rheological behaviour of two-phase flow of solid particles in a gas

The present investigation was concerned with the rheological behaviour of dilute suspensions of solid particles in a gas in a vertical cocurrent flow moving upwards. Starting from the experimentally determined dependence of the pressure drop on the concentration of solid particles and the Reynolds number of the carrier medium in the steady flow region, the rheological parameters were estimated using pseudo-shear diagrams. Air was the carrier medium and the dispersed phase was one of six fractions of polypropylene powder and five fractions of glass ballotini. The results show that the investigated two-phase systems have pseudoplastic character which becomes more pronounced with increases in concentration, equivalent diameter and density of solid particles in the flowing suspension. C _d coefficient of particle resistance - d _e equivalent diameter of particles - D column diameter - Fr Froude number - g gravitational acceleration - K rheological parameter - L length - n rheological parameter - p _t pressure drop due to friction - p _m total pressure drop - p _ag pressure drop due to acceleration of the gas phase - p _as pressure drop due to acceleration of the solid phase - p _g hydrostatic pressure of the gas phase - p _s specific effective weight of the dispersed phase - r radius - Re Reynolds number - Re _p Reynolds number of a particle - Re _G generalized Reynolds number - Re _G1 generalized Reynolds number relating to the end of the laminar flow region - Re _G2 generalized Reynolds number relating to the beginning of the turbulent flow region - w _z axial component of velocity - u _t steady free-fall velocity of a single particle - w average velocity - w _g average velocity of the gas phase - w _s average velocity of the dispersed phase of solid particles - relative mass fraction of solid particles - x _s volume fraction of solid particles - _g coefficient of pressure drop due to friction - µ dynamic viscosity - _g density of the gas phase - _m density of the suspension - _s density of solid particles - _ds density of the dispersed phase - _w shear stress at the wall     

ChemInform Abstract: Structure and Conformational Properties of Azido(difluoro)phosphane,F2PN3.

The title compound is characterized by IR (gas phase, Ar matrix), Raman (liquid, amorphous, and crystalline solid), and ¹⁹F, ³¹P, ¹⁴N and ¹⁵N NMR spectroscopy, as well as by quantum chemical DFT calculations.