Identifiability of competitive intermolecular three-state excited-state processes

Boens, Noël; Kowalczyk, Andrzej

doi:10.1016/0009-2614(96)00859-7

Cited by 9 publications

(6 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since the first identifiability study of an intermolecular twostate excited-state process, 12 identification studies of a broad range of models of intermolecular and intramolecular twostate and three-state excited-state processes have been reported [13][14][15][16][17][18][19][20][21][22][23][24] (see ref. 25 and 26 for supplementary literature data).…”

Section: Introductionmentioning

confidence: 99%

Identifiability of models for time-resolved fluorescence with underlying distributions of rate constants

Boens

Auweraer

2014

Photochem Photobiol Sci

Self Cite

View full text Add to dashboard Cite

The deterministic identifiability analysis of photophysical models for the kinetics of excited-state processes, assuming errorless time-resolved fluorescence data, can verify whether the model parameters can be determined unambiguously. In this work, we have investigated the identifiability of several uncommon models for time-resolved fluorescence with underlying distributions of rate constants which lead to non-exponential decays. The mathematical functions used here for the description of non-exponential fluorescence decays are the stretched exponential or Kohlrausch function, the Becquerel function, the Förster type energy transfer function, decay functions associated with exponential, Gaussian and uniform distributions of rate constants, a decay function with extreme sub-exponential behavior, the Mittag-Leffler function and Heaviside's function. It is shown that all the models are uniquely identifiable, which means that for each specific model there exists a single parameter set that describes its associated fluorescence δ-response function.

show abstract

Section: Introductionmentioning

confidence: 99%

Identifiability of models for time-resolved fluorescence with underlying distributions of rate constants

Boens

Auweraer

2014

Photochem Photobiol Sci

Self Cite

View full text Add to dashboard Cite

show abstract

“…Identifiability analyses of compartmental models for excited-state processes have only rather recently been reported. − We have done extensive studies of the deterministic identifiability of a whole range of compartmental models with time-invariant rate constants for intermolecular as well as intramolecular two-state and three-state excited-state processes in the presence and absence of added quencher. − For the linear, time-invariant models, the parameters to be identified are rate constants and spectral parameters related to absorption and emission. For models with transients, we have shown that transient effects change the identifiability criteria compared to the models with time-invariant rate coefficients …”

Section: Introductionmentioning

confidence: 99%

Identifiability of the Model of the Intermolecular Excited-State Proton Exchange Reaction in the Presence of pH Buffer

Boens¹,

Basarić²,

Novikov

et al. 2004

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

In this report, we describe the fluorescence kinetics and the deterministic identifiability of the intermolecular excited-state proton dissociation reaction and how the addition of pH buffer affects both. In the absence of buffer, the time-resolved fluorescence decays as a biexponential function with decay times that are invariant with pH. The information that the proton association rate in the excited state is negligible in combination with fluorescence decay traces measured at different pH, excitation, or emission wavelengths does not provide enough useful information for the unique determination of the rate constants and the spectral parameters related to absorption and emission. Hence, the model of intermolecular excited-state proton dissociation in the absence of pH buffer is not identifiable. When a pH buffer is added to this photophysical system, the proton exchange becomes reversible and the decay times now are a function of pH and buffer concentration. The deterministic identifiability analysis shows that for the unique determination of all rate constants one should collect a minimum of three fluorescence decays characterized by at least two different pH and at least two different nonzero buffer concentrations. In addition to these three traces, minimally one biexponential fluorescence trace corresponding to the pH probe in the absence of buffer has to be recorded. The requirement that at least two of these traces should be collected at the same pH, excitation, and emission wavelengths leads to unique identifiability.

show abstract

“…Although identifiability analyses have been extensively used in biomedicine, pharmacology, ecology, and engineering, 1,2 their use in photophysics is of recent vintage. [3][4][5][6][7][8][9][10][11][12][13][14] We have reported on the deterministic identifiability of inter-and intramolecular two-state and three-state excited-state processes in the presence and absence of added quencher. 3,[5][6][7][8][9][10][11][12][13] For the linear, timeinvariant models that we considered, the parameters to be identified are rate constants and spectral parameters related to absorption (the excited-state species concentrations at time zero) and emission (the emission weighting factors).…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5][6][7][8][9][10][11][12][13][14] We have reported on the deterministic identifiability of inter-and intramolecular two-state and three-state excited-state processes in the presence and absence of added quencher. 3,[5][6][7][8][9][10][11][12][13] For the linear, timeinvariant models that we considered, the parameters to be identified are rate constants and spectral parameters related to absorption (the excited-state species concentrations at time zero) and emission (the emission weighting factors). It was found that some excited-state processes are uniquely identifiable, others are only locally identifiable, and still others are unidentifiable without prior knowledge of some of the system parameters; for example, for intramolecular two-state excited-state processes in the presence of added quencher it is possible to determine only bounds on the rate constants.…”

Section: Introductionmentioning

confidence: 99%

“…Although identifiability analyses have been extensively used in biomedicine, pharmacology, ecology, and engineering, , their use in photophysics is of recent vintage. − We have reported on the deterministic identifiability of inter- and intramolecular two-state and three-state excited-state processes in the presence and absence of added quencher. ,− For the linear, time-invariant models that we considered, the parameters to be identified are rate constants and spectral parameters related to absorption (the excited-state species concentrations at time zero) and emission (the emission weighting factors). It was found that some excited-state processes are uniquely identifiable, others are only locally identifiable, and still others are unidentifiable without prior knowledge of some of the system parameters; for example, for intramolecular two-state excited-state processes in the presence of added quencher it is possible to determine only bounds on the rate constants. , The methods available for testing deterministic identifiability of linear, time-invariant models are well-established 1,2 and include among others the Laplace transform approach, the normal-mode method, the Markov parameters, and the similarity transformation method …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Transient Effects and the Identifiability of Excited-State Processes

1998

Self Cite

View full text Add to dashboard Cite

The identifiability of excited-state processes in the presence of transient effects is studied. The Smoluchowski and Collins-Kimball models of diffusion-mediated association are considered. The kinetic parameters of single-species quenching and related kinetic schemes (double-species quenching without excited-state interchange, and irreversible association with separated excited-species spectra) can be uniquely recovered from the same or a smaller number of decay traces than are necessary within classical kinetics where time-invariant rate constants are used. For single-species quenching in low dimensions, 1D and 2D, the system parameters can be uniquely recovered from a single decay trace at one nonzero quencher concentration. In three dimensions, decays traces measured at two concentrations are necessary and sufficient to recover the parameters. For double-species quenching without interchange of the excited states, decay traces at two wavelengths collected in the absence and presence of quencher guarantee local identifiability of the model in each dimension with or without transient effects. Irreversible association with separate excited-species spectra is identifiable in each dimension, given decay traces at two quencher concentrations and two wavelengths.

show abstract

Identifiability of competitive intermolecular three-state excited-state processes

Cited by 9 publications

References 8 publications

Identifiability of models for time-resolved fluorescence with underlying distributions of rate constants

Identifiability of models for time-resolved fluorescence with underlying distributions of rate constants

Identifiability of the Model of the Intermolecular Excited-State Proton Exchange Reaction in the Presence of pH Buffer

Transient Effects and the Identifiability of Excited-State Processes

Contact Info

Product

Resources

About