title: On the mechanism of photochromism of 4'-N,N-dimethylamino-7-hydroxyflavylium in pluronic F127.
abstract: The photochromism of the compound 4'-N,N-dimethylamino-7-hydroxyflavylium incorporated in Pluronic F127 micelles and gels was studied in great detail. The red flavylium ion (AH(+)) or the quinoidal base (A), depending on pH, are the irradiation products of the colorless trans-chalcone (Ct). Absorption and fluorescence (steady-state, time-resolved, and anisotropy), pH jumps, and flash photolysis were used to characterize the system. At moderately acidic to neutral pH values, the Ct species is distributed between the core and corona of the Pluronic micelle, as well as in the aqueous phase. At acidic pH values, AH(+) remains most probably in the water phase. The Ct maximum absorption wavelength constitutes a good sensor for the critical micelle concentration (CMC) or critical micelle temperature (CMT). The apparent acidity constant pK'(a) was found to be a relatively good sensor for CMC and also for detection of the sol-gel critical temperature. The Ct photochromic mechanism was analyzed by comparing the photophysics in pure solvents and the pluronic media. Solvatochromic effects show a lack of solvent polarity dependence of the Stokes shift, indicating a low dipolar moment change between the ground and the locally excited state. An internal charge transfer nonradiative process (ICT) competes with Ct photoisomerization and is the dominant process in highly polar solvents, preventing the appearance of photochromism, in contrast with lower polar environments, such as micelles and ethanol. In high viscous environments as those found in the core of the Pluronic F127 micelles or glycerol, both ICT and photoisomerization are reduced, enhancing the Ct fluorescence quantum yield. According to the data from fluorescence measurements and pH jumps, evidence for the Ct distribution among different sites within the pluronic aggregate was found, (i) a hydrophilic/fluid region where Ct has poor fluorescence and isomerization yields, bulk region; (ii) the corona of the micelle where photoisomerization is maximized; and (iii) the hydrophobic/viscous region where the fluorescence quantum yield is higher (and photoisomerization lower). This effect leads to a selective Ct photochemistry.
authors.affiliation: REQUIMTE, Departamento de Química, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
authors.forename: Raquel
authors.initials: R
authors.lastname: Gomes
authors.forename: César A T
authors.initials: CA
authors.lastname: Laia
authors.forename: Fernando
authors.initials: F
authors.lastname: Pina
mesh_terms: D005021:Ethylamines / Q000737:chemistry; D005419:Flavonoids / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D010777:Photochemistry; D020442:Poloxamer / Q000737:chemistry*; D013050:Spectrometry, Fluorescence
chemical_list: C510029:7-(N,N-diethylamino)-4'-hydroxyflavylium; D005021:Ethylamines; D005419:Flavonoids; D020442:Poloxamer