Effect of crystal packing on the structures of polymeric metallocenes

The pressure dependencies of the crystal structures of the polymeric metallocenes lithium cyclopentadienide (LiCp) and potassium cyclopentadienide (KCp) have been determined by synchrotron X-ray powder diffraction. The decrease of the volume of LiCp by 34% up to a pressure of p = 12.2 GPa and of KCp by 23% at p = 5.3 GPa as well as the bulk moduli of K = 7.7 GPa for LiCp and 4.9 GPa for KCp indicate a high compressibility for these compounds. The crystal structures of KCp have been determined up to p = 3.9 GPa. An increase of the bend angle is found from 45 degrees at p = 0 GPa up to 51 degrees at p = 3.9 GPa. This variation is completely explained by a model invoking attractive K+ Cp- interaction and repulsive nonbonded carbon-carbon interactions. It is proposed that the bend angle in the polymeric alkali metal metallocenes is the result of the optimization of the crystal packing.     

Estrogen receptor microarrays: subtype-selective ligand binding

We present the first example of a nuclear hormone receptor microarray, using for illustration the ligand-binding domains of the two estrogen receptors, ERalpha-LBD and ERbeta-LBD. The proteins are printed and allowed to attach to aldehyde slides; the efficiency of attachment depends on whether the LBD is liganded with agonists (low attachment) versus liganded with antagonists or unliganded (high attachment). This suggests that attachment is orientation specific and involves principally a single lysine residue. The attached ERs retain good ligand-binding activity that can be assessed using an estradiol-fluorophore conjugate, and specific and ER subtype-selective binding of ligands can be determined conveniently in competitive binding assays. This powerful new, high-throughput technique to study ligand binding to ER-LBDs can be extended to other nuclear hormone receptors and adapted to assay the recruitment of coregulator proteins.     

Accuracy of free energies of hydration for organic molecules from 6-31g*-derived partial charges

Absolute free energies of hydration have been computed for 13 diverse organic molecules using partial charges derived from ab initio 6-31G* wave functions. Both Mulliken charges and charges fit to the electrostatic potential surface (EPS) were considered in conjunction with OPLS Lennard–Jones parameters for the organic molecules and the TIP4P model of water. Monte Carlo simulations with statistical perturbation theory yielded relative free energies of hydration. These were converted to absolute quantities through perturbations to reference molecules for which absolute free energies of hydration had been obtained previously in TIP4P water. The average errors in the computed absolute free energies of hydration are 1.1 kcal/mol for the 6-31G* EPS charges and 4.0 kcal/mol for the Mulliken charges. For the EPS charges, the largest individual errors are under 2 kcal/mol except for acetamide, in which case the error is 3.7 kcal/mol. The hydrogen bonding between the organic solutes and water has also been characterized. © John Wiley & Sons, Inc.     

Harmonic maps from compact Kähler manifolds to exceptional hyperbolic spaces

It has been conjectured that a lattice in a noncompact group of real rank one, other than SU(1,n), cannot be isomorphic to the fundamental group of a compact Kähler manifold; moreover, it is known to be true for SO(1,n). In this note it is shown that this conjecture also holds for the case of uniform lattices in F_4(?20), the group of isometries of the Cayley hyperbolic plane. The result is a consequence of a classification theorem for harmonic maps between Kähler and Cayley hyperbolic manifolds.     

Muon diffusion and trapping studies in high purity vanadium

We present the first results of a study of the effects of varying impurity concentration on the temperature dependence of the depolarization rate of positive muons implanted into vanadium. Data are reported for the most highly purified polycrystalline sample yet measured, and the same sample subsequently doped with about 500 ppm oxygen by weight. The data for the pure sample shows a low depolarization rate (<.15 sec^–1) at all temperatures measured, showing a broad minimum centered at 35 K, followed by a sharp peak near 90 K and a rapid drop to negligible values at 200 K. The data is contrasted with previously published data [2] on less pure samples, and calls into question previous interpretations of the behavior of the ⁺ at low temperatures in impure vanadium [1] as one-phonon-assisted tunneling.This work was supported by the U. S. Department of Energy