0000000000139960
AUTHOR
M. Alexandra Bernardo
Polyamine Linear Chains Bearing Two Identical Terminal Aromatic Units. Evidence for a Photo Induced Bending Movement
Abstract Several chemosensors bearing a fluorescent unit at both ends of a linear polyamine chain were synthesised. The protonation as well as the association constants with Cu2+ and Zn2+ were determined by potentiometry in 0.15 mol dm−3 NaCl at 298.1 K. In the case of 1,16-bis(1-naphthylmethyl)-1,4,7,10,13,16-hexaazadecane hexahydrochloride (L1), formation of an excimer emission in aqueous acidic solutions was observed. The system was characterized by steady state fluorescence emission and by time resolved fluorescence. In the ground state the molecule is expected to adopt a more or less linear conformation, while in the excited state a bending movement of the chain must occur in order to …
ChemInform Abstract: Fluorescent Chemosensors Containing Polyamine Receptors
Chemosensors have attracted interest in many different scientific fields, such as environmental chemistry, medicine, and the processing and storage of information. These molecular-scale devices have the advantage of working on the same spatial scale as the chemical structures that are responsible for macroscopic behaviour observed in the environment or those associated with health problems. Moreover, they allow the construction of molecular-scale devices for information storage. In this review, we describe a family of chemosensors based on a polyamine receptor and a fluorescent signalling unit. Polyamine receptors are water-soluble ambidentate receptors; they are able to coordinate either m…
Thermodynamics and fluorescence emission studies on potential molecular chemosensors for ATP recognition in aqueous solution †
The interaction of the open-chain polyamine N-(3-aminopropyl)-N′-[3-(anthrylmethyl)aminopropyl]ethane-1,2-diamine (L) with the relevant anionic forms of adenosine 5′-triphosphate (ATP), adenosine 5′-diphosphate (ADP) and adenosine 5′-monophosphate (AMP) is described. Unambiguous criteria for defining thermodynamic selectivity based on the use of effective stability constants are presented. The interaction of L and several other topologically similar polyammonium receptors with ATP has been shown to occur through electrostatic and π-stacking intermolecular forces. The π-stacking binding mode is modulated by the protonation degree of ATP as indicated by fluorescence emission titrations. Evide…
Fluorescent chemosensors containing polyamine receptors
Chemosensors have attracted interest in many different scientific fields, such as environmental chemistry, medicine, and the processing and storage of information. These molecular-scale devices have the advantage of working on the same spatial scale as the chemical structures that are responsible for macroscopic behaviour observed in the environment or those associated with health problems. Moreover, they allow the construction of molecular-scale devices for information storage. In this review, we describe a family of chemosensors based on a polyamine receptor and a fluorescent signalling unit. Polyamine receptors are water-soluble ambidentate receptors; they are able to coordinate either m…
Steady-state fluorescence emission studies on polyazacyclophane macrocyclic receptors and on their adducts with hexacyanocobaltate(III)
The steady-state fluorescence emission spectra of the azacyclophanes 2,5,8,11-tetraaza[12] paracyclophane (L1), 2,6,9,13-tetraaza[14]paracyclophane (L2), 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L3) and 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L4) as a function of pH have been measured. The fully protonated species of each cyclophane gives the highest fluorescence-emission quantum yield. The shapes of the titration curves have been explained by the existence of an electron-transfer quenching effect from a non-protonated amine to the benzene chromophore. This effect is greater for macrocycles in which the first deprotonated amine group is closer to the…
Chemosensors displaying pH controlled multistage fluorescence emission
A large number of systems displaying pH controlled multistages of fluorescence emission intensity, have not been recognized from this point of view. In this work we present two paradigmatic cases: (i) polyamine receptors linked to a fluorophore unit, in which the signal is modulated by an intra-molecular pH dependent electron transfer process, (ii) phenols presenting adiabatic excited state proton transfer. In the first example the chemosensors are constituted by a receptor unit containing a polyaza moiety suitable for binding protons (but also metal ions or anions). The receptor is linked to a benzene or naphthalene unit that acts as a fluorophore. The fluorescence signal is dependent on t…
A New ZnIITweezer Pyridine-Naphthalene System - An Off-On-Off System Working in a Biological pH Window
Their basic idea consisted of the connec-tion of an amine to a fluorophoric anthracene unit on oneside and to a pyridine moiety on the other. At acidic pHvalues the amino and the pyridine groups are protonatedand a photoinduced electron transfer (PET) occurs fromthe π-π* excited state of the anthracene to the protonatedpyridinium unit, leading to quenching of the fluorescence.However, at high pH values, where the amino group is notprotonated, PET alternatively takes place from the aminelone pair to the same excited state of the fluorophore, yield-ing the same inhibitory effect on the fluorescence. Betweenthese two pH values, there is a pH window where PET doesnot take place and fluorescence…
Polyamines containing naphthyl groups as pH-regulated molecular machines driven by light
A series of compounds made up by linking methylnaphthalene fragments at both ends of different polyamine chains have shown to behave as pH-regulated molecular machines driven by light and fluorescence emission studies have proved the formation of an excimer between the two naphthalene units whose appearance, fluorescence intensity and decay times depend on the pH value of the media. Albelda Gimeno, Maria Teresa, Teresa.Albelda@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es ; Soriano Soto, Concepción, Concepcion.Soriano@uv.es