Isothermal and Photostimulated Emissions of Indole and Tryptophan in Two Polar Matrices at 77 °K

1974 ◽  
Vol 52 (3) ◽  
pp. 407-417 ◽  
Author(s):  
D. Muller ◽  
M. Ewald ◽  
G. Durocher

The isothermal delayed fluorescence along with the visible photostimulated fluorescence and phosphorescence emissions have been recorded and studied for the following systems: a 10−3 M solution of indole in an ether glassy matrix, a 10−3 M solution of indole in an ethylene glycol–water glassy matrix (EG–W) (70–30 by volume), a 10−3M solution of tryptophan in an EG–W glassy matrix (70–30 by volume). All these experiments have been performed at the temperature of liquid nitrogen. It has also become possible to record the action spectra of the photostimulated emissions which give us information about the entities playing an active part in the recombination processes. The electron–cation recombination after visible light stimulation has been analyzed in terms of a kinetic model based on the assumption that upon neutralization an intermediate state is formed from which the molecule decides what its spin multiplicity will be. It was found that in an EG–W glass at 77 °K about 80% of the recombination events lack the energy necessary to reach the first excited singlet state of the amines studied. In an ether glass this percentage decreases to about 28%. This result is qualitatively in accord with the fact that the photostimulated electrons are more stabilized in an EG–W glass by an amount of energy equal to 1.5 eV.

1974 ◽  
Vol 52 (22) ◽  
pp. 3707-3715 ◽  
Author(s):  
D. Muller ◽  
M. Ewald ◽  
G. Durocher

The isothermal delayed fluorescence along with the visible (6000 Å) photostimulated fluorescence and phosphorescence emissions have been recorded and analyzed in the following systems: diphénylamine (DPA) – ether rigid glass and carbazole (C) – ether rigid glass at 77°K. The electron–cation recombination after visible light stimulation has been analyzed in terms of a kinetic model already described (10). The triplet quantum yields of the DPA and C molecules are calculated and compared to the existing experimental values. The rate constant ratio (β) of populating the first triplet (T1) relative to populating the first excited singlet (S1) after the recombination event has taken place, is equal to about 2 in both systems investigated here. A value of 4.4 was obtained for indole and tryptophan in the same matrix. This difference can only be explained in terms of various singlet state energies for these molecules and also in terms of the stimulating energies used in these experiments.


1969 ◽  
Vol 24 (5) ◽  
pp. 520-523 ◽  
Author(s):  
Giiti Tomita

The photovoltaic effects of free and bound acriflavine were studied to find the elemenatary processes in photochemical behaviours of the dye. The observed photopotential in aqueous acriflavine solution is positive or negative against the dark electrode, depending on pH. The positive sign implys that the photoreduction of dye is more predominant than the photooxidation. The negative sign is obtained when the photooxidation is the predominant reaction.Using the electrode coated directly or indirectly with a very thin film of acriflavine-dispersed collodion, the contributions from photo-reduction and -oxidation to the photopotential were separated. The spectral sensitivity of photopotentials gives us an useful information about the oxidationreduction mechanism of bound dyes. The photo-ejection of an electron from the excited singlet state of dye molecule, which was considered by LIM and others1 to be responsible for the delayed fluorescence of acriflavine in rigid media, seems to be favourable for understanding of photopotential properties at shorter wavelengths of excitation.


The nature of radiation-induced fluorescence from solutions of anthracene, naphthalene and pyrene in cyclohexane has been investigated. Evidence is presented for the formation of excited singlet solute molecules via charge recombination processes. Rate constants, measured by the pulse radiolysis technique, are reported for the quenching of excited singlet state molecules of naphthalene and pyrene by oxygen, xenon, iodine, 1,3-cyclohexadiene, nitrous oxide, sulphur hexafluoride and nitromethane.


1972 ◽  
Vol 50 (9) ◽  
pp. 1338-1344 ◽  
Author(s):  
A. W. Jackson ◽  
A. J. Yarwood

Vibrationally excited singlet and triplet states of 2,3-pentanedione are formed by photolysis at 365 nm. The processes removing these excited states in the gas phase are studied by measuring the fluorescence and phosphorescence yields. Fluorescence can occur from the vibrationally excited, as well as the vibrationally equilibrated, singlet state. The fluorescence and phosphorescence data are considered in terms of mechanisms which involve either weak or strong collisions. Although the data cannot distinguish between the alternatives, there are two significant conclusions. The fluorescence data require that emission occur from at least two levels in the singlet manifold. To explain the phosphorescence data, the highest emitting singlet level must not lead to a vibrationally equilibrated triplet state.


2015 ◽  
Vol 24 (01) ◽  
pp. 1550005 ◽  
Author(s):  
Saleh Al-Omari

Using vis absorption, fluorescence spectral experimental data, and time-resolved measurement, we have examined the kinetics of Zinc(II)-2,9,16,23-phthalocyanine tetracarboxylate ( ZnPc ( COONa )4), which is interesting photosensitizer of far red-absorption in water: NaOH solution. The kinetic parameters were measured and/or calculated. The photophysical properties originate principally from the planar macrocycle while the outer substituent and degree of carboxylation seem not to have a considerable influence on the kinetic parameters. The nonradiative rate constants of the first excited state were dominant due to the heavy metal effect. Using the obtained photophysical parameters, the population dynamics were calculated by kinetic model. On nanosecond scale of 15 ns, about 63% population of the first excited-singlet state is retrieved by the ground state. Whereas, the rest of population are deactivated to the first excited-triplet state. Later on, during about 7 μs starting from the initial decay of the first excited singlet state, the first excited singlet state and the first excited triplet state were completely empty, meanwhile the ground state retrieved its initial population. Due to the fact that ZnPc ( COONa )4 has strong absorption, long lifetimes of the first singlet and triplet excited states, and fast intersystem crossing, it may be suitable for nonlinear optical studies.


2002 ◽  
Vol 76 (1) ◽  
pp. 47 ◽  
Author(s):  
Joakim Andréasson ◽  
Gerdenis Kodis ◽  
Su Lin ◽  
Ana L. Moore ◽  
Thomas A. Moore ◽  
...  

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