Quantum yield, effect

Gaunt, J. A. Knight, A. E. Windsor, S. A. and Chechik, V. (2005). Stability and quantum yield effects of small molecules additives on solutions of semiconductor nanoparticles. /. Colloid and Interface Science, 290 (2), 437-443. 

These data can be compared with those for a/w films shown in Figure 15. Such comparison suggests that there is substantially less protein at the interface in o/w thin films, indeed almost five times less. However, care needs to be exercised when equating surface concentration to fluorescence intensity. It is possible that the fluorophore is located in different environments in the two types of thin film and that the difference in fluorescence intensity is a fluorescence quantum yield effect. However, this is unlikely since the surface concentration, as judged by the surface fluorescence signal at which surface diffusion is first observed, in both a/w and o/w films is very similar at approximately 600 counts per channel. It is reasonable to assume that the structure of the adsorbed layer is similar at the point where surface diffusion is first observed. The presence of similar surface counts indicates that the quantum yield of fluorescence is similar at both o/w and a/w interfaces. Thus, this strongly supports the... 

Torikai A, Ohno M, Fueki K (1990) Photodegradation of poly(methyl methacrylate) by monochromatic light - quantum yield, effect of wavelength, and light-intensity. J Appl Polym Sci 41 1023... 

Figure A3.6.12. Photolytic cage effect of iodme in snpercritical ethane. Points represent measured photodissociation quantum yields [37] and the solid curve is the result of a numerical simnlation [111].

The simple difhision model of the cage effect again can be improved by taking effects of the local solvent structure, i.e. hydrodynamic repulsion, into account in the same way as discussed above for bimolecular reactions. The consequence is that the potential of mean force tends to favour escape at larger distances > 1,5R) more than it enliances caging at small distances, leading to larger overall photodissociation quantum yields [H6, 117]. 

Sensitivity From equations 10.32 and 10.33 we can see that the sensitivity of a fluorescent or phosphorescent method is influenced by a number of parameters. The importance of quantum yield and the effect of temperature and solution composition on f and p already have been considered. Besides quantum yield, the sensitivity of an analysis can be improved by using an excitation source that has a greater... 

A substantial effort has been appHed to iacreaskig i by stmctural modification (114), eg, the phthalaziQe-l,4-diones (33) and (34) which have chemiluminescence quantum yields substantially higher than luminol (115,116). The fluorescence quantum yield of the dicarboxylate product from (34) is 14%, and the yield of singlet excited state is calculated to be 50% (116). Substitution of the 3-amino group of lumiaol reduces the CL efficiency > 10 — fold, whereas the opposite effect occurs with the 4-amino isomer (117). A series of pyridopyridaziae derivatives (35) have been synthesized and shown to be more efficient than luminol (118). 

The effect of forming a more rigid structure in fluorescent dyes of the rhodamine series has been clearly demonstrated (18) with the remarkable dye designated Rhodamine 101 [41175A3-3] (19). This dye has its terminal nitrogen atoms each held in two rings and has a fluorescence quantum yield of virtually 100% independent of the temperature. 

As a rule, the fluorosolvatochromic effects are less as the dipole moment decreases on excitation, but the media environment can considerably influence quantum yield (61). 

The ion-pair complex formed by the interaction of hydroxobis(8-quinolyloxo) vanadium (V) [VOQ2OH] and /i-butyl amine is also effective in photoinitiation of polymerization of MMA in bulk and in solution [40]. The quantum yield of initiation and polymerization determined are equal to 0.166 and 35.0, respectively. Hydroxyl radical ( OH) is reported to be the initiating radical and the following photoreaction is suggested ... 

However, the method will not enhance the external quantum yield of the LED, moreover, proper optical coupling between the layers has to be achieved in order not to decrease the QY loo much [61. One of the obvious problems is the principal requirement of having the ITO-covered glass substrate between the color converter and the cmitLer layer. This can also lead to color bleeding, an effect where the emitter layer excites not only the conversion layer, it is supposed to address but also neighboring ones. 

Fig. 3.1.5 Effects of salt concentration on the activity of Cypridina luciferase (solid lines) and quantum yield (dotted lines). In the activity measurement, Cypridina luciferin (1 pg/ml) was luminesced with a trace amount of luciferase in 2.5 mM HEPES buffer, pH 7.5, containing a salt to be tested, at 20°C. In the measurement of quantum yield, luciferin (1 pg/ml) was luminesced with luciferase (20 pg/ml) in 20 mM sodium phosphate buffer (for the NaCl data) or MES buffer (for the CaCl2 data), pH 6.7.

Fig. 3.1.7 Effects of temperature on the activity of Cypridina luciferase (solid line) and the quantum yield of Cypridina luciferin (dashed line). Luciferin (1 pg/ml) was luminesced in the presence of luciferase (a trace amount for the activity measurement 20 pg/ml for the quantum yield) in 50 mM sodium phosphate buffer, pH 6.8, containing 0.1 M NaCl.

Fig. 3.3.3 Effects of temperature on the activities of luciferase ( ) and the quantum yields of coelenterazine (o) in the Oplophorus bioluminescence reaction. The activity was measured with coelenterazine (4.5 pg) and luciferase (0.05 pg), and the quantum yields with coelenterazine (0.2 pg) and luciferase (200 pg), in 5 ml of 15 mM Tris-HC1 buffer, pH 8.3 (at 25°C), containing 50 mM NaCl. Coelenterazine was first added to the buffer solution at the designated temperature, then the luminescence reaction was started by a rapid injection of 0.1 ml of luciferase solution. Replotted from Shimomura et al., 1978, with permission from the American Chemical Society.

To measure the total light emission of a photoprotein sample, it was necessary to add 1-5 pM Fe2+ several times due to the short effective life of Fe2+ under the conditions involved. The total amount of light measured in this manner was always proportional to the weight of photoprotein used, with both CPA and CPC (4.7 x 1013 photons/mg at 25°C Shimomura and Johnson, 1968d). Thus, the quantum yield is estimated at roughly 0.01 for CPA, and 0.015 for CPC. 

Oplopborus luminescence, 82-87 effects of pH and temperature, 83-86 luminescence spectrum, 84 mechanism, 85-87 quantum yield of coelenterazine, 85 Orfelia, 2, 27, 337... 

Although the electrostatic field on the polyelectrolyte surface effectively impedes back ET, it is unable to retard very fast back ET or charge recombination of the primary ion pair within the photochemical cage. The overall quantum yield of photoinduced ET is actually controlled in most cases by the charge recombination. Hence, its retardation is the key problem for attaining high quantum yields in the photoinduced ET. 

Hurley and Testa (Ref 17) exposed nitrobenzene in isopropyl alcohol, degassed and in air, to a mercury lamp at 3660A Products in the absence of air were acetone and phenyl-hydroxylamine (PHA). In air PHA was oxidized to nitro sob enzene which couples with PHA to form azoxybenzene. They hypothesized that the triplet molecule abstracted H-atoms from the solvent no effect was noted with ben zene as solvent. They also worked with nitrobenzene in isopropyl alcohol-water mixts containing HC1 with a mercury lamp at 3660A (Ref 18), and found that the quantum yields depended on pH and isopropyl alcohol content, but were independent of oxygen with acid present. Their conclusion was that the quantum yield consisted of two parts, H abstraction by the triplet, and protonation of the triplet... 

Solid-surface room-temperature phosphorescence (RTF) is a relatively new technique which has been used for organic trace analysis in several fields. However, the fundamental interactions needed for RTF are only partly understood. To clarify some of the interactions required for strong RTF, organic compounds adsorbed on several surfaces are being studied. Fluorescence quantum yield values, phosphorescence quantum yield values, and phosphorescence lifetime values were obtained for model compounds adsorbed on sodiiun acetate-sodium chloride mixtures and on a-cyclodextrin-sodium chloride mixtures. With the data obtained, the triplet formation efficiency and some of the rate constants related to the luminescence processes were calculated. This information clarified several of the interactions responsible for RTF from organic compounds adsorbed on sodium acetate-sodium chloride and a-cyclodextrin-sodium chloride mixtures. Work with silica gel chromatoplates has involved studying the effects of moisture, gases, and various solvents on the fluorescence and phosphorescence intensities. The net result of the study has been to improve the experimental conditions for enhanced sensitivity and selectivity in solid-surface luminescence analysis. 

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