No abstract

The methylene-bridged triphenylamine 2 has been oxidized to planar radical cation 2(•+) by B(C6F5)3 or Ag(+). Further reaction of 2(•+)[Al(ORF)4](-) and 2 with trace amounts of silver salt resulted in dication 3(2+), providing a rare example of structurally characterized bis(triarylamine) "bipolarons". 3(2+) can be directly prepared by the reaction of 3 with 2 equiv of Ag(+). X-ray structural analysis together with theoretical calculation shows that 3(2+) has singlet diradical character and is analogous to Chichibabin's hydrocarbons.

Single crystal X-ray diffraction is arguably the most definitive method for molecular structure determination, but the inability to grow suitable single crystals can frustrate conventional X-ray diffraction analysis. We report herein an approach to molecular structure determination that relies on a versatile toolkit of guanidinium organosulfonate hydrogen-bonded host frameworks that form crystalline inclusion compounds with target molecules in a single-step crystallization, complementing the crystalline sponge method that relies on diffusion of the target into the cages of a metal-organic framework. The peculiar properties of the host frameworks enable rapid stoichiometric inclusion of a wide range of target molecules with full occupancy, typically without disorder and accompanying solvent, affording well-refined structures. Moreover, anomalous scattering by the framework sulfur atoms enables reliable assignment of absolute configuration of stereogenic centers. An ever-expanding library of organosulfonates provides a toolkit of frameworks for capturing specific target molecules for their structure determination.

The noble gas xenon has been shown to be protective in preconditioning settings against renal ischemic injury. The aims of this study were to determine the protective effects of the other noble gases, helium, neon, argon, krypton and xenon, on human tubular kidney HK2 cells in vitro. Cultured human renal tubular cells (HK2) were exposed to noble gas preconditioning (75% noble gas; 20% O(2); 5% CO(2)) for three hours or mock preconditioning. Twenty-four hours after gas exposure, cell injury was provoked with oxygen-glucose deprived (OGD) culture medium for three hours. Cell viability was assessed 24 h post-OGD by a 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide assay. Other cohorts of cultured cells were incubated in the absence of OGD in 75% noble gas, 20% O(2) and 5% CO(2) and cellular signals phospho-Akt (p-Akt), hypoxia-inducible factor-1alpha (HIF-1alpha) and Bcl-2 were assessed by Western blotting. OGD caused a reduction in cell viability to 0.382 +/- 0.1 from 1.0 +/- 0.15 at control (P < 0.01). Neon, argon and krypton showed no protection from injury (0.404 +/- 0.03; 0.428 +/- 0.02; 0.452 +/- 0.02; P > 0.05). Helium by comparison significantly enhanced cell injury (0.191 +/- 0.05; P < 0.01). Xenon alone exerted a protective effect (0.678 +/- 0.07; P < 0.001). In the absence of OGD, helium was also detrimental (0.909 +/- 0.07; P < 0.01). Xenon caused an increased expression of p-Akt, HIF-1alpha and Bcl-2, while the other noble gases did not modify protein expression. These results suggest that unlike other noble gases, preconditioning with the anesthetic noble gas xenon may have a role in protection against renal ischemic injury.