Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Taking advantage of luminescent lanthanide ions

Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

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Lanthanide luminescence for functional materials and bio-sciences

Lanthanide-based luminescent hybrid materials.

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

Fuel cells, as devices for direct conversion of the chemical energy of a fuel into electricity by electrochemical reactions, are among the key enabling technologies for the transition to a hydrogen-based economy. Of several different types of fuel cells under development today, polymer electrolyte fuel cells (PEFCs) have been recognized as a potential future power source for zero-emission vehicles. However, to become commercially viable, PEFCs have to overcome the barrier of high catalyst cost caused by the exclusive use of platinum and platinum-based catalysts in the fuel-cell electrodes. Here we demonstrate a new class of low-cost (non-precious metal)/(heteroatomic polymer) nanocomposite catalysts for the PEFC cathode, capable of combining high oxygen-reduction activity with good performance durability. Without any optimization, the cobalt-polypyrrole composite catalyst enables power densities of about 0.15 W cm(-2) in H2-O2 fuel cells and displays no signs of performance degradation for more than 100 hours. The results of this study show that heteroatomic polymers can be used not only to stabilize the non-precious metal in the acidic environment of the PEFC cathode but also to generate active sites for oxygen reduction reaction.

A class of non-precious metal composite catalysts for fuel cells

Organo lanthanide metal complexes for electroluminescent materials.

Organic dye-doped polymers have been widely investigated as gain media in solid-state dye lasers. Dye molecules which have large absorption and induced emission cross sections due to allowed π-π transitions are ideal active dopants for the generation and amplification of intense light pulses. However, continuous wave operation is not feasible with organic dyes because of the triplet losses. On the other hand, lanthanide ions that have long metastable state lifetimes are widely used in silica glass-based fiber amplifiers and for both continuous and pulsed lasers. It has been more than 30 years since the first lanthanide lasers were reported.1-3 During this period a wide variety of lanthanide lasers and amplifiers have been investigated, and extensive progress has been made by many researchers. Many reviews have been written concentrating primarily on the physical and chemical properties of lanthanides in many matrices for laser action.4-8 Recently, several books have focused on lanthanide-doped fiber amplifiers for optical communications.9-11 The success of lanthanide-doped fiber amplifiers has inspired thousands of publications and continues to motivate research on the many diverse components that are required in these systems. Optical links are now used primarily in applications such as telecommunications with single-mode silica optical fibers, which have the ability to provide high-bandwidth and long-distance communications. However, as the demand for bandwidth increases in the office and home, it has become increasingly important to develop very low cost optical links that can be readily installed by users. Plastic optical fibers (POF) have received increasing attention because of their clear technical advantages over glass fibers, such as flexibility and a large core diameter, which enables efficient connection and coupling resulting in a low-cost system for a local area network. Recently a low-loss (100 db/km), highbandwidth 5.12 GHz for 100 m transmission graded index plastic optical fiber (GI-POF) has been developed.12 Also, an all fluorinated POF, whose low loss region is extended to the visible and near-infrared, has been successfully prepared.13 Plastic optical fiber amplifiers (POFA) that generate signal light in the visible and near-infrared are potentially important because of their adaptability for POF-based short span optical local distribution networks. This review describes recent progress on plastic optical fiber lasers and amplifiers with lanthanides. We focus especially on the design and selection of plastic optical fiber and chelate materials.

Plastic optical fiber lasers and amplifiers containing lanthanide complexes.

A new class of amperometric biosensor incorporating a polymeric electron-transfer mediator

Electrical communication between the flavin adenine dinucleotide redox centers of glucose oxidase and a conventional carbon paste electrode has been achieved by using electron-transfer relay systems based on polysiloxanes. Six materials for amperometric biosensors are described in which ferrocene and dimethylferrocene electron relays are covalently attached to insoluble siloxane polymers. Sensors containing these polymeric relay systems and glucose oxidase respond rapidly to glucose, with steady-state current responses achieved in less than 10 s. The dependence of the sensor response on the nature of the siloxane polymer and the type of polymer-bound relay is discussed

Yoshi Okamoto

Papers

Organo lanthanide metal complexes for electroluminescent materials.

Plastic optical fiber lasers and amplifiers containing lanthanide complexes.

A new class of amperometric biosensor incorporating a polymeric electron-transfer mediator

Amperometric glucose biosensors based on redox polymer-mediated electron transfer

Rare earth metal containing polymers. 3. Characterization of ion-containing polymer structures using rare earth metal fluorescence probes