Rare luminescence

Although only rarely luminescent in ambient fluid solutions, square-planar transition metal bis(dithiolene) complexes do display significant and varied photochemical reactivity. Much of the photoreactivity described above for dianionic bis(dithiolene) complexes involves excited-state oxidation and often leads to radical formation. In addition, the excited states of these complexes are receiving attention for their potential as materials for optical (15), nonlinear optical (10-13), and electrooptical (16) devices. The relevance of this work to those applications is addressed in other parts of chapter 8 in this volume (87b). 

The equivalence point of a given redox titration occurs at a particular electrochemical potential, governed by the standard redox potentials of the reactants and the reaction conditions. A redox indicator is a compound that reversibly changes its colour (or, rarely, luminesces) at a particular potential. Thus the indicator is chosen so that its transition potential overlaps the equivalence potential of the titration system. 

Lanthanide luminescence apphcations have already reached industrial levels of consumption. Additionally, the strongly specific nature of the rare-earths energy emissions has also led to extensive work in several areas such as photostimulable phosphors, lasers (qv), dosimetry, and fluorescent immunoassay (qv) (33). 

The divalent rare-earth ion Eu has the 4f electronic configuration at the ground states and the 4f 5d electronic configuration at the excited states. The broadband absorption and luminescence of Eu are due to 4f - 4 f 5d transitions. The emission of Eu is very strongly dependent on the host lattice. It can vary from the ultraviolet to the red region of the electromagnetic spectrum. Furthermore, the 4f-5d transition of Eu decays relatively fast, less than a few microseconds [33]. 

Compounds presented in Scheme 9 have provided evidence for the influence of the otherwise rarely investigated />-anilino-ethynyl group and a variety of auxiliary ligands on the luminescence, NLO, and mesogenic properties of this type of complexes.98... 

Furthermore, in more recent studies high [Ca2+]mt signals are seen in only a few mitochondria within a given cell, and reports claiming very high [Ca2+]mt under physiological conditions are based on cells isolated by enzymatic dispersion. This, coupled with the uncertainty of calibration of luminescent and fluorescent Ca2+ indicators within the mitochondrial matrix, (for nuclei see Perez-Terzic et al 1997) should raise serious questions about the correct values of [Ca2+]mt. It is unfortunate that, with rare exceptions, very few available studies compare free with total mitochondrial Ca in the same cell type observed under the same condition. 

This form of luminescence occurs sporadically in a wide range of natural organisms, such as protists (bacteria, fungi), animals, marine invertebrates and fish. It even exists naturally, albeit rarely, in plants or in amphibians, reptiles, birds, or mammals. 

See also Emission rare-earth-based, 14 650-651 Luminescent dendrimers, 3 254-273 26 801-804... 

The most prominent nanomaterials for bioanalysis at present are semiconductor QDs. Rare-earth doped upconverting nanocrystals and precious metal nanoparticles are becoming increasingly popular, yet they are still far from reaching the level of use of QDs. Other luminescent nanoparticles like carbon-based nanoparticles start to appear, but the synthesis and application of these materials are still in their infancy and not significant for practitioners in the field of bioanalysis. 

The photoluminescence of these nanoparticles has very different causes, depending on the type of nanomaterial semiconductor QDs luminescence by recombination of excitons, rare-earth doped nanoparticles photoluminescence by atom orbital (AO) transitions within the rare-earth ions acting as luminescent centers, and metallic nanoparticles emit light by various mechanisms. Consequently, the optical properties of luminescent nanoparticles can be very different, depending on the material they consist of. 

Trigonal ML3 metal complexes exist as optically active pairs. The complexes can show enantiomeric selective binding to DNA and in excited state quenching.<34) One of the optically active enantiomers of RuLj complexes binds more strongly to chiral DNA than does the other enantiomer. In luminescence quenching of racemic mixtures of rare earth complexes, resolved ML3 complexes stereoselectively quench one of the rare earth species over the other. 35-39 Such chiral recognition promises to be a useful fundamental and practical tool in spectroscopy and biochemistry. 

The [Re(dmpe)3] + cation is one of the rare examples of a complex that is luminescent in fluid solution. It has a reducible metal and an oxidizable strong field 7r-acid ligand, and is highly emissive in acetonitrile solution with a high quantum efficiency. ... 

Flow-through sensors based on integrated optical detection and a liquid-liquid separation are relatively scant since the analytes are rarely determined by their photometric or luminescence properties. Thus, with few exceptions, these sensors use amperometric detection —as noted earlier, ISEs and ISFETs are dealt with separately in Section 4.6. 

---