Energy transfer from a fluorescent hydrogel to a hosted fluorophore

The fluorescent properties of a new 1,3,5-cyclohexyltricarboxamide-based low-molecular-weight hydrogelator (1) derivatized with one hydrophobic fluorophore and two hydrophilic substituents have been investigated. Gels of 1 are composed of long, nonbranched fibers of uniform diameter, as shown by cryo-transmission electron microscopy (cryo-TEM). The aggregation of the naphthalene fluorophore moieties of the gelator molecules in the gel fibers favors the occurrence of a fast energy migration process that allows a very efficient sensitization of the fluorescence of a hosted fluorophore. Such processes have been investigated by the addition of propyldansylamide (PDNS), at two different concentrations, to gels of 1. Around 30% of the total PDNS added to the gels was found to be incorporated in the gel fibers, as confirmed by deconvolution of the fluorescence spectrum, excited-state lifetime measurements, and steady-state and time-resolved fluorescence anisotropy measurements. Moreover, anisotropy measurements show that the fluorophore that is incorporated within the gel fibers is almost completely immobilized, indicating that the interactions of PDNS with the gelator moieties are very strong. This particular configuration of donor (1) and acceptor (PDNS) molecules leads to a very efficient antenna effect, where 50% of the absorbed photons are funneled through to the dansyl derivative when one PDNS molecule is incorporated in the gel fibers for every 100 gelator molecules. A 5-fold higher concentration of PDNS increases the percentage of funneled photons to 75%.     

Highly Enantioselective Catalytic Kinetic Resolution of α-Branched Aldehydes through Formal Cycloaddition with Homophthalic Anhydrides

A new catalytic methodology was developed to promote an efficient one-pot kinetic resolution of racemic aldehydes with selectivity (s*) of up to 91 (99:1 d.r., >99 % ee) in a cycloaddition reaction with enolizable anhydrides to afford dihydroisocoumarin products (a core prevalent in natural products and molecules of medicinal interest) containing three contiguous stereocentres.     

Sull’integrazione frazionaria anisotropa

Riassunto In questa nota si indica il tipo della singolarità nell'origine della trasformata di Fourier di certe funzioni; mediante, tale risultato si possono rapidamente ritrovare alcune maggiorazioni circa i nuclei di integrazione frazionaria anisotropa già stabiliti daP. I. Lizorkin.

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Summary In this paper the form of the singularity near the origine of the Fourier trasform of certain functions is shown; with the aid of this result some estimates for the kernel of non-isotropic fractional integration previously proved byP. I. Lizorkin are established in a very simple way.

     

Complementi per una formula di rappresentazione per funzioni analitiche in un cono aperto diR n

Riassunto Si prova una formula di rappresentazione per funzioni analitiche in un cono aperto Ω⊂R ⁿ

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Summary An integral representation formula for analytic functions in any open cone Ω⊂R ⁿ is proved.

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Lavoro eseguito nell’ambito dell’attività del Gruppo Nazionale per l’Analisi Funzionale e le sue Applicazioni.     

Synthesis of sulphur containing fused ring heterocycles by intramolecular 1,3-dipolar-cycloadditions

Sulfur containing fused triazoles and pyrazoles are synthesized through intramolecular cycloadditions of properly functionalized azides and nitrileimines, respectively.     

Reaction of 2-dimethylaminomethylene-1,3-diones with dinucleophiles. I. Synthesis of 1,5-disubstituted 4-acylpyrazoles

Reaction of open-chain and cyclic sym-1,3-diones with N,N-dimethylformamide dimethyl acetal gave, generally in high yield, a series of sym-2-dimethylaminomethylene-1,3-diones which reacted with phenylhydrazine and methylhydrazine to afford, generally in satisfactory yield, a number of 1,5-disubstituted 4-acylpyrazoles. The applications and limits of this new pyrazole synthesis are presented and discussed.     

On the reaction between coumarins and hydroxylamine

The Posner reaction between coumarin and hydroxylamine was studied and extended to several substituted coumarins. Isolation of some significant reaction intermediates permitted rationalization of a possible reaction pathway.