Direct atomic absorption spectrometric determination of chromium,cobalt and nickel in fish protein concentrate and dried fish solubles

Solid-sampling atomic absorption spectrometry was used for the determination of chromium, cobalt and nickel in four types of fish protein concentrate and a sample of dried fish solubles. The samples (0.3–10 mg) were introduced through the injection port of the graphite furnace by means of a special injector. The metals in the fish protein concentrate were determined from peak height measurements, by comparison with the International Atomic Energy Agency reference standard Dried Fish Solubles as the solid standard. The contents (in ppm) of chromium, cobalt and nickel were found to lie in the ranges 0.2–1.8, 0.07–0.3, and 0.7–2.8, respectively; the relative standard deviations were 5–16%.     

Mass spectrometric determination of ergosterol in a prairie natural wetland

Packed capillary liquid chromatography–electrospray mass spectrometry (LC–ESI-MS) was used for the analysis of a snow sample that was accidentally contaminated with an organophosphorus chemical warfare agent during the destruction of a chemical munition. Sarin, its hydrolysis products and a number of related compounds were identified on the basis of acquired LC–ESI-MS data. Full mass spectra were acquired for 14 compounds, with all exhibiting MH⁺, [MH+ACN]⁺ ions and/or protonated dimers that could be used to confirm molecular mass. Sampling cone voltages from 20 to 70 V were utilized with the higher sampling voltages enhancing formation of structurally important product ions in the ESI interface. All data were acquired with a time-of-flight mass spectrometer with a resolution of 5000 (50% valley definition), a resolution that aided in the assignment of elemental composition of the observed ions. The application of LC–ESI-MS to snow analysis appears to be an attractive alternative to the GC–MS methods, since both chemical warfare agents and their hydrolysis products may be analysed directly, eliminating the need for additional sample handling and derivatization steps.     

Direct determination of cadmium in placenta. Comparison with a destruction atomic absorption spectrometric method

Summary A comparison of performance characteristics of a destruction ETA-AAS method and the solid sampling ETA-AAS method experienced in analyzing cadmium in placenta is described. The accuracy of both methods is good; the precision of the destruction method was better. It was concluded that the direct method was preferable for the determination of cadmium in placenta and other tissues as it has a higher speed of analysis and is less sensitive to contamination. Problems with both methods are mentioned and homogenization of samples is shortly described.

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Direkte Bestimmung von Cadmium in Placenta. Vergleich mit einer AAS-Methode mit Aufschluß

Zusammenfassung Die Leistungsfähigkeit einer ETA-AAS-Methode mit Aufschluß wird verglichen mit derjenigen einer Feststoff-ETA-AAS-Methode. Die Richtigkeit beider Verfahren ist gut, während die Präzision bei der Methode mit Aufschluß besser ist. Es wurde der Schluß gezogen, daß die direkte Methode zur Cadmiumbestimmung in Placenta und anderen Geweben vorzuziehen ist, da sie eine größere Analysengeschwindigkeit bietet und geringere Störanfälligkeit gegenüber Verunreinigungen aufweist. Probleme, die bei beiden Verfahren auftauchen, werden aufgezeigt. Die Homogenisierung der Probe wird kurz beschrieben.

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Lecture given at the colloquium on the Analysis of Solids by AAS, Wetzlar, October 8–10, 1984

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These investigations were supported in part by the Netherlands Technology Foundation (STW).     

Mass spectrometric amino acid sequence determination in arginine-containing peptides

Methods of converting arginine residues into ornithine, N^δ-pyrimidylornithine, N^δ-imidazolidinonidenornithine residues in peptides have been developed. The modified peptides undergo the amino acid type of fragmentation, so that mass spectrometry can now be used for amino acid sequence determination in arginine-containing peptides.     

Mass spectrometric determination of selenenylsulfide linkages in rat selenoprotein P

The reversible formation of a selenenylsulfide linkage in mammalian thioredoxin reductase was identified as having a key role in its activity. Identification of selenenylsulfide and/or diselenide linkages is therefore critical to the determination of the structure and function of selenoproteins. A selenopeptide, (298)SGSAITUQCAENLPSLCSUQGLFAEEK(324) (U=selenocysteine), was isolated from a tryptic digest of rat selenoprotein P. Its two cysteine residues and two selenocysteine (Sec) residues were determined to be present in oxidized form by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The selenopeptide was subjected to partial reduction by dithiothreitol with immediate alkylation by iodoacetamide. This process was monitored by MALDI-TOFMS to determine the number of alkylations that had taken place. The partially reduced and alkylated peptides were then analyzed by nano-electrospray ionization tandem mass spectrometry and the results indicated that selenenylsulfide linkages Sec304-Cys314 and Cys306-Sec316 were present. It is concluded that selenoprotein P contains these two selenenylsulfide bonds.     

Gas chromatographic-mass spectrometric determination of oxolinic acid in fish using selected ion monitoring

A gas chromatographic-mass spectrometric (GC-MS) method is described for the determination of oxolinic acid in fish tissues. oxolinic acid is reduced with sodium tetrahydroborate to permit GC analysis. The sample is homogenized with phosphate buffer (pH 6) and extracted with ethyl acetate. The extract is partitioned between sodium hydrogencarbonate solution and the aqueous phase is acidified and re-extracted with ethyl acetate. The residue from the ethyl acetate extract is dissolved in methanol and reduced with sodium tetrahydroborate. The reduction product is extracted with diethyl ether and analysed by GC-MS in the selected ion monitoring mode for the ions at m/z 204, 219 and 176. The detection limit is 0.001 mg/kg and the recoveries were 95.6% [relative standard deviation (R.S.D.) 7.7%] at 0.1 mg/kg and 72.9% (R.S.D. 13.3%) at 0.01 mg/kg fortification levels in fish.     

Capillary gas chromatographic — Mass spectrometric determination of iprodione in chicory and leek

Summary A capillary GC/MS method is presented for the analysis of iprodione (CAS registry number 36734-19-7) in chicory and in leek. Preliminary extraction was carried out using methanol, and the extracts were cleaned up using two liquid-liquid extractions and Bakerbond SPE Florisil? cartridges. The eluates were evaporated to dryness under reduced pressure, and the residues dissolved in hexane. Iprodione was then monitored by capillary Gas Chromatography, with Mass Spectrometric Detection, in the selective ion mode at m/z 314. Recoveries of 89 % to 108 % were obtained for chicory and leek fortified at 100 and 500 μg kg⁻¹. The proposed method of analysis has a detection limit of 2 μg kg⁻¹ for chicory and 4 μg kg⁻¹ for leek.     

Mass spectrometric determination of ILPR G-quadruplex binding sites in insulin and IGF-2

The insulin-linked polymorphic region (ILPR) of the human insulin gene promoter region forms G-quadruplex structures in vitro. Previous studies show that insulin and insulin-like growth factor-2 (IGF-2) exhibit high affinity binding in vitro to 2-repeat sequences of ILPR variants a and h, but negligible binding to variant i. Two-repeat sequences of variants a and h form intramolecular G-quadruplex structures that are not evidenced for variant i. Here we report on the use of protein digestion combined with affinity capture and MALDI-MS detection to pinpoint ILPR binding sites in insulin and IGF-2. Peptides captured by ILPR variants a and h were sequenced by MALDI-MS/MS, LC-MS and in silico digestion. On-bead digestion of insulin-ILPR variant a complexes supported the conclusions. The results indicate that the sequence VCG(N)RGF is generally present in the captured peptides and is likely involved in the affinity binding interactions of the proteins with the ILPR G-quadruplexes. The significance of arginine in the interactions was studied by comparing the affinities of synthesized peptides VCGERGF and VCGEAGF with ILPR variant a. Peptides from other regions of the proteins that are connected through disulfide linkages were also detected in some capture experiments. Identification of binding sites could facilitate design of DNA binding ligands for capture and detection of insulin and IGF-2. The interactions may have biological significance as well.     

Mass spectrometric determination of the nitrogen-15 content of different Egyptian fertilizers

Different nitrogen fertilizers produced in Egypt were analyzed mass-spectrometrically for their¹⁵N content. The results indicate that nitrate fertilizers are relatively enriched in¹⁵N compared with ammonium fertilizers. The isotopic fractionation of nitrogen encountered in the production processes of fertilizers are discussed.     

Mass spectrometric determination of the heats of formation of the silane bromides

The reaction of SiBr₄(g) with H₂(g) in the temperature range 900–1143 K has been studied by a mass spectrometric method. Second and third law reaction enthalpies were obtained for SiBr₄(g) + H₂(g) = SiHBr₃(g) + HBr(g), SiHBr₃(g) + H₂(g) = SiH₂Br₂(g) + HBr(g), and SiH₂Br₂(g) + H₂(g) = SiH₃Br(g) + HBr(g). From the heats of reaction, third-law ΔH_£298 values of ?72.5 ± 1, ?43.2 ± 1.5 and ?15.3 ± 0.5 kcal/mole were obtained for SiHBr₃(g), SiH₂Br₂(g), and SiH₃Br(g), respectively.     

Phytoecdysones of Serratula III. Mass spectrometric study of the acetates and acetonides of ecdysterone and viticosterone e

Summary Features of the fragmentation of the side chain of the acetates and acetonides of ecdysterone and of viticosterone E have been studied. It has been shown that the presence of an oxygen-containing function at C₂₅ in these compounds imparts to the spectra certain distinguishing features which have analytical value.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 155–158, March–April, 1975.     

Radiochemical thermal neutron activation analysis of fish solubles

A rapid and simple method has been developed for the determination of Mn, Zn, Cr and Ag by radiochemical thermal neutron activation analysis, involving solvent extraction and precipitation technique. Mn, Zn, Cr and Ag can be determined with an accuracy of 8.9, 5.8, 7.7 and 7.6%, respectively. The method has been employed for determination of the elements in fish solubles. Two samples and a standard can be analyzed in three hours.