Lewis Base-Catalysed Enantioselective Radical Conjugate Addition for the Synthesis of Enantioenriched Pyrrolidinones

We report a catalytic asymmetric protocol for the preparation of chiral pyrrolidinones proceeding via a radical pathway. The chemistry exploits the combination of photoredox catalysis and Lewis base catalysis to realise the first example of asymmetric radical conjugate addition to α,β-unsaturated anhydrides and esters. The reaction is initiated by photoredox activation of N-arylglycines to generate, upon decarboxylation, α-amino radicals. These radicals are then intercepted stereoselectively by α,β-unsaturated acyl ammonium intermediates, whose formation is mastered by a chiral isothiourea organocatalyst. Cyclisation leads to catalyst turnover and formation of enantioenriched pyrrolidinones. The utility of the protocol was demonstrated with application to the synthesis of biologically-active γ-amino butyric acids

Green solvents and restoration: Application of biomass-derived solvents in cleaning procedures

Blends of solvents from non-renewable sources, often polluting and toxic to humans, are routinely used in the restoration of painted artifacts. Here we present the application of three different green solvents (and their mixtures) as a viable alternative to the standard triad of solvents (acetone, ethanol, and isooctane) used in the solubility test for cleaning polychromic artworks. Solketal (SOLK), γ-valerolactone (GVL), and 2-ethylhexyl pelargonate (ARGO) were selected among the solvents achievable from bio-based synthons such as glycerol, levulinic acid, and pelargonic acid, which are mainly produced from biomass and renewable feedstocks as exhausted vegetable oils, carbohydrates, and lignocellulose. Specifically, ARGO solvent was prepared by esterification reaction and characterized by nuclear magnetic resonance (NMR) and mass spectroscopy coupled to gas chromatography (GC–MS). Hansen solubility parameters for each solvent were determined by a group contribution method, thus enabling their placement in the Teas graph. Their penetration ability in wooden specimens was investigated by evaluating the volume retention of each solvent with different coated specimens. The solvent ability of the selected compounds was tested by visible and UV observations on specimens prepared with film-forming substances (Dammar, Mastic, Shellac, Paraloid® B72 and linseed oil) brushed onto glass plates. Our results pointed out the suitability of this solvent triad for application to panel painting surfaces. The effectiveness of mixtures made with the above green solvent was successfully tested to remove a terpenic varnish from a 16th century oil painting on a wooden panel

Photovoltaic characterization of di-branched organic sensitizers for DSSCs.

In this work, the data on the effect of peripheral functionalization of a series of triphenylamine based di-branched dyes used as sensitizers in dye-sensitized solar cells are presented. The effect of different alkyl functionalities on the donor moiety upon the optical and photovoltaics parameters have been investigated in dye-sensitized solar cells (DSSCs) using a 10-μm TiO2 active layer. The absorption spectra, output efficiency, and incident photon to conversion efficiency of the DSSCs have been collected. The data can be exploited for properly designing efficient, stable, and industrially viable dyes for third generation solar devices

The quest for a molecular capsule assembled via halogen bonds

A halogen-bonded capsule is obtained via directed assembly of a rigid tetra(3-pyridyl) cavitand and a flexible tetra(4-iodotetrafluorophenyl) calix[4]arene. The pyridyl nitrogen atoms from one cavitand molecule interact with the iodine atoms of a single calixarene molecule through short and directional I…N halogen bonds. The flexibility of the ethylenedioxy moieties on the calixarene platform results in positional flexibility of the iodotetrafluorobenzene sites which, coupled with a supramolecular chelating effect, allow for an effective partner-induced geometric fitting between four nitrogen atoms on the cavitand and four iodine atoms on the calixarene

Assessment of Streptococcus pneumoniae pilus islet-1 prevalence in carried and transmitted isolates from mother–infant pairs on the Thailand–Burma border

AbstractStreptococcus pneumoniae pilus islet-1 (PI–1)-encoded pilus enhances in vitro adhesion to the respiratory epithelium and may contribute to pneumococcal nasopharyngeal colonization and transmission. The pilus subunits are regarded as potential protein vaccine candidates. In this study, we sought to determine PI–1 prevalence in carried pneumococcal isolates and explore its relationship with transmissibility or carriage duration. We studied 896 pneumococcal isolates collected during a longitudinal carriage study that included monthly nasopharyngeal swabbing of 234 infants and their mothers between the ages of 1 and 24 months. These were cultured according to the WHO pneumococcal carriage detection protocol. PI-1 PCR and genotyping by multilocus sequence typing were performed on isolates chosen according to specific carriage and transmission definitions. Overall, 35.2% of the isolates were PI-1-positive, but PI-1 presence was restricted to ten of the 34 serotypes studied and was most frequently associated with serotypes 19F and 23F; 47.5% of transmitted and 43.3% of non-transmitted isolates were PI-1-positive (OR 1.2; 95% CI 0.8-1.7; p 0.4). The duration of first-ever infant pneumococcal carriage was significantly longer with PI-1-positive organisms, but this difference was not significant at the individual serotype level. In conclusion, PI-1 is commonly found in pneumococcal carriage isolates, but does not appear to be associated with pneumococcal transmissibility or carriage duration

The effects of two gold-N-heterocyclic carbene (NHC) complexes in ovarian cancer cells: a redox proteomic study

Purpose: Ovarian cancer is the fifth leading cause of cancer-related deaths in women. Standard treatment consists of tumor debulking surgery followed by platinum and paclitaxel chemotherapy; yet, despite the initial response, about 70-75% of patients develop resistance to chemotherapy. Gold compounds represent a family of very promising anticancer drugs. Among them, we previously investigated the cytotoxic and pro-apoptotic properties of Au(NHC) and Au(NHC)2PF6, i.e., a monocarbene gold(I) complex and the corresponding bis(carbene) complex. Gold compounds are known to alter the redox state of cells interacting with free cysteine and selenocysteine residues of several proteins. Herein, a redox proteomic study has been carried out to elucidate the mechanisms of cytotoxicity in A2780 human ovarian cancer cells. Methods: A biotinylated iodoacetamide labeling method coupled with mass spectrometry was used to identify oxidation-sensitive protein cysteines. Results: Gold carbene complexes cause extensive oxidation of several cellular proteins; many affected proteins belong to two major functional classes: carbohydrate metabolism, and cytoskeleton organization/cell adhesion. Among the affected proteins, Glyceraldehyde-3-phosphate dehydrogenase inhibition was proved by enzymatic assays and by ESI-MS studies. We also found that Au(NHC)2PF6 inhibits mitochondrial respiration impairing complex I function. Concerning the oxidized cytoskeletal proteins, gold binding to the free cysteines of actin was demonstrated by ESI-MS analysis. Notably, both gold compounds affected cell migration and invasion. Conclusions: In this study, we deepened the mode of action of Au(NHC) and Au(NHC)2PF6, identifying common cellular targets but confirming their different influence on the mitochondrial function

Formulación y propiedades de biopolímero de recubrimiento para semillas de maní (Arachis hypogaea L.)

En este trabajo se presenta el diseño de una biopelícula de recubrimiento biodegradable, formulada con macromoléculas naturales como almidón, proteína y glicerol para ser aplicada sobre semillas de maní, a fin de aumentar la resistencia del tegumento y favorecer la fluidez en la siembra. Se ensayaron diversas formulaciones variando la concentración y tipo de los almidones. Dos formulaciones, una a base de almidón de maíz y otra de almidón de mandioca, fueron caracterizadas en su reología y en las biopelículas se determinaron propiedades de barrera, hidratación y solubilidad en agua. Aplicadas sobre semillas se evaluaron sus características tecnológicas como espesor de capa, capacidad de absorción-desorción de humedad y su aporte a la fluidez y resistencia al daño mecánico. Las semillas recubiertas con el biopolímero constituido con 3 % de almidón de mandioca evidenciaron mayor resistencia mecánica y fluidez y buenas propiedades de barrera. Este trabajo aporta una formulación para el recubrimiento biopolimérico de semillas de maní, que al estar constituido por sustancias naturales de grado alimenticio y biodegradables, posee potencialidad de implementación en el marco de la agricultura sustentable.This work shows a biodegradable coating biofilm design formulated with natural macromolecules such as starch, proteins, and glycerol, for its application on peanut seeds, to increase tegument resistance and fluency in sowing. Several formulations were assayed varying the concentration and types of starch. Two formulations, one based on corn starch and the other on cassava starch, were characterized in their rheology and their barrier, hydration and water solubility properties were determined. In coated seeds, biofilm technological characteristics, such as layer thickness, moisture absorption-desorption, contribution to fluency and mechanical damage resistance were tested. Seeds coated with biopolymer made up of 3 % cassava starch showed increased mechanical resistance and enhanced fluency and barrier properties. This work provides a formulation for the biopolimeric coating of peanut seeds, which being composed of natural, food grade and biodegradable substances, has the potential to be implemented in sustainable agriculture.Fil: Montoya, P.. Universidad Nacional de Córdoba; ArgentinaFil: Cosiansi, J.. Universidad Nacional de Córdoba; ArgentinaFil: Grasso, F.. Universidad Nacional de Córdoba; ArgentinaFil: Melchiorre, Mariana Noemi. Instituto Nacional de Tecnología Agropecuaria. Centro de Investigaciones Agropecuarias. Unidad de Estudios Agropecuarios - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Unidad de Estudios Agropecuarios; Argentin

Linearly π-conjugated oligothiophenes as simple metal-free sensitizers for dye-sensitized solar cells

Four linear oligothiophenes containing 4, 5 and 7 thiophene rings substituted by a variable number of octyl chains attached at the beta-position of some of the thiophene rings and possessing a terminal cyanoacrylic acid anchoring group have been synthesized. Results of UV-Vis absorption spectroscopy and cyclic voltammetry show that as expected the extension of the π-conjugated system leads to a decrease of the optical gap with an increase of the HOMO level. The four compounds have been evaluated as sensitizers in dye-sensitized solar cells (DSSCs) using a iodide/triiodide liquid electrolyte and the results are discussed in terms of the structure–property relationship with regard to the extension of the conjugated system and the number and position of the octyl side chains using N719 as the reference system. A power conversion efficiency of ~7.30% corresponding to 90% of the value given by N719 under identical conditions has been obtained with one of the heptamers