Surface-induced chromism and enhanced fluorescence of the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane), at a solid/solution interface: An evanescent-wave induced fluorescence study

Gary Rumbles, Alan J. Brown, David Phillips, David Bloor

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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 languageEnglish
Pages (from-to)3313-3318
Number of pages6
JournalJournal of the Chemical Society - Faraday Transactions
Volume88
Issue number22
DOIs
Publication statusPublished - 1992

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evanescent waves
Solid solutions
solid solutions
Fluorescence
fluorescence
Polymers
Glass
glass
Rate constants
polymers
Spectroscopy
spectroscopy
Fluorescence spectroscopy
internal conversion
Hexanes
Quantum yield
Fused silica
Chloroform
chloroform
Excited states

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Surface-induced chromism and enhanced fluorescence of the soluble polydiacetylene, poly(4-butoxycarbonylmethylurethane), at a solid/solution interface: An evanescent-wave induced fluorescence study",
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.",
author = "Gary Rumbles and Brown, {Alan J.} and David Phillips and David Bloor",
year = "1992",
doi = "10.1039/FT9928803313",
language = "English",
volume = "88",
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journal = "Physical Chemistry Chemical Physics",
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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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