Kinetics of partly diffusion controlled reactions. III. Competition between physical and chemical kinetics. Experimental results

André, Jean‐Claude; Bouchy, M.; Ware, William R.

doi:10.1016/0301-0104(79)80011-7

Cited by 30 publications

(1 citation statement)

References 21 publications

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“…In theory, the phase plane method could be applied every time there is a linear relationship, with constant parameters, between u(t) and its derivatives and g(t) and its derivatives. This occurs in particular with single exponential fluorescence decays with a scattered light component or with decays that are the sum of two exponentials [but this method cannot be used to determine experimental parameters when this is no longer true (Smoluchowski decays (7) for example)].…”

Section: Resultsmentioning

confidence: 99%

Estimation of fast fluorescence lifetimes with a single photon counting apparatus and the phase plane method

Jezequel¹,

Bouchy²,

André³

1982

Anal. Chem.

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The phase plane deconvolutlon method allows a rapld determlnation of the lifetimes of emlttlng electronically exclted states In the case of single exponentlal decays. We demonstrate that the phase plane method Is also suitable for more complex decays, when there Is a scattered light component or the sample exhibits a decay which Is ai sum of two exponentlals. Under these conditions, this technique Is very useful for the rapid determlnatlon of the parameters of the decays; In partlcular, It Is useful with mini-or mbrocomputers.with the following initial condition: u(0) = 0.By puttingrelationship 6 can be rewritten in the simpler form 1 (8)Relationship 8 can be rewritten as An important problem in many scientific fields is to extract the maximum information from the result of an experimental measurement. In particular, the accurate measurement offluorescence decays, obtained via the single photon counting technique, is crucial in the field of spectroscopy, chemical kinetics, analysis, photochemistry, and photophysics. In practice, the continuous fluorescence response function, u(t), is significantly distorted by the real time profile of the excitating flash, f ( t ) , and by the response function of the electronics, e(t). If z ( t ) is the real fluorescence time profile of the system exicited by a Dirac pulse, then we have the convolution product (eq 1) (the definitions of symbols appear in the Glossary at the end of this paper). (1)The recovery of z(t) from experimental fluorescence time profiles and g(t) == f(t)*e(t) can be achieved by using several techniques of deconvolution as explained previously (1,2). This paper will deal with the recent phase plane technique. THEORYSingle Exponcsntial Decay. Recently Greer, Reed, and Demas ( 3 , 4 ) have described a fast and accurate deconvolution technique: the "phase plane method". This technique allows the measurement of the lifetime, r, of emitting electronically excited states exhibiting the single exponential decaywhere A is a proportionality factor. We can write the convolution product asTaking the derivative of eq 4 leads toIntegration on both sides of this equation leads to (5) -Plotting u(t)/sg(t) vs. su(t)/sg(t) a t several values of the time t should lead to a straight line of slope -1 /~. The value of T is then determined by use of the least-squares fitting method.Biexponential Decay. Now we show here that the same method can also be used in the case of a biexponential decay (10)with zl(t) = Ale-t/TlPutting Ul(t) = g(t)*z,(t) u&) = g(t)*zz(t)the total fluorescence u ( t ) is given by u ( t ) = g(t)*z(t) = u1(t) + UJt)As previously (cf. ref 6), we can write By taking the derivative of these two equations and adding them, we get knowing that

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Section: Resultsmentioning

confidence: 99%

Estimation of fast fluorescence lifetimes with a single photon counting apparatus and the phase plane method

Jezequel¹,

Bouchy²,

André³

1982

Anal. Chem.

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On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments

Rosspeintner

Kattnig

Angulo

et al. 2007

Chemistry A European J

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The fluorescence quenching by electron transfer of a fluorophore, 2,5-bis(dimethylamino)-1,3-benzenedicarbonitrile, to 1,3-dimethyl-2-nitrobenzene, has been studied by means of time-resolved and steady-state experiments at different viscosities and up to large quencher concentrations. Differential Encounter Theory (DET) has been used to rationalize the results, in combination with electron transfer modelled by the Marcus theory. Additionally, the solvent structure and the hydrodynamic effect on the diffusion coefficient have been taken into account. Any simpler model failed to simultaneously fit all the results. The large number of quencher concentrations used is crucial to unambiguously extract the electron transfer parameters.

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Morphosynthesis by space resolved thermal polymerization induced by IR lasers

et al. 1992

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This paper describes a process for the manufacture of three‐dimensional objects, layer by layer, using thermal irradiation by moving the beam of a computer controlled CO2 laser. Computer simulations of the system performance under different experimental conditions (for example, irradiation time, characteristics of the reactive medium), combined with experiments prove the feasibility of the process. The objects are spatially well resolved since the reactive area is matched with the laser beam surface area.

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Kinetics of partly diffusion controlled reactions. III. Competition between physical and chemical kinetics. Experimental results

Cited by 30 publications

References 21 publications

Estimation of fast fluorescence lifetimes with a single photon counting apparatus and the phase plane method

Estimation of fast fluorescence lifetimes with a single photon counting apparatus and the phase plane method

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments

Morphosynthesis by space resolved thermal polymerization induced by IR lasers

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