Synthesis, ion-exchange properties and analytical applications of stannic selenoarsenate: Comparison with other heteropolyacid salts

Summary Stannic selenoarsenate samples have been prepared by adding a mixture which is 0.05 M in sodium arsenate and 0.05 M in sodium selenite to a 0.05 M solution of stannic chloride in different volume ratios at pH 1. Its ion-exchange properties, pH titration curves and X-ray pattern were studied. Adsorption behaviour of 24 metal ions in different solvent systems has been examined. The analytical importance of this material has been demonstrated by achieving the following binary and ternary separations: Hg²⁺-Cd²⁺, Co²⁺-Fe³⁺, Cu²⁺-Fe³⁺, Hg²⁺-Zn²⁺-Al³⁺, Hg²⁺-Cu²⁺-Al³⁺, Hg²⁺-Ni²⁺-Al³⁺, Hg²⁺-Zn²⁺-Fe³⁺ and Hg²⁺-Ni²⁺-Fe³⁺. A comparison of the ion-exchange properties of this material has also been made with some other tin(IV) based ion-exchangers.

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Synthese, Ionenaustauscher-Eigenschaften und analytische Anwendungen von Zinn-Selenoarsenat: Vergleich mit anderen Heteropolysalzen

Zusammenfassung Zinn-Selenoarsenat wurde durch Mischen von 0,05 M Natriumarsenat-, 0,05 M Natriumselenitund 0,05 M Zinn(IV)-Chlorid-Lösungen bei pH 1 in verschiedenen Verhältnissen hergestellt. Die Ionenaustauscher-Eigenschaften, pH-Titrationskurven sowie Röntgendiagramme wurden untersucht und das Adsorptionsverhalten von 24 Metallionen in verschiedenen Lösungsmittelsystemen geprüft. Die analytische Verwertbarkeit wurde an Hand der folgenden Trennungsmöglichkeiten gezeigt: Hg²⁺-Cd²⁺, Co²⁺-Fe³⁺, Cu²⁺-Fe³⁺, Hg²⁺-Zn²⁺-Al³⁺, Hg²⁺-Cu²⁺-Al³⁺, Hg²⁺-Ni²⁺-Al³⁺, Hg²⁺-Zn²⁺-Fe³⁺, Hg²⁺-Ni²⁺-Fe³⁺. Vergleiche mit anderen Ionenaustauschern auf Zinn(IV)-Basis werden ebenfalls beschrieben.

     

210Pb and 210Po concentrations in the Venice lagoon ecosystem (Italy) and the potential radiological impact to the local public and environment

In order to evaluate the possible radiological impact to the local public and environment from a phosphogypsum stockpile, ²¹⁰Po and ²¹⁰Pb concentrations in river water, lagoon water, suspended matter, superficial sediment, algae and bivalves samples collected in Venice lagoon area have been investigated. The results show that the mean ²¹⁰Po and ²¹⁰Pb concentrations in river water are 1.42±0.36 mBq^.l^-1 and 1.46±0.39 mBq^.l^-1 with a mean ²¹⁰Po/²¹⁰Pb ratio of 0.98±0.17 and about 60% of them are associated with the particulate; ²¹⁰Po and ²¹⁰Pb contribution from the phosphogypsum stockpile to the river water is negligible. Higher ²¹⁰Po (2.61-5.67 mBq^.l^-1) and ²¹⁰Pb (1.31-3.62 mBq^.l^-1) concentrations in the lagoon waters have been observed if compared with the literature values. About 60% of ²¹⁰Po and ²¹⁰Pb are found in the soluble form with a mean ²¹⁰Po/²¹⁰Pb ratio of 1.79±1.47. ²¹⁰Po and ²¹⁰Pb concentrations in 28 out 37 sediment samples ranged from 26 to 45 Bq^.kg^-1 (dry weight), only 9 sediments with ²¹⁰Po and ²¹⁰Pb concentrations greater than 45 Bq^.kg^-1 are found and most of them are located 1-4 km near the phosphogypsum stockpile. The elevated ²¹⁰Po and ²¹⁰Pb concentrations in the sediments may be due to the contamination from the phosphogypsum stockpile. The mean ²¹⁰Po/²¹⁰Pb ratio (0.986±0.049) in the sediments shows that ²¹⁰Po and ²¹⁰Pb exist in nearly secular equilibrium. ²¹⁰Po and ²¹⁰Pb concentrations in algae vary with different species. The mean ²¹⁰Po and ²¹⁰Pb concentrations in Gracilaria compress and Ulva laetevirens which show a similar behavior, are 3.18±1.23 Bq^.kg^-1 and 2.42±1.26 Bq^.kg^-1 (fresh weight), respectively, with a mean ²¹⁰Po/²¹⁰Pb ratio of 1.45±0.34. The mean concentration factors with respect to the filtered water are 1096±424 for ²¹⁰Po and 1299±680 for ²¹⁰Pb. The mean ²¹⁰Po and ²¹⁰Pb concentrations in the soft part of Mytilus edulis are 23.2±9.7 Bq^.kg^-1 and 0.537±0.203 Bq^.kg^-1 (fresh weight), respectively, with a mean ²¹⁰Po/²¹⁰Pb ratio of 43.6±10.0. The mean concentration factors with respect to the filtered water are 8006±3351 for ²¹⁰Po and 290±109 for ²¹⁰Pb, showing a very high accumulation effect for ²¹⁰Po. The accumulation behaviors of Cerastoderma glaucum and Tapes philippinarum for ²¹⁰Po are similar to Mytilus edulis, but that for ²¹⁰Pb seems less effective, corresponding to a relatively higher ²¹⁰Po/²¹⁰Pb ratio. The estimated committed effective doses from ²¹⁰Po for the individual local public through ingestion of bivalves are in the range of 0.050-0.231 mSv^.y^-1.     

Determination of129I and127I in environmental samples by neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP-MS)

In order to assess the levels and behavior of¹²⁹I (half-life: 1.6×10⁷ y) and¹²⁷I (stable) in the environment, we have developed analytical procedures involving neutron activation analysis (NAA). Environmental samples collected around Tokaimura, Ibaraki Prefecture, Japan, have been analyzed using this method. Ranges of¹²⁹I and¹²⁷I concentrations in surface soil were 0.9–180 mBq kg^–1 and 1–60 mg kg^–1, respectively. Higher¹²⁹I concentrations were found in soil samples collected from coniferous forests, suggesting a contribution from tree canopies in the deposition of this nuclide. Most of the¹²⁹I in soil, was found to be retained in the first 10 cm. The¹²⁹I/¹²⁷I ratios in wheat fields were lower than those in rice paddy fields.A soil sample collected by IAEA from an area contaminated by the Chemobyl accident was also determined. The¹²⁹I concentration and the¹²⁹I/¹²⁷I ratio were 1.6 mBq kg^–1 and 1.7×10^–7, respectively. The¹²⁹I level in this sample was higher than the values obtained in areas far from nuclear facilities in Japan. It was suggested that the analysis of¹²⁹I in soils in the Chernobyl area may be useful in evaluating the¹³¹I levels at the time of the accident.Analyses of¹²⁹I and¹²⁷I by ICP-MS in water samples were also made. The analytical speed of this method was very high, i.e., 3 minutes for a sample. However, there is a sensitivity limitation for¹²⁹I detection due to interference from¹²⁹Xe with the¹²⁹I peak. The detection limits for¹²⁹I and¹²⁷I in water samples were about 0.5 mBq ml^–1 and 0.1 ng ml^–1, respectively.     

Measurement of lead-210, bismuth-210, and polonium-210 in environmental samples

Mathematical equations governing the ratio of²¹⁰Bi/²¹⁰Pb and²¹⁰Po/²¹⁰Pb activities are used to explain the ingrowth of²¹⁰Bi and²¹⁰Po in environmental samples during post collection. Procedures are described for radiochemical separation of²¹⁰Pb,²¹⁰Bi, and²¹⁰Po in a state of radioactive disequilibrium and quantification by alpha- and beta-counting. Also, the special case is considered where²¹⁰Bi is in equilibrium with²¹⁰Pb, but both are in disequilibrium with²¹⁰Po. In this case, the activities of both²¹⁰Pb and²¹⁰Po are computed by measuring²¹⁰Po activity twice, using alpha-counting.     

Zero-Field Splittings and Redox Potentials in an Isostructural Series of Dinuclear FeIITiIV,FeIIITiIV, and MnIITiIV Complexes with a Face-Sharing Bridging Motive

The ligand H₆ioan has been used to synthesize the three dinuclear complexes [(ioan)Mn^IITi^IV], [(ioan)Fe^IITi^IV], and [(ioan)Fe^IIITi^IV]⁺. The face-sharing bridging mode of the three phenolates provides short M-Ti^IV distances of ≈3.0 Å. Mössbauer spectra of [(ioan)Fe^IIITi^IV]⁺ show a magnetically split six-line spectrum at 3 K in zero magnetic field demonstrating a slow magnetic relaxation. Magnetic measurements provide a zero-field splitting of |D|=5 cm⁻¹ in [(ioan)Fe^IITi^IV]. EPR spectroscopy demonstrates sizable zero-field splittings of the S=5/2 spin systems of [(ioan)Mn^IITi^IV] (D=0.246 cm⁻¹) and [(ioan)Fe^IIITi^IV]⁺ (D<−1 cm⁻¹) that can be related to enforced covalency of the M-O^ph bonds. [(ioan)Fe^IIITi^IV]⁺ exhibits a reversible reduction at −0.26 V vs. Fc⁺/Fc demonstrating the facile accessibility of Fe^III and Fe^II. In contrast to an irreversible oxidation in [(ioan)Ni^IITi^IV] at 0.78 V vs. Fc⁺/Fc, the reversible oxidation at 0.25 V vs. Fc⁺/Fc in [(ioan)Mn^IITi^IV] indicates even the access of Mn^III. These results indicate that pentanuclear complexes [(ioan)FeM¹M²M¹Fe(ioan)]ⁿ⁺ are meaningful targets to access electron delocalization in mixed-valence systems over five ions due to the facile accessibility of both Fe^II and Fe^III in the terminal positions. This study provides important local spin-Hamiltonian and Mössbauer parameters that will be essential for the understanding of the potentially complicated electronic structure in the anticipated pentanuclear complexes.     

Ambidenticity of a tridentate oxygen-nitrogen donor towards bivalent and trivalent transition metal ions

Summary N-salicylidene anthranilamide (H₂SAA) and its Cr^III, Mn^II, Fe^III, Co^II, Ni^II and Cu^II complexes were prepared and characterized by physicochemical and spectroscopic data. H₂SAA enolizes to give a dibasic ONO donor set in the divalent metal complexes. It also binds to the trivalent metal ions in a nonenolized form using a monobasic ONN donor set. Co^II is oxidized to Co^III during complexation. Octahedral geometries are proposed for Cr^III, Mn^II, Fe^III and Co^III complexes, while square planar geometries are suggested for the Ni^II and Cu^II complexes. Phenoxide bridging in the Cr^III and Fe^III complexes and enoxide bridging in the Ni^II and Cu^II complexes is proposed.     

Solvated positron chemistry. II. The reaction of hydrated positrons with Cl−, Br− and I− ions

The reaction of the hydrated positron, e_aq⁺ with Cl^?, Br^?, and I^? ions in aqueous solutions was studied by means of positron The measured angular correlation curves for [Cl^?, e⁺], [Br^?, e⁺, and [I^?, e⁺] bound states were in good agreement with th Because of this agreement and the fact that the calculated positron wavefunctions penetrate far outside the X^? ions in the [X^?, e⁺] sta propose that a bubble is formed around the [X^?, e⁺] state, similar to the Ps bubble found in nearly all liquids. F^?ions did not react w Preliminary results showed that CN^? ions react with e_aq⁺ while OH^?ions are non reactive. The rate constants were 3.9 × 10¹⁰ M^?1 s^?1, 4.4 × 10¹⁰ M^?1 s^?1, and 6.3 × 10¹⁰ M^?1 s^?1 for Cl^?, Br^?, and I^?, respectively, at low (? 0.03 M) X^? concentrations. A 25% decrease in the rate constant caused by the addition of 1 M ethanol to the I^? solutions was i The influence of halide ions on the positronium (Ps) yields in pure water was studied by use of lifetime measurements. The Cl^?, Br^?, and I^? ions reduced the Ps yields at low concentrations (? 0.03 M), while F^? ions only reduced the Ps-yield However, the Ps yields saturated (e.g. at ≈ 21% ortho-Ps yield in the Cl^? case) at higher concentrations. This saturation and the high-concentration effects-in the angular correlation results were interpreted as caused by rather complicated spur effects, wh It is proposed that spur electrons may pick off the positron from the [X^?, e⁺ states with an efficiency which depends on the structure of the     

Stability Constants of Some Univalent Cation Complexes of 2,3-Naphtho-15-crown-5 in Nitrobenzene Saturated with Water

The extraction of micro amounts of cesium by nitrobenzene solutions of sodium, potassium and rubidium dicarbollylcobaltates (M⁺B⁻;M⁺=Na⁺,K⁺,Rb⁺) has been investigated in the presence of 2,3-naphtho-15-crown-5 (N15C5, L). The equilibrium data were explained by assuming that ML⁺ and ML₂⁺ complexes (M⁺=Na⁺,K⁺,Rb⁺, Cs⁺; L=N15C5) were present in the organic phase. The stability constants of the complex species ML⁺ and ML₂⁺ have been determined in nitrobenzene saturated with water. It was found that the stability of the complex cation ML⁺ (where M⁺=Na⁺,K⁺,Rb⁺, Cs⁺; L=N15C5) in water-saturated nitrobenzene solutions increases along the series Cs⁺<Rb⁺<K⁺<Na⁺, whereas that of the species ML₂⁺ in the same medium increases in the order Cs⁺<Rb⁺<Na⁺<K⁺.     

Reference material for radionuclides in sediment IAEA-384 (Fangataufa Lagoon sediment)

A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides (⁴⁰K, ⁶⁰Co, ¹⁵⁵Eu, ²³⁰Th, ²³⁸U, ²³⁸Pu, ^239+240Pu and ²⁴¹Am). Information values are given for 12 radionuclides (⁹⁰Sr, ¹³⁷Cs, ²¹⁰Pb (²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁴U, ²³⁵U, ²³⁹Pu, ²⁴⁰Pu and ²⁴¹Pu). Less reported radionuclides include ²²⁸Th, ²³⁶U, ²³⁹Np and ²⁴²Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides in the environment, as well as for the development and validation of analytical methods and for training purposes. The material is available from IAEA in 100 g units. Retired from IAEA in 2003.     

Contribution to the thermodynamics of complexes of alkali metal cations with 18-crown-6 in the water—nitrobenzene extraction system

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq)+NaL⁺(nb)⇄ML⁺(nb)+Na⁺(aq) taking place in the two-phase water-nitrobenzene system (M⁺=Li⁺, K⁺, Rb⁺, Cs⁺; L=18-crown-6; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. The stability constants of the ML⁺ complexes in nitrobenzene saturated with water were calculated; they are found to increase in the cation order Cs⁺Li⁺Na⁺Rb⁺K⁺. Further, the individual extraction constants for the NaL⁺, KL⁺, RbL⁺ and CsL⁺ complex species in the wate-nitrobenzene system were determined; their values increase in the series Na⁺Rb⁺Cs⁺K⁺.     

Diffusion mobility of alkali metals in perfluorinated sulfocationic and carboxylic membranes as probed by <Superscript>1</Superscript>H, <Superscript>7</Superscript>Li, <Superscript>23</Superscript>Na,and <Superscript>133</Superscript>Cs NMR spectroscopy

Water self-diffusion and ion mobilities in various ionic forms (H⁺, Li⁺, Na⁺, Rb⁺, Cs⁺, and Ba²⁺) of perfluorinated sulfocationic membranes MF-4SK were studied by NMR and impedance spectroscopy. When degrees of hydration are low, the self-diffusion coefficients of water and ionic conductivities are considerably affected by the water content of the membrane. The self-diffusion coefficients decrease in the order H⁺ > Ba²⁺ > Cs⁺ > Rb⁺ > Na⁺ > Li⁺, whereas the ion mobility decreases in the order H⁺ > Li⁺ > Na⁺ > Cs⁺ > Ba²⁺.     

Metal Ion Interaction of Two New Tritopic N2O13 Macrobicycles with B15C5 Moieties in Acetonitrile Solution

The synthesis of two new tritopic crown ligands (L1 and L2) bearing two benzo-15-crown-5 lateral moieties linked through a dibenzo-trioxa chain together with their interaction with metal ions, in acetonitrile and acetonitrile–water (50%, v/v) solutions is reported. The influence of K⁺, Na⁺, Li⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺ and Al³⁺, on the spectroscopic properties of these diaza-polyoxa ligands was investigated by absorption spectrophotometry and in some cases by fluorescence emission spectroscopy. Coordination with alkaline (Na⁺, K⁺ and Li⁺) and alkaline earth (Ca²⁺and Ba²⁺) metal ions is assumed to be weak with both macrobicyclic ligands, while the interaction with both imine and amine derivatives causes a minor effect in the absorption spectra. Coordination with Cu²⁺, Zn²⁺ and Pb²⁺ in acetonitrile solution causes a major change in the absorption spectra of the chromophores. In the case of Cu²⁺, addition of the metal to L1 or L2 leads to a blue–violet complex in solution with an absorbance maximum centred at 590 nm. Interaction of the Schiff-base L1 with Pb²⁺ leads to a short wavelength shift in the absorption bands, comparable with the ZnL1 complex. Presence of transition metal ions such as Co²⁺, Ni²⁺and Cd²⁺ do not remarkably affect the absorption spectra of L1 and L2 in solution. Trivalent aluminium has a modest effect in the absorption bands of both N₂O₁₃ donor set bismacrocyclic ligands. The fluorescence study of L2 in the presence of Na⁺, K⁺, Ca²⁺, Ba²⁺, Co²⁺, Cu²⁺, Ni²⁺, Pb²⁺ and Al³⁺shows that Cu²⁺, Pb²⁺ and Al³⁺ complexes form non-fluorescent complexes.     

Radioactivity of coals and fly ashes

The level and the behavior of the naturally occurring primordial radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³²Th, ²²⁸Ra and ⁴⁰K in coals and fly ashes are described. The activity concentrations of the examined coals and originated from coal mines in Greece ranged from 117 to 435 Bq·kg⁻¹ for ²³⁸U, from 44 to 255 Bq·kg⁻¹ for ²²⁶Ra, from 59 to 205 Bq·kg⁻¹ for ²¹⁰Pb, from 9 to 41 Bq·kg⁻¹ for ²²⁸Ra and from 59 to 227 Bq·kg⁻¹ for ⁴⁰K. These levels are comparable to those appeared in coals of different countries worldwide. The activity concentrations of the examined fly ashes and produced in coal-fired power plants in Greece ranged from 263 to 950 Bq·kg⁻¹ for ²³⁸U, from 142 to 605 Bq·kg⁻¹ for ²²⁶Ra, from 133 to 428 Bq·kg⁻¹ for ²¹⁰Pb, from 27 to 68 Bq·kg⁻¹ for ²²⁸Ra and from 204 to 382 Bq·kg⁻¹ for ⁴⁰K. The results showed that there is an enrichment of the radionuclides in fly ash relative to the input coal during the combustion process. The enrichment factors (EF) ranged from 0.60 to 0.76 for ²³⁸U, from 0.69 to 1.07 for ²²⁶Ra, from 0.57 to 0.75 for ²¹⁰Pb, from 0.86 to 1.11 for ²²⁸Ra and from 0.95 to 1.10 for ⁴⁰K.     

Determination of137Cs,90Sr and fallout Pu in the volcanic soil of Korea

The cumulative depositions of¹³⁷Cs,⁹⁰Sr and fallout Pu in the volcanic ash soil of Korea were determined. The average accumulated depositions of¹³⁷Cs,⁹⁰Sr and fallout Pu in the volcanic soil were much higher than those in other forest sites of Korea. From depth profiles, it was found that¹³⁷Cs,⁹⁰Sr and^239,240Pu in the volcanic soil are more mobile than those in other forest sites of Korea, and that the downward movement of⁹⁰Sr is faster than¹³⁷Cs and^239,240Pu. A significant correlation was found between the concentration of¹³⁷Cs and those of⁹⁰Sr and^239,240Pu. The activity ratios of²³⁸Pu/^239,240Pu and²⁴¹Pu/^239,240Pu in soils are close to those observed in the cumulative deposit from the global fallout of nuclear weapon testings.     

CI study of rovibrational dependence of nuclear quadrupole coupling constants of all isotopic variants of OH+ in the X3Σ− state

The ¹⁷O and ²H quadrupole coupling constants of rovibrational levels of ¹⁷O¹H⁺, ¹⁷O²H⁺, and ¹⁶O²H⁺ in their X³Σ⁻ state have been calculated from molecular wave functions that explicitly describe nuclear motion. The ¹⁷O quadrupole coupling is predicted to be strong and its vibrational dependence differs from that known for other nuclei A in the first-row hydrides AH or AH⁺. The deuterium coupling in ¹⁷O²H⁺ and ¹⁶O²H⁺ is found to be weak and its behavior is similar to that of other first-row hydrides. The change with rotational excitation is unimportant. The quadrupole hyperfine patterns of ¹⁷O²H⁺ in its ground state are dominated by the strong oxygen coupling. © 1996 John Wiley & Sons, Inc.     

Electron-exchange processes on simple columns of kel-f supporting tetrachlorohydroquinone

The preparation of simple electron-exchange columns is reported. An organic porous material (Kel-F powder) is used to support a water-insoluble redox reagent. Of the organic compounds tested, tetrachlorohydroquinone was best. Very stable columns were obtained with a sufficiently high redox capacity (1.59 $\text{meq}\text{g}$ dry material) and a satisfactory reaction rate.The following oxidation reactions were carried out: Fe²⁺→Fe³⁺, Cu⁺→Cu²⁺, Sn²⁺→Sn⁴⁺, I^-→I,ascorbic acid → dehydroascorbic acid, as well as the following reduction reactions: Fe³⁺→Fe²⁺, I→I^-, Ce⁴⁺→Ce³⁺, V⁵⁺→V⁴⁺, Cr⁶⁺→Cr³⁺. The effect of hydrogen ion concentration on the redox reactions was also studied.The Kel-F-tetrachlorohydroquinone columns can be used for indirect titration of redox systems and for selective oxidations or reductions, e.g. Fe³⁺ in presence of Fe²⁺ and vice versa, Cr⁶⁺ in presence of Fe³⁺, Ce⁴⁺ in presence of Ce³⁺, ascorbic acid in the presence of glucose, and Sn²⁺ in presence of Sn⁴⁺ or Fe²⁺.     

Analytical methods to determine Po and Pb in marine samples

This paper describes the methods of sampling, preconcentration, chemical separation and final count of ²¹⁰Po and ²¹⁰Pb present in different marine matrices to determine their background levels in a marine ecosystem. Complex, time consuming and selective radioanalytical methods have been used to prepare final clear sources for alpha spectrometry and beta count; in fact, gamma spectrometry, a method direct and non destructive, cannot be taken into account because the ²¹⁰Pb activity is very low which does not allow to carry out sufficiently accurate measurements and ²¹⁰Po is not a gamma emitter but it emits only alpha particle at 5.40 MeV. The results of ²¹⁰Po and ²¹⁰Pb activity concentrations obtained in different marine samples collected in the first two campaigns are still very few to discuss about the ²¹⁰Po and ²¹⁰Pb behavior in marine environment.     

Stability of complexes of alkali metal cations with dibenzo-24-crown-8 in water saturated nitrobenzene

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq)+NaL⁺(nb)⇄ML⁺(nb)+Na⁺(aq) taking place in the two-phase water-nitrobenzene system (M⁺=Li⁺, K⁺, Rb⁺, Cs⁺; L=dibenzo-24-crown-8; aq=aqueous phase, nb=nitrobenzene phase) were evaluated. Further, the stability constants of the ML⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the Cs⁺Rb⁺L⁺Na⁺ order.     

Electrically induced fluorescence Fe sensing behavior of nanostructured Tiron doped polypyrrole

Nanostructured polypyrrole (PPy) film doped with Tiron was electrodeposited from aqueous solution on the surface of transparent electrode and used for sensitive, selective and rapid electrically controlled fluorescence detection of Fe³⁺ in aqueous media. The fluorescence intensity of PPy-Tiron film decreases linearly in the presence of Fe³⁺ by applying negative potential over a concentration range from 5.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol L⁻¹, with a relatively fast response time of less than 30 s at pH 7.4. The detection is not affected by the coexistence of other competitive metal ions such as Al³⁺, Ce³⁺, Tl³⁺, La³⁺, Bi³⁺, Cr²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺. The proposed electro-fluorescence sensor has a potential application to the determination of Fe³⁺ in environmental and biological systems. The fluorescent thin film sensor was also used as a novel probe for Fe³⁺/Fe²⁺ speciation in aqueous solution.     

Molecular constants of OCS isotopes in the (0110) vibrational state measured by molecular-beam electric-resonance spectroscopy

The ΔJ = 0,l-doublet transitions of OCS isotopes (¹⁶O¹²C³²S, ¹⁶O¹²C³³S, ¹⁶O¹²C³⁴S, ¹⁶O¹³C³²S and ¹⁸O¹²C³²S) in the (01¹0) vibrational state have been measured in a molecular-beam electric-resonance spectrometer equipped with a nozzle source. Rotation-vibration coupling constants and electric dipole moments have been determined for all isotopes, and the spin-rotation and the quadrupole coupling constants for the ³³S nucleus in ¹⁶O¹²C³³S in the υ₂=0 and υ₂=1 states.