Global Compartmental Analysis of the Fluorescence Decay Surface of the Halato Telechelic Polymer (N,N-Dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)trifluoromethanesulfonate-End-Capped Poly(tetrahydrofuran)

Hermans, Bart; Schryver, F. C. De; Stam, Jan van; Boens, N.; Jérôme, Robert; Teyssié, Philippe; Trossaert, Geert; Goethals, E.; Schacht, Etienne

doi:10.1021/ma00113a043

Cited by 6 publications

(29 citation statements)

References 17 publications

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“…At this concentration, all processes are intramolecular and described by Scheme 2 with all rate constants being first-order. The goal is to estimate the values of the rate constants of Scheme 2, based on the results from the two model compounds PROBE 61 and POLYPROBE 62 and through global compartmental analysis.…”

Section: Resultsmentioning

confidence: 99%

“…Bis[(N,N-dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)trifluoromethanesulfonate]-end-capped poly(tetrahydrofuran) (POLYDIPROBE) was synthesized in the same way as POLYPROBE, 62 but with the bifunctional triflate anhydride ((CF3SO2)O) as initiator. Polytetrahydrofuran was synthesized via cationic ring-opening polymerization with methyl triflate (CF3SO3CH3) as initiator.…”

Section: Synthesis and Characteristics Of Bis[(nn-dimethyl-n-[3-(1-pmentioning

confidence: 99%

“…The theory of global compartmental analysis of fluorescence decay surfaces is thoroughly described, [43][44][45][46][47][48][49][50][51][52]61,62 and only the fundamental aspects of tricompartmental systems will briefly be summarized. The special case of an intramolecular tricompartmental system will be discussed in detail.…”

Section: Excited-state Processes In Compartmentalized Systemsmentioning

confidence: 99%

“…47,48,58,62 Eqs 14 predict that plotting S 1 + S 2 and P -S 1 S 2 vs k 32 should yield plateaus from which the average values S 1 + S 2 and P -S 1 S 2 can be determined.…”

Section: Tricompartmental Systems Without Added Quenchermentioning

confidence: 99%

“…The same was found for the PROBE and POLYPROBE studies. 61,62 The photophysical system can thus be described by the model depicted in Scheme 3. Unique values of six rate constants of that scheme have to be determined for the system to be indentifiable.…”

Section: Time-resolved Measurementsmentioning

confidence: 99%

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Intramolecular Excited-State Processes of a Halato-Telechelic Polymer, Evaluated by Global Compartmental Analysis of the Fluorescence Decay Surface with the Use of Model Compounds

et al. 1997

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The excited-state processes of the halato-telechelic polymer bis [(N,N-dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)trifluoromethanesulfonate]-end-capped poly(tetrahydrofuran) at low concentrations are investigated by time-resolved fluorescence. The photophysical processes can be described by an intramolecular three-state excited-state model. Such a system is not identifiable in the absence of a priori information. It is possible to perform a global compartmental analysis of the fluorescence decay surface using the scanning technique, based on model compound data previously obtained [Hermans et al., J. Phys. Chem. 1994, 98, 13583 and Hermans et al. Macromolecules 1995, 28, 3380]. The value boundaries on the rate constant for ring closure of the chain ends show that this process is close to diffusion-controlled.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis and Characteristics Of Bis[(nn-dimethyl-n-[3-(1-pmentioning

confidence: 99%

Section: Excited-state Processes In Compartmentalized Systemsmentioning

confidence: 99%

“…47,48,58,62 Eqs 14 predict that plotting S 1 + S 2 and P -S 1 S 2 vs k 32 should yield plateaus from which the average values S 1 + S 2 and P -S 1 S 2 can be determined.…”

Section: Tricompartmental Systems Without Added Quenchermentioning

confidence: 99%

Section: Time-resolved Measurementsmentioning

confidence: 99%

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Intramolecular Excited-State Processes of a Halato-Telechelic Polymer, Evaluated by Global Compartmental Analysis of the Fluorescence Decay Surface with the Use of Model Compounds

et al. 1997

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Kinetics and Identifiability of an Intermolecular Two-State Excited-State Process in the Presence of a Fluorescent Impurity

Kowalczyk¹,

Meuwis²,

Boens³

et al. 1995

J. Phys. Chem.

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This paper presents a study analyzing the conditions for the recovery of the rate constants and the spectral parameters from the fluorescence decay surface due to three-state excited-state processes. The studied system models a situation when, in addition to a fluorescence indicator which undergoes an excited-state reaction with a co-reactant, a fluorescent impurity is present. It is demonstrated theoretically that, if the fluorescence decay surface contains traces measured in the absence of co-reactant and additionally at two nonzero coreactant concentrations, all five rate constants can always be recovered. In some cases the measurement in the absence of co-reactant is not necessary. If the fluorescence decay surface is collected at three different emission wavelengths and two co-reactant concentrations, the ratios of the absorbances of the free and bound form of the fluorescent indicator can be determined. If two different emission wavelengths are used in combination with three excitation wavelengths (or three co-reactant concentrations), the ratios of the emission weighting factors of the free and bound form of the fluorescent indicator can be obtained. Under both previous conditions no spectral information about the fluorescent impurity can be acquired. The ground-state dissociation constant can be determined from the fluorescence decay traces excited at an isosbestic point.

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Three-State 2‘,7‘-Difluorofluorescein Excited-State Proton Transfer Reactions in Moderately Acidic and Very Acidic Media

et al. 2005

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2',7'-Difluorofluorescein (Oregon Green 488, OG488) is a novel fluorescein dye derivative which presents important advantages for improving the fluorimetric applications in the biomedical and biochemical sciences. In aqueous solution it displays four prototropic forms, namely cation (C), neutral (N), monoanion (M), and dianion (D). In previous works, we found (J. Phys. Chem. A 2005, 109, 734-747, 2840-2846) that OG488 undergoes excited-state proton transfer reactions, which may affect the results from applications using this dye. We established that the excited-state proton transfer (ESPT) reactions between neutral, monoanionic, and dianionic forms of OG488 are promoted by acetate buffer, and we characterized the ground and excited species involved. We also solved the kinetics of the prototropic reactions using global compartmental analysis. In the present paper, we extend our study on the ESPT reactions of OG488 to acidic media, in which only the three prototropic species cation, neutral, and monoanion coexist. We have solved the kinetics of the three-state ESPT reaction by means of global three-compartmental analysis of a fluorescence decay surface in moderately acidic media (pH between 1.1 and 3.0), recovering the kinetic and spectral parameters of this three-state system. This system is one of the most complex solved to date, due to the strong overlap of the absorption and emission spectra of the neutral and monoanionic forms of OG488. We also found that the cation behaves as "super" photoacid, showing a very high deprotonation rate constant (1.04 x 10(11) s(-1)) and an enhanced acidity. Therefore, we also carried out experiments at very high perchloric acid concentrations, dealing with some other effects which become noteworthy at these [H(+)]. The presence of xanthylium cation quenching due to "free" water molecules, and the reduction in the amount of water clusters acting as proton acceptors, are processes which alter notably the time course of the excited-species in this high [H(+)] range.

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Global Compartmental Analysis of the Fluorescence Decay Surface of the Halato Telechelic Polymer (N,N-Dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)trifluoromethanesulfonate-End-Capped Poly(tetrahydrofuran)

Cited by 6 publications

References 17 publications

Intramolecular Excited-State Processes of a Halato-Telechelic Polymer, Evaluated by Global Compartmental Analysis of the Fluorescence Decay Surface with the Use of Model Compounds

Intramolecular Excited-State Processes of a Halato-Telechelic Polymer, Evaluated by Global Compartmental Analysis of the Fluorescence Decay Surface with the Use of Model Compounds

Kinetics and Identifiability of an Intermolecular Two-State Excited-State Process in the Presence of a Fluorescent Impurity

Three-State 2‘,7‘-Difluorofluorescein Excited-State Proton Transfer Reactions in Moderately Acidic and Very Acidic Media

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