Relating the polarity-dependent fluorescence response of pyrene to vibronic coupling. Achieving a fundamental understanding of the py polarity scale

Karpovich, Dzmitry; Blanchard, G. J.

doi:10.1021/j100012a014

Cited by 385 publications

(358 citation statements)

References 8 publications

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“…However, the I 1 /I 3 ratio was found to exhibit rather poor correlation with measured solvatochromic polarity parameters [24], using established correlation equations. This is because the "polarity" sensed by pyrene is related only to dipole-induced dipole interactions based on vibronic coupling [23], and essentially ignores hydrogen bonding effects. This is crucial because one cannot ignore the significant effects induced by H-bonding on probe environments.…”

Section: Discussionmentioning

confidence: 99%

“…Plotting the changes in intensity of the I 1 and I 3 vibronic bands ( Figure 4c for the P65 polymer film), shows that the rate of decrease in intensity was greater for the first vibronic (373.5 nm) band compared to the third band (384.2 nm). Thus it appears that temperature changes in rigid polymer media affects more strongly the I 1 (S 1 ν=0 → S 0 ν=0 ) vibronic band transition than the I 3 (S 1 ν=0 → S 0 ν=1 ) band and this is probably due to differences in vibronic coupling contributions [23]. Analysis of the excitation spectra monitored at the emission of the first vibronic band of pyrene doped polymer films recorded at various temperatures, indicated that there was no excimer formation associated with these mild experimental conditions [32][33][34][35][36][37][38].…”

Section: Pyrene Fluorescencementioning

confidence: 98%

“…The changes observed in the spectra are due to dipole-induced dipole interactions based on vibronic coupling [22,23]. The emission spectra (Figure 2a) show that the shape and position of the vibronic bands in the emission spectra are not affected by the composition of the film and there is also no evidence of an excimer band at 470 nm which implies that emission occurs only from pyrene monomers in the poly(NIPAM-co-NtBA) films.…”

Section: Pyrene Fluorescencementioning

confidence: 98%

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Polarity Assessment of Thermoresponsive Poly(NIPAM-co-NtBA) Copolymer Films Using Fluorescence Methods

et al. 2010

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The in-situ, non-contact, and non-destructive measurement of the physicochemical properties such as the polarity of thin (nm to µm), hydrophilic polymer films is desirable in many areas of polymer science. Polarity is a complex factor and encompasses a range of noncovalent interactions including dipolarity/polarizability and hydrogen bonding. A polarity measurement method based on fluorescence would be ideal, but the key challenge is to identify suitable probes which can accurately measure specific polarity related parameters. In this manuscript we assess a variety of fluorophores for measuring the polarity of a series of relatively hydrophilic, thermoresponsive N-isopropylacrylamide/N-tert-butylacrylamide (NIPAM/NtBA) copolymers. The emission properties of both pyrene and 3-Hydroxyflavone (3-HF) based fluorophores were measured in dry polymer films. In the case of pyrene, a relatively weak, linear relationship between polymer composition and the ratio of the first to the third vibronic band of the emission spectrum (I 1 /I 3 ) is observed, but pyrene emission is very sensitive to temperature and thus not suitable for robust polarity measurements. The 3-

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Section: Discussionmentioning

confidence: 99%

Section: Pyrene Fluorescencementioning

confidence: 98%

Section: Pyrene Fluorescencementioning

confidence: 98%

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Polarity Assessment of Thermoresponsive Poly(NIPAM-co-NtBA) Copolymer Films Using Fluorescence Methods

et al. 2010

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“…transitions show a large increase in polar solvents This broad band for the sample studied was assigned to [17,20,21]. The sulfonamide group in position 1 does "excimer-like" emission, in which exciplex is the main not alter the symmetry of the molecule very much, and contribution [11].…”

Section: /I 5 Band Ratio Variationmentioning

confidence: 86%

Untitled

González‐Benito

Aznar

Lima³

et al. 2000

Journal of Fluorescence

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E-glass fibers were silanized using a 1% (v/v) aqueous solution of ␥-aminopropyltriethoxysilane (APES). Pyrenesulfonamide conjugates were formed by reaction of 1-pyrenesulfonyl chloride (PSC) in acetonitrile (AcN), with the amine groups immobilized on the glass fiber surface. These pyrene-sulfonamide conjugates were used as fluorescence probes, being a relatively simple analytical method to study the coating microstructure of polyorganosiloxane layer on glass fibers. The first aim of this work was to estimate possible interactions of the polyaminosiloxane coating with surrounding molecules of different solvents (solvent accessibility to the chromophore). For this study, the fluorescence response of pyrene-sulfonamide dye (PSA) was correlated with solvent polarity parameters. It was concluded that all the studied solvents were accessible to the chromophore, and they can gather in two groups, depending on their ability to swell the poliorganosiloxane layer. The second objective was to estimate the rigidity of the coating polymer from the temperature dependence of PSA emission. At about 180 K, a sudden change in the behavior of different photophysical parameters of PSA were observed. This phenomenon was interpreted as a density change in the polyaminosiloxane attached to the glass fibers.

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“…25, 30 The decrease of the I 3 /I 1 ratio with media polarity allows us to compare the three different environments pyrene experiences in the cavities of the three hosts. Fig.…”

Section: Steady State Luminescencementioning

confidence: 99%

Pyrene—p-tert-butylcalixarenes inclusion complexes formation: a surface photochemistry study

Branco

Ferreira

Rego

et al. 2006

Photochem Photobiol Sci

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Diffuse reflectance and luminescence techniques were used to study the photophysics and photochemistry of pyrene within p-tert-butylcalix [n]arenes with n = 4, 6, and 8, and to study their ability to form inclusion complexes in heterogeneous media. Evidences for inclusion complex formation were found for the three hosts under study. [8]arene. This feature is particularly relevant for calix [6]arene, suggesting a very favourable situation for the hydrogen atom abstraction to occur. The analysis of the degradation products revealed the presence of hydroxypyrene as a major photodegradation product for the three hosts. Dihydro-hydroxypyrene was also formed in the case of calix[6]arene and calix [8]arene. The formation of the calixarene's phenoxyl radical and subsequent hydrogen abstraction is consistent with the formation of dihydro-dihydroxypyrene.

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Relating the polarity-dependent fluorescence response of pyrene to vibronic coupling. Achieving a fundamental understanding of the py polarity scale

Cited by 385 publications

References 8 publications

Polarity Assessment of Thermoresponsive Poly(NIPAM-co-NtBA) Copolymer Films Using Fluorescence Methods

Polarity Assessment of Thermoresponsive Poly(NIPAM-co-NtBA) Copolymer Films Using Fluorescence Methods

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Pyrene—p-tert-butylcalixarenes inclusion complexes formation: a surface photochemistry study

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