On the temperature dependence of non-radiative deactivation processes

Pantke, E.R.; Labhart, Heinrich

doi:10.1016/0009-2614(72)80266-5

Cited by 24 publications

(8 citation statements)

References 14 publications

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“…The uorescence quantum yields of F, TF, FPO and PFD (Table 2) in the organic solvents used are above 0.5, with the exception of F in chloroform. When data are available, such as for F 81 in ethanol, 82 f values obtained are in a good agreement with the literature values. The low value in chloroform is probably due to formation of contact charge transfer species, as has been reported for various other aromatics and chlorinated hydrocarbons.…”

Section: Solventsupporting

confidence: 86%

From molecular modelling to photophysics of neutral oligo- and polyfluorenes incorporated into phospholipid bilayers

et al. 2015

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The combination of various experimental techniques with theoretical simulations has allowed elucidation of the mode of incorporation of fluorene based derivatives into phospholipid bilayers. Molecular dynamics (MD) simulations on a fully hydrated 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) bilayer, with benzene (B), biphenyl (BP), fluorene (F) and tri-(9,9-di-n-octylfluorenyl-2,7-diyl), TF, have provided insights into the topography of these molecules when they are present in the phospholipid bilayer, and suggest marked differences between the behavior of the small molecules and the oligomer. Further information on the interaction of neutral fluorenes within the phospholipid bilayer was obtained by an infrared (IR) spectroscopic study of films of DMPC and of the phospholipid with PFO deuterated specifically on its alkyl chains (DMPC-PFO-d34). This was complemented by measurements of the effect of F, TF and two neutral polymers: polyfluorene poly(9,9-di-n-octylfluorenyl-2,7-diyl), PFO, and poly(9,9-di-n-dodecylfluorenyl-2,7-diyl), PFD, on the phospholipid phase transition temperature using differential scanning calorimetry (DSC). Changes in liposome size upon addition of F and PFO were followed by dynamic light scattering. In addition, the spectroscopic properties of F, TF, PFO and PFD solubilised in DMPC liposomes (absorption, steady-state and time-resolved fluorescence) were compared with those of the same probes in typical organic solvents (chloroform, cyclohexane and ethanol). Combining the insight from MD simulations with the results at the molecular level from the various experimental techniques suggests that while the small molecules have a tendency to be located in the phospholipid head group region, the polymers are incorporated within the lipid bilayers, with the backbone predominantly orthogonal to the phospholipid alkyl chains and with interdigitation of them and the PFO alkyl chains.

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Section: Solventsupporting

confidence: 86%

From molecular modelling to photophysics of neutral oligo- and polyfluorenes incorporated into phospholipid bilayers

et al. 2015

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“…While there are numerous reports showing that raising the sample temperature reduces fluorescence QY, reversed temperature effect, increased total QY with an increased temperature has been reported for anthracene in ethanol over the temperature range of 100−200 K. 34,35 However, the temperature range used in the latter study can complicate the data interpretation due to the relatively poor solubility of anthracene in ethanol and the possible phase transition of ethanol in this temperature range. Ethanol's melting point is ∼100 K. Besides the intrinsic temperature effects, the possible solution-phase transition and the inevitable temperaturedependent anthracene solubility variation can induce significant changes in anthracene's photophysical properties.…”

Section: Resultsmentioning

confidence: 87%

Back to the Drawing Board: A Unifying First-Principle Model for Correlating Sample UV–Vis Absorption and Fluorescence Emission

Wamsley

Nawalage

et al. 2022

Anal. Chem.

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The popular textbook and literature model I(λ x ,λ m ) = λ λ − − K( , )(1 10 ) A x m x or its variants for correlating the sample absorption and fluorescence often fails even for the simplest samples where the fluorophore is the only light absorber. Reported is a first-principle model I(λ x ,λ m ) = λ λ − + K A ( , ) 10 A d A d x m x,f ( ) x,s x m,s m for correlating the sample fluorescence measured with a conventional spectrofluorometer and its UV−vis absorbance quantified with a conventional UV−vis spectrophotometer. This model can be simplified or expanded for a variety of fluorescence analyses. First, it enables curve-fitting fluorescence intensity as a function of the fluorophore or sample absorbance over a sample concentration range impossible with existing models. Second, it provides the theoretical foundation for an inner-filter-effect (IFE)-correction method developed earlier and explains mathematically the linearity between the IFE-corrected fluorescence and the fluorophore concentration or absorbance. Third, this model can be expanded for quantitative mechanistic studies of fluorescence intensity variations triggered by stimuli treatments. One demonstrated example is to quantify temperature effects on the emission-wavelength-specific and total fluorescence quantum yield of anthracene.We expect that this first-principle model will be broadly adopted for both student education that promotes evidence-based learning and a variety of fluorescence applications where disentangling sample absorption and emission are critical for reliable data analysis.

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“…With an extinction of e 1 0 (363 nm) % 332 dm 3 mol À1 cm À1 at the excitation wavelength (see Fig. 2), F ISC % 0.5 15 and the anthracene concentration of %1.4 Â 10 À5 mol dm À3 , an upper limit of the initial triplet concentration [T 1 ] 0,max can be estimated to be 3.2 Â 10 À9 mol dm À3 for an excitation time of t exc % 30 ms at a laser fluence of %450 mJ cm À2 (laser power 3 W, beam diameter %5 mm). This value is smaller than in the preceding investigation.…”

Section: Is Based On the Following Criteriamentioning

confidence: 98%

“…Although the interference effect was improved to %30% by this approach (theoretically 50% effects are possible upon full interference -see eqn. (15) for b ¼ 1), the detection setup was not designed for that particular excitation geometry and the measured time dependence of the delayed fluorescence was very noisy and hence the analysis results were again severely affected.…”

Section: Spatially Periodic Excitationmentioning

confidence: 99%

Application of Smoluchowski's generalized theory to the kinetics of triplet–triplet annihilation of anthracene in viscous solution after long-pulse excitation

Nickel

Borowicz

Ruth

et al. 2004

Phys. Chem. Chem. Phys.

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The validity of Smoluchowski's theory is demonstrated by its application to the bimolecular triplet-triplet annihilation (TTA) T 1 þ T 1 ! S 0 þ S 1 in viscous solution. For that purpose the delayed S 1 ! S 0 fluorescence of anthracene in cis-1,3-dimethylcyclohexane/trans-1,4-dimethylcyclohexane (1:1) was measured after UV excitation with long laser pulses ($30 ms) in a temperature range where TTA is completely diffusion controlled. Through the adequate treatment of the kinetics of TTA upon spatially homogeneous and spatially periodic excitation (which is partially based on the results of previous publications) absolute values for the diffusion coefficients D of triplet molecules, for the effective annihilation distance R A and for the Fö rster radius R ST of heterogeneous annihilation S 1 þ T 1 ! S 0 þ T n were determined. The temperature dependence of all three parameters (D, R A and R ST ) is discussed. From the decrease of R A with increasing temperature, the parameters A and L can be determined, which define the exponential distance dependence of the annihilation of a triplet pair in the kinetic model of Butler and Pilling (1977). Differences of the two models and applicability criteria are discussed.

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On the temperature dependence of non-radiative deactivation processes

Cited by 24 publications

References 14 publications

From molecular modelling to photophysics of neutral oligo- and polyfluorenes incorporated into phospholipid bilayers

From molecular modelling to photophysics of neutral oligo- and polyfluorenes incorporated into phospholipid bilayers

Back to the Drawing Board: A Unifying First-Principle Model for Correlating Sample UV–Vis Absorption and Fluorescence Emission

Application of Smoluchowski's generalized theory to the kinetics of triplet–triplet annihilation of anthracene in viscous solution after long-pulse excitation

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