Intermolecular Dipole–Dipole Relaxation of Xe Dissolved in Water

Intermolecular ¹²⁹Xe–¹H nuclear Overhauser effects and ¹²⁹Xe longitudinal relaxation time measurements were used to demonstrate that the dipole–dipole coupling is the dominant relaxation mechanism for ¹²⁹Xe in water, at room temperature. ¹²⁹Xe–¹H cross-relaxation rates were derived to be ς_XeH 3.2 ± 0.3 × 10⁻³ s⁻¹, independent of xenon pressure (in the range of 1–10 bar) and of the presence of oxygen. Corresponding xenon–proton internuclear distances were calculated to be 2.69 ± 0.12 Å. Using the magnitude of the dipole–dipole coupling and the spin density ratio between dissolved xenon and bulk water, it is estimated that ¹²⁹Xe–¹H spin polarization-induced nuclear Overhauser effects would yield little net proton signal enhancement in water.     

XeF4 as a Ligand for a Metal Ion

Noble molecule : [Mg(XeF₂)(XeF₄)](AsF₆)₂ is the first coordination compound in which XeF₄ acts as a ligand to a metal center. It is also the first known compound, in which XeF₂ and XeF₄ are simultaneously coordinated to the same metal center (see structure; purple Xe, green F, gray Mg, yellow As).

     

Nuclear Spin‐Noise Spectra of Hyperpolarized Systems

Spin‐noise appeal : Detection of NMR spin‐noise is very appealing when dilute hyperpolarized species are considered. Continuous monitoring of the noise absorption at the Larmor frequency enables determination of T₁ and T₂*, independently of the static magnetic field. An inductively coupled microcoil located inside the NMR tube (see picture) allows acquisition of ¹²⁹Xe spin‐noise spectra without radio‐frequency excitation.

     

The dependence on temperature and concentration of 129Xe NMR chemical shift values of organoxenon(II) salts [RXe][Y] and of the parent molecule XeF2

The dependence of the 129Xe NMR chemical shift value of XeF2 on temperature and concentration was determined in a variety of prototypic media: in acidic (anhydrous HF, aHF), nonprotic but polar (dichloromethane), and basic (CD3CN-EtCN, 1:3 v/v) solvents. The 129Xe NMR spectra of a representative series of organoxenon(II) salts [RXe][Y] (R = C6F5, heptafluoro-1,4-cyclohexadien-1-yl (cyclo-1,4-C6F7), pentafluoro-1,4-cyclohexadien-3-on-1-yl (cyclo-3-O-1,4-C6F5), CF2=C(CF3), (CF3)2CFC[triple bond]C, C4H9C[triple bond]C; Y = BF4, AsF6) in aHF showed, compared with XeF2-aHF, a quantitatively less distinct but qualitatively related dependence of delta(129Xe) vs temperature. The dependence of their delta(129Xe) values on concentration in aHF is negligible. An explanation for the different behavior of [RXe][Y] and XeF2 is offered.     

Mass Measurements of 114–124,130Xe with the ISOLTRAP Penning Trap Spectrometer

The masses of the xenon isotopes with 114≤A≤123 were directly measured for the first time. The experiments were carried out at the ISOLTRAP triple trap spectrometer at the on-line mass separator ISOLDE/CERN. A mass resolving power of the Penning trap spectrometer of m/Δm≈500 000 was chosen and an accuracy of δm≈12keV for all investigated Xe isotopes was achieved. An atomic mass evaluation was performed and the results of this adjustment are compared with theoretical predictions. The new results for the xenon isotopes and their effects on neighboring nuclides are discussed within the two-neutron separation energy picture. This revised version was published online in July 2006 with corrections to the Cover Date.     

Consequences of Xe–H Cross Relaxation in Aqueous Solutions

We have investigated the transfer of polarization from ¹²⁹Xe to solute protons in aqueous solutions to determine the feasibility of using hyperpolarized xenon to enhance ¹H sensitivity in aqueous systems at or near room temperatures. Several solutes, each of different molecular weight, were dissolved in deuterium oxide and although large xenon polarizations were created, no significant proton signal enhancement was detected in -tyrosine, α-cyclodextrin, β-cyclodextrin, apomyoglobin, or myoglobin. Solute-induced enhancement of the ¹²⁹Xe spin–lattice relaxation rate was observed and depended on the size and structure of the solute molecule. The significant increase of the apparent spin–lattice relaxation rate of the solution phase ¹²⁹Xe by α-cyclodextrin and apomyoglobin indicates efficient cross relaxation. The slow relaxation of xenon in β-cyclodextrin and -tyrosine indicates weak coupling and inefficient cross relaxation. Despite the apparent cross-relaxation effects, all attempts to detect the proton enhancement directly were unsuccessful. Spin–lattice relaxation rates were also measured for Boltzmann ¹²⁹Xe in myoglobin. The cross-relaxation rates were determined from changes in ¹²⁹Xe relaxation rates in the α-cyclodextrin and myoglobin solutions. These cross-relaxation rates were then used to model ¹H signal gains for a range of ¹²⁹Xe to ¹H spin population ratios. These models suggest that in spite of very large ¹²⁹Xe polarizations, the ¹H gains will be less than 10% and often substantially smaller. In particular, dramatic ¹H signal enhancements in lung tissue signals are unlikely.     

Fission Gas Bubbles Characterisation in Irradiated UO2 Fuel by SEM, EPMA and SIMS

The behaviour of gases produced by fission is of great importance for nuclear fuel operation. Within this context, an experimental method for the characterisation of the fission gas including gas bubbles in an irradiated UO₂ nuclear fuel was developed in our laboratory using SIMS, EPMA and SEM results. SIMS and EPMA have been used to measure the radial distribution of xenon and SEM gives information on bubble formation across the fuel pellet radius. Using SIMS, xenon concentration can be determined in the matrix and in the bubbles. A quantification method, allowing the determination of the total inventory of xenon, is proposed and qualified with EPMA results. It is concluded that the complementary micro-analytical techniques SIMS, EPMA and SEM are very powerful tools for the characterisation of the fission gas bubbles in irradiated nuclear fuel.     

Synthesis of bis(difluoronitroacetoxy)iodoarenes

Two methods for synthesizing bis(difluoronitroacetoxy)iodoarenes, new compounds of tervalent iodine, have been proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1629–1630, September, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-4566).