title: Ultrafast proton transfer of pyranine in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and CTAC.
abstract: Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulfonate, HPTS) is studied in a polymer-surfactant aggregate using femtosecond emission spectroscopy. The polymer-surfactant aggregate is a supramolecular assembly consisting of a triblock copolymer (PEO)(20)-(PPO)(70)-(PEO)(20) (P123) and a cationic surfactant, cetyltrimethylammonium chloride (CTAC). ESPT of the protonated species (HA) in HPTS leads to the formation of A(-). The dynamics of ESPT may be followed from the decay of the HA emission (at approximately 440 nm) and rise of the A(-) emission (at approximately 550 nm). Both steady-state and time-resolved studies suggest that ESPT of HPTS in P123-CTAC aggregate is much slower than that in bulk water, in P123 micelle, or in CTAC micelle. The ratio of the steady-state emission intensities (HA/A(-)) in P123-CTAC aggregate is 2.2. This ratio is approximately 50, 12, and 2 times higher than that respectively in water, in P123 micelle, and in CTAC micelle. Retardation of ESPT causes an increase in the rise time of the A(-) emission of HPTS. In P123-CTAC aggregate, A(-) displays three rise times: 30, 250, and 2400 ps. These rise times are longer than those in CTAC micelle (23, 250, and 1800 ps), in bulk water (0.3, 3, and 90 ps), and in P123 micelle (15 and 750 ps). The rate constants for initial proton transfer, recombination, and dissociation of the ion pair are estimated using a simple kinetic scheme. The slow fluorescence anisotropy decay of HPTS in P123-CTAC aggregate is analyzed in terms of the wobbling-in-cone model.
authors.affiliation: Physical Chemistry Department, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India.
authors.forename: Subhadip
authors.initials: S
authors.lastname: Ghosh
authors.forename: Shantanu
authors.initials: S
authors.lastname: Dey
authors.forename: Ujjwal
authors.initials: U
authors.lastname: Mandal
authors.forename: Aniruddha
authors.initials: A
authors.lastname: Adhikari
authors.forename: Sudip Kumar
authors.initials: SK
authors.lastname: Mondal
authors.forename: Kankan
authors.initials: K
authors.lastname: Bhattacharyya
mesh_terms: D001190:Arylsulfonates / Q000737:chemistry*; D000077286:Cetrimonium; D002593:Cetrimonium Compounds / Q000737:chemistry*; D005454:Fluorescence Polarization; D011092:Polyethylene Glycols / Q000737:chemistry*; D011409:Propylene Glycols / Q000737:chemistry*; D011522:Protons; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet
chemical_list: D001190:Arylsulfonates; D002593:Cetrimonium Compounds; C116176:PEO-PPO-PEO; D011409:Propylene Glycols; D011522:Protons; D011092:Polyethylene Glycols; C005047:pyranine; D000077286:Cetrimonium