ESR, STESR, DFT, and MD Study of the Dynamical Structure of Cucurbituril[7]-Spin Probe Guest-Host Complexes.

We study the molecular dynamics and structures of the guest-host complexes of cucurbituril, CB[7], with spin probes through the conventional electron spin resonance (ESR), saturation transfer ESR (STESR), density functional theory (DFT), and molecular dynamics (MD) computations. Protonated TEMPOamine (I), a derivative of TEMPO having a positive charge and an octyl group on the quaternary nitrogen atom (II), and the neutral spin-labeled indole (III) are used as guests. To eliminate the overall complex rotation, the solutions of complexes in a solid CB[7] matrix were prepared. Resultantly, for all of the spin probes, the combined study of the conventional ESR and STESR spectra indicates the librational character of the rotational motion within the CB[7] cavity as opposed to the diffusional rotation over the whole solid angle. The kinetic accessibilities of the reporter NO groups to the paramagnetic complexes in aqueous solutions, determined by Heisenberg exchange broadening of the ESR spectra, together with the environment polarities from the hyperfine interaction values, as well as DFT computation results and MD simulations, were used to estimate the spin probe location relative to CB[7]. Utilizing the concept of the aqueous clusters surrounding the spin probes and CB[7] molecules and MD simulations has allowed the application of DFT to estimate the aqueous environment effects on the complexation energy and spatial structure of the guest-host complexes.

DNA analysis of a 30,000-year-old Urocitellus glacialis from northeastern Siberia reveals phylogenetic relationships between ancient and present-day arctic ground squirrels.

In contrast to the abundant fossil record of arctic ground squirrels, Urocitellus parryii, from eastern Beringia, only a limited number of fossils is known from its western part. In 1946, unnamed GULAG prisoners discovered a nest with three mummified carcasses of arctic ground squirrels in the permafrost sediments of the El'ga river, Yakutia, Russia, that were later attributed to a new species, Citellus (Urocitellus) glacialis Vinogr. To verify this assignment and to explore phylogenetic relationships between ancient and present-day arctic ground squirrels, we performed 14C dating and ancient DNA analyses of one of the El'ga mummies and four contemporaneous fossils from Duvanny Yar, northeastern Yakutia. Phylogenetic reconstructions, based on complete cytochrome b gene sequences of five Late Pleistocene arctic ground squirrels and those of modern U. parryii from 21 locations across western Beringia, provided no support for earlier proposals that ancient arctic ground squirrels from Siberia constitute a distinct species. In fact, we observed genetic continuity of the glacialis mitochondrial DNA lineage in modern U. parryii of the Kamchatka peninsula. When viewed in a broader geographic perspective, our findings provide new insights into the genetic history of U. parryii in Late Pleistocene Beringia.