A solid-phase approach to the synthesis of N-1-alkyl analogues of cyclic inosine-diphosphate-ribose (cIDPR)

We report here an efficient solid-phase synthesis of N-1-alkyl-substituted analogues of cyclic inosine-diphosphate-ribose (cIDPR), a mimic of cyclic ADP-ribose (cADPR). Our synthetic strategy makes use of a polystyrene support to which inosine was bonded through a 2′,3′-acetal linkage. Insertion of a ω-hydroxy-polymethylene chain of variable length on N-1, followed by conversion into N-1-alkylinosine-bis-phosphate derivatives and cyclization, allowed to obtain analogues of cIDPR of various ring size. The cyclization step was carried out both in solid-phase and in solution by pyrophosphate bond formation. The effect of the N-1-polymethylene chain length on the cyclization yields as well as the reaction conditions, which led to the solid-phase pyrophosphate bond formation, were thoroughly investigated.     

Polarized Absorption,Spontaneous and Stimulated Blue Light Emission of J‐type Tetraphenylbutadiene Monocrystals

Blue amplified spontaneous emission at room temperature is demonstrated from the exposed face of the strongly emitting organic semiconductor 1,1,4,4‐tetraphenyl‐1,3‐butadiene in single crystal form. The symmetry of the crystal and calculation of lattice sums indicate the J‐type organization of the molecular transition moments. The minimum in the lowest exciton dispersion branch, from which emission takes place, is found at the edge of the Brillouin zone leading to a dominant vibronic emission since the zero‐phonon line is forbidden. The observed gain narrowed line is attributed to the vibronic replica which becomes amplified with increased pumping. The reported emission is along the normal to the exposed crystal face, important for the development of vertical cavity geometry lasers based on organic single crystals. The threshold excitation fluence of 400 μJ cm^?2 is comparable to other organic crystalline systems, even if the amplification path is much reduced as a consequence of the vertical geometry. Considering these relevant aspects, the optical characterization of this material is provided. The polarized absorption spectra are reported and the properties of the lowest‐energy excitonic state investigated. Calculation of the electronic transitions for the isolated molecule, lattice sums for the transition at lowest energy, and the symmetry of the crystal allow attributing the largest face of the samples and the observed optical bands in the spectra. Polarized time‐resolved spectra are also reported allowing to identify the intrinsic excitonic emission.     

An entropy-based approach to automatic image segmentation of satellite images

An entropy-based image segmentation approach is introduced and applied to color images obtained from Google Earth. Segmentation refers to the process of partitioning a digital image in order to locate different objects and regions of interest. The application to satellite images paves the way to automated monitoring of ecological catastrophes, urban growth, agricultural activity, maritime pollution, climate changing and general surveillance. Regions representing aquatic, rural and urban areas are identified and the accuracy of the proposed segmentation methodology is evaluated. The comparison with gray level images revealed that the color information is fundamental to obtain an accurate segmentation.     

A finite element formulation satisfying the discrete geometric conservation law based on averaged Jacobians

In this article, a new methodology for developing discrete geometric conservation law (DGCL) compliant formulations is presented. It is carried out in the context of the finite element method for general advective–diffusive systems on moving domains using an ALE scheme. There is an extensive literature about the impact of DGCL compliance on the stability and precision of time integration methods. In those articles, it has been proved that satisfying the DGCL is a necessary and sufficient condition for any ALE scheme to maintain on moving grids the nonlinear stability properties of its fixed‐grid counterpart. However, only a few works proposed a methodology for obtaining a compliant scheme. In this work, a DGCL compliant scheme based on an averaged ALE Jacobians formulation is obtained. This new formulation is applied to the θ family of time integration methods. In addition, an extension to the three‐point backward difference formula is given. With the aim to validate the averaged ALE Jacobians formulation, a set of numerical tests are performed. These tests include 2D and 3D diffusion problems with different mesh movements and the 2D compressible Navier–Stokes equations. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of new fluorous modular chiral ligand derivatives from amino alcohols and application in enantioselective carbon–carbon bond-forming alkylation reactions

N-Trifluoracyl β-chalcogeno amides and N-perfluoracyl β-thio amide ligands were prepared by a simple and efficient reaction sequence. These new ligands were evaluated in palladium-catalyzed alkylation of rac-(E)-1,3-diphenyl-2-propenyl acetate in the presence of dimethyl malonate and an enantioselectivity of up to 99% was obtained. After catalysis, the fluorous ligand can be easily recovered by liquid–liquid extraction and reused without loss in the activity.     

Growth under Visible Light Increases Conidia and Mucilage Production and Tolerance to UV‐B Radiation in the Plant Pathogenic Fungus Colletotrichum acutatum

Light conditions can influence fungal development. Some spectral wavebands can induce conidial production, whereas others can kill the conidia, reducing the population size and limiting dispersal. The plant pathogenic fungus Colletotrichum acutatum causes anthracnose in several crops. During the asexual stage on the host plant, Colletototrichum produces acervuli with abundant mucilage‐embedded conidia. These conidia are responsible for fungal dispersal and host infection. This study examined the effect of visible light during C. acutatum growth on the production of conidia and mucilage and also on the UV tolerance of these conidia. Conidial tolerance to an environmentally realistic UV irradiance was determined both in conidia surrounded by mucilage on sporulating colonies and in conidial suspension. Exposures to visible light during fungal growth increased production of conidia and mucilage as well as conidial tolerance to UV. Colonies exposed to light produced 1.7 times more conidia than colonies grown in continuous darkness. The UV tolerances of conidia produced under light were at least two times higher than conidia produced in the dark. Conidia embedded in the mucilage on sporulating colonies were more tolerant of UV than conidia in suspension that were washed free of mucilage. Conidial tolerance to UV radiation varied among five selected isolates.     

Propagation of periodic long waves

Summary A method is developed for the computation of the steady solution of the shallow water equations with quasi periodic boundary conditions. Because of dissipation the influence of the initial conditions becomes negligible with increasing time and the solution finally depends on the boundary conditions. The unknowns variables (velocity and surface elevation) and the boundary conditions are developed in power series of a small perturbation parameter. The problem is then transformed in a sequence of linear problems which have the same associated homogeneous problem. By separating the time and space variables in the homogeneous problem we obtain an homogeneous elliptic problem of which we compute the first eigenvalues and eigensolutions. These are related to the characteristic oscillations of the water in the basin. The solution of each linear problem is then obtained as an eigensolution expansion with time dependent coefficients. These coefficients are solutions of ordinary differential equations which can be solved directly without proceeding step by step in time. In this way we are reduced to a stationary problem i.e. the determination of the eigenvalues and eigensolutions of the elliptic problem and to the computation of several integrals needed for the determination of the time dependent coefficients. A first test of the method has been carried out for a one-dimensional problem i.e. the tidal wave in a canal of finite length and constant depth. In this case the various steps of the procedure outlined above can be performed analitically. The results have been compared with those obtained by a step by step numerical integration of the shallow water equations. The agreement between these sets of results is good for the range of values of the parameters currently used in the applications.

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Sommario Viene presentato un metodo per il calcolo della soluzione a regime delle equazioni delle onde lunghe, dipendente dalle sole condizioni al contorno quasi-periodiche, dopo aver mostrato che l'influenza delle condizioni iniziali diventa col tempo trascurabile a causa del termine di resistenza. Il metodo si basa sullo sviluppo in serie di potenze di un piccolo parametro sia delle incognite (velocità ed elevazioni del pelo libero) sia delle condizioni al contorno al fine di trasformare il problema non lineare in una serie di problemi lineari aventi lo stesso problema omogeneo associato. Con la separazione delle variabili spazio, tempo quest'ultimo problema viene ricondotto ad un problema ellittico omogeneo di cui si calcolano i primi autovalori ed autosoluzioni. Da ultimo la soluzione di ciascun problema lineare è ottenuta come sviluppo in serie di autosoluzioni a coefficienti dipendenti dal tempo: questi si ricavano risolvendo analiticamente delle equazioni differenziali ordinarie. Si elimina cosi la necessità di procedere passo passo nel tempo analogamente ai classici metodi armonici di soluzione di sistemi lineari. Riassumendo, l'applicazione del metodo riconduce alla soluzione di un problema stazionario (determinazione di autovalori ed autosoluzione del problema ellittico) e quindi al calcolo dei vari integrali necessari per la determinazione dei coefficienti temporali. Il metodo è stato provato nel caso semplice della propagazione di onde di marea in un canale di lunghezza finita e sezione costante. Per questo esempio i vari passi di calcolo possono essere svolti analiticamente. I risultati sono stati confrontati con quelli ottenuti dalla integrazione numerica delle equazioni col metodo delle caratteristiche, ottenendo un buon accordo.

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Work sponsored by the CNR (National Research Council) in the framework of Project ?Conservazione del suolo? Subproject ?Dinamica dei Litorali? Publ. n° 46.     

The synthesis and application of polyamino polycarboxylic bifunctional chelating agents

Bifunctional chelating agents (BFCAs) are molecules which contain two different moieties: a strong metal chelating unit and a reactive functional group. The latter is directed to react with amines, thiols, alcohols or other reactive molecules to form stable covalent bonds while the chelating moiety is able to strongly coordinate a metal ion. In this way, it is possible to label a molecule of interest (e.g. an antibody or a peptide) with a metal or a radioactive metal ion. Of all the ligands reported so far, those based on a polyamino polycarboxylic structure are most efficient and are widely employed for the chelation of metal ions. The resulting metal complexes have found a broad range of applications in chemistry, biology and medicine. Diagnostic imaging (MRI, SPECT, PET), molecular imaging, tumour therapy and luminescent materials are only a few examples. The present critical review gives an overview of the syntheses and most important applications of polyamino polycarboxylic BFCAs (334 references).