Sintesi asimmetrica di ammine benziliche ed eterobenziliche

C2-Symmetrical, enantiopure 2,6-di[1-(1-aziridinyl)alkyl]pyridines (DIAZAPs) were prepared by a high-yielding, three-step sequence starting from 2,6-pyridinedicarbaldehyde and (S)-valinol or (S)-phenylglycinol. The new compounds were tested as ligands in palladium-catalyzed allylation of carbanions in different solvents. Almost quantitative yield and up to 99% enantiomeric excess were obtained in the reactions of the enolates derived from malonate, phenyl- and benzylmalonate dimethyl esters with 1,3-diphenyl-2-propenyl ethyl carbonate. Asymmetric synthesis of 2-(2-pyridyl)aziridines from chiral 2-pyridineimines bearing a stereogenic center at the nitrogen atom was development. The envisioned route involves the addition of chloromethyllithium to the imine derived from 2-pyridinealdehyde and (S)-valinol, protected as O-trimethylsilyl ether. The analogous reaction performed on the imine derived from (S)-valine methyl ester gave the product containing the aziridine ring as well as the α-chloro ketone group coming from the attack of chloromethyllithium to the ester function. Other stereogenic alkyl substituents at nitrogen gave less satisfactory results. Moreover, the aziridination protocol did not work on other aromatic imines, e.g. 3-pyridineimine and benzaldimine, which are not capable of bidentate chelation. The N-substituent could not be removed, but aziridine underwent ring-opening by attack of nitrogen, sulfur, and oxygen nucleophiles. Complete or prevalent regioselectivity was obtained using cerium trichloride heptahydrate as a catalyst. In some cases, the N-substituent could be removed by an oxidative protocol. The addition of organometallic (lithium, magnesium, zinc) reagents to 2-pyrroleimines derived from (S)-valinol and (S)-phenylglycinol gave the N-substituted-1-(2-pyrrolyl)alkylamines with high yields and diastereoselectivities. The (S,S)-diastereomers were useful intermediates for the preparation of enantiopure 1-[1-(2-pyrrolyl)alkyl]aziridines by routine cyclization of the β-aminoalcohol moiety and of (S)-N-benzoyl 1-[1-(2-pyrrolyl)alkyl]amines and their N-substituted derivatives by oxidative cleavage of the chiral auxiliary. 1-Allyl-2-pyrroleimines obtained from (S)-phenylglycinol and (S)-valinol underwent highly diastereoselective addition of allylmetal reagents, used in excess amounts, to give the corresponding secondary amines with concomitant allyl to 1-propenyl isomerisation of the 1-pyrrole substituent. Protection of the 2-aminoalcohol moiety as oxazolidinone, amide or Boc derivate followed by ring closing metathesis of the alkene groups gave the unsaturated bicyclic compound, whose hydrogenation afforded the indolizidine derivative as a mixture of separable diastereomers. The absolute configuration of the main diastereomer was assessed by X-ray crystallographic analysis

Teorie cometarie pre-newtoniane (Bologna, 1650-1680)

La tesi prende in esame il dibattito de cometis in un periodo nel quale esso assunse una importanza prioritaria nella contesa fra ‘nuova’ scienza e difesa della tradizione cosmologica e scientifica, ovvero fra gli anni “galileiani” (segnati dalla comparsa delle celebri comete del 1618-19) e gli anni ’80 del XVII secolo (quando le comete costituirono uno dei fattori di affermazioni della meccanica celeste newtoniana). Ci si interessa in particolare alle apparizioni cometarie dei bienni 1652-1653 e 1664-1665, che pure furono occasione per la pubblicazione di numerosissimi lavori e alimentarono una discussione accesa in tutto il Continente, veicolata anche grazie al sorgere delle nuove Accademie scientifiche. Si è scelto di ambientare la ricerca a Bologna, dove l’astronomia rivestiva un ruolo cruciale e si realizzava una convivenza quasi paradigmatica di diverse espressioni di pensiero (talvolta in contrasto), custodite e propugnate da Collegio Gesuita, Studio e dalle accademie cittadine, e incarnate da figure quali Riccioli, Cassini e Montanari. Accanto ai loro contributi, si presentano quelli di personaggi ‘secondari’, come pure i loro rapporti con la Corte medicea (dove opera Borelli) e altri scienziati d’Europa, come Ward, Bouilliau e Auzout

The Equivalence of Fourier-based and Wasserstein Metrics on Imaging Problems

We investigate properties of some extensions of a class of Fourier-based probability metrics, originally introduced to study convergence to equilibrium for the solution to the spatially homogeneous Boltzmann equation. At difference with the original one, the new Fourier-based metrics are well-defined also for probability distributions with different centers of mass, and for discrete probability measures supported over a regular grid. Among other properties, it is shown that, in the discrete setting, these new Fourier-based metrics are equivalent either to the Euclidean-Wasserstein distance $W_2$, or to the Kantorovich-Wasserstein distance $W_1$, with explicit constants of equivalence. Numerical results then show that in benchmark problems of image processing, Fourier metrics provide a better runtime with respect to Wasserstein ones.Comment: 18 pages, 2 figures, 1 tabl

Fluorescence Spectroscopy for the Diagnosis of Endometritis in the Mare

By exploiting the PMN property to produce high quantities of oxygen peroxide to neutralize pathogens, the oxygen peroxide content of uterine cells was measured to diagnose endometritis. After preliminary in vitro studies in which endometrial cells from slaughtered mares were mixed with leukocytes from peripheral blood, endometrial samples were collected by uterine flushing from mares before insemination. Staining endometrial cells with H2DCF‐DA was combined with hydroethidine to normalize the fluorescence intensity with the cellular content of the sample. Stained cell smears were assumed as the gold standard of endometritis, and based on this assay, the samples were considered positive (C+) and negative (C−) for endometritis. The amount and the turbidity of fluid recovered by uterine flushing were significantly (p < 0.01) higher in C+ than in C−. Moreover, the oxygen peroxide content of the endometrial cells was significantly higher in the C+ than in the C− group (6.31 ± 1.92 vs. 3.12 ± 1.26, p = 0.001). Using the value of 4.4 as the cutoff level of this fluorescence cytology assay, it was found that only one C− sample exceeded the cutoff level (false positives = 7.7%) while three C+ samples showed values below the cutoff level (false negative = 11.5%)

Dual Photoredox and Nickel Catalysed Reductive Coupling of Alkynes and Aldehydes

A regioselective vinylation of aromatic and aliphatic aldehydes promoted by the merging of photoredox and nickel catalysis is here reported. A comprehensive investigation on the reaction conditions allowed the disclosure of a valid and reproducible protocol based on a nickel-mediated reductive coupling approach under visible light irradiation. The employment of 3CzClIPN (2,4,6-tris(carbazol-9-yl)-5-chloro-isophthalonitrile) as the photocatalyst and Hantzsch's ester as the sacrificial organic reductant replace the use of boron-, silicon- or zinc-based reducing agents, making this method a worthy alternative to the already known protocols. The developed mild reaction conditions allow the access to a wide range of substituents decorating both the aldehyde and the alkyne. Moreover, careful photophysical investigations shed light on the mechanism of the reaction

Fast Coprecipitation of Calcium Phosphate Nanoparticles inside Gelatin Nanofibers by Tricoaxial Electrospinning

We present an effective method for fabricating electrospun gelatin nanofibers containing well-dispersed inorganic nanoparticles. The new method encompasses the use of a special triaxial needle where mixing calcium and phosphate aqueous solutions in an intermediate needle yield calcium phosphate (CaP) nanoparticles that immediately after precipitation are dragged by the outer polymeric solution and incorporated directly in the electrospinning jet, before nanofiber formation. Gelatin electrospun mats containing different amounts of CaP nanoparticles were prepared and characterized by SEM, TEM, TGA, and stress-strain measurements. The results demonstrate that CaP particles having diameter of few tens of nanometers were successfully introduced in the gelatin nanofibers during the electrospinning process and that they were well dispersed throughout the fiber length. In addition, the use of the special triaxial needle enabled modulating the CaP amount in the nanofibers

Effect of the iodine atom position on the phosphorescence of BODIPY derivatives: a combined computational and experimental study

A new BODIPY derivative (o-I-BDP) containing an iodine atom in the ortho position of the meso-linked phenyl group was prepared. Photophysical and electrochemical properties of the molecule were compared to previously reported iodo BODIPY derivatives, as well as to the non-iodinated analog. While in the case of derivatives featuring iodine substituents in the BODIPY core, efficient population of the triplet state is accompanied by a substantial positive shift of the reduction potential compared to pristine BODIPY, o-I-BDP displays phosphorescence and simultaneously maintains the electrochemical properties of unsubstituted BODIPYs. A theoretical investigation was settled to analyze results and rationalize the influence of iodine position on electronic and photophysical properties, with the purpose of preparing a fully organic phosphorescent BODIPY derivative. TD-DFT and spin-orbit coupling calculations shed light on the subtle effects played by the introduction of iodine atom in different positions of BODIPY

Light-Induced Access to Carbazole-1,3-dicarbonitrile: A Thermally Activated Delayed Fluorescent (TADF) Photocatalyst for Cobalt-Mediated Allylations

The stability of a photocatalyst under irradiation is important in photoredox applications. In this work, we investigated the stability of a thermally activated delayed fluorescence (TADF) photocatalyst {3DPAFIPN [2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile]}, recently employed in photoredox-mediated processes, discovering that in the absence of quenchers the chromophore is unstable and is efficiently converted by irradiation with visible light into another species based on the carbazole-1,3-dicarbonitrile moiety. The new species obtained is itself a TADF emitter and finds useful applications in photoredox transformations. At the excited state, it is a strong reductant and was efficiently applied to cobalt-mediated allylation of aldehydes, whereas other TADFs (4CzIPN and 3DPAFIPN) failed to promote efficient photocatalytic cycles