The copper chelator methanobactin from Methylosinus trichosporium OB3b binds copper(I)

The oxidation state of copper bound to methanobactin, a small siderophore-like molecule from the methanotroph Methylosinus trichosporium OB3b, was investigated. Purified methanobactin loaded with Cu(II) exhibits a weak EPR signal probably due to adventitious Cu(II). The EPR signal intensity increases significantly upon addition of the strong oxidant nitric acid. Features of the X-ray absorption near edge spectrum, including a 1s --> 4p transition at 8985 eV, further indicate the presence of Cu(I). EXAFS data were best fit using a multiple scattering model generated from previously reported crystallographic parameters. These results establish definitively that M. trichosporium OB3b methanobactin binds Cu(I) and suggest that methanobactin itself reduces Cu(II) to Cu(I).     

Effect of interfacial liquid structuring on the coherence length in nanolubrication

The degree of interfacial structuring of n-hexadecane and octamethylcyclotetrasiloxane (OMCTS) was measured within a nanometer boundary regime to silicon surfaces. Boundary-layer effects on lubricating sliding (in terms of a thermodynamic stress activation parameter) and the layer thickness were determined by scanning force microscopy. A 2.0+/-0.3 nm thick, entropically cooled layer was found for n-hexadecane. Measurements on spherically shaped OMCTS molecules exhibited only an interfacial "monolayer," and identified the molecular shape of n-hexadecane responsible for augmented interfacial structuring. Interfacial liquid structuring was found to reduce friction.     

An extremely stable open-framework metal-organic polymer with expandable structure and selective adsorption capability

A novel porous framework polymer with expandable structure, over 8% volume expansion upon inclusion, has been characterized.     

Unusually long cooperative chain of seven hydrogen bonds. An alternative packing type for symmetrical phenols

Conformational flexibility in a symmetrical tris-phenol leads to close packed structures that are also characterised by an extended though finite cooperative chain of hydrogen bonds.     

The reaction mechanism of xanthine oxidase: evidence for two-electron chemistry rather than sequential one-electron steps

Current research on xanthine oxidase has favored a mechanism involving base-catalyzed proton abstraction from a Mo-OH group, allowing nucleophilic attack on the substrate and hydride transfer from the substrate to Mo=S group in the active site. During the course of this reaction mechanism, the molybdenum redox cycles from MoVI to MoIV, with reoxidation of the MoIV speices to form the EPR active MoV intermediate. However, it has also been suggested that the reaction occurs in two subsequent one-electron steps. We have determined kinetic parameters kred and kred/Kd for a variety of plausible substrates as well as the one-electron reduction potentials for these substrates. Our data indicate no correlation between these kinetic parameters and their one-electron reduction potentials, as would be expected if the enzyme were using two subsequent one-electron reduction steps. Our results provide additional support to current evidence for the favored two-electron reduction mechanism.     

A new mass spectrometric method for determining the degree of labeling with heavy isotopes: The study of deuterated toluenes

A new method of general applicability for determining the percentage deuterium labeling in organic compounds is described. It uses the heights of ‘metastable peaks’ in the mass spectrum to determine the relative amounts of deuterated and undeuterated species. The method is illustrated by describing the analysis of mixtures of toluene-o-d₁ and toluene, of toluene α-d₁ and toluene, and of toluene-2,6-d₂, toluene-o-d₁ and toluene.     

Interesting behavior of alpha,beta-unsaturated oximes in intramolecular [4 + 2] cycloaddition reactions

[structure: see text] Intramolecular [4 + 2] cycloaddition using alpha,beta-unsaturated oximes was explored. The reactions proceeded under unusually facile conditions to furnish the nitrones. The latter were subsequently reacted with DMAD to afford [3 + 2] cycloaddition products.     

Interassociates of Monogenic Semigroups

Given a monogenic semigroup, (S, ·) , we characterize all interassociates of (S, ·) . We determine necessary and sufficient conditions under which an interassociate of (S, ·) is isomorphic to (S, ·) . Finally, we find necessary and sufficient conditions under which two interassociates of (S, ·) are isomorphic.     

11-W average power Ti:sapphire amplifier system using downchirped pulse amplification

We demonstrate a high-power laser system that employs a new scheme in which pulses with negative chirp are amplified and then recompressed by dispersion in a block of transparent material. This scheme has significant advantages for amplification of intermediate energy pulses at high average power, including insensitivity to small misalignments of the pulse compressor, elimination of compressor gratings and their thermal loading issues, low compressor energy and bandwidth throughput losses, and a simplified optical design. Using this scheme, we demonstrate what we believe is the highest-average-power single-stage Ti:sapphire amplifier system with 11-W compressed output.