Recombination luminescence

The surface-state model, in which the luminescent recombination occurs via surface states, was proposed to explain certain properties of the PL from PS, for example long decay times or sensitivity of the PL on chemical environment. In the frame of this model the long decay times are a consequence of trapping of free carriers in localized states a few hundred meV below the bandgap of the confined crystallite. The sensitivity of the PL to the chemical environment is interpreted as formation of a trap or change of a trap level by a molecule bonding to the surface of a PS crystallite. The surface-state model suffers from the fact that most known traps, e.g. the Pb center, quench the PL [Me9], while the kinds of surface state proposed to cause the PL could not be identified. 

If the recombination is delayed, e.g., by migration of excited electrons, luminescence takes place by a second-order bimolecular reaction. The probability of a luminescent recombination of the excited electron with the holes is then proportional to the product of the concentration of electrons and the concentration of holes. The lower the initial intensity is, and the further the decay has progressed, the slower the decay to the half value is. This hyperbolic decay law is only of limited validity. If the excited electron is momentarily trapped before recombination, very complex interactions can arise. 

Fig. 88. Schematic energy diagram for p-GaP showing the O - Zn red luminescence. The quantum yield of photoluminescence will clearly be affected by alternative, non-luminescent recombination pathways, particularly those associated with surface states, as shown.

Sakaguchi T, Kitagawa K, Ando T, Murakami Y, Morita Y, Yamamura A, Yokoyama K, Tamiya E. A rapid BOD sensing system using luminescent recombinants of Escherichia coli. Biosens Bioelectron 2003 19 115-21. 

In solid state materials, single-step electron transport between dopant species is well known. For example, electron-hole recombination accounts for luminescence in some materials [H]. Multistep hopping is also well known. Models for single and multistep transport are enjoying renewed interest in tlie context of DNA electron transfer [12, 13, 14 and 15]. Indeed, tliere are strong links between tire ET literature and tire literature of hopping conductivity in polymers [16]. 

Examples include luminescence from anthracene crystals subjected to alternating electric current (159), luminescence from electron recombination with the carbazole free radical produced by photolysis of potassium carba2ole in a fro2en glass matrix (160), reactions of free radicals with solvated electrons (155), and reduction of mtheiiium(III)tris(bipyridyl) with the hydrated electron (161). Other examples include the oxidation of aromatic radical anions with such oxidants as chlorine or ben2oyl peroxide (162,163), and the reduction of 9,10-dichloro-9,10-diphenyl-9,10-dihydroanthracene with the 9,10-diphenylanthracene radical anion (162,164). Many other examples of electron-transfer chemiluminescence have been reported (156,165). 

Finally, an electric current can produce injection luminescence from the recombination of electrons and holes in the contact 2one between differendy doped semiconductor regions. This is used in light-emitting diodes (LED, usually ted), in electronic displays, and in semiconductor lasers. 

A simplified schematic diagram of transitions that lead to luminescence in materials containing impurides is shown in Figure 1. In process 1 an electron that has been excited well above the conduction band et e dribbles down, reaching thermal equilibrium with the lattice. This may result in phonon-assisted photon emission or, more likely, the emission of phonons only. Process 2 produces intrinsic luminescence due to direct recombination between an electron in the conduction band... 

Recent work with multi-layer polymer LEDs has achieved impressive results and highlights the importance of multi-layer structures [46]. Single-layer, two-layer and three-layer devices were fabricated using a soluble PPV-based polymer as the luminescent layer. The external quantum efficiencies of the single-layer, two-layer, and three-layer devices were 0.08%, 0.55%, and 1%, respectively, with luminous efficiencies of about 0.5 hn/W, 3 lm/W, and 6 lm/W. These results clearly demonstrate improvement in the recombination current because of the increase in quantum efficiency. The corresponding increase in luminous efficiency demonstrates that the improvement in recombination efficiency was achieved without a significant increase in the operating bias. 

In electroluminescence devices (LEDs) ionized traps form space charges, which govern the charge carrier injection from metal electrodes into the active material [21]. The same states that trap charge carriers may also act as a recombination center for the non-radiative decay of excitons. Therefore, the luminescence efficiency as well as charge earner transport in LEDs are influenced by traps. Both factors determine the quantum efficiency of LEDs. 

U. Lemmer. R. F. Malm, Y. Wada, A. Greiner, H. Basslcv. E.O. Gobel, Time resolved luminescence study of recombination processes in electroluminescent polymers, Appl. Phys. Lett. 1993, 62, 2827. 

Trilayer structures offer the additional possibility of selecting the emissive material, independent of its transport properties. In the case of small molecules, the emitter is typically added as a dopant in either the HTL or the ETL, near the interface between them, and preferably on the side where recombination occurs (see Fig. 13-1 c). The dopant is selected to have an cxciton energy less than that of its host, and a high luminescent yield. Its concentration is optimized to ensure exciton capture, while minimizing concentration quenching. As before, the details of recombination and emission depend on the energetics of all the materials. The dopant may act as an electron or hole trap, or both, in its host. Titus, for example, an electron trap in the ETL will capture and hold an election until a hole is injected nearby from the HTL. In this case, the dopant is the recombination mmo.-... 

The protein contains an N-terminal signal peptide of 17 amino acid residues for secretion. The luminescence reaction of coelenterazine catalyzed by the recombinant luciferase shows a luminescence emission maximum at 485 nm, whereas the luminescence catalyzed by the native luciferase shows a maximum at 480 nm. 

Fig. 4.1.15 Comparison of the luminescence and fluorescence emission spectra of natural aequorin (left panel) and recombinant e-aequorin (right panel) the luminescence spectra of Ca2+ -triggered reaction (dark solid lines), the fluorescence emission spectra of the spent solution containing 2 mM Ca2+ (dashed lines), and the luminescence spectra of the spent solution after addition of coelenterazine (light solid lines). Reproduced with permission, from Shimomura, 1995d. the Biochemical Society.

Preparation of semisynthetic aequorins. The best yield of semisynthetic aequorins can be obtained by using the apoaequorin prepared from aequorin immediately before use. Apoaequorin stored, even for 2-3 days, or recombinant apoaequorin isolated from a bacterial culture will give a significantly lower yield due to their somewhat unfolded molecular conformation. Fresh apoaequorin prepared by the Ca2+-triggered luminescence reaction appears to have the conformation best suited for regeneration. 

Fig. 4.2.1 Luminescence spectra of the Ca2+-triggered light emission of recombinant obelins (dotted lines), and the fluorescence emission spectra of their spent solution after luminescence (solid lines). Left obelin derived from O. geniculata right obelin derived from O. longissima. Reproduced from Markova etal., 2002, with permission from the American Chemical Society.

Concerning the Ca2+-triggered luminescence of obelin, Deng et al. (2001) reported an interesting observation (Fig. 4.2.2) the luminescence of the recombinant obelin from O. longissima is blue (7max 475 nm), whereas a mutant of this obelin, in which the amino acid residue-92 has been changed from tryptophan to phenylalanine, emits... 

The cDNA encoding the luciferase of Renilla reniformis has been obtained and expressed in Escherichia coli (Lorenz et al., 1991). The cDNA contained an open reading frame encoding a 314-amino acid sequence. The recombinant Renilla luciferase obtained had a molecular weight of 34,000, and showed an emission maximum at 480 nm in the luminescence reaction of coelenterazine, in good agreement with the data of natural Renilla luciferase. 

Quantum yield of luciferin. Various values of quantum yield have been reported for coelenterazine in the luminescence reaction catalyzed by Renilla luciferase 0.055 (Matthews et al., 1977a), 0.07 (Hart, et al., 1979), and 0.10-0.11 (with a recombinant form Inouye and Shimomura, 1997). The quantum yield is significantly increased in the presence of Renilla green fluorescent protein (GFP) see below. 

The spectra of the luminescence of coelenterazine catalyzed by recombinant Renilla luciferase in the presence and absence of Renilla GFP are shown in Fig. 4.6.3 (Lorenz et al., 1991). Note that the luminescence intensity at the emission peak is increased more than... 

Molecular characteristics of luciferase. A molecule of the luciferase of G. polyedra comprises three homologous domains (Li et al., 1997 Li and Hastings, 1998). The full-length luciferase (135 kDa) and each of the individual domains are most active at pH 6.3, and they show very little activity at pH 8.0. Morishita et al. (2002) prepared a recombinant Pyrocystis lunula luciferase consisting of mainly the third domain. This recombinant enzyme catalyzed the light emission of luciferin (luminescence A.max 474 nm) and the enzyme was active at pH 8.0. The recombinant enzyme of the third domain of G. polyedra luciferase was crystallized and its X-ray structure was determined (Schultz et al., 2005). A -barrel pocket putatively for substrate binding and catalysis was identified in the structure, and... 

Em., luminescence emission Q, quantum yield of coelenterazine (unpublished data included). Recombinant protein. 

Bondar, V. S., etal. (1995). Cadmium-induced luminescence of recombinant photoprotein obelin. Biochim. Biophys. Acta 1231 29-32. 

Shislov14 16 observed radiothermoluminescence associated with the recombination of radical-anion pairs in y-irradiated DMSO-d6 (peak at 105 K) and DESO (peak at 153 K). The equation of the reaction giving the indicated luminescence can be written in general as follows ... 

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