Light metal luminescence

Decrease in the size of a metal particle below a critical dimension results in dramatic changes in the electronic properties of the bulk metal. Properties like conductivity, magnetism, light absorption, luminescence, electrochemical, and catalytic activity depend on the particle size. Many heterogeneous catalysts are based on finely divided metal particles on various supports. However, this section deals with the catalytic properties of unsupported nanoparticles. 

Sabbatini et al. 1993). An efficient antenna is expected to lead to metal luminescence much more intense than that obtained upon metal excitation since lanthanide ions are characterized by very low molar absorption coefficients. These complexes can be considered light-conversion molecular devices because they are able to transform light absorbed by the ligand into light emitted by the ions via an intramolecular energy transfer (Balzani and Scandola 1991). 

Analytical Applications. Chemiluminescence and bioluminescence are useful in analysis for several reasons. (/) Modem low noise phototubes when properly instmmented can detect light fluxes as weak as 100 photons/s (1.7 x 10 eins/s). Thus luminescent reactions in which intensity depends on the concentration of a reactant of analytical interest can be used to determine attomole—2eptomole amounts (10 to 10 mol). This is especially useful for biochemical, trace metal, and pollution control analyses (93,260—266) (see Trace and residue analysis). (2) Light measurement is easily automated for routine measurements as, for example, in clinical analysis. 

Lighting. An important appHcation of clear fused quartz is as envelop material for mercury vapor lamps (228). In addition to resistance to deformation at operating temperatures and pressures, fused quartz offers ultraviolet transmission to permit color correction. Color is corrected by coating the iaside of the outer envelope of the mercury vapor lamp with phosphor (see Luminescent materials). Ultraviolet light from the arc passes through the fused quartz envelope and excites the phosphor, produciag a color nearer the red end of the spectmm (229). A more recent improvement is the iacorporation of metal haHdes ia the lamp (230,231). 

Luciferase-catalyzed luminescence of luciferin. Odontosyllis luciferin emits light in the presence of Mg2+, molecular oxygen and luciferase. The relationship between the luminescence intensity and the pH of the medium shows a broad optimum (Fig. 7.2.8). The luminescence reaction requires a divalent alkaline earth ion, of which Mg2+ is most effective (optimum concentration 30 mM). Monovalent cations such as Na+, K+, and NH have little effect, and many heavy metal ions, such as Hg2+, Cu2+, Co2+ and Zn2+, are generally inhibitory. The activity of crude preparations of luciferase progressively decreases by repeated dialysis and also by concentrating the solutions under reduced pressure. However, the decreased luciferase activity can be completely restored to the original activity by the addition of 1 mM HCN (added as KCN). The relationship between the concentration of HCN and the luciferase activity is shown in Fig. 7.2.9. Low concentrations of h and K3Fe(CN)6 also enhance luminescence, but their effects are only transient. 

Blue luminescence of zinc complexes of pyridyl-containing complexes is an area of current interest.277 Design of blue luminescent materials is of relevance to display applications, as blue-light-emitting diodes, and to this end Che examined solution luminescence of zinc pyridylamine complexes.73,278 Che and co-workers studied the complex Zn40(7-azaindoyl)6 which has a blue emission at 433 nm in the solid state.279,280 In an attempt to improve on stability Wang et al. examined compounds with neutral 7-azaindole and an A-functionalized pyridyl derivative.281 In contrast with other metal complexes of the neutral 7-azaindole (32), Zn(7-azaindole)2(OAc)2 is a blue luminescent compound and a A-(2-pyridyl) 2-azaindole (33) and its complexes were also... 

Keywords. Metal-based dendrimers, electrochemistry, multielectron processes, luminescence, light harvesting. 

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