Charge quantum yields

Goelenterate. Coelenterates Penilla reformis (sea pansy) -cradViequoreaforskalea (jelly fish) produce bioluminescence by similar processes (223). The basic luciferin stmcture is (49) (224) and excited amide (50) is the emitter. The stmctural relationship to Varela is evident. A stmctural analogue where R = CH is active ia bioluminescence. The quantum yield is about 4% (223), with at 509 nm (56). This reaction iavolves a charge transfer between green fluorescent proteia and the excited-state coelenterate oxylucifetin. 

Irradiation of coordination compounds in the charge-transfer spectral region can often enhance redox reactions. The quantum yields are variable. 

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. 

Delaire et al. [124] have reported that laser photolysis of an acidic solution (pH 2.8) containing PMAvDPA (23) and MV2 + allows the formation of surprisingly long-lived MV + - and DPA cation radicals with a very high charge escape quantum yield. The content of the DPA chromophores in PMAvDPA is as low as less than 1/1000 in the molar ratio DPA/MAA. Figure 20 shows a decay profile of the transient absorption due to MV + monitored at 610 nm [124]. The absorption persists for several milliseconds. As depicted in Fig. 20, the decay obeys second-order kinetics, which yields kb = 3.5 x 10s M 1 s. From the initial optical density measured at 610 nm, the quantum yield for charge escape was estimated to be 0.72 at 0.2 M MV2 +. ... 

The experimental results on poly(methacrylic acid) containing a small mole fraction of either 3-vinylperylene (PMAvPER, (30)) or lV-[12-(4-aminonaphthali-mide)]-2-methylacrylamide (PMAANI, (31)) show charge separation which is efficient for PMAvPER but not much for PMAANI. The quantum yields of charge separation for various chromophores covalently bound to PMA at pH 2.8 are summarized in Table 7. 

Table 7. Quantum yields of charge separation, (pcs, for poly(methacrylic acid)-bound chromophores at pH 2.8 [77]...

Neither the scavenger for electrons nor the scavenger for positive holes are adsorbed at the colloidal particles and both are rather unreactive. Neither of the two can compete efficiently with the recombination of the charge carriers, the result being that the quantum yields of the products are very low. 

The quantum yield for the formation of 8-oxodGuo 44 from guanine in relation to the formation of products arising from the oxidation of other nucle-obases may be considered as a marker of charge transfer efficiency. This parameter was therefore used to study the influence of duplex stability on... 

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