1 and 2-photon fluorescence anisotropy decay in silicon alkoxide sol-gels: Interpretation in terms of self- assembled nanoparticles

C.D. Geddes, J. Karolin, D.J.S. Birch

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

We have studied the one- and two-photon induced fluorescence anisotropy decay of rhodamine 6G (R6G) during polymerization of tetramethyl orthosilicate (TMOS) approaching the sol-to-gel transition, a time denoted tg, using time-correlated single-photon counting and femtosecond Ti:sapphire laser excitation. A biexponential decay of fluorescence anisotropy is observed at all times. We propose a different interpretation to the widely accepted view, that fluorescence anisotropy reports solely on molecular viscosity in sol-gels. We think our results are consistent with the presence of both free dye and dye bound to nm-size silica particles rather than just the coexistence of different discrete viscosity domains as reported previously. A corollary of our interpretation is that the microviscosity changes very little from that of the initial bulk sol throughout the sol-gel polymerization. Nanometer-size particles are known from small angle scattering studies to be precursors to gelation in sol-gels over a wide range of conditions and our interpretation might prove to be an important step toward understanding the self-assembly mechanisms of silicon alkoxide based materials at the molecular level. According to our measurements and interpretation, for TMOS at pH 2.3 for example, primary silica particles of 0.8-nm mean radius grow by monomer-monomer or monomer-cluster addition to produce larger structures 1.1-nm mean radius after one month.
Original languageEnglish
Pages (from-to)3835-3841
Number of pages6
JournalJournal of Physical Chemistry B
Volume106
Issue number2002
DOIs
Publication statusPublished - 2002

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alkoxides
Silicon
Sol-gels
Anisotropy
Photons
Monomers
Fluorescence
gels
Polymethyl Methacrylate
Sols
Nanoparticles
fluorescence
nanoparticles
anisotropy
monomers
photons
silicon
decay
Coloring Agents
Gels

Keywords

  • anisotropy decay
  • silicon alkoxide sol-gels
  • nanoparticles
  • nanoscience

Cite this

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title = "1 and 2-photon fluorescence anisotropy decay in silicon alkoxide sol-gels: Interpretation in terms of self- assembled nanoparticles",
abstract = "We have studied the one- and two-photon induced fluorescence anisotropy decay of rhodamine 6G (R6G) during polymerization of tetramethyl orthosilicate (TMOS) approaching the sol-to-gel transition, a time denoted tg, using time-correlated single-photon counting and femtosecond Ti:sapphire laser excitation. A biexponential decay of fluorescence anisotropy is observed at all times. We propose a different interpretation to the widely accepted view, that fluorescence anisotropy reports solely on molecular viscosity in sol-gels. We think our results are consistent with the presence of both free dye and dye bound to nm-size silica particles rather than just the coexistence of different discrete viscosity domains as reported previously. A corollary of our interpretation is that the microviscosity changes very little from that of the initial bulk sol throughout the sol-gel polymerization. Nanometer-size particles are known from small angle scattering studies to be precursors to gelation in sol-gels over a wide range of conditions and our interpretation might prove to be an important step toward understanding the self-assembly mechanisms of silicon alkoxide based materials at the molecular level. According to our measurements and interpretation, for TMOS at pH 2.3 for example, primary silica particles of 0.8-nm mean radius grow by monomer-monomer or monomer-cluster addition to produce larger structures 1.1-nm mean radius after one month.",
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author = "C.D. Geddes and J. Karolin and D.J.S. Birch",
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1 and 2-photon fluorescence anisotropy decay in silicon alkoxide sol-gels: Interpretation in terms of self- assembled nanoparticles. / Geddes, C.D.; Karolin, J.; Birch, D.J.S.

In: Journal of Physical Chemistry B, Vol. 106, No. 2002, 2002, p. 3835-3841.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 1 and 2-photon fluorescence anisotropy decay in silicon alkoxide sol-gels: Interpretation in terms of self- assembled nanoparticles

AU - Geddes, C.D.

AU - Karolin, J.

AU - Birch, D.J.S.

PY - 2002

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N2 - We have studied the one- and two-photon induced fluorescence anisotropy decay of rhodamine 6G (R6G) during polymerization of tetramethyl orthosilicate (TMOS) approaching the sol-to-gel transition, a time denoted tg, using time-correlated single-photon counting and femtosecond Ti:sapphire laser excitation. A biexponential decay of fluorescence anisotropy is observed at all times. We propose a different interpretation to the widely accepted view, that fluorescence anisotropy reports solely on molecular viscosity in sol-gels. We think our results are consistent with the presence of both free dye and dye bound to nm-size silica particles rather than just the coexistence of different discrete viscosity domains as reported previously. A corollary of our interpretation is that the microviscosity changes very little from that of the initial bulk sol throughout the sol-gel polymerization. Nanometer-size particles are known from small angle scattering studies to be precursors to gelation in sol-gels over a wide range of conditions and our interpretation might prove to be an important step toward understanding the self-assembly mechanisms of silicon alkoxide based materials at the molecular level. According to our measurements and interpretation, for TMOS at pH 2.3 for example, primary silica particles of 0.8-nm mean radius grow by monomer-monomer or monomer-cluster addition to produce larger structures 1.1-nm mean radius after one month.

AB - We have studied the one- and two-photon induced fluorescence anisotropy decay of rhodamine 6G (R6G) during polymerization of tetramethyl orthosilicate (TMOS) approaching the sol-to-gel transition, a time denoted tg, using time-correlated single-photon counting and femtosecond Ti:sapphire laser excitation. A biexponential decay of fluorescence anisotropy is observed at all times. We propose a different interpretation to the widely accepted view, that fluorescence anisotropy reports solely on molecular viscosity in sol-gels. We think our results are consistent with the presence of both free dye and dye bound to nm-size silica particles rather than just the coexistence of different discrete viscosity domains as reported previously. A corollary of our interpretation is that the microviscosity changes very little from that of the initial bulk sol throughout the sol-gel polymerization. Nanometer-size particles are known from small angle scattering studies to be precursors to gelation in sol-gels over a wide range of conditions and our interpretation might prove to be an important step toward understanding the self-assembly mechanisms of silicon alkoxide based materials at the molecular level. According to our measurements and interpretation, for TMOS at pH 2.3 for example, primary silica particles of 0.8-nm mean radius grow by monomer-monomer or monomer-cluster addition to produce larger structures 1.1-nm mean radius after one month.

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