The magnetic isotope effect and oxygen isotope selection in chain processes of polymer oxidation

Experimental evidence based on the dependence of molecular oxygen isotope enrichment on the oxygen conversion, temperature and kinetic chain length indicate that, in chain processes of polymer oxidation, the elementary, reactions (recombination or disproportionation) of peroxy radicals are responsible for the selection of both ¹⁷O and ¹⁸O isotopes. The ¹⁷O selection is induced by a magnetic isotope effect and is sensitive to the molecular dynamics, while ¹⁸O selection is due to a classical mass-dependent isotope effect and is much less effective.     

Surface analysis of a glass leached with stable isotopes

The distribution of oxygen and other elements within the leached layer of a soda-lime glass after a short-time treatment (15–60 min) in pure H₂ ¹⁸O and D₂ ¹⁸O was investigated by means of neutral primary beam secondary ion mass spectrometry (NPB-SIMS). The¹⁸O^– profiles resulting from the penetration of an oxygen containing species are not disturbed by interference of the species H₂ ¹⁶O^–, originating from the residual gas in the vacuum chamber. In agreement with previous results, no isotope effect could be detected. Hydration of the glass leads to a pronounced matrix effect which impedes oxygen analysis in the negative secondary ion mode. The ratio of the maximum¹⁸O^– intensity in the leached layer to the¹⁶O^– intensity in the bulk was recorded as a function of time for one series of experiments. The result is in accordance with the time-dependence of the Na₂O concentration in the leached layer.     

99Tc NMR determination of the oxygen isotope content in 18O‐enriched water

⁹⁹Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen‐18‐enriched water, a precursor for the production of radioisotope fluorine‐18 used in positron emission tomography. To this end, solutions of NH₄TcO₄ or NaTcO₄ (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled ¹⁸O‐enriched water have been studied by ⁹⁹Tc NMR. The method is based on ¹⁶O/¹⁷O/¹⁸O intrinsic isotope effects in the ⁹⁹Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO₄⁻ and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the ⁹⁹Tc NMR signals of the Tc¹⁶O_4−n¹⁸O_n⁻ isotopologues. Because the oxygen exchange between TcO₄⁻ and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant ⁹⁹Tc NMR shift induced by a single ¹⁶O→¹⁸O substitution (−0.43 ± 0.01 ppm) in TcO₄⁻ and spin coupling constant ¹J(⁹⁹Tc–¹⁷O) (131.46 Hz) favourable for the observation of individual signals of Tc¹⁶O_4−n¹⁸O_n⁻ isotopologues.     

Synthesis of water and molecular oxygen highly enriched in <Superscript>17</Superscript>O and <Superscript>18</Superscript>O isotopes from carbon oxides

The reaction of carbon oxides and hydrogen in the presence of the Raney nickel catalyst has been used for water synthesis. A procedure has been developed for the recovery and collection of the synthesized water with minimal losses and without deteriorating the ¹⁷O or ¹⁸O isotope enrichment as compared to the initial CO₂ and CO. The recovery of oxygen with high concentrations of ¹⁷O and ¹⁸O isotopes is based on the reaction of xenon difluoride with water. The yield based on oxygen achieves 99% without reduction of isotope enrichment, which is confirmed by mass-spectral measurements of oxygen isotope concentrations in the initial reagents and final reaction products.     

Determination of oxygen in fluoride glass by proton activation analysis

Oxygen was determined in three kinds of ZrF₄-based fluoride glass [ZrF₄–BaF₂–GdF₃–AlF₃ (ZBGA), ZrF₄–BaF₂–LaF₃–YF₃–AlF₃–LiF–NaF (ZBLYALN) and ZrF₄–BaF₂–LaF₃–YF₃–AlF₃–LiF (ZBLYAL)] used for fabricating optical fiberby¹⁸O(p, n)¹⁸F reaction without significant nuclear interference. The main long life⁹⁶Nb nuclide was produced by the⁹⁶Zr(p,n) reaction in a non-destructive analysis of ZBGA-fluoride glass and reduced by using a coincidence system with Ge(Li) and NaI(T1) detectors. Substoichiometric separation of¹⁸F was also used to determine oxygen in fluoride glass, especially in glass containing yttrium as a component element because the⁸⁹Zr produced by the⁸⁹Y(p,n) reaction is a positron emitter, the same as¹⁸F. It was confirmed that the oxygen concentration in fluoride glass was 13–2460 ppm related to the loss by scattering.     

MECHANISM OF PHOTOOXYGENATION OF THE CD (II) COMPLEX OF PYROPHEOPHORBIDE A METHYL ESTER

Photooxygenation of (pyropheophorbidato a methyl ester)cadmium (II) was studied using ^18,18O₂ labeling of the molecular oxygen required for cleavage of the macrocycle. After reductive demetallation of the primary oxidation product (4,5-dioxo-4,5-secopyropheophorbidato a methyl ester)cadmium (II), the isotope content of formylbilinone 4a was analyzed by repeated-scan fast atom bombardment mass spectrometry. Comparison of the spectroscopic data of the labeled pigment 4a with the statistical probabilities of¹⁸ O isotope incorporation calculated for four possible reaction mechanisms clearly proves that photooxidative ring cleavage occurred by the one-molecule mechanism, i.e. the terminal oxygen atoms of 4a were derived from one oxygen molecule. Furthermore, a study of the exchange of the¹⁸ O-labeled atoms revealed that no exchange occurs within the pH 4.5–9.5 range. In stronger alkaline or acidic solutions, only the oxygen atom of the formyl group is exchanged. Hydrolysis of the methyl ester group of 4a was achieved, without loss of the¹⁸ O label on the formyl group, at pH 7.2 in the presence of pig liver esterase.     

Study of the mechanism of recyclization of furans into thiophenes and selenophenes in conditions of acid catalysis. 6. Experiments with labeled atoms. Quantum chemical calculations of intermediates of recyclization and hydrolysis

The reaction of 2-methyl-5-R-furans (R=Me, Bu, 2,2-pentyl-2-methylpentyl) with H₂ ¹⁸O was investigated. Furans and the corresponding 2,5-alkanediones containing the¹⁸O isotope were obtained. The general characteristics of the recyclization and isotope exchange reactions were established. A kinetic study of recyclization of 2,5-dimethylfuran with¹⁶O and¹⁸O into 2,5-dimethylthiophene was conducted. A reverse kinetic isotope effect was found. The schemes of the mechanisms of these processes were refined based on the experimental data and quantum-chemical calculations of the recyclization and hydrolysis intermediates.See [1] for Communication 5.Scientific-Research Institute of Chemistry, N. G. Chernyshevskii Saratov State University, Saratov 410026. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1035–1042, August, 1997.     

Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

The¹³C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphpric acids (PA) and by 85% H₃PO₄ has been studied in the temperature interval of 60–150°C. The values of the¹³C₍₁₎ isotope effects in the decarbonylation of lactic acid in 100% H₃PO₄, in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C₍₁₎–OH bond is broken in the rate-controllin gstep of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90–130°C the experimental¹³C fractionation factors determined in concentrated PA approach quite closely the¹³C fractionation corresponding to C₍₂₎–C₍₁₎ bond scission. the¹³C₍₁₎ kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110–150°C coincide with the¹³C isotope effects calculated assuming that the frequency corresponding to the C₍₁₎–OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H₃PO₄ has been suggested. A possible secondary¹⁸O and a primary¹⁸O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too.     

Determination of Nitrogen and Oxygen Isotopes in Nitrates: A Minireview

Nitrogen and oxygen isotope ratios (δ¹⁵N and δ¹⁸O) in nitrates are important in hydrology, oceanography, atmospheric chemistry, and agriculture. This paper reviews current isotope ratio mass spectrometry methods for the determination of nitrogen and oxygen isotopes in nitrates that include graphite combustion, AgNO₃-ion exchange, Ba(NO₃)₂-acetone, two-step chemical conversion, bacterial approaches, and off-axis integral cavity output laser spectroscopy. This paper introduces the principles, processes, advantages, and disadvantages of these procedures. Future studies should focus on the determination of oxygen isotopes. The development of novel spectroscopic or other isotopic methodology may also be new research directions. In addition, in some nitrates, δ¹⁷O is more sensitive than traditional δ¹⁸O and further development for this isotope is of interest. In addition, the determination of δ¹⁷O may be used to more accurately evaluate δ¹⁸O.     

Photo-oxidation of water by molecular oxygen: isotope exchange and isotope effects

Photolysis of (17,18)O-labeled water in the presence of molecular oxygen is accompanied by transfer of (17)O and (18)O isotopes from water to oxygen, demonstrating that photoinduced oxidation of water does occur. The reaction exhibits the following isotope effect: oxidation of H(2)(17)O is faster by 2.6% (in the Earth's magnetic field) and by 6.0% (in the field 0.5 T) than that of H(2)(18)O. The effect is supposed to arise in the two spin-selective, isotope-sorting reactions-recombination and disproportionation-in the pairs of encountering HO(2) radicals. The former is spin allowed from the singlet state; the latter occurs only in the triplet one. Nuclear spin sorting produced by these reactions proceeds in opposite directions with the dominating contribution of recombination, which provides observable (17)O/(18)O isotope fractionation in favor of magnetic isotope (17)O. Neither isotope exchange nor the reaction itself occurs in the dark.     

Oxygen isotope homogeneity assessment for apatite U-Th-Pb geochronology reference materials

Secondary ion mass spectrometry (SIMS) measurement of oxygen isotopes in apatite has been employed more and more in petrogenetic, metallogenic, and climate change studies. Well-characterised reference materials are needed due to the matrix effect, but they are yet to be well established. In this study, we conducted in-situ oxygen isotopic and chemical analyses on six commonly used apatite reference materials (ie, Emerald, Kovdor, McClure, Mud Tank, Otter Lake, and Slyudyanka) and two in-house apatite references (Qinghu and GEMS 203) to assess their oxygen isotope homogeneity and applicability for microbeam analyses. Our results show that all these apatite references are in general chemically homogeneous. In terms of oxygen isotopes, GEMS 203 (δ¹⁸O = 9.85 ± 0.40‰ [2SD], corrected by Durango 3), Kovdor (δ¹⁸O = 6.55 ± 0.38‰, 2SD), and McClure (δ¹⁸O = 5.94 ± 0.42‰, 2SD) are fairly homogeneous, whereas Emerald (δ¹⁸O = 10.37 ± 0.45‰, 2SD), Mud Tank (δ¹⁸O = 6.35 ± 0.46‰, 2SD), Otter Lake (δ¹⁸O = 9.71 ± 0.47‰, 2SD), Qinghu (δ¹⁸O = 5.44 ± 0.49‰, 2SD), and Slyudyanka (δ¹⁸O = 17.49 ± 0.43‰, 2SD) are less homogenous. This indicates that the former group represents better reference materials for in-situ oxygen isotopic analyses, whilst the latter group can be used as secondary reference material for analytical quality control.     

Isotope effect in the formation of hydrogen peroxide by the sonolysis of light and heavy water

The kinetics of the formation of hydrogen peroxide by the sonolysis of light and heavy water in argon and oxygen atmospheres was investigated. The sonochemical reaction has a zero order with respect to hydrogen peroxide (H₂O₂, D₂O₂, or DHO₂). The measurement of the kinetic isotope effect (α), defined as the ratio of the reaction rates in H₂O and D₂O, carried out under argon gave a value of 2.2±0.3. The observed isotope effect decreases with an increase in the concentration of light water in H₂O−D₂O mixtures. No isotope effect is displayed in the oxygen atmosphere (α=1.05±0.10). The isotope effect is determined presumably by the mechanism of sonochemical decomposition of water molecules, which includes the H₂O−Ar^* and D₂O−Ar^* energy exchange (where Ar^* are argon atoms in the³P_2.0 excited state) in the nonequilibrium plasma generated by a shock wave, arising upon a cavitation collapse. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 645–649, April, 2000.     

Study of formation mechanism of 1,3-benzodioxanes from tertiary phenoloalcohols and carbonyl compounds using labeled atoms

It was shown that the reaction of o-hyroxyphenyldiphenylmethanol with benzaldehyde labeled with ¹⁷O and ¹⁸O isotopes proceeds in such a way that oxygen atoms of the starting phenoloalcohol are retained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 632–633, May, 1991.     

Mass spectrometric investigation of reactions of oxygen exchange and partial oxidation of methane in molten catalysts

This work has been devoted to a mass spectrometric investigation of the interaction of atmospheric oxygen or an air-methane mixture with molten V₂O₅-NaPO₃, selected as a model catalyst; the work has been further aimed at studying the reaction mechanisms. The data on the change in isotope composition¹⁸O/¹⁶O have been analyzed, and the rate constants and order of reaction with respect to oxygen have been determined.A mechanism has been proposed for the interaction of both atmospheric oxygen and the air-methane mixture with the melt.Institute of General and Inorganic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 99–104, January–February, 1991. Original article submitted May 3, 1990.     

Origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate—application of the 18O isotope effect in 31P NMR

Potassium persulfate oxidizes triphenylphosphine to triphenylphosphine oxide in 60% aqueous acetonitrile. It has been suggested that the oxygen of the product, triphenylphosphine oxide, might originate from solvent water, following nucleophilic attack on an intermediate phosphonium ion. We have investigated the origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate in 60% aqueous acetonitrile containing 20% [¹⁸O]water. The product was analyzed by using the ¹⁸O isotope effect in ³¹P NMR spectroscopy. The magnitude of the ¹⁸O isotope-induced shift was determined by synthesizing triphenylphosphine [¹⁸O]oxide and was found to be 0.038 ppm upfield. The product of the oxidation reaction in 20% [¹⁸O]water displayed no ¹⁸O isotope effect. The origin of the oxygen in the oxidation reaction is the persulfate ion, consistent with an alternative mechanism involving nucleophilic attack by water at the sulfur atom of a phosphonium peroxysulfate intermediate.     

Infrared spectra (700–200 cm−1) and6Li/7Li and H2O/D2O isotope effects for four isotopically substituted lithium formate monohydrates

The infrared spectra, in the 700–200 cm^–1 region, have been reported for⁶LiHCO₂ · H₂O,⁶LiHCO₂ · D₂O,⁷LiHCO₂ · H₂O and⁷LiHCO₂ · D₂O and the observed fundamental bands have been discussed taking into account the⁶Li/⁷Li and H₂O/D₂O isotope wavenumber shifts on the fundamental vibrations.

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Infrarotspektren (700–200 cm^–1) und⁶Li/⁷Li- und H₂O/D₂O-Isotopeneffekte für vier isotopensubstituierte Lithiumformat-monohydrate

Zusammenfassung Die Infrarotspektren in der Region von 700–200 cm^–1 werden für⁶LiHCO₂ · H₂O,⁶LiHCO₂ · D₂O,⁷LiHCO₂ · H₂O und⁷LiHCO₂ · D₂O angegeben und die beobachteten Grundschwingungen zusammen mit den isotopischen Verschiebungen der Wellenzahlen diskutiert.

     

Pore-water anomalies in gas hydrate-bearing sediments of the deeper continental margins: Facts and problems

Naturally occurring gas hydrates, discovered under the deeper parts of the continental margins (generally below 500 m water depth) during the Deep Sea Drilling Project and the Ocean Drilling Program, impregnate terrigenous sediments 0.5 to 1 km thick. They form from biogenic as well as thermogenic hydrocarbon gases and are associated with characteristic chemical and isotopic anomalies in the pore waters resulting from hydrate decomposition. Typical downward trends derived from water samples squeezed on board ship show decreasing chlorinity coupled with increases in the heavy oxygen and hydrogen isotopes resulting from the combined effects of sediment compaction and salt and isotope fractionation by hydrates. Carbon isotopes can be used to differentiate between biogenic ( ¹³C < –55) and thermogenic ( ¹³C > –559) gas hydrates except where acetate-derived methane is involved. Smooth downward trends in the chemical and isotopic anomalies suggest steady increases in the proportion of hydrates among the pore-filling substances. Spikes are attributed to high local hydrate concentrations (or massive hydrate layers or nodules). Problems encountered in delineating the detailed relationships between hydrate occurrence and pore-water anomalies concern (i) the roof-effect of a hydrate zone which should be marked by a positive Cl^– and a negative ¹⁸O anomaly (the opposite of the hydrate decomposition effect) (ii) the composition ofin-situ pore waters from within hydrate zones; (iii) the suppression of a positive ¹⁸O hydrate-decomposition anomaly due to superposition of other oxygen-isotope fractionation effects (such as volcanic glass alteration); and (iv) the non-linear correlation between Cl^– depletion and¹⁸O enrichment, and the magnitude of the¹⁸O enrichment. The hydrate-decomposition mechanism still provides the most successful explanation for the chemical and isotopic porewater anomalies observed in hydrate-bearing sediments, but the problems encountered underscore the urgency for future research through deep-sea drilling in hydrate zones.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Electronic structure and reactivity of Mg+(H2O)n cluster ions

Electronically excited states of magnesium-water cluster ions, Mg⁺(H₂O) _n ,n=1–5, are studied by photodissociation after mass selection. The observed photodissociation spectra are assigned to the²P–²S type transitions localized on the Mg⁺ ion with the aid of ab initio CI calculations. In addition to evaporation of water molecules, photoinduced intracluster reaction to produce MgOH⁺(H₂O) _n is found to occur efficiently, with pronounced size dependence. The intriguing features observed in the mass spectrum of nascent cluster ions are discussed in relation to the stepwise solvation of this reaction.     

Mutual Influence of Electrode Processes during Electrodeposition of Layered Structures by a Single-Bath Method: Effect of Nickel Deposition and Hydrogen Evolution on the Mass Transfer of Copper in a Sulfosalicylate Electrolyte

The work justifies the selection of a sulfosalicylate copper–nickel electrolyte and its composition for obtaining nanostructures comprising alternate magnetic and nonmagnetic layers by a single-bath method. According to calculations of an equilibrium composition of the electrolyte and electrodiffusion fluxes of discharging species, in a neutral region of pH copper exists in the form of multicharged anions CuSSA^3–, and the migration effects must reduce the rate of the mass transfer of copper-containing species with increasing current of the parallel reaction of discharge of nickel ions. Dependences of the partial current density of copper deposition on the electrode potential are studied at various values of pH of the copper and copper–nickel electrolytes. Experimental results are analyzed on the basis of modeling concepts. It is shown that the drop of the partial current density of copper deposition below its limiting value at potentials of deposition of a magnetic layer is connected with the emergence of migration effects.     

Die Bestimmung des Sauerstoffgehaltes in Silizium nach Ionenimplantation durch eine SiO2-Deckschicht mit Hilfe der Reaktion18O(p, α)15N

The recoil implantation yield of oxygen atoms recoiled from¹⁸O-enriched SiO₂ layers into silicon substrates has been studied using the¹⁸O(p, α)¹⁵N nuclear reaction. The method to determine the number of oxygen atoms in silicon is described in detail and the results are compared to the theoretical predictions.