Osmium determination

Consequent potentiometric titration of osmium(IV) and laithenium (IV) in their mixtures has been canied out in broad range of concentrations from 1 mkg to 200 mkg in samples of 20 ml. It has been shown the possibility of amperemetric determination of osmium(VI) in binary and triple systems with silver(I), platinum(IV), palladium(II), gold(III), founded on formation of corresponding compounds with dimerkaptotiopiron, having a different solubility. The deteriuination of Os(VI) is possible under tenfold - hundredfold excess of above mentioned metals. 

The extraction of osmium(VI) and osmium(IV) compounds with dimerkaptotiopiron by polar solvents has been resear ched. 50 -100 - multiple concentrating has been carried out in acid solutions regardless from chemical form of Os(VI) and Os(IV) with the following determination of each of them from one sample by amperemetric titration of reextracts by means of DT. A methodic of atom absor ption determination of osmium has been suggested. 

F.13 Osmium forms a number of molecular compounds with carbon monoxide. One light-vellow compound was analyzed to give the following elemental composition 15.89% C, 21.18% O, and 62.93% Os. (a) What is the empirical formula of this compound (b) From the mass spectrum of the compound, the molecule was determined to have a molar mass of 907 g-mol 1. What is its molecular formula ... 

Most of the reports of osmium complexes containing 1,1-dithio ligands are concerned in the use of dithiocarbamate complexes for the analytical determination of the metal (296) a violet color forms when OSO4 and NaR2dtc are mixed in aqueous solution (84). 

Because of- the similarity in the backscattering properties of platinum and iridium, we were not able to distinguish between neighboring platinum and iridium atoms in the analysis of the EXAFS associated with either component of platinum-iridium alloys or clusters. In this respect, the situation is very different from that for systems like ruthenium-copper, osmium-copper, or rhodium-copper. Therefore, we concentrated on the determination of interatomic distances. To obtain accurate values of interatomic distances, it is necessary to have precise information on phase shifts. For the platinum-iridium system, there is no problem in this regard, since the phase shifts of platinum and iridium are not very different. Hence the uncertainty in the phase shift of a platinum-iridium atom pair is very small. 

Determination of Nuclear Parameters of Osmium Mossbauer Isotopes... 

Mossbauer measurements with determination of the electric quadrupole moments have been reported in [253, 254,259]. Wagner et al. [254] measured the quadrupole hyperfine interaction in OSO2 and OSP2 of the Mossbauer isotopes The ratios of the quadrupole moments of the 4 = 72 states in the even osmium isotopes and of the 4 = 5/2 (69.6 keV) and 4 = 3/2 states in Os were deduced very accurately. In Table 7.8, the experimental results [254] are given, from which the following ratios can be calculated ... 

The structure of the styryl derivative Os ( ,)-CH=CHPh Cl(CO)(PIPr3)2 has been determined by X-ray diffraction analysis.33 In agreement with OsHCl(CO) (P Pr3)2, the coordination polyhedron around the osmium atom can be rationalized as square-pyramidal with the phosphines, mutually tram disposed, the chloride and the carbonyl group occupying the basal sites, and the alkenyl located at the... 

The molecular structure of this compound determined by X-ray diffraction analysis reveals a significant contribution of the resonance form b (Scheme 34) to the osmium alkenyl bond, which is improved by the presence of the carboxyl substituent.71... 

Carbyne complex chemistry of osmium and ruthenium is discussed in this section. These studies demonstrate clearly the parallels that exist between the metal-carbon bonds in carbene and carbyne complexes and again emphasize the importance of metal basicity in determining complex reactivity. 

The a-osmiumdiazo compound 91 decomposes in a thermal reaction to yield the metallacyclic complex 93 (130). This resembles the electrophilic carbene insertion reaction forming OsCl(CO)2(PPh2C6H4CHCl) (PPh3) (77) (see Section V,D,2), and we suggest that a similar insertion reaction of an electrophilic, cationic osmium carbyne 92 is the key step in this transformation. An X-ray structure determination has confirmed the formulation of 93. 

The X-ray structure determination of 107 reveals that the osmium-carbon bond length is increased by 0.07 A on going from the parent carbyne complex 79 to the silver adduct 107. This may be contrasted with the weaker interaction between the metal-carbon bond and the Aul fragment in Os(CH2AuI)Cl(NO)(PPh3)2 (see Section IV,C,1). 

A particular interest for clinical applications was a possibility for detection of dopamine by its oxidation on nickel [19], cobalt [65], and osmium [66] hexacyanofer-ates. Except for oxidation of dopamine, cobalt and osmium hexacyanoferrates were active in oxidation of epinephrine and norepinephrine. For clinical analysis it is also important to carry out the detection of morphine on cobalt [67] and ferric [68] hexacyanoferrates, as well as the detection of oxidizable amino acids (cystein, methionine) by manganous [69] and ruthenium [70] hexacyanoferrate-modified electrodes. In general, oxidation of thiols was first shown for Prussian blue [71] and nickel hexacyanoferrate [72], This approach has been used for the detection of thiols in rat striatum microdialysate [73], Alternatively, the detection of thiocholine with Prussian blue was employed for pesticide determination in acetylcholine-esterase test [74],... 

The above reaction is close to being quantitative. Stoichiometry was determined by varying molar ratios of reactants. The Cz Hio was identified by mass spectrometry. In this reaction oxygen is abstracted from Cz H80 (THF) by boron to form the B303 unit. Two hydrogens from BH3 add to the C He unit to form C H10 while the third hydrogen adds to the osmium cluster. 

Koide et al. [528,529] determined osmium in seawater by passing the water down an anion exchange resin column, followed by distillation of the osmium tetroxide and detection by resonance ionization mass spectrometry. 

Kiba et al. [93] has described a method for determining this element in marine sediments. The sample is heated with a mixture of potassium dichromate and condensed phosphoric acid (prepared by dehydrating phosphoric acid at 300 °C). The ruthenium is distilled off as RuC>4, collected in 6 M hydrochloric acid-ethanol and determined spectrophotometrically (with thiourea) or radiometrically. Osmium is separated by prior distillation with a mixture of condensed phosphoric acid and Ce(S04)2. In the separation of ruthenium-osmium mixtures recovery of each element ranged from 96.8 to 105.0%. 

The sarcoplasmic reticulum (SR) was first identified as the major mobilizable intracellular store of Ca2+ in skeletal muscles through the work of S. Ebashi, W. Hasselbach and A. Weber (review in Ebashi 1991). Identification of the SR and its role in smooth muscle met some early difficulties, partly due to the destructive effects of osmium fixation. Eventually the SR of smooth muscle was also identified, quantitated and its spatial distribution, peripheral and central, determined (Somlyo et al 1971, Devine et al 1971). Strontium (Sr), used as an electron opaque analogue of Ca2+, permitted direct, electron microscopic visualization of divalent cation transport into the SR (Somlyo Somlyo 1971). 

It is commonly known that lipids, carbohydrates, and glycolipids are present in the Golgi apparatus (27). The determination of the components that react with the ZIO mixture was carried out by removing each component from tissues before incubation in the ZIO mixture. After lipid extraction by acetone (14), chloroform-methanol (15), or propylene oxide (27), no osmium-zinc precipitates could be detected in structures that normally reacted with ZIO. Blumcke et al. (15) summarized the nature of the lipids that react with the ZIO mixture as follows lipids and lipoproteins of cell membranes, neutral fat droplets (41), and lipid globules of type II pneumocytes and alveolar macrophages were, however, not as electron dense as the normally reactive lamellae containing highly unsaturated fatty acids. 

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