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By C. H. Evans (auth.)

By a contented accident, the finishing touch of this article coincided with the two hundredth anniversary of the invention of gadolinite, the mineral with which the lanthanide tale starts off. For a gaggle of parts which take place in just hint quantities biologically, and that have no identified metabolic position, the lanthanides have spawned a shockingly huge biochemicalliterature. Se­ rious curiosity within the biochemical homes ofthese components may be traced to matters concerning the security of radioactive lanthanides towards the tip of global warfare eleven. As contemporary occasions at Chernobyl point out, this crisis re­ mains topical. although, the literature on lanthanide biochemistry pre­ dates the atomic period, starting with sporadic, medically influenced experiences within the latter a part of the nineteenth century. a lot of the current biochemical task related to the lanthanides facilities round their skill to supply 2 very important info at the interactions of Ca + with macromolecules and with eukafyotic cells. With the expanding business use of the lan­ thanides, their toxicological homes might want to be tested extra heavily. infrequent earth pneumonoconiosis has already been pointed out as a sickness produced via business publicity to lanthanides. a number of of the biochemical homes of the lanthanides are of relevance to fashionable medication. Already cerium-based ointments are used to regard burn wounds, whereas paramagnetic lanthanides locate software in nuclear magnetic res­ onance imaging. This publication is an try to collate and to offer in moderate aspect present wisdom of lanthanide biochemistry ahead of the literature be­ comes unmanageable.

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In this respect, the narrowness ofthe absorption peaks aids specificity. However, eITors can be introduced by the ability of various counterions or chelators to shift the absorption peaks. This means that the standard curves used for calibration should contain the same population of chelators and counterions as the sampie. The main obstacle to spectrophotometric determinations remains the low molar absorptivities of the lanthanides (Table 2-3). Greatest absorptivity is possessed by Ce3+ and Tb 3 +.

0005 • FES: ftame emission spectroscopy; AAS: atomic absorption spec· troscopy; AFS: atomic ftuorescence spectroscopy; ICP: induction coupled plasma; NAA: neutron activation analysis. • From DeKaib and Fassel (1979). , From Ryabchikov and Ryabukhin (1970). emit at characteristic wavelengths, which can be analyzed to identify and to quantitate the metal concemed. The quantitative determination of lanthanides by flame emission spectroscopy (FES), in which the elements are excited by a flame, has been used for many decades.

8) suggest that organic sulfates (-O-SO» are poor ligands for lanthanides. The formation of stable complexes requires coordination through at least two donor groups; complexes with monodentate 0 ligands tend 18 Chapter 2 to dissociate in aqueous solution. Chelation is the predominant form of lanthanide complex formation. Complexes formed in nonchelated structures are weaker than those formed by the same donor atoms when present in chelates. Coordination numbers of 6 to 12 have been reported for lanthanides.

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