The determination of metals in organic compounds

Summary A comprehensive review of the methods available for the determination of metals in organic compounds has been made. The following metals have been considered:—sodium, potassium, lithium, rubidium, caesium, magnesium, calcium, barium, strontium, boron, thallium, silicon, germanium, antimony, bismuth, tin, lead, selenium, tellurium, silver, gold, osmium, platinum, copper, cadmium, zinc, mercury, vanadium, chromium, iron, cobalt, nickel, niobium, tantalum, rhenium, titanium, zirconium and uranium.

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Zusammenfassung Eine vollständige Übersicht über Methoden zur Bestimmung von Metallen in organischen Verbindungen wird gegeben. Für folgende Metalle werden Methoden beschrieben: Natrium, Kalium, Lithium, Rubidium, Cäsium, Magnesium, Calcium, Barium, Strontium, Bor, Thallium, Silicium, Germanium, Antimon, Wismut, Zinn, Blei, Selen, Tellur, Silber, Gold, Osmium, Platin, Kupfer, Cadmium, Zink, Quecksilber, Vanadium, Chrom, Eisen, Kobalt, Nickel, Niob, Tantal, Rhenium, Titan, Zirkonium und Uran.

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Résumé On donnait une revue complète des méthodes valables pour le dosage des métaux dans des substances organiques. Des méthodes sont décrites pour les métaux suivants: sodium, potassium, lithium, rubidium, caesium, magnésium, calcium, barium, strontium, bore, thallium, silicium, germanium, antimoine, bismuth, étain, plomb, sélénium, tellure, argent, or, osmium, platine, cuivre, cadmium, zinc, mercure, vanadium, chrome, fer, cobalt, nickel, niobe, tantale, rhenium, titane, zirconium et urane.

     

Strategy for water analysis using ICP-MS

The developed strategy permits determination in three steps of sixty-seven elements using inductively coupled plasma mass spectrometry (ICP-MS). Sodium, Mg, Si, S, Cl, K, and Ca are determined in a first step; B, Al, P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, and Pb are determined in a second step; and Li, Be, Ti, V, Co, Ga, Ge, Br, Rb, Sr, Y, Zr, Nb, Mo, Sn, Te, I, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Pt, Au, Tl, Bi, Th, and U are analyzed in a third step. The figures of merit obtained are adequate to carry out water quality monitoring and other hydrochemical studies, such those based in the application of hydrochemical fingerprinting to water management.     

NAA and ICP analysis of obsidian from Central Europe and the Aegean: Source characterisation and provenance determination

INAA and ICPES are compared for their discriminative power in obsidian source characterisation. Geological samples from the Aegean and Carpathian sources were analysed for Na, Sc, Fe, Co, Rb, Sb, Cs, Ba, La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, Ta, Th, U by INAA and for B, Na, Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Zn, Y, Yr, Cs, Ba, La, Ce, Sm, Eu, Gd, Tb, Yb, Lu, Hf by two ICPES procedures. It is shown that all techniques work successfully, however, INAA is more efficient in the chemical discrimination of neighbouring sources.     

A systematic neutron activation analysis of peat from Burundi

Mean concentrations of Al, As, Au, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Cu, Eu, Fe, Ga, Hf, Ho, I, K, La, Lu, Mg, Mn, Na, Pr, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Ti, Th, V, W, Yb, and Zr, determined in 6 samples of peat from Burundi, were equal to 3911, 1.7, 0.025, 33, 21, 472, 14, 55, 4.2, 16, 0.43, 14, 0.27, 14675, 1. 2, 1.5, 0.09, 2.9, 203, 5.6, 0.29, 745, 20, 70, 1.5, 13, 2.1, 6.5, 0.8, 6, 0.4, 0.2, 2.9, 392, 15.7, 0.43, 0.09 and 101 ppm resp. The peat in Burundi contain approximately the same concentrations of elements as the peat in other countries. It is enriched in Br and depleted in Ca, K, Mn, Na, Sr and Yb.     

Elemental content in wheat products of Al-Qusim region, Saudi Arabia using the INAA technique

Wheat is one of the most grown crops in Saudi Arabia. It is grown in various regions of the country. Accurate knowledge of the elemental concentrations in wheat and its products (bran and flour) is of great importance from a nutritional point of view. Wheat samples were obtained from the Al-Qusim region, 300 km northwest of Riyadh, and analyzed. Up to 50 elements (Al, Sb, As, Ba, Br, Cd, Ca, Cs, Cl, Cr, Co, Cu, Ga, Au, Hf, In, I, Ir, Fe, Mg, Mn, Hg, Mo, Ni, K, Rb, Sc, Se, Ag, Na, Sr, Ta, Te, Th, Sn, Ti, W, U, V, Zn, Zr, Ce, Dy, Eu, La, Lu, Nd, Sm, Tb and Yb) were determined in the wheat products. It was observed that the elemental content of bran was much higher than that of white flour.     

Traceability along the production chain of Italian tomato products on the basis of stable isotopes and mineral composition

The paper shows the variability of stable isotope ratios and mineral composition in tomato and derivatives along the production chain (juice, passata and paste) in order to evaluate the possibility of tracing their geographical origin. The ratios (13)C/(12)C, (15)N/(14)N, (18)O/(16)O, D/H, (34)S/(32)S and the content of Li, Be, B, Na, Mg, Al, P, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Ag, Cd, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Tm, Yb, Ir, Tl, Pb, U and of nitrates, chlorides, sulphates and phosphates were measured by Isotope Ratio Mass Spectrometry, Inductively Coupled Plasma Mass Spectrometry and Ion Chromatography, respectively. The tomato products were from three Italian regions - Piedmont, Emilia Romagna, and Apulia. By applying linear discriminant analysis on 17 of these parameters (Gd, La, Tl, Eu, Cs, Ni, Cr, Co, δ(34)S, δ(15)N, Cd, K, Mg, δ(13)C, Mo, Rb and U) excellent discrimination among products from the three regions was achieved. Irrespective of the processing technology, over 95% of the samples were correctly reclassified in cross-validation into the production site. The use of these parameters will allow the development of analytical control procedures that can be used to check the geographical provenance of Italian tomatoes and products derived from them.     

Synthesis of 2‐Arylquinazolin‐4(3H)‐ones by N‐Aryl Benzamidines with Aromatic Carbonates

The reaction of N‐aryl benzamidines 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h , 1i , 1j , 1k , 1l , 1m , 1n with diphenyl carbonate 2a or ethyl phenyl carbonate 2b synthesized 2‐arylquinazolin‐4(3H)‐ones 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k , 3l , 3m , 3n in simple and safe process with good yields (71–90%). It was suggested that different electron‐donating substituent in N‐aryl benzamidines 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h , 1i , 1j , 1k , 1l , 1m , 1n afforded similar effect to the yields of 2‐arylquinazolin‐4(3H)‐ones 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k , 3l , 3m , 3n . In these reactions, N‐aryl benzamidines 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h , 1i , 1j , 1k , 1l , 1m , 1n built up intermediate compounds by nucleophilic addition to carbonates 2 to give annulation products 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k , 3l , 3m , 3n , following to cyclization involving the elimination of ethanol/phenol.     

Der Nachweis organischer Farbstoffe durch Mikrosublimation. II Besonderer Teil

Zusammenfassung Folgende organische Farbstoffe, die entweder als Pulver oder auch als Ausfärbung oder als Druck vorlagen, gaben kennzeichnende Sublimate:Indischgelb G, Dianilgelb G, die Hansagelbsorten 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R, Litholechtgelb RN, Helioechtgelb 6 GL, Litholechtorange RN, Permanentrot R extra, Litholechtscharlach RN (Hansarot B), Litholechtscharlach B, Permanentrot FRL, Autolrot BL, Autolrot RLP, Brillant-Indigo BASF, Indanthrengelb G, Indanthrenbraun G, Indanthrenblau RSN, Indanthrenviolett FFBN, Indanthrengelb 7 GK, Indanthrenbrillantorange GR, Indanthrenbrillantorange RK.

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Summary The following organic dyestuffs which were present either as powders or as dyed or printed material, gave characteristic sublimates:Indian yellow G, dianil yellow G, the 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R brands of Hansa yellow, lithol-fast yellow RN, helio-fast yellow 6 GL, lithol-fast orange RN, permanent red R extra, lithol-fast scarlet RN (Hansa red B), lithol-fast scarlet B, permanent red FRL, autol red BL, autol red RLP, brilliant indigo BASF, indanthrene yellow G, indanthrene brown G, indanthren blue RSN, indanthrene violet FFBN, indanthrene yellow 7 GK, indanthrene brilliant orange GR, indanthrene brilliant orange RK.

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Résumé Les pigments organiques suivants, qui étaient à notre disposition, soit comme poudre, soit comme colorisation ou comme impression, donnèrent des sublimés caractéristiques:Indischgelb G, Dianilgelb G, les sortes de Hansagelb 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R, Litholechtgelb RN, Helioechtgelb 6 GL, Litholechtorange RN, Permanentrot R extra, Litholechtscharlach RN (Hansarot B). Litholechtscharlach B, Permanentrot FRL, Autolrot BL, Autolrot RLP, Brillant-Indigo BASF, Indanthrengelb G, Indanthrenbraun G, Indanthrenblau RSN, Indanthrenviolett FFBN, Indanthrengelb 7 GK, Indanthrenbrillantorange GR, Indanthrenbrillantorange RK.

     

Determinations de traces dans les semi-conducteurs par activation neutronique

Résumé On décrit la détermination de traces dans le germanium, le silicium et le sélénium. En appliquant des techniques gamma spectrométriques, précédées ou non de séparations chimiques il est possible de doser les éléments suivants dans (1) germanium: As, Cu, Au, Ga, Zn, Hg, Cr, Sn, Sb, Co, In, Ni, Ir, Se, Sc, Ag, Ta, Hf et U; (2) silicium: P, Au, Sb, Ga, Fe, K, Cr, Mo, Sn, As, Co, In, Zn, Cu, W, Ta, Na, Eu, Sm, La, Sc et T1; (3) sélénium: Cl, Br, I, P, S, Te, Na, K, Cr, Fe, Co, Cu, Zn, Ga, Sc, Ag, Cd, La, W, Au et Tl. Les concentrations et ou limites de détections varient de quelques parties par million à 10⁻³ parties par milliard.     

金属有机化合物中金属-配体键能的研究进展

介绍了金属有机物质热力学研究的进展,概述了过渡金属-配体键能的基本概念、估测方式、实验和理论研究方法.收集了已测得的第三副族到第八族所有中性金属有机络合物金属-配体σ-单键绝对键焓的实验值.对第三副族及锕系元素,收集了钪-氢、钪-碳、钍-氢、钍-碳、钍-氮、钍-氧、钍-硫、钍-氯、铀-氢、铀-碳、铀-硅、铀-氧、铀-氯、铀-溴、铀-碘、钐-氢、钐-碳、钐-硅、钐-氮、钐-磷、钐-氧、钐-硫、钐-氯、钐-溴和钐-碘键的键焓.对第四副族元素,收集了钛-碳、锆-氢、锆-碳、锆-硅、锆-氮、锆-氧、锆-氯、锆-碘、铪-氢、铪-碳键的键焓.对第五副族元素,收集了钒-氢、钽-碳键的键焓.对第六副族元素,收集了铬-氢、铬-碳、铬-硅、铬-氮、铬-氙、钼-氢、钼-碳、钼-硅、钼-氮、钼-磷、钼-氯、钼-溴、钼-碘、钼-氙、钨-氢、钨-碳、钨-硅、钨-氮、钨-氩、钨-氪、钨-氙键的键焓.对第七副族元素,收集了锰-氢、锰-碳、锰-硅、锰-氧、锰-硫、锰-氯、锰-溴、锰-碘、锝-氯、锝-溴、锝-碘、铼-氢、铼-碳、铼-氯、铼-溴、铼-碘键的键焓.对第八族元素,收集了铁-氢、铁-碳、铁-氮、铁-氩、铁-氪、铁-氙、钌-氢、钌-碳、钌-磷、锇-氢、锇-碳、钴-氢、钴-碳、铑-氢、铑-碳、铱-氢、铱-碳、铱-氯、铱-溴、铱-碘、镍-碳、镍-硫、钯-碳、铂-氢、铂-碳键的键焓.但未包括平均键焓值.此外,还收集了铁-氢、铁-碳、铁-氮、铁-磷、铁-羰基、铁-亚硝基、铁-氧分子、铁-硼、铁-铝、铁-镓、铁-铟、铁-铊键的理论计算值以及金属有机片断和离子的键焓.     

Synthesis of Three New Macrocyclic Tetraamide Ligands

A facile route is described for the synthesis of a series of macrocyclic tetraamides 1, 4, 9, 12 - tetraazacyclo - 2, 3, 6, 7, 10, 11, 14, 15-tetrabenzo-cetanan - 5, 8, 13, 16 - tetraone (TCTCT), 1, 4, 10, 13 - tetraazacyclo -2, 3, 6, 8, 11, 12, 15, 17-tetrabenzo-octadecan-5, 9, 14, 18-tetraone(TCTOT) and 1, 4, 10, 13-tetraaza-cyclo-2, 3, 11, 12-dibenzo-6, 8, 15, 17-dipyrdyl-octadecan-5, 9, 14, 18-tetraone (TCPOT) derived from 1, 2-diaminobenzene based on a stepwise approach using diacid dichloride (1, 2-diacid dichloride benzene, 1, 3- diacid dichloride benzene, 2, 6 - diacid dichloride pyridine) or mix dianhydrides for ring closure. This method is applicable for the preparation of a variety of receptors of various ring size, heteroatom substitution and pendant chains.     

Determination of trace element impurities in aspirin tablets by neutron activation analysis

Twenty five trace and minor elements (aluminium, arsenic, barium, bromine, cerium, chlorine, cobalt, chromium, cesium, europium, iron, hafnium, potassium, magnesium, manganese, sodium, rubidium, antimony, scandium, selenium, strontium, thorium, titanium, vanadium and zinc) in five different Egyptian aspirin brands (Aspo, Askin, Aspocid, Aspeol and Rivo) have been determined by instrumental neutron activation analysis. It has been concluded that the concentration of arsenic, barium, bromine, cobalt, chromium, iron (except in Aspocid), magnesium, manganese, rubidium, selenium, strontium and zinc in the Egyptian brands is below or within the concentration range reported for these elements in 16 American aspirin and aspirin-like brands.     

Systematic study of the solvent extraction of metal oxinates

The extraction of 32 metals (Be, Mg, Ca, Sr, Ba, Sc, La, Ti, Zr, Th, V, Nb, Cr, Mo, W, U, Mn, Fe, Co, Ni, Pd, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Pb and Bi) with oxine solution has been studied. The effects of pH, oxine concentration and water-soluble complexing agents (oxalic acid, tartaric acid, hydrocyanic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and 1,2-diaminocyclohexanetetraacetic acid) have been investigated. From these results the extraction constants and stability constants ot the metal complexes with the various complexing agents investigated have been calculated.     

Elemental content in ground and soluble/instant coffee

The concentration of thirty-four elements in twelve coffee brands has been measured using instrumental neutron activation analysis. The samples investigated included four brands of commercially available ground coffee and eight brands of soluble/instant coffee. The elements measured were Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Gd, Hf, K, La, Lu, Mg, Mn, Na, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, Tm, U, V, Yb and Zn. Twenty four elements were found to be below the detection limit in one or more samples. These elements were Ce, Cr, Fe, V, As, Eu, Ba, Dy, Gd, Hf, La, Lu, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, Yb, Tm, and U.     

Mg(OH)_2共沉淀和直接稀释联用ICP-MS法准确测定海水中的多种常量-微量元素

对海水中多种常量/微量元素分别用Mg(OH)_2共沉淀和直接稀释ICP-MS法进行方法比较研究,分别确定了这些元素适宜的准确分析方法,为海水中常量/微量元素的ICP-MS测定提供了实用的检测手段。结果表明,Mg(OH)_2共沉淀法能够实现对V,Cr,Mn,Co,Cd及稀土元素(La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)等19种微量元素的分离富集和准确测定;10倍直接稀释法能够同时准确测定海水中B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn 13种微量元素,但不适合Zn,Ni,Co和Pb,以及稀土元素等在海水中浓度过低元素的测定;两种方法对适宜测定的元素均操作简便快速,具有较高的准确度和精密度。这两种方法联用,就可用约50 mL的海水实现大洋和近海海水中Co,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu(这15个元素采用Mg(OH)_2共沉淀法)及B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn(这13个元素采用10倍直接稀释法)等28种元素的准确测定。     

Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders

In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the ⁸⁷Sr/⁸⁶Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with ⁸⁷Sr/⁸⁶Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and ⁸⁷Sr/⁸⁶Sr isotope abundance ratio as original variables.     

Trace element profile of a wild edible mushroom (Suillus granulatus)

Seventeen elements, Al, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, V, and Zn (macroelements and trace elements) were investigated by Atomic Spectrometries on a particular wild edible mushroom collected in the central region of Argentina during 2 different years in the same season. The metal content profile in Suillus granulatus samples is given. The found quantities of Na, K, Ca, Mg, Fe, P, V, and Al were 0.40, 10.84, 0.48, 0.30, 0.57, 4.24, 0.18, and 1.23 g/kg dry weight, respectively. The levels of Li, Cu, Zn, Cd, Co, Ni, Cr, and Mn were 0.98, 23.02, 22.30, 0.26, 0.16, 1.17, 0.90, and 28.75 mg/kg dry weight, respectively. Pb was not detected at the investigated levels. The results indicate that the levels of metals in the analyzed samples are not considered to be a health risk. In order to demonstrate the validity of our method, a recovery study was performed with acceptable results.     

Excretion of biotrace elements using the multitracer technique in mice

A radioactive multitracer solution obtained from the nuclear reaction of selenium with 25 MeV/nucleon⁴⁰Ar ions was applied to the investigation of the trace elements behavior in feces and urine of mouse. The excretion rates of 23 elements, Na, K, Rb, Mg, Ca, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Zn, Y, Zr, Mo, Nb, Tc, Ru, Ag and In were simultaneously detected under strictly identical experimental conditions, in order to clarify the excretion behavior of the elements in mice. Fecal and urinary excretion rates of the elements in mice reached the highest value separately at 48 and 24 hours. The total excretion of Mo, Tc and Co within 96 hours were all larger, more than 60%. Accumulative excretion rates of Ca, Nb, Mg, Sr, V, Sc, Na, Cr, Fe, Ag, Mn and Zr were 60-30%. The total rates of Ru, K, As, Zn, Rb, Y, Ga and In were less than 30%, and low excretion. The main excretion pathway of Mo, Co, Mg, Fe and Ag was through urine, and Na, K, As and Rb were eliminated from the body also in urine. But fecal excretion of Tc, Nb, Sr, Y, Ru, and In were larger than urinary excretion, and Ca, Sc, Mn, Zr, Zn were eliminated from the body in feces.     

Determination of elemental levels in radiopharmaceuticals by instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) was applied to thedetermination of the concentration levels of Na, Mg, Al, Cl, K, Sc, Ti, V,Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Ag, Cd, Sb, I, Cs,Ba, La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu, Hf, Ta, Hg, Th and U in three radiopharmaceuticals.The irradiation of the samples was carried out in a 0.5 kW Bariloche RA-6Research Nuclear Reactor and the induced gamma-activity was measured by gamma-spectrometry.INAA proves to be an accurate and precise technique to obtain a quick informationon the concentration levels of several minor and trace components in radiopharmaceuticals.The quantification of heavy toxic elements is required for the registrationof radiopharmaceuticals.