Thioetherphenolate group 4 metal complexes in the ring opening polymerization of rac‐β‐Butyrolactone

Group 4 complexes 1 – 3 [ 1 = (t‐BuOS)₂Ti(O‐i‐Pr)₂; 2 = (t‐BuOS)₂Zr(O‐t‐Bu)₂; 3 = (t‐BuOS)₂Hf(O‐t‐Bu)₂] supported by two phenolate bidentate ligands (t‐BuOS‐H = 4,6‐di‐tert‐butyl‐2‐phenylsulfanylphenol) promote the well‐controlled ring opening polymerization of rac‐β‐butyrolactone. In presence of isopropanol, low dispersities and molecular weights proportional to the equivalents of isopropanol are achieved. Moreover, the zirconium complex is effective in the copolymerization of rac‐β‐butyrolactone with rac‐lactide. The 13 C nuclear magnetic resonance analysis revealed that the obtained copolymers have a tapered diblock microstructure consisting of an initial block composed of lactide sequences and a terminal block composed of butyrolactone sequences. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3132–3139     

LC–MS methods combination for identification and quantification of trans-sinapoylquinic acid regioisomers in green coffee

The present study aims to both identify and quantify trans-sinapoylquinic acid (SiQA) regioisomers in green coffee by combined UHPLC-ESI-QqTOF-MS/MS and UHPLC-ESI-QqQ-MS/MS methods. Among the various mono-acyl chlorogenic acids found in green coffee, SiQA regioisomers are the least studied despite having been indicated as unique phytochemical markers of Coffea canephora (known as Robusta). The lack of commercially available authentic standards has been bypassed by resorting to the advantages offered by high-resolution LC–MS as far as the identification is concerned. SiQA regioisomers have been identified in several samples of Robusta and Coffea arabica (known as Arabica) commercial lots from different geographical origin and, for the first time, in different samples of coffee wild species (Coffea liberica and Coffea pseudozanguebariae). Quantification (total SiQA ranging from 3 to 5 mg/100 g) let to reconsider these chlorogenic acids as unique phytochemical markers of Robusta being present in the same quantity and distribution in C. liberica as well. Gardeniae Fructus samples (fruits of Gardenia jasminoides) have additionally been characterized as this matrix is recognized as one of the few naturally occurring SiQA sources. The SiQA regioisomer content (total SiQA about 80 mg/100 mg) fully supports the proposal to use this matrix as a surrogate standard for further studies.     

Metal Catalyzed Polymerization: From Stereoregular Poly(α-olefins) to Tailor-Made Biodegradable/Biorenewable Polymers and Copolymers

Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a “mature” area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of “green” and possibly biodegradable alternatives to olefin-based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal-catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter.     

Smart Coatings Prepared via MAPLE Deposition of Polymer Nanocapsules for Light-Induced Release

Herein, smart coatings based on photo-responsive polymer nanocapsules (NC) and deposited by laser evaporation are presented. These systems combine remotely controllable release and high encapsulation efficiency of nanoparticles with the easy handling and safety of macroscopic substrates. In particular, azobenzene-based NC loaded with active molecules (thyme oil and coumarin 6) were deposited through Matrix-Assisted Pulsed Laser Evaporation (MAPLE) on flat inorganic (KBr) and organic (polyethylene, PE) and 3D (acrylate-based micro-needle array) substrates. SEM analyses highlighted the versatility and performance of MAPLE in the fabrication of the designed smart coatings. DLS analyses, performed on both MAPLE- and drop casting-deposited NC, demonstrated the remarkable adhesion achieved with MAPLE. Finally, thyme oil and coumarin 6 release experiments further demonstrated that MAPLE is a promising technique for the realization of photo-responsive coatings on various substrates.     

Antiprotozoal and Antibacterial Activity of Ravenelin,a Xanthone Isolated from the Endophytic Fungus Exserohilum rostratum

The natural compound ravenelin was isolated from the biomass extracts of Exserohilum rostratum fungus, and its antimicrobial, antiplasmodial, and trypanocidal activities were evaluated. Ravenelin was isolated by column chromatography and HPLC and identified by NMR and MS. The susceptibility of Gram-positive and Gram-negative bacteria strains to ravenelin was determined by microbroth dilution assay. Cytotoxicity was evaluated in hepatocarcinoma cells (HepG2) and BALB/c peritoneal macrophages by using MTT. SYBR Green I-based assay was used in the asexual stages of Plasmodium falciparum. Trypanocidal activity was tested against the epimastigote and intracellular amastigote forms of Trypanosoma cruzi. Ravenelin was active against Gram-positive bacteria strains, with emphasis on Bacillus subtilis (MIC value of 7.5 µM). Ravenelin’s antiparasitic activities were assessed against both the epimastigote (IC₅₀ value of 5 ± 1 µM) and the intracellular amastigote forms of T. cruzi (IC₅₀ value of 9 ± 2 µM), as well as against P. falciparum (IC₅₀ value of 3.4 ± 0.4 µM). Ravenelin showed low cytotoxic effects on both HepG2 (CC₅₀ > 50 µM) and peritoneal macrophage (CC₅₀ = 185 ± 1 µM) cells with attractive selectivity for the parasites (SI values > 15). These findings indicate that ravenelin is a natural compound with both antibacterial and antiparasitic activities, and considerable selectivity indexes. Therefore, ravenelin is an attractive candidate for hit-to-lead development.     

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.     

Grain shear flow in a rotating drum

 In the present paper we report on the experimental activities carried out on a rotating drum partially filled with grains or glass beads. The experiments give information about rheology through velocity profiles and through the velocity covariance tensor structure. We used a LDV system to measure the velocity of the grains at several points along three vertical sections. The data were also used to obtain the grain volume concentration, with encouraging results. Instantaneous velocity data were elaborated in order to obtain velocity and pseudotemperature profiles for all the experiments; for a subset of the experiments a large set of data were elaborated to obtain the velocity covariance. The velocity covariance is not collinear with the rate of deformation tensor. An attempt to justify the rotation of the tensor axes as a consequence of the kinetically induced anisotropy and of some free surface perturbations slowly moving upstream was partially successful. Received: 23 April 1999 / Accepted: 15 July 2001     

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.