Samarium determination

The absolute configuration of C-3 of the chromophore 459 of isopyoverdins was determined to be S from the circular dichroism (CD) spectrum (Cotton effect +242 nm, —290 nm, +358 nm) of 460 obtained from isopyoverdin by acidic hydrolysis <2001T1019>. Diorganotin(iv) complexes with 4//-pyrido[l,2-/z pyrimidin-4-ones 461 <1996AOM47>, complexes of 2-methyl- and 2-methyl-8-nitro-9-hydroxy-4//-pyrido[l,2-tf]pyrimidin-4-ones with Ag(i), Cu(ll), Ni(n), Co(n), and Mn(n) ions <2000RJD587>, 2,4-dimethyl-9-hydroxypyrido[l,2-tf]pyrimidinium perchlorate and its complexes with prasedynium, neodymium, samarium, and europium <2000RJD310> were characterized by UV spectroscopy. 

The crystal structure of the 1 2 adduct 145 obtained by the reaction of [Cp SmH]2 with MMA was determined by X-ray analysis. One of the two monomer units is in the O-enolate form and the other unit coordinates to the samarium atom by the carbonyl group. A comparison between 145 and the... 

Time-resolved approaches for multi-analyte immunoassays have been described recently. Simultaneous determination of LH, follicle stimulating hormone (FSH), hCG, and prolactin (PRL) in a multisite manual strip format has been reported. 88 Four microtiter wells are attached to a plastic strip, two-by-two and back-to-back, such that the wells can be read on a microtiter plate reader. In a quadruple-label format, the simultaneous quantitative determination of four analytes in dried blood spots can be done using europium, samarium, dysprosium, and terbium. 89 In this approach, thyroid-stimulating hormone, 17-a-hydroxyprogesterone, immunoreactive trypsin, and creatine kinase MM (CK-MM) isoenzyme are determined from dried blood samples spotted on filter paper in a microtiter well coated with a mixture of antibodies. Dissociative fluorescence enhancement of the four ions using cofluorescence-based enhancement solutions enables the time-resolved fluorescence of each ion to be measured through four narrow-band interference filters. 

Samarium - the atomic number is 62 and the chemical symbol is Sm. The name derives from the mineral Samarskite, in which it was found and which had been named for Colonel von Samarski , a Russian mine official. It was originally discovered in 1878 by the Swiss chemist Marc Delafontaine, who called it decipium. It was also discovered by the French chemist Paul-Emile Lecoq de Boisbaudran in 1879. In 1881, Delafontaine determined that his decipium could be resolved into two elements, one of which was identical to Boisbaudran s samarium. In 1901, the French chemist Eugene-Anatole Demar9ay showed that this samarium earth also contained europium. 

Mysen B. O. (1977b). Experimental determination of cesium, samarium and thulium partitioning between hydrous liquid, garnet peridotite minerals and pargasite. Carnegie Inst. Wash. Yb., 76 588-594. 

Ganguly J., Tirone M., and Hervig R.L. (1998b) Diffusion kinetics of samarium and neodymium in garnet, and a method for determining cooling rates of rocks. Sdence 281, 805-807. 

In some cases, thermal neutrons can also be used to measure the absolute abundances of other elements. Transforming the neutron spectrum into elemental abundances can be quite involved. For example, to determine the titanium abundances in lunar spectra, Elphic et at. (2002) first had to obtain FeO estimates from Clementine spectral reflectances and Th abundances from gamma-ray data, and then estimate the abundances of the rare earth elements gadolinium and samarium from their correlations with thorium. They then estimated the absorption of neutrons by major elements using the FeO data and further absorption effects by gadolinium and samarium, which have particularly large neutron cross-sections. After making these corrections, the residual neutron absorptions were inferred to be due to titanium alone. 

Kleinerman and co-workers (158) reported an enhancement of fluorescent yield of chelated lanthanide ions by Lewis bases. They observed that in liquid, plastic, and glassy solutions containing terbium europium, and samarium chelates, the use of Lewis bases accomplishes the same effect as substituting deuterium for hydrogen. Not all bases, however, are equally effective. The molecular size of the base does not appear to be particularly important, since strong enhancement effects can be obtained with both bulky and small molecules. The nature of the atom of the base having the unshared electron pair is not a determining factor in the enhancement phenomenon. 

A number of X-ray crystal determinations have made the principles of lanthanide cryptate structural chemistry fairly clear. In [La(N03)2(2,2,2-cryptate)][La(N03)6] (Figure 8), the La3+ ion is 12-coordinated with two bidentate nitrate ions coordinating in two of the three spaces between the cryptate chains the third space is thus too compressed to be occupied also.508 [Sm(N03)(2,2,2-cryptate)][Sm(N03)5(H20)] shows only one such space occupied511 and the structure of [Eu(C104)2,2,2-cryptate](C104)2MeCN is similar to the samarium cryptate.512,513 Intemuclear distances in these complexes are shown in Table 10. 

A large number of radical reactions proceed by redox mechanisms. These all require electron transfer (ET), often termed single electron transfer (SET), between two species and electrochemical methods are very useful to determine details of the reactions (see Chapter 6). We shall consider two examples here - reduction with samarium di-iodide (Sml2) and SRN1 (substitution, radical-nucleophilic, unimolecular) reactions. The SET steps can proceed by inner-sphere or outer-sphere mechanisms as defined in Marcus theory [19,20]. 

Scheme 10.28 Use of the 5-hexenyl radical clock to determine Arrec n for primary alkyl radicals by Smb in a samarium Barbier reaction (Ar = p-methoxyphenyl).

Neodymium, determination of atomic weight of, in neodymium oxalate, 2 61 separation of, from samarium from monazite, as magnesium nitrate double salt, 2 56, 57... 

Another completely different approach consists in choosing a dye, that already possesses aminocarboxylate functions (Meshkova et al., 1992a), such as triphenylmethane dyes. The latter can be used for selective luminescent determination of Nd111 and Ybm in samarium oxide, for instance. As previously described in the section devoted to /3-diketonates (section 3.2.1), the triplet excited states of /i-dikctonatcs lie at energies >20 000-25 000 cm-1, above most of the accepting levels of Lnm ions. As a consequence, determination of Ndm and Yb111 in europium or samarium oxides is difficult using /3-dike to nates since these two ions exhibit luminescence in the NIR, especially Smm with emission lines at 908, 930, 950, and 1038 nm close to the analytical lines of Ndm and Ybm. Therefore, the detection limit of Ndm and Ybm in samarium compounds by luminescence of their ternary complexes with tta and phen is only 0.1-1 wt%. 

Addition of DBU to a solution of 149 in THF induced an elimination reaction accompanied by loss of a molecule of CO2 and provided the unstable amine 150, which was converted in situ into isocyanate 151 by reaction with phosgene and triethylamine. After filtration to remove hydrochloride salts, the solution of 151 was treated with samarium (II) iodide in the presence of lithium chloride. These conditions, which had been previously determined to be optimal for spirooxindole generation on a model system, provided compound 152 as an inseparable 7 1 mixture of diastereoisomers [43]. The major component of this mixture was determined by NOE analysis to have the required configuration, which is consistent with bond formation from the less hindered, convex face of 151 (Scheme 35). 

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