Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate

Eric D. Bott, Erin A. Riley, Bart Kahr, Philip J. Reid

Research output: Contribution to journalArticle

Abstract

The excited-state decay kinetics of single 2′, 7′- dichlorofluorescein (DCF) molecules oriented and overgrown within crystals of potassium acid phthalate (KAP) are reported. Time-correlated single-photon counting measurements (TCSPC) of 56 DCF molecules in KAP reveal that single-exponential decay is exhibited by roughly half of the molecules. The remainder demonstrates complex excited-state decay kinetics that are well fit by a stretched exponential function consistent with dispersed kinetics. Histograms of single-molecule luminescence energies revealed environmental fluctuations and distinct chemical species. The TCSPC results are compared to Monte Carlo simulations employing a first-passage model for excited-state decay. Agreement between experiment and theory, on both bulk and single-molecule levels, suggests that a subset of the DCF molecules in KAP experience fluctuations in the surrounding environment that modify the energy barrier to proton transfer leading to dispersed kinetics.

Original languageEnglish (US)
Pages (from-to)2403-2411
Number of pages9
JournalACS Nano
Volume3
Issue number8
DOIs
StatePublished - Aug 25 2009

Fingerprint

phthalates
Proton transfer
Potassium
potassium
Hydrogen
Molecules
Kinetics
protons
kinetics
decay
hydrogen
Excited states
molecules
counting
Photons
excitation
Exponential functions
Energy barriers
exponential functions
photons

Keywords

  • Dispersed kinetics
  • Fluorescence intermittency
  • Fluorescence lifetime
  • Proton transfer
  • Single molecule microscopy

ASJC Scopus subject areas

  • Engineering(all)
  • Materials Science(all)
  • Physics and Astronomy(all)

Cite this

Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate. / Bott, Eric D.; Riley, Erin A.; Kahr, Bart; Reid, Philip J.

In: ACS Nano, Vol. 3, No. 8, 25.08.2009, p. 2403-2411.

Research output: Contribution to journalArticle

Bott, Eric D. ; Riley, Erin A. ; Kahr, Bart ; Reid, Philip J. / Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate. In: ACS Nano. 2009 ; Vol. 3, No. 8. pp. 2403-2411.
@article{8fac953313ec496ba84f2e0a0241a6d9,
title = "Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate",
abstract = "The excited-state decay kinetics of single 2′, 7′- dichlorofluorescein (DCF) molecules oriented and overgrown within crystals of potassium acid phthalate (KAP) are reported. Time-correlated single-photon counting measurements (TCSPC) of 56 DCF molecules in KAP reveal that single-exponential decay is exhibited by roughly half of the molecules. The remainder demonstrates complex excited-state decay kinetics that are well fit by a stretched exponential function consistent with dispersed kinetics. Histograms of single-molecule luminescence energies revealed environmental fluctuations and distinct chemical species. The TCSPC results are compared to Monte Carlo simulations employing a first-passage model for excited-state decay. Agreement between experiment and theory, on both bulk and single-molecule levels, suggests that a subset of the DCF molecules in KAP experience fluctuations in the surrounding environment that modify the energy barrier to proton transfer leading to dispersed kinetics.",
keywords = "Dispersed kinetics, Fluorescence intermittency, Fluorescence lifetime, Proton transfer, Single molecule microscopy",
author = "Bott, {Eric D.} and Riley, {Erin A.} and Bart Kahr and Reid, {Philip J.}",
year = "2009",
month = "8",
day = "25",
doi = "10.1021/nn900596a",
language = "English (US)",
volume = "3",
pages = "2403--2411",
journal = "ACS Nano",
issn = "1936-0851",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate

AU - Bott, Eric D.

AU - Riley, Erin A.

AU - Kahr, Bart

AU - Reid, Philip J.

PY - 2009/8/25

Y1 - 2009/8/25

N2 - The excited-state decay kinetics of single 2′, 7′- dichlorofluorescein (DCF) molecules oriented and overgrown within crystals of potassium acid phthalate (KAP) are reported. Time-correlated single-photon counting measurements (TCSPC) of 56 DCF molecules in KAP reveal that single-exponential decay is exhibited by roughly half of the molecules. The remainder demonstrates complex excited-state decay kinetics that are well fit by a stretched exponential function consistent with dispersed kinetics. Histograms of single-molecule luminescence energies revealed environmental fluctuations and distinct chemical species. The TCSPC results are compared to Monte Carlo simulations employing a first-passage model for excited-state decay. Agreement between experiment and theory, on both bulk and single-molecule levels, suggests that a subset of the DCF molecules in KAP experience fluctuations in the surrounding environment that modify the energy barrier to proton transfer leading to dispersed kinetics.

AB - The excited-state decay kinetics of single 2′, 7′- dichlorofluorescein (DCF) molecules oriented and overgrown within crystals of potassium acid phthalate (KAP) are reported. Time-correlated single-photon counting measurements (TCSPC) of 56 DCF molecules in KAP reveal that single-exponential decay is exhibited by roughly half of the molecules. The remainder demonstrates complex excited-state decay kinetics that are well fit by a stretched exponential function consistent with dispersed kinetics. Histograms of single-molecule luminescence energies revealed environmental fluctuations and distinct chemical species. The TCSPC results are compared to Monte Carlo simulations employing a first-passage model for excited-state decay. Agreement between experiment and theory, on both bulk and single-molecule levels, suggests that a subset of the DCF molecules in KAP experience fluctuations in the surrounding environment that modify the energy barrier to proton transfer leading to dispersed kinetics.

KW - Dispersed kinetics

KW - Fluorescence intermittency

KW - Fluorescence lifetime

KW - Proton transfer

KW - Single molecule microscopy

UR - http://www.scopus.com/inward/record.url?scp=69549116938&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=69549116938&partnerID=8YFLogxK

U2 - 10.1021/nn900596a

DO - 10.1021/nn900596a

M3 - Article

VL - 3

SP - 2403

EP - 2411

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 8

ER -