Rapid separation of mercury,arsenic, thallium and chromium species

Radiochemical neutron activation analysis is the only method to determine the galactic cosmic ray (GCR) produced radionuclide⁵³Mn (T=3.8·10⁶) in small meteorite samples. A large number of such samples was analyzed using extremely thermalized neutrons of the DIDO reactor at the KFA Jülich. The detection limit of 10^–14 g/g was recently achieved in our laboratory through the improvement of pre- and postirradiation chemistry. The main purpose of our studies of meteorite finds from Antarctica and the Southwestern United States is to establish their exposure ages up to 12·10⁶ a by means of⁵³Mn. Especially in the case of Antarctic meteorites terrestrial ages up to several 10⁵ years have been observed by combining⁵³Mn and²⁶Al (T=7.2·10⁵ a) measurements.     

Influence of the linking chain length on the recombination kinetics of covalently bonded triplet radical pairs and magnetic field effects

Nanosecond laser flash photolysis technique is used to study the formation and decay kinetics of covalently linked triplet radical pairs (RP) formed after photoinduced electron transfer in the series of 21 zinc porphyrin—chain—viologen (Pph—Sp_n—Vi²⁺) dyads, where the number of atoms (n) in the chain increases from 2 to 138. In poorly viscous polar solvents (acetone, CHCl₃—CH₃OH (1 : 1) mixture), the dependence of the rate constant of RP formation on n can be described by the equation k _e = k _e ⁰ n ^–a at k _e ⁰ = 2.95·10⁸ s^–1 anda = 0.8. In the zero magnetic field, the RP recombination rate constant (k _r(B = 0)) is significantly lower than k _e and ranges from 0.7·10⁶ to 8·10⁶ s^–1. The dependence of k _r(B = 0) on n is extreme. The dependence k _r(B = 0) reaches a maximum at n = 20. In the strong magnetic field (B = 0.21 T), the significant retardation of triplet RP recombination is observed. The chain length has an insignificant effect on k _r(B = 0.21 T), which ranges from 0.3·10⁶ to 0.9·10⁶ s^–1. The regularities found are discussed in terms of the interplay of molecular and spin dynamics.     

Transition state geometry in radical abstraction reactions: comparison of interatomic distances in the intersecting parabolas and Morse curves models with quantum-chemical calculations

Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H^· + H₂, H^· + HCl, H^· + CH₄, N^·H₂ + NH₃, HO^· + H₂O, HO₂ ^· + HOOH, and C^·H₃ + SiH₄. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10^–12 m for IPM and a = +1.9·10^–12 m for IMM.     

INAA determination of holmium in submilligram samples of cosmochemical and geochemical interest and the second-order activation interference

Second-order neutron activation becomes a serious interference in NAA determinations of REE in submilligram samples of meteoritic and terrestrial materials when neutron fluences reach levels of 10²⁰ n·cm^–2 or more. The Dy-interference to Ho determination and the Eu-interference to Gd determination are quite, large. We discuss the importance of second-order activation interferences in REE determinations, and present an experimental method to correct the Dy-interference to Ho determination by INAA. Ho concentrations in splits of less than 0.2 mg of BCR-1 and SP can be accurately determined by INAA with a neutron fluence of 2·10²⁰ n·cm^–2 in spite of large Dy interferences of up to 200%. It is necessary for NAA determinations of REE with high neutron fluences that each REE standard be separated from its neighboring REE, in order to correct the second-order activation interferences experimentally.     

Dissociative ionization of triethylamine molecules on a tungsten surface in an electric field

The surface ionization of triethylamine molecules (M) in accelerating fields of strength F from 2·10⁴ to 4·10⁶ V/cm has been studied under stationary conditions with the aid of mass spectrometry. The predominant formation of (M-H)⁺ fragment ions has been discovered. The logarithm of the relative intensity of the ion currents at T = const varies linearly with the value of F. The temperature dependence of the ion currents I(T) at F = const, which are in good agreement with the experimental dependences and make it possible to determine the kinetic parameters of the reaction, have been obtained with the aid of the theory of monomolecular dissociation of molecules in the gaseous phase and the theory of surface ionization.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 24, No. 1, pp. 62–67, January–February, 1988.We thank N. D. Potekhina and é. Ya. Zandberg for some useful discussions.     

Langmuir aggregation of Evans blue on cetyltrimethylammonium bromide and on proteins and its application

The microphase adsorption-spectral correction (MPASC) technique is described and applied to the study of the interactions of Evans blue (EB) with cetyltrimethylammonium bromide (CTAB) and with four proteins: bovine serum albumin (BSA), myoglobin (Mb), hemoglobin (Hb) and ovalbumin (OVA). EB can be adsorbed on a cationic surfactant and on protein by electrostatic force and the aggregation obeys the Langmuir isotherm. Results have shown that the products are formed as follows: monomer aggregate EB·CTAB, micellar aggregate (EB·CTAB)₇₈ and protein aggregates (EB₆₈·BSA), (EB₁₄·OVA), (EB₁₂₆·Mb) and (EB₅₈·Hb). The adsorption constant of the aggregates are calculated to be K_EB·CTAB=2.95×10⁶, K_EB68·BSA=3.40×10⁴, K_EB14·OVA=5.20×10², K_EB126·Mb=6.81×10² and K_EB58·Hb=5.73×10², respectively. The aggregation of EB in proteins is sensitive in the presence of CTAB and selective in the presence of EDTA and it has been applied to the analysis of samples with satisfactory results.     

The reactivity of the electron formed in the radiolysis of aerated alkaline aqueous solutions containing tetracycline hydrochloride,at 77 K

The present study deals with the radiolysis of tetracycline hydrochloride dissolved in aerated alkaline aqueous solutions containing 0.1, 0.5 and 1M NaOH, at 77 K, as followed by ESR. The rate constants for the reactions between the electron and physical and chemical traps which are present in these solutions are calculated. These values are k_ph= =9.6·10¹⁵ l·mol^–1·s^–1 and k_ch=1.3·10¹⁰ l·mol^–1·s^–1. The reactivity of electrons that are formed in the radiolysis of water decreases in the following proportions: physical traps: chemical traps: molecules of water: 4.8·10¹⁴: 6.5·10⁸: 1.0. The electrons react preferentially with the solute instead of the solvent.From a thesis submitted by S.M.L.Guedes to the University of São Paulo in partial fulfillment of the requirements for a Doctor of Science Degree in Nuclear Technology.     

Formation and decay of phenoxyl radicals: Variation with pH and pulse dose

Phenoxyl type radicals were produced from tyrosine methyl ester (TME) using azide (N ₃ ^. ) radicals. The rate constant of formation increased from 2·10⁸ dm³·mol^–1·s^–1 at pH 7 to 4·10⁹ dm³·mol^–1·s^–1 at pH 11, whereas that of the decay, 2k=(6±1)·10⁸ dm³·mol^–1·s^–1, remained constant. The maximum yield of the radicals varied with pH and pulse dose consistently with the kinetic scheme, which involved a competition of the oxidation of TME by azide radicals with the natural decay of N ₃ ^. .     

A New Inclusion Compound between 2,4,5,7,9,10-hexachloro-1,3,6,8-tetrakis (4-methoxyphenylthio)pyrene Host and Cyclohexane Guest Stabilized by C–H···π and C–H···Cl Interaction

Crystal structure analysis shows the 2,4,5,7,9,10-hexachloro-1,3,6,8-tetrakis-(4-methoxyphenylthio) pyrene host and its cyclohexane guest in the Pnma crystal lattice. The crystal data and refinement parameter for the title compound are: a = 15.864(3), b = 30.455(6), c = 9.231(5) Å, V = 4459.2 (14) ų. For Z = 4 and M _w = 1045.76, the calculate density Dcal = 1.558 g/cm³. The C–H···π interaction and C–H Cl interaction stabilized the inclusion of cyclohexane molecules. The S···Cl weak interaction assembled the host molecules into a two-dimensional layer structure, and a three-dimensional structure was obtained by connecting the layers with C–H···O hydrogen bonding.Electronic Supplementary Material Supplementary material is available for this article at ^*Supplementary data: crystallographic data (atomic coordinates, anisotropic displacement parameters, selected bond distance and angles) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Center with CCDC 270603 as supplementary publication.     

205T1 NMR study of t1(III) ethylenediaminetetra acetates

Conclusions The²⁰⁵T1 NMR method was used to study the thallium ethylenediaminetetraacstates HTlA·2.5H₂O and Tl₂A·SO₄·10H₂O. Two signals, which were assigned to the inner and outer sphere cations, are observed for Tl₂A·SO₄·10H₂O. The thallium ions in T1₂A·SO₄·10H₂O are nonequivalent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1195–1196, May, 1978.     

An NMR study of proton exchange in the system p-nitrosophenol—p-quinone monooxime

The solvent used was dimethylformamide at neutral and alkaline pH. The equilibrium constants are determined by spectrophotometry. The rate of proton exchange has been measured as a function of temperature and concentration. The rate constants and activation energies have been measured; for uncatalyzed exchange k_n=(1.5±0.5) ·· 10³ M^–1 sec^–1, E=8±1 kcal/mole, while base-catalyzed exchange has k=(0.3±0.1) · 10⁶ M^–1 sec^–1 and E=6±1 kcal/mole.We are indebted to A. I. Brodskii for assistance in this work, and to V. I. Oshkaderov and L. A. Kichakova for recording the NMR spectra.     

Synthesis and study of binuclear vanadyl complexes with acyldihydrazones of salicylaldehyde and dicarboxylic acids

The binuclear vanadyl(ii) complexes [(VO)₂·2Py·2EtOH]·mH₂O with acyldihydrazones of salicylaldehyde (H₄L) and dicarboxylic acids were synthesized and studied. In these complexes, two chelate vanadyl(ii) complexes with the tridentate bicyclic ligands are linked to each other by the polymethylene bridges —(CH₂) _n — of different lengths varying from one to four units. The ESR spectra of solutions of these complexes, unlike those of analogous copper(ii) complexes, have an isotropic signal with an eight-line hyperfine structure (g = 1.972, a _V = 93·10^–4 cm^–1) typical of monomeric vanadyl complexes, which indicates that no exchange interactions occur between the paramagnetic centers through the polymethylene chain.     

Determination of a strong organic ligand dissolved in seawater: Thorium-complexing capacity of oceanic dissolved organic matter

Studies have been made of loose water tritium (LWT) distribution and behavior in the soil samples taken from the region within a radius of 2 km to the HWRR stack of CIAE. The analytical results show that the LWT concentrations in most soil samples of the region are in the range from 24.8 Bq/l (3.6 Bq/kg) to 116 Bq/l (16.0 Bq/kg) with an average value of 58.1±24.8 Bq/l (10.3±4.5 Bq/kg). There are two areas with a higher LWT content; the first one (4.61 · 10⁴ m²) is located near HWRR with ahighest LWT concentration of 287 Bq/l (55.8 Bq/kg) and the second one (3.27 ·10⁵ m²) is located near Lab. A with a highest LWT concentration of 2.35 · 10⁴ Bq/l (2.56 · 10³ Bq/kg). It is estimated that the LWT inventories deposited in soil of the two areas are about 1.52 · 10⁹ Bq and 1.42 · 10¹⁰ Bq, respectively. The analytical results have been evaluated by comparing the possible tritium intake of the human body with the annual limit of intake recommended by ICRP, it can be concluded that the operations of all the nuclear facilities releasing tritium in CIAE are safe without causing any notable tritium contamination.     

Comparison of Scintillation Detection Efficiencies of Depleted Uranium (DU) in Wounds

Three tissue-equivalent cylindrical wound phantoms with varying activities of DU metal imbedded at varying depths were used to compare the efficiencies of a bismuth germinate (BGO) detector, a sodium iodide (NaI), and two identical wound probes with smaller sodium iodide crystals. Our results show that the BGO detector had the highest efficiency (1.0·10^-3) and the lowest minimum detectable activity (MDA = 5.8 kBq) for the shallow depth DU phantom, relative to the other detectors. The BGO detector also had the highest peak efficiencies (1.7·10^-3 and 5.8·10^-4) and the lowest MDAs (3.5 and 10.0 kBq) for the medium and deep phantoms, respectively. Other detectors' performance data are presented.     

ESR determination of the rate constant for the addition of CpW(CO)3 to spin traps

Conclusions The reaction of [CpW(CO)₃]₂ with PhCH₂Cl and the decomposition of CpW(CO)₃Me were studied by ESR spectroscopy using 2,4,6-tri-tert-butyinitrobenzene (BNB) and -phenyl-N-tert-butylnitrone (PNB) as spin traps. The rate constants for the addition of CpW(CO)₃ radicals to the spin traps at 20°C were determined by identification of the intermediate radicals in these reactions: k _ad ^BNB =6.7·10⁵-7.0·10⁵ and k _ad ^PNB =5.8·10⁴-6.1·10⁴ liters/mole · sec.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2631–2633, November, 1984.     

Sulfurization of polymers. 6. Poly(vinylene polysulfide), poly(thienothiophene), and related structures from polyacetylene and elemental sulfur

Polyacetylene obtained by the dehydrochlorination of polyvinyl chloride in the NaOH—DMSO system undergoes sulfurization with elemental sulfur at 120—300 °C to liberate hydrogen sulfide and to form electroconducting (0.7·10^–12—5.8·10^–15Sm nm^–1) and paramagnetic (1.5·10¹⁷—1.7·10¹⁹sp g^–1, g = 2.0035—2.0045, H= 0.44—0.66 mT) dark powders with a metallic luster. Their IR spectra and comparison with the samples of sulfurized polyethylene show that sulfurized polyacetylene contains poly(vinylene polysulfide), poly(thienothiophene), and related structures. The polymers afford the cathode discharge capacity of lithium batteries up to 950 mA h g^–1(in the first cycle) and stable cycling at a level of 500—300 mA h g^–1(25 cycles).     

Rates of reactions of some aqueous free radicals with platinum-ammine complexes using pulse radiolysis

The fast reaction technique of pulse radiolysis in conjunction with UV- visible absorption detection was used to determine the rate of reactions of hydrated electron, hydrogen atom, hydroxyl radical and dichloride anion radical with tetraammineplatinum(II) perchlorate and with trans- dihydroxotetraammineplatinum(IV) perchlorate complexes. Generally these reactions proceed at near diffusion-controlled rates. The second-order rate constant for the reaction of e _aq ^– , H, OH and Cl ₂ ^– radical with the Pt(II) complex are (1.9±0.1)·10¹⁰ M^–1·s^–1, (2.8±0.3)·10¹⁰ M^–1·s^–1, (6.6±0.4)·10⁹ M^–1·s^–1 and (9±1)·10⁹ M^–1·s^–1, respectively. The rate constant for the reaction of e _aq ^– with the Pt(IV) complex is (4.9±0.3)·10¹⁰ M^–1·s^–1, however, H atom and OH radical reactions proceed at relatively slower rates.     

Nitric acid transport across TBP—Kerosene oil supported liquid membranes

HNO₃ transport across tri-n-butyl phosphate kerosene oil supported liquid membrane with or without uranyl ion transport has been studied. Parameters studied are the effect of TBP in the membrane, nitric acid in the feed solution and nitrate ion concentration in the feed solution. The flux of protons for 1 to 10 mol·dm^–3 HNO₃ solution is in the range of (0–25)·10^–4 mol·m^–2·s^–1 and for the TBP concentration range of 0.359 to 3.59 mol·dm^–3, the flux determined is (8.9 to 22)·10^–4 mol·m^–2·s^–1. From the experimental data and using theoretical equations the complex under transport through the membrane appears to be 2TBP·HNO₃ both in the presence and absence of uranyl ions. The diffusion coefficient for H⁺ ions through the membrane as a function of TBP concentration varies from (53 to 6)·10^–12 m²·s^–1, based on experimental flux and permeability data. The values of this coefficient supposing 2TBP·HNO₃ as diffusing species, based on viscosity data and theoretical estimation varies from (82.50 to 3.30)·10^–12 m²·s^–1. The value of distribution coefficient varies in the reverse direction from 0.06 to 1.46 at the same TBP concentration.     

Auxiliary aromatic-acid effect on the structures of a series of Zn coordination polymers: Syntheses, crystal structures, and photoluminescence properties

Five novel Zn^II-(pyridyl)imidazole derivative coordination polymers, [Zn(L)₂] (1), [Zn₂(μ₃-OH)L(m-BDC)] (2), [Zn₂(μ₃-OH)L(p-BDC)]·H₂O (3), [Zn₂L(BTC)(H₂O)]·2.5H₂O (4) and [Zn_3.5(μ₃-OH)L₂(BTEC)(H₂O)]·H₂O (5) (L=4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, p-H₂BDC=1,4-benzenedicarboxylic acid, m-H₂BDC=1,3-benzenedicarboxylic acid, H₃BTC=1,3,5-benzenetricarboxylic acid, H₄BTEC=1,2,4,5-benzenetetracarboxylic acid), were successfully synthesized under hydrothermal conditions through varying auxiliary aromatic-acid ligands and structurally characterized by X-ray crystallography. Compound 1 exhibits a 1D chain linked via double L bridges. Compound 2 features a well-known pcu topology with bent dicarboxylate ligand (m-H₂BDC) as an auxiliary ligand, while 3 displays a bcu network with linear dicarboxylate ligand (p-H₂BDC) as an auxiliary ligand. The structure of compound 4 is a novel 3D (3,5)-connected network with (4·6²)(4·6⁴·8²·10·12²) topology. It is interesting that compound 5 shows an intricate (3,4,8)-connected framework with (4·6²)(4²·6³·8)(4²·6⁴)(4²·6¹⁸·7·8⁶·10) topology. In addition, their infrared spectra (IR), X-ray powder diffraction (XPRD) and photoluminescent properties were also investigated in detail.