Caustics of 1/rn1/r^n binary gravitational lenses: from galactic haloes to exotic matter

We investigate the caustic topologies for binary gravitational lenses made up of two objects whose gravitational potential declines as $1/r^n$. With $n<1$ this corresponds to power-law dust distributions like the singular isothermal sphere. The $n>1$ regime can be obtained with some violations of the energy conditions, one famous example being the Ellis wormhole. Gravitational lensing provides a natural arena to distinguish and identify such exotic objects in our Universe. We find that there are still three topologies for caustics as in the standard Schwarzschild binary lens, with the main novelty coming from the secondary caustics of the close topology, which become huge at higher $n$. After drawing caustics by numerical methods, we derive a large amount of analytical formulae in all limits that are useful to provide deeper insight in the mathematics of the problem. Our study is useful to better understand the phenomenology of galaxy lensing in clusters as well as the distinct signatures of exotic matter in complex systems.Comment: 28 pages, 19 figures, focus expanded to galactic haloe

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

Photochemical Organocatalytic Functionalization of Pyridines via Pyridinyl Radicals

We report a photochemical method for the functionalization of pyridines with radicals derived from allylic C–H bonds. Overall, two substrates undergo C–H functionalization to form a new C(sp2)–C(sp3) bond. The chemistry harnesses the unique reactivity of pyridinyl radicals, generated upon single-electron reduction of pyridinium ions, which undergo effective coupling with allylic radicals. This novel mechanism enables distinct positional selectivity for pyridine functionalization that diverges from classical Minisci chemistry. Crucial was the identification of a dithiophosphoric acid that masters three catalytic tasks, sequentially acting as a Brønsted acid for pyridine protonation, a single electron transfer (SET) reductant for pyridinium ion reduction, and a hydrogen atom abstractor for the activation of allylic C(sp3)–H bonds. The resulting pyridinyl and allylic radicals then couple with high regioselectivit

A General Organocatalytic System for Enantioselective Radical Conjugate Additions to Enals

Herein, we report a general iminium ion-based catalytic method for the enantioselective conjugate addition of carbon-centered radicals to aliphatic and aromatic enals. The process uses an organic photoredox catalyst, which absorbs blue light to generate radicals from stable precursors, in combination with a chiral amine catalyst, which secures a consistently high level of stereoselectivity. The generality of this catalytic platform is demonstrated by the stereoselective interception of a wide variety of radicals, including non-stabilized primary ones which are generally difficult to engage in asymmetric processes. The system also served to develop organocatalytic cascade reactions that combine an iminium-ion-based radical trap with an enamine-mediated step, affording stereochemically dense chiral products in one-step

Di qua e di là dal mondo. Umani e non umani nei burattini di Bepe Pastrello

Volume relativo al progetto omonimo, raccoglie contributi che coprono tutti gli aspetti contemplati dal progetto: catalogazione, restauro, patrimonio culturale, storia del teatro di figure

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

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

Analysis of the muscarinic receptor subtype mediating inhibition of the neurogenic contractions in rabbit isolated vas deferens by a series of polymethylene tetra-amines

1. The pharmacological characteristics of the presynaptic muscarinic receptor subtype, which mediates inhibition of the neurogenic contractions in the prostatic portion of rabbit vas deferens, have been investigated by using a series of polymethylene tetra-amines, which were selected for their ability to differentiate among muscarinic receptor subtypes. 2. It was found that all tetra-amines antagonized McN-A-343-induced inhibition in electrically stimulated rabbit vas deferens in a competitive manner and with affinity values (pA2) ranging between 6.27 ± 0.09 (spirotramine) and 8.51 ± 0.02 (AM170). 3. Competition radioligand binding studies, using native muscarinic receptors from rat tissues (M1, cortex; M2, heart; M3, submaxillary gland) or from NG 108-15 cells (M4) and human cloned muscarinic M1-M4 receptors expressed in CHO-K1 cells, were undertaken with the same tetraamines employed in functional assays. All antagonists indicated a one-site fit. 4. The affinity estimates (pKi) of tetra-amines calculated in binding assays using native receptors were similar to those obtained using cloned receptors. Among these compounds some displayed selectivity between muscarinic receptor subtypes, indicating that they may be valuable tools in receptor characterization. Spirotramine was selective for M1 receptors versus all other subtypes (pKi native: M1, 7.32 ± 0.10; M2, 6.50 ± 0.11; M3, 6.02 ± 0.13; M4, 6.28 ± 0.16; pKi cloned: M1, 7.69 ± 0.08; M2, 6.22 ± 0.14; M3, 6.11 ± 0.16; 6.35 ± 0.11) whereas CC8 is highly selective for M2 receptors versus the other subtypes (pKi native: M1 7.50 ± 0.04; M2, 9.01 ± 0.12; M3, 6.70 ± 0.08; M4, 7.56 ± 0.04; pKi cloned: M1, 7.90 ± 0.20; M2, 9.04 ± 0.08; M3, 6.40 ± 0.07; M4, 7.40 ± 0.04). Furthermore, particularly relevant for this investigation were tetra-amines dipitramine and AM172 for their ability to significantly differentiate M1 and M4 receptors. 5. The apparent affinity values (pA2) obtained for tetra-amines in functional studies using the prostatic portion of rabbit vas deferens correlated most closely with the values (pKi) obtained at either native or human recombinant muscarinic M4 receptors. This supports the view that the muscarinic receptor mediating inhibition of neurogenic contractions of rabbit vas deferens may not belong to the M1 type but rather appears to be of the M4 subtype