Electron spin relaxation of Mn(II) ions under conditions of slow molecular motions

The reorientational mobility of Mn(II) complexes in diethylphosphoric acid has been studied by ESR over a broad temperature range. An analysis of the spectra has been carried out on the basis of a theory of line shapes developed for Mn(II) ions (S=5/2, I=5/2) under the condition _0c 1. It has been established that the widths of the hyperfine components of the spectrum of Mn(II) depend on the square of the nuclear magnetic quantum number even in the case of very slow molecular re-orientation, in which the spectrum is complicated by fine-structure effects that are not completely averaged.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 24, No. 1, pp. 57–62, January–February, 1988.We express our sincerest thanks to G. P. Vishnevskaya for participating in the discussion of the results and R. Sh. Safin for helping to carry out the experiments.     

Selective Spectrophotometric Determination of Aluminium in the Presence of Beryllium and Lanthanide Cations

A spectrophotometric method for the selective determination of Al(III) in the presence of Be and Ln (lanthanide) cations is proposed. It is based on the selective reaction of SXO (Semi-Xylenol Orange) with Al(III) at pH 2.6. The presence of 8%v/v of 1,2-ethanediol serves to stabilize the chelate formed by heating at 100°C for 5min. 0.5mg each of Be(II), Ce(III), La(III), 4mg of Mn(II), 1.2mg of Pb(II), 1mg of Tl(I), 40mg each of Ca(II) and Mg(II) and 1.9mg of sodium dihydrogen phosphate are tolerable. A ligand buffer of HEDTA-Pb is incorporated to further enhance the selectivity of the color reaction. Under the specified conditions SXO reacts with Al(III) to form a 1:1 chelate. Its molar absorptivity at 526nm was found to be 3.3×10⁴Lmol^–1cm^–1. The linear regression equation for 2–20µg of Al(III) is A=0.04458C+0.0112 (where C stands for the concentration of Al(III), µg per 25mL) and correlation coefficient =0.9988. The RSD at the level of 10µg (n=10) and LOQ were found to be 3.5% and 2µg, respectively.     

Simultaneous determination of iron(III) and cobalt(II) withN-phenylcinnamohydroxamic acid and thiocyanate by extraction and spectrophotometry

Simple, precise, sensitive, and highly selective methods for the separate determination of iron(III) and cobalt(II) and for the simultaneous determination of both metal ions are described. Iron(III) and cobalt(II) react with thiocyanate in the presence ofN-phenylcinnamohydroxamic acid (PCHA) to form pinkish red and blue coloured complexes, respectively. Both the iron(III) and cobalt(II) complexes having stoichiometric composition of 122 (FeSCN^–PCHA) and 14 (CoSCN^–), respectively, are quantitatively extractable into ethylacetate from 0.5–1.5 M hydrochloric acid solutions. The spectra of iron(III) and cobalt(II) complexes in the visible region exhibit absorption maxima at 495 and 625 nm, respectively. The coloured systems obey Beer's law in the concentration range of 0.2–4.0g/ml of iron and 2–40g/ml of cobalt. The effects of foreign ions and of various experimental parameters were studied to establish the optimum conditions for the extraction and determination of iron and cobalt. The methods have been applied successfully to the analysis of blood, vitamin B₁₂, and standard steels for iron and cobalt.     

An lonophoretic study of the interactions between metal lons and 1-phenyl-3-pyrazolidinone

Summary The ionic behaviour of 1-phenyl-3-pyrazolidinone (phenidone) at different pH values and its complexes with a selected group of metal ions such as Mg(II), Al(III), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) were investigated in the pH range of 1–13 by paper electrophoresis. pH-mobility curves were determined for phenidone, the nine metal ions and 21 metal-ligand systems with 1, 110 and 1100 metal: ligand ratios. The effect of the pH on complex formation and the influence of the phenidone concentration on the metal ion mobilities are discussed.Presented at the XXII International Conference on Coordination Chemistry, August 23–27, 1982, Budapest (Hungary).     

151Eu Mössbauer Study of Calcium Aluminate Glass and Glass Ceramics Containing a Small Amount of Europium(III)

¹⁵¹Eu Mössbauer spectrum of IR-transmitting calcium aluminate glass, 60CaO·32Al₂O₃·5Fe₂O₃·3Eu₂O₃, consists of a broad peak due to distorted Eu(III) with and values of 0.91 and –2.02 mm·s^–1, respectively. Debye temperatures (_D) of 360 and 320 K were obtained from the temperature dependence of absorption area (A) and that of , respectively. These _D values indicate that Eu(III) atoms occupy substitutional sites of distorted Al(III)O₄ tetrahedra in calcium aluminate glass. The value of 0.62 mm/s obtained from the heat-treated sample (glass ceramic) indicates that Eu(III)-O bonds became less covalent. A smaller value of –1.20 mm·s^–1 was obtained for Eu(III) in the glass ceramic, indicating less distorted Eu(III)O₄ tetrahedra.     

Structure of lophopterol

Summary When suberosin is allowed to stand in chloroform at room temperature with access of atmospheric oxygen, photooxidation takes place with the formation of at least three substances: (II), C₁₅H₁₆O₄, mp 172–174°C; (III), C₁₅H₁₆O₅, mp 184–185°C; and (IV).It has been established by NMR and mass spectroscopy and also by their chemical properties, that (II) is 6-(3-hydroxyisopent-2-en-1-yl)-7-methoxycoumarin (trans-suberenol) and (III) is 6-(1,2-epoxy-3-hydroxyisopentyl)-7-methoxycoumarin (lophopterol). The nature of (IV) has not yet been determined.It has been shown experimentally that no such oxidation takes place with an isomer of (I) — osthole (IX). A scheme for the biogenesis of coumarins in the organism of the plant investigated has been put forward.Leningrad Sanitary-Hygienic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 131–133, March–April, 1975.     

Potentiometrische Manganbestimmung mit Kaliumhexacyanoferrat(III) in alkalischer Mannitl?sung

Zusammenfassung Zur potentiometrischen Manganbestimmung wird die Oxydation des Mangan(II)-Mannit-Komplexes mit Kaliumhexacyanoferrat(III) in alkalischer Lösung benutzt. Die Oxydation ist durch zwei gut ausgeprägte Potentialsprünge gekennzeichnet, die den Wertigkeitsübergängen Mangan(II) Mangan(III) und Mangan(III) Mangan(IV) entsprechen. Die Lösung soll 1 Mol/l KOH und 0,25–0,5 Mol/l Mannit enthalten. Der Konzentrationsbereich des bestimmbaren Mangans liegt zwischen 0,9 · 10^–3 und 2,3 · 10^–2 Mol/l.Die Bestimmung, die durch eine Reihe von Metallen nicht gestört wird, ist mit einem relativen Fehler von — 1% behaftet. Der störende Einfluß von Kobalt(II) wurde bis zu einem bestimmten Grad durch Zugabe von ÄDTA eliminiert, wobei nur ein gut meßbarer Potentialsprung auftritt, der der Oxydation Mangan(II) Mangan(IV) entspricht. Die Methode wurde mit guten Ergebnissen bei der Manganbestimmung im Schiefer und Kalkstein angewandt.

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Summary The oxidation of complexes of manganese (II)-mannitol with hexacyanoferrate(III) in alkaline medium was utilized for the potentiometric determination of manganese. The oxidation is characterized by 2 potential jumps belonging to the reactions manganese(II) manganese(III) and manganese(III) manganese(IV). The optimum medium is 1 Mol/l of KOH and 0.25–0.5 Mol/l of mannitol, concentration range of manganese being between 0.9×10^–3 and 2.3×10^–2 Mol/l. The presence of some metals does not influence the determination, the relative error being — 1%. The interfering influence of cobalt(II) is eliminated to a certain extent by the addition of EDTA. In this medium, only one potential jump belonging to the oxidation of manganese(II) manganese(IV) appears. The method yields good results when applied to slate and limestone.

     

Kinetics of the interaction of aquo-ethylenediaminetetraacetatoruthenate(III) with ferricyanide ion in water

Summary The interaction of aquo-ethylenediaminetetraacetatoruthenate(III) with ferricyanide ion was studied spectrophotometrically as a function of ferricyanide ion concentration, pH (1.5–8.5) and temperature (30–45°C) at ionic strength 0.2 M (NaClO₄). Kinetic and activation parameters (H=27.1±1.75 KJ mol^–1, S=–136.7±5.57 J mol^–1 deg^–1) are consistent with the proposed mechanism.     

Using enzymes isolated from diverse sources to determine metal ion cofactors

Oxidoreductases and hydrolases isolated from different sources (horseradish and peanut peroxidases, alcohol dehydrogenases from bakers yeast and horse liver, and alkaline phosphatases from Escherichia coli, chicken and seal intestine) were used to determine their metal ion cofactors: Fe(III), Zn(II) and Mg(II), respectively. Studying the effects of the metal ion cofactors on the catalytic activity of the enzymes of different origin showed that the extent of their inhibition, activation, or reactivation of their apoenzymes depended on the structure and accessibility of the enzyme active site, which varies among the biocatalysts isolated from different sources. The developed procedures are based on the inhibiting (Zn(II)) or activating (Mg(II)) effects of the metal ions on the catalytic activity of the enzymes, or on reactivating effects (Fe(III) and Zn(II)) on the apoenzymes. The procedures are characterized by high sensitivity and selectivity; the detection limits of Fe(III) using horseradish peroxidase, Zn(II) using alcohol dehydrogenase from bakers yeast, alkaline phosphatase from seal intestine and its apoenzyme, and Mg(II) using alkaline phosphatase from chicken intestine equal 10 ng L^–1, 20 ng L^–1, 3 g L^–1, 8 g L^–1 and 0.2 g L^–1, respectively.Presented at the 8th Symposium Kinetics in Analytical Chemistry, Rome, Italy, 5–8 July 2004.     

The effect of zinc(II) on the formation of 2,2′- and 2,3′-bipyridine complexes of [Ru2II(ttha)]2−(ttha6−=triethylenetetraminehexaacetate)

Ru2II(ttha)(H2O)2]2– (ttha6–= triethylene tetramine hexa-acetate), prepared by the reduction of the ruthenium(III) precursor, reacts with 2,2-bipyridine (2,2-bpy) in a multi-step fashion. The first 2,2-bpy equivalent (1:1) adds with bidentate chelation at one ruthenium(II) site as revealed by separate ruthenium(II)/(III) waves at 0.03 and 0.54V vs. n.h.e. A second equivalent of 2,2-bpy (1:2) is initially stored and retained as the [Zn(2,2-bpy)]2+ complex. Further addition of 2,2-bpy initiates coordination at the second ruthenium(II) site. [Ru2(ttha)-(2,2-bpy)(H2O)]2– forms a strong ion-pair with zinc(II) that is in rapid equilibrium with the Zn(H2O)62+/Zn(2,2-bpy)]2+ pool. The solubility of the ion-pair is low. The ion-pair exhibits a shifted ruthenium(II)/(III) wave at 0.60V. Higher amounts of 2,2-bpy recomplex the zinc(II), solubilizing the complex and returning the E1/2 value to 0.54V. Other ligands which either have a higher affinity for ruthenium(II) centres than for zinc(II) as bidentate donors (1,10-phenanthroline), or ligands that cannot form bidentate zinc(II) complexes [(2-methylpyrazine, 4,4-bipyridine (4,4-bpy), and 2,3-bipyridine (2,3-bpy)] do not exhibit the unusual competition by zinc(II). These ligands all add statistically to the ruthenium(II) centres forming 1:2 complexes with 1:2 stoichiometries. 1H-n.m.r. studies of the Ru(II)polyaminopolycarboxylate complexes [RuII(hedta)(H2O)]– complex, and [Ru2(ttha)(H2O)2]2– itself, reveal that substitution of 2,3-bpy at ruthenium(II) sites occurs with an initial kinetic split between the pyridyl rings of the 3- less-hindered and 2-more-hindered ring. A slower rearrangement occurs, producing the isomer of the more-hindered 2-substituted ring. A process is driven by forming a more -accepting system when ruthenium(II) binds to the 2-ring of 2,3-bpy. Understanding the unusual influence of zinc(II) on the substitution of 2,2-bpy with [Ru2(ttha)(H2O)2]2– clarifies the nature of the 1:1 complex – namely that the 2,2-bpy becomes bidentate at one ruthenium(II) centre rather than serving as a trans-bridging ligand between both ruthenium(II) centres within one [Ru2(ttha)]2– unit.     

The structure of nitrarine

Summary Dehydrogenation of the alkaloid nitrarine with selenium has given 3-(quinolin-8-yl)--carboline (II) and 3-(5, 6, 7, 8-tetrahydroquinolin-8-yl)--carboline (III).On the basis of the results of a study of the chemical and physical properties of nitrarine, and also from the results of x-ray structural analysis, structure (I) has been established for it.Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow, Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 334–345, May–June, 1976.     

Determination of Arsenic in Food Samples by Hydride Generation – Atomic Absorption Spectrometry

A method for the determination of trace amounts of arsenic in food samples using flow injection analysis and atomic absorption spectrometry with hydride generation (FI-HG AAS) was developed. The parameters of the flow injection system and the hydride generation were optimized with respect to reagent concentrations, atomization temperature, injection volume, reaction coil length and carrier flow rate. The limits of detection and quantification were 0.34µgL^–1 and 1.2µgL^–:1, respectively, and the analytical curve is linear up to 30.0µgL^–1 arsenic. The relative standard deviation for 12 replicates varies between 5% for 4.0µgL^–1 As and 1.8% for 30.0µgL^–1 As, with an injection frequency of up to 135h^–1. Interferences from Ni(II), Cu(II), Fe(III), Cr(III), Mo(II), Bi(III), Se(IV), Se(VI), Sb(III) and Sb(V) could be masked with a mixture of ascorbic acid-KI in a 5.0molL^–1 HCl solution. The accuracy of the proposed method was evaluated by using certified reference materials of biological samples, and the method was used to determine the content of arsenic in fish and coffee beans.     

Triterpene glycosides of Thalictrum squarrosum. IV. Structures of squarrosides A1, A2, B1, and B2

Four new cycloartane glycosides have been isolated from a methanolic extract ofThalictrum squarrosum Stephan ex Willd.: squarroside A1 (I) — (21R, 22S, 23R)-3-(-D-glucopyranosyloxy)-21-methoxy-21,23-epoxycycloart-24-ene-22,30-diol, C₃₀H₆₀O₁₀; squarroside A2 (II) — the (21S)-epimer of compound (I); squarroside B1 (III) (21R, 22S, 23R)-3gb-[O--L-rhamnopyranosyl-(1 6)--D-glucopyranosyloxy]-21-methoxy-21,23-epoxycycloart-24-ene-22,30-diol, C₄₃H₇₀O₁₄; and squarroside B2 (IV) — the (21S)-epimer of compound (III). The proposed structures were determined on the basis of¹H and¹³C NMR spectroscopy, FAB mass spectrometry, and chemical transformations.Irkutsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 516–523, July–August, 1989.     

Nuclear magnetic resonance investigation of intramolecular scrambling processes in meso-(2,3-butylenediamine)tetraacetate. Diamagnetic complexes of transition metal ions

Summary The acetate scrambling processes (, conversion and N inversion) occurring in the complexes formed from meso-(2,3-butylenediamine)tetraacetic acid (BDTA) with zinc(II), cadmium(II), mercury(II), scandium(III), yttrium(III) and lanthanum(III) ions have been investigated by line shape analysis of their n.m.r. spectra. Between 308 and 373 K fast conversion between and isomers and slow nitrogen inversion occur except for mercury(II) and yttrium(III) in the latter case. H^* = 2.3±0.1 kJ mol^–1 and S^* = –6.9±0.2 mol^–1 J K^–1 for the mercury complex; H^* = 2.6 ±0.2 kJ mol^–1 and S^* = –5.5±0.5 mol^–1 JK^–1 for the yttrium complex. Exchange mechanisms proceeding through different reaction intermediates are discussed on the light of the results obtained in this work as well as previously on other polyaminepolycarboxylate complexes of the same ions.     

Metal Sorption,Solid Phase Extraction and Preconcentration Properties of Two Silica Gel Phases Chemically Modified with 2-Hydroxy-1-Naphthaldehyde

Active silica gel phase (I) was chemically modified to the corresponding amino- (SiNH₂) and chloro- (SiCl) derivatives via silylation reactions. These were used to synthesize two newly modified silica gel phases (II, III) by direct chemical reaction with 2-hydroxynaphthaldehyde (2-HNA). The surface coverage values are 370, 432µmolg^–1 and 320, 355µmolg^–1 for (II) and (III), on the basis of thermal desorption and metal probe testing method, respectively. The metal sorption properties of silica gel phases (II, III) were studied and compared with active silica gel phase (I). The maximum determined metal capacity values were found to be 10–110, 20–290 and 20–370µmolg^–1 for phases I, II and III, respectively. The distribution coefficient values (K_d) were also determined for a series of metal ions, and the results showed that the two new chemically modified phases (II and III) were highly selective for Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. The potential applications of silica gel phases (II, III) as solid phase extractors for the same five metal ions spiked in drinking tap water (1.000µgmL^–1) were found to give percentage recovery values in the range of 90.2–96.3±4.1–6.3%, while pre-concentration of the same five metal ions spiked in drinking tap water (50.0ngmL^–1) was successfully accomplished with a percentage recovery range of 92.6–95.8±4.8–5.7%.Received December 16, 2002; accepted May 14, 2003 published online September 1, 2003     

A sensitive and highly selective extractive spectrophotometric method for the determination of palladium

Summary A Sensitive and Highly Selective Extractive Spectrophotometric Method for the Determination of Palladium Palladium forms an anionic chelate with 4-(2-pyridylazo)resorcinol (PAR, H₂R) which is extractable with xylometazolonium cation (XMH) into chloroform in the pH range 7.2–7.8 giving an intensely pinkish red coloured solution. The coloured species exhibits maximum absorbance at 520 nm with molar absorptivity 3.34×10⁴1·mole^–1·cm^–1 and obeys Beer's law in the range 0.8–5.30g/ml of palladium. The composition of the extracting species is found to be 111 for Pd(II)PARXMH. Large concentrations of EDTA and oxalate have no interference in the spectrophotometric determination of palladium by this procedure. Based on this a highly selective and sensitive method for the determination of palladium in the presence of Zn(II), Cd(II), Hg(II), Fe(III), Mn(II), Co(III), Mo(VI), Ru(IV), Sb(III), Al(III) is described. The application of this method for the determination of palladium in synthetic mixtures corresponding to the composition of jewel alloy and stibiopalladinite mineral is also demonstrated.     

The electrical conductance of hexaamminemetal nitrates in liquid ammonia

The electrical conductance behavior of hexaamminemetal nitrates of Cr(III), Co(II–III), Ni(II), and Cu(II) in liquid ammonia has been measured at temperatures varying from –40 to –75°C. Both univalent and divalent dissociations have been considered. The two outer-sphere association constantsK ₁ andK ₂, which control the properties in the concentration range employed, have been determined together with ₀ in a way described earlier by Fuoss. The thermodynamic quantities H^o and S^o of the univalent dissociation, evaluated from the temperature dependence of the association constants, are remarkably independent of the nature and charge of the metal ion. Walden products of the cations are presented and discussed.     

Kinetics and mechanism of oxidation ofd-xylose by Mn(III) pyrophosphate

The oxidation ofd-xylose by Mn(III) pyrophosphate in sulphuric acid has been found to be first order with respect to [Mn(III)]. Variation of rate with [d-xylose] suggests the rapid formation of reversible cyclic complex between Mn(III) and id-xylose, which further disproportionates in a slow rate determining step. Oxidation rate has been found to increase with [H⁺]. Retardation of rate due to [pyrophosphate] and increase due to [Mn(II)] have been also observed. The value of thermodynamic parameters E, S, and G have been found to be 17.6±0.1 kcal/mole, –10.1±0.1 e.u. and 20.6±0.1 kcal/ mole respectively. A mechanism involving a free radical has been proposed for the reaction under study.     

NMR investigation of complex formation between metalloporphyrins and π-donors

The formation of molecular complexes between Co(II), Fe(III), and Mn(III) porphyrins and -donors in chloroform solution has been investigated using¹H NMR. It was shown that their stability is controlled to a large extent by the dimensions of the -donor; interaction of the porphyrins with phenanthroline and anthracene, which contain a condensed aromatic system, is substantially more effective than interaction with benzene-derivative -donors. In the case of Co(II) and Fe(III) porphyrins the affinity to it-acceptors is much more pronounced than the affinity to -donors, whereas the acetate of Mn(III) hematoporphyrin forms molecular complexes with phenanthroline, anthracene, and trinitrobenzene with similar stability constants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1755–1760, August, 1990.