Determination of mercury by radiochemical displacement method

A radiochemical displacement method for the determination of micro amounts of Hg(II) has been developed. 65Zn was displaced from the Zn-1-(2-pyridylazo-2-naphthol) complex at pH 5 in borate buffers by Hg (II). 10-80 micrograms of mercury could be determined. Interference of various metal ions and methods for suppression have also been carried out.     

Determination of mercury by radiochemical displacement

2–15 g of mercury has been determined by exchange with zinc in⁶⁵Zn labelled zinc sulphide. The influence of various ions which are likely to interfere in the determination of mercury has also been studied.     

Determination of nickel and cobalt by radiochemical displacement

A radiochemical displacement method has been developed for the determination of nickel and cobalt based on the release of Zn-65 from labelled Zn(PAN)₂ [1-(2-pyridylazo) 2-naphthol] complex in chloroform. The displacement behavior of Zn-65 by nickel and cobalt was studied in the pH range 5–7.5. The effect of various ions on the displacement was also examined. 2–20 g of nickel and cobalt was determined by the aid of calibration plots.     

Trace determination of nickel (and cobalt) in biological reference materials by radiochemical neutron activation analysis

Summary Very few biological reference materials are certified for nickel below 1 mg · kg^–1. Neutron activation analysis was only rarely considered as a possible approach; reported sensitivities were usually not very good, unless preconcentration was applied.In the present work, the relatively high fast neutron flux of our TRIGA reactor was used to induce the ⁵⁸Ni(n, p)⁵⁸Co reaction, and ⁵⁸Co (E =811 keV) was radiochemically separated from other radionuclides by classical anion-exchange chromatography in hydrochloric acid. ⁵⁷Co was added to the irradiated sample before decomposition as a radioisotopic yield monitor. By concentrating the final sample fraction and measurement in a well-type HP Ge detector, Ni concentrations down to the 10-g · kg^–1 level could be determined for samples irradiated for 1 day. ⁶⁰Co, produced by neutron capture on ⁵⁹Co, is also coseparated and quantified from the gamma spectrum, so that both elements Ni and Co are determined. Results are reported for a series of NBS and other biological reference materials in the concentration range 10 g-10 mg · kg^–1. Possibilities for further increases in sensitivity are discussed.

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Spurenbestimmung von Nickel (und Cobalt) in biologischen Referenzmaterialien durch radiochemische Neutronenaktivierungsanalyse

     

Determination of copper by a radiochemical displacement method

Determination of copper/II/ by radiochemical displacement of labelled cobalt from cobalt-o-hydroxybenzaldehyde isonicotinoyl hydrazone /Co-BIH/ complex has been studied. Borate buffer of pH 5 was found to be a suitable medium for quantitative displacement. 10–70 g of copper could be determined. The effect of various foreign metal ions on the determination has also been studied.     

Trace analysis of ancient gold objects using radiochemical neutron activation analysis

Radiochemical neutron activation analysis has been applied to investigate the microelements in gold samples with archaeological importance. Chemical separation has allowed the determination of traces of Ir, Os, Sb, Zn, Co, Fe, Ni. Instrumental neutron activation analysis has been used for the determination of Cu.     

Ion-sieve properties of an inorganic gel loaded with some complex cations of cobalt(III) a radiochemical study

Distribution coefficients of a number of uni-, di-, tri- and quadrivalent metal ions have been determined on chromium ferrocyanide gel loaded with [Co(NH₃)₆]³⁺ and [Co(en)₃]³⁺ ions at 25 °C, and the observed K_d values are compared with those obtained on the unloaded exchanger in H-form. The gel is found to develop ion-sieve properties after being loaded with the complex cations. The variation in K_d values with the pH of Rb⁺, Cs⁺, Ti⁺ and Ag⁺ solutions has also been studied to understand the mechanism of their uptake.     

Determination of chromium by radiochemical displacement

A rapid and sensitive method has been developed for the determination of microgram amounts of chromium based on the radiochemical displacement of⁶⁵Zn from labeled Zn-[1-(2-pyridylazo-2-naphthol]₂ complex by chromium. The effect of pH on the displacement of⁶⁵Zn was studied. 5–65 g of chromium could be determined with great accuracy. The effect of various ions on the displacement of⁶⁵Zn by chromium was investigated and the method developed was utilized for the determination of chromium content present in geological water samples. The results were compared with values obtained by Atomic Absorption Spectrophotometry.     

Determination of copper by radiochemical displacement

5–25 g of copper has been determined by exchange with zinc-65 labelled zinc sulphide. The effect of diverse ions on the determination has also been reported.     

Determination of manganese by radiochemical displacement

The possibility of determination of 10–80 g of manganese by radiochemical displacement of zinc from a labelled zinc-PAN complex has been demonstrated. pH 6 borate buffer was suitable for quantitative displacement. The effect of diverse ions on the displacement reaction is also reported.     

Determination of cadmium by radiochemical displacement

Determination of cadmium by radiochemical displacement of zinc from a labelled ZnPAN complex has been studied. pH 5.5 in borate buffer was suitable for quantitative displacement. The effects of diverse ions on the displacement reaction are also reported.     

Photocleavage of lysozyme by cobalt(III) complexes

Photochemical reagents that cleave proteins at specific sites (photoproteases) are useful for studying protein structure and protein-ligand interactions. PolyammineCo(III) complexes are tested here as photochemical probes to cleave proteins. Irradiation of a mixture of lysozyme, a model protein, and polyammineCo(III) complexes resulted in the facile cleavage of the peptide backbone. Photocleavage yielded two fragments of molecular weights 10.6 and 3.7 kDa, and these masses sum to the molecular mass of lysozyme (14.3 kDa). No cleavage was detected in the absence of the metal complex, in the dark, or upon irradiation at wavelengths of >420 nm. The photocleavage yield increased with irradiation time and with the concentrations of the metal complex and the protein. N-terminal sequencing of the 10.6 kDa fragment indicated residues that are identical to the N-terminus of lysozyme, and sequencing of the 3.7 kDa fragment indicated Val-Ala-Trp-Arg, an internal sequence of lysozyme. From the known primary sequence of lysozyme and the sequencing data, the cleavage site was assigned to Trp108-Val109. Molecular modeling indicates that the observed cleavage site is within few angstroms from the proposed metal binding site at Glu35-Asp52. This is the first report of the successful photocleavage of proteins, with high selectivity, by transition metal complexes. This novel observation can facilitate the rational design of transition metal complexes for the photochemical footprinting of metal binding sites on proteins.     

Determination of thallium(III) by use of a mercury reductor

A convenient method has been developed for the determination of thallium(III) by using a mercury reductor. Thallium(III) is reduced to thallium(I) in 0.5–4N hydrochloric or sulphuric acid medium and the determination is completed by oxidative titration with potassium bromate. The method is extended to analysis of thallium(III)-thallium(I) and thallium(III)-iron(III) mixtures.     

Oxidation of plutonium by cobalt(III) green

A stable green solution of tricarbonatocobaltate(III) has been prepared and used for the redox titrimetric determination of plutonium in HNO₃ medium. Quantitative oxidation could be achieved and excess oxidant could be destroyed by NaNO₂. Pu(VI) was deter-ined by adding known excess of Fe(II) and carrying out potentiometric titration. The precision at the level of 0.5–5.0 mg was 2% RSD.     

A radiochemical neutron activation analysis method for the determination of total mercury in coal

A radiochemical neutron activation analysis method has been developed based on pyrolysis followed by double gold amalgamation for the determination of mercury in solid samples. Accurate results were obtained for mercury in six standard reference materials of varying matrices, including coal. Linearity was demonstrated up to mercury concentrations of 10,000 ng/g. The method is capable of yielding precise, reproducible values with a detection limit of 5 ng/g for mercury in coal.     

Simultaneous determination of cobalt(III)-copper(II) and cobalt(III)-nickel(II) mixtures by differential kinetic methods

A procedure is reported for the simultaneous determination of binary mixtures of cobalt(III)-copper(II) and cobalt(III)-nickel(II) by differential kinetic methods based on complex formation reactions with 3-(1H-1,2,4-triazolyl-3-azo)-2,6-diaminotoluene. The single-point method is used in both cases. The simultaneous determination of Co-Cu and Co-Ni is possible in the concentration range from 10/1 to 1/1. The interference caused by various ions is also studied. The method has been used to determine cobalt-copper and cobalt-nickel mixtures in synthetic samples, hydrofining catalysts and low alloy steels.