Abstract
Using evanescent-wave induced fluorescence (EWIF) spectroscopy, from the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane) (poly-4BCMU), has been studied in solutions of 2-methyltetrahydrofuran and a chloroform-hexane mixture, in contact with a fused silica surface. The system requires up to 4 h to attain equilibrium, at which point the EWIF emission intensity is observed to be 20 and 60 times greater than expected for the yellow (Y) and red (R) form solutions, respectively. This has been interpreted as adsorption of the polymer onto the glass surface which leads to a reduction in the efficiency of the non-radiative, internal conversion deactivation mechanism of the excited state, with consequent increase in the fluorescence quantum yield. In the case of a Y-form poly-4BCMU solution, at times less than 10 min, following the introduction of the solution to the surface, the EWIF spectrum resembles the R-form of the polymer. This spectrum grows in with a rate constant of ca. 0.7 min-1 and is attributed to a transient effect induced by a hydrophilic, non-solvent-conditioned glass surface, causing the equilibrium between the Y- and R-forms of the polymer to be shifted in favour of the R-form. The spectrum then disappears with a rate constant of 0.025 min-1 as equilibrium is reattained and the glass surface becomes conditioned, or 'solvated'. The kinetic data support the theory of an intramolecular fringed micellar structure for the R-from of poly-4BCMU in solution.
| Original language | English |
|---|---|
| Pages (from-to) | 3313-3318 |
| Number of pages | 6 |
| Journal | Journal of the Chemical Society - Faraday Transactions |
| Volume | 88 |
| Issue number | 22 |
| DOIs | |
| Publication status | Published - 1992 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Surface-induced chromism and enhanced fluorescence of the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane), at a solid/solution interface : An evanescent-wave induced fluorescence study. / Rumbles, Gary; Brown, Alan J.; Phillips, David; Bloor, David.
In: Journal of the Chemical Society - Faraday Transactions, Vol. 88, No. 22, 1992, p. 3313-3318.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Surface-induced chromism and enhanced fluorescence of the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane), at a solid/solution interface
T2 - An evanescent-wave induced fluorescence study
AU - Rumbles, Gary
AU - Brown, Alan J.
AU - Phillips, David
AU - Bloor, David
PY - 1992
Y1 - 1992
N2 - Using evanescent-wave induced fluorescence (EWIF) spectroscopy, from the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane) (poly-4BCMU), has been studied in solutions of 2-methyltetrahydrofuran and a chloroform-hexane mixture, in contact with a fused silica surface. The system requires up to 4 h to attain equilibrium, at which point the EWIF emission intensity is observed to be 20 and 60 times greater than expected for the yellow (Y) and red (R) form solutions, respectively. This has been interpreted as adsorption of the polymer onto the glass surface which leads to a reduction in the efficiency of the non-radiative, internal conversion deactivation mechanism of the excited state, with consequent increase in the fluorescence quantum yield. In the case of a Y-form poly-4BCMU solution, at times less than 10 min, following the introduction of the solution to the surface, the EWIF spectrum resembles the R-form of the polymer. This spectrum grows in with a rate constant of ca. 0.7 min-1 and is attributed to a transient effect induced by a hydrophilic, non-solvent-conditioned glass surface, causing the equilibrium between the Y- and R-forms of the polymer to be shifted in favour of the R-form. The spectrum then disappears with a rate constant of 0.025 min-1 as equilibrium is reattained and the glass surface becomes conditioned, or 'solvated'. The kinetic data support the theory of an intramolecular fringed micellar structure for the R-from of poly-4BCMU in solution.
AB - Using evanescent-wave induced fluorescence (EWIF) spectroscopy, from the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane) (poly-4BCMU), has been studied in solutions of 2-methyltetrahydrofuran and a chloroform-hexane mixture, in contact with a fused silica surface. The system requires up to 4 h to attain equilibrium, at which point the EWIF emission intensity is observed to be 20 and 60 times greater than expected for the yellow (Y) and red (R) form solutions, respectively. This has been interpreted as adsorption of the polymer onto the glass surface which leads to a reduction in the efficiency of the non-radiative, internal conversion deactivation mechanism of the excited state, with consequent increase in the fluorescence quantum yield. In the case of a Y-form poly-4BCMU solution, at times less than 10 min, following the introduction of the solution to the surface, the EWIF spectrum resembles the R-form of the polymer. This spectrum grows in with a rate constant of ca. 0.7 min-1 and is attributed to a transient effect induced by a hydrophilic, non-solvent-conditioned glass surface, causing the equilibrium between the Y- and R-forms of the polymer to be shifted in favour of the R-form. The spectrum then disappears with a rate constant of 0.025 min-1 as equilibrium is reattained and the glass surface becomes conditioned, or 'solvated'. The kinetic data support the theory of an intramolecular fringed micellar structure for the R-from of poly-4BCMU in solution.
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U2 - 10.1039/FT9928803313
DO - 10.1039/FT9928803313
M3 - Article
VL - 88
SP - 3313
EP - 3318
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 22
ER -