Effects of the Chodura sheath on tungsten ionization and emission in tokamak divertors

The decay of the electric potential in the sheath region in tokamak divertors occurs on a scale length on the order of the main ion gyroradius (Chodura sheath) due to magnetic fields lines intersecting the divertor plates at grazing incidence. As a consequence, high-Z impurities like tungsten ionize within the sheath region in attached plasma conditions. The modification of the electron distribution in the sheath region must thus be taken into account to accurately model ionization and emission of impurities within the sheath region. To that end, an analytical expression of the distribution of the vertical ionization path for impurities sputtered from divertor plasma-facing components is derived. This expression is then used to estimate the fraction of neutral impurities ionizing within the sheath and the average vertical ionization path, and to derive an effective SXB (the number of ionizations per emitted photon) coefficient which includes the effects of the variation of the electron distribution in the sheath region. These results are applied to tungsten impurities sputtered from divertor plates. It is shown that the SXB coefficient for neutral tungsten is significantly reduced in high-density attached divertor plasma conditions (n_e ≳ 5 × 10¹³ cm⁻³) because of the ionization of neutral tungsten well within the sheath region.     

Addressing the Structural Complexity of Fluorinated Glucose Analogues: Insight into Lipophilicities and Solvation Effects

In this work, we synthesized all mono-, di-, and trifluorinated glucopyranose analogues at positions C-2, C-3, C-4, and C-6. This systematic investigation allowed us to perform direct comparison of ¹⁹F resonances of fluorinated glucose analogues and also to determine their lipophilicities. Compounds with a fluorine atom at C-6 are usually the most hydrophilic, whereas those with vicinal polyfluorinated motifs are the most lipophilic. Finally, the solvation energies of fluorinated glucose analogues were assessed for the first time by using density functional theory. This method allowed the log P prediction of fluoroglucose analogues, which was comparable to the C log P values obtained from various web-based programs.     

Hydrostibination of Alkynes: A Radical Mechanism**

The addition of Sb−H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov Z-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring open-shell neutral intermediates. Density-functional theory (DFT) calculations are consistent with this model, predicting an activation barrier that is in agreement with the experimental value (Eyring analysis) and a rate limiting step that is congruent with the experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb^II and Sb^III intermediates to yield the observed Z-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a synthetic methodology.     

Full assignment of the proton and carbon-13 nmr spectra of 2,3,6 -tri-o-methyl-β-cyclodextrin

The proton and carbon-13 NMR spectra of 2,3,6 -tri-O-methyl-β-cyclodextrin in deuteriochloroform have been fully and unambiguously assigned using homonuclear and selective heteronuclear spin decoupling and two-dimensional homo- and heteronudear correlation NMR spectroscopy. Corrections are made to some earlier literature assignments.     

A reversible safety-catch method for the hydrogenolysis of N-benzyl moieties

The benzyl groups of β-hydroxy-N-benzyl sulfonamides are labile toward hydrogenolysis-unlike N-benzyl sulfonamides lacking the β-hydroxy moiety. We find that N-acyl-N-benzyl sulfonamides undergo hydrogenolysis under very mild conditions. Based upon these observations, we developed a reversible safety-catch method using tert-butoxycarbonyl moieties to activate N-benzyl sulfonamides toward hydrogenolysis. We also explored the utility of the safety-catch activation method for other nitrogen-based functionality such as N-benzyl carboxamides, imides, and related functionality.     

Phase transformation in He+ and H+ ion irradiated type 304 stainless steel

γ (fcc)→α (bcc) phase transformation in type 304 stainless steel has been observed after irradiation of He⁺ and H⁺ ions up to fluence levels of 10¹⁷ and 10¹⁹ ions/cm², respectively. Depth selective conversion Mössbauer spectroscopy and surface-sensitive X-ray diffractometry were employed to study the effect of irradiation. It is shown that the amount of the ion induced phase is highly sensitive to the fluence, the ion species and depth from the surface. It is worth noting that H⁺ ion irradiation is rather ineffective in inducing the transformation.     

Use of a urea and guanidine-HCl-propanol solvent system to purify a growth inhibitory glycopeptide by high-performance liquid chromatography

Reversed-phase high-performance liquid chromatography was used to purify an inhibitory glycopeptide where resolution and recovery were enhanced by using urea or guanidine-HCl-isopropanol-water as a solvent system. Isopropanol alone or other solvent systems that have been proposed for such purification steps were not effective in eluting hydrophobic proteins from the reversed-phase column. The application of the urea or guanidine-HCl solvent systems in the separation and purification of membrane proteins, and other hydrophobic macromolecules, could greatly enhance recovery and efficiency of purification.