Oxoiron(IV) in chloroperoxidase compound II is basic: implications for P450 chemistry

With the use of x-ray absorption spectroscopy, we have found that the Fe-O bond in chloroperoxidase compound II (CPO-II) is much longer than expected for an oxoiron(IV) (ferryl) unit; notably, the experimentally determined bond length of 1.82(1) A accords closely with density functional calculations on a protonated ferryl (Fe(IV)-OH, 1.81 A). The basicity of the CPO-II ferryl [pKa > 8.2 (where Ka is the acid dissociation constant)] is attributable to strong electron donation by the axial thiolate. We suggest that the CPO-II protonated ferryl is a good model for the rebound intermediate in the P450 oxygenation cycle;with elevated pKa values after one-electron reduction, thiolate-ligated ferryl radicals are competent to oxygenate saturated hydrocarbons at potentials that can be tolerated by folded polypeptide hosts.     

Lamellar twinning explains the nearly racemic composition of chiral, single crystals of hexahelicene

Solvent etching of single crystals of hexahelicene grown from a racemic solution reveals an unusual layer-like pattern in which pure (+)- and pure (-)-layers alternate through the crystal; this arrangement results in a nearly racemic composition although the crystal is ostensibly chiral, space group P2(1)2(1)2(1). Etched crystals of enantiomerically pure hexahelicene display no such pattern. The two kinds of crystal are indistinguishable by x-ray diffraction.     

Surface of young Jupiter family comet 81P/Wild 2: view from the Stardust Spacecraft

Images taken by the Stardust mission during its flyby of 81P/Wild 2 show the comet to be a 5-kilometer oblate body covered with remarkable topographic features, including unusual circular features that appear to be impact craters. The presence of high-angle slopes shows that the surface is cohesive and self-supporting. The comet does not appear to be a rubble pile, and its rounded shape is not directly consistent with the comet being a fragment of a larger body. The surface is active and yet it retains ancient terrain. Wild 2 appears to be in the early stages of its degradation phase as a small volatile-rich body in the inner solar system.     

A major human histone gene cluster on the long arm of chromosome 1

A human histone gene cluster was assigned to chromosome 1 by Southern blot analysis of DNA's from a series of mouse-human somatic cell hybrids with 32P-labeled cloned human H4 and H3 histone DNA as probes. Localization of this histone gene cluster on the long arm of chromosome 1 was confirmed by in situ hybridization of this DNA probe to metaphase chromosomes.     

An active role for tRNA in decoding beyond codon:anticodon pairing

During transfer RNA (tRNA) selection, a cognate codon:anticodon interaction triggers a series of events that ultimately results in the acceptance of that tRNA into the ribosome for peptide-bond formation. High-fidelity discrimination between the cognate tRNA and near- and noncognate ones depends both on their differential dissociation rates from the ribosome and on specific acceleration of forward rate constants by cognate species. Here we show that a mutant tRNA(Trp) carrying a single substitution in its D-arm achieves elevated levels of miscoding by accelerating these forward rate constants independent of codon:anticodon pairing in the decoding center. These data provide evidence for a direct role for tRNA in signaling its own acceptance during decoding and support its fundamental role during the evolution of protein synthesis.     

Self-similarity in the distribution and abundance of species

If the fraction of species in area A that are also found in one-half of that area is independent of A, the distribution of species is self-similar and a number of observed patterns in ecology, including the widely cited species-area relationship connecting species richness to censused area, follow. Self-similarity also leads to a species-abundance distribution, which deviates considerably from the commonly assumed lognormal distribution and predicts considerably more rare species than the latter. Because the abundance distribution is derived under the condition of self-similarity, it may be widely applicable beyond ecology.     

Light adaptation in the rat retina: evidence for two receptor mechanisms

Light adapting the rat retina with transient white flashes too dim to bleach a substantial amount of visual pigment produces a change in electroretinogram spectral sensitivity and an increase in flicker fusion frequency. Increment threshold curves obtained with a long wavelength adapting stimulus and a short wavelength test stimulus show rod saturation.