Chiral synthetic pseudopeptidic derivatives as triplet excited state quenchers

The behavior of 6 pseudopeptidic models, synthesized by connecting different protected amino acids (Trp, Tyr, Phe, and Lys) with various diamino spacers, as quenchers of the triplet excited state of tiaprofenic acid (and its methyl ester), has been investigated. A series of quenching constants have been determined, which depend on the nature of the quencher and on the stereochemistry of the excited drug. A significant degree of stereodifferentiation has been found for the peptidomimetic synthesized with Phe and Tyr linked by a piperazine bridge. The obtained results support the utility of laser flash photolysis (LFP) as a tool to investigate the interactions between photoexcited drugs and s…

Aromatic Ketones as Photocatalysts: Combined Action as Triplet Photosensitiser and Ground State Electron Acceptor

Photoreaction Between Benzoylthiophenes and N-BOC-Tryptophan Methyl Ester‡

Drug-induced photoallergy requires as the first step formation of covalent drug-protein photoadducts. One of the key amino acids involved in this process is tryptophan (Trp). In this context, several diaryl ketones, including 2-benzoylthiophene (BT), [2-(5-benzoyl-5-thienyl)]-2-methylpropanoic methyl ester (TPA methyl ester) and 4-(2-thienylcarbonyl)phenyl]-2-methylpropanoic methyl ester (SUP methyl ester) have been irradiated in the presence of N-BOC-(L)-tryptophan methyl ester. Laser flash photolysis has allowed to detect three neutral radicals (ketyl, indolyl and skatolyl radicals) resulting from formal hydrogen-atom abstraction. This correlates well with the isolation of homodimers, as …

Triplet exciplexes as energy transfer photosensitisers

Experimental evidence is provided for the occurrence of triplet–triplet energy transfer from benzoylthiophene–indole exciplexes to naphthalenes with a remarkable stereodifferentiation; chiral recognition is also observed in the decay of the generated naphthalene triplets. Perez Prieto, Julia, Julia.Perez@uv.es ; Galian, Raquel Eugenia, Raquel.Galian@uv.es ; Morant Miñana, Maria Carmen, Maica.Morant@uv.es

Stereodifferentiation in the formation and decay of the encounter complex in bimolecular electron transfer with photoactivated acceptors.

Experimental evidence has been obtained for the involvement of encounter complexes between both enantiomers of a π,π* triplet excited ketone and a chiral phenol or indole. Determination of the pre-equilibrium constants (KEC) and the intrinsic decay rate constants (kd) indicates a significant stereodifferentiation in both steps of the quenching process. Perez Prieto, Julia, Julia.Perez@uv.es ; Galian, Raquel Eugenia, Raquel.Galian@uv.es ; Morant Miñana, Maria Carmen, Maica.Morant@uv.es

Quantum dot/cyclodextrin supramolecular systems based on efficient molecular recognition and their use for sensing.

A supramolecular system based on ketoprofen functionalised CdSe/ZnS nanoparticles and pyrene-modified β-CD was prepared and successfully used for molecular sensing of different analytes. In addition, a strategy for the individual recovery of all the components of the sensing assay is reported.