Reactions of One-Electron-Oxidized Methionine with Oxygen: An ab initio study

A one-electron oxidation of a methionine residue is thought to be a key step in the neurotoxicity of the beta amyloid peptide of Alzheimer's disease. The chemistry of the radical cation of N-formylmethioninamide (11+) and two model systems, dimethyl sulfide (1+) and ethyl methyl sulfide (6+), in the presence of oxygen have been studied by B3LYP/6-31G(d) and CBS-RAD calculations. The stable form of 11+ has a three-electron bond between the sulfur radical cation and the carbonyl oxygen atom of the i - 1 residue. The radical cation may lose a proton from the methyl or methylene groups flanking the oxidized sulfur. Both 11+ and the resultant C-centered radicals may add oxygen to form peroxy radicals. The calculations indicate that unlike C-centered radicals the sulfur radical cation does not form a covalent bond to oxygen but rather forms a loose ion-induced dipole complex with an S-O separation of about 2.7 Å, and is bound by about 13 kJ mol-1 (on the basis of 1+ + O2). Direct intramolecular abstraction of an H atom from the C site is unlikely. It is endothermic by more than 20 kJ mol-1 and involves a high barrier (G = 79 kJ mol-1). The -to-S C-centered radicals will add oxygen to form peroxy radicals. The OH BDEs of the parent hydroperoxides are in the range of 352-355 kJ mol-1, similar to SH BDEs (360 kJ mol-1) and C-H BDEs (345-350 kJ mol-1). Thus, the peroxy radicals are oxidizing species comparable in strength to thiyl radicals and peptide backbone C-centered radicals. Each peroxy radical can abstract a hydrogen atom from the backbone C site of the Met residue to yield the corresponding C-centered radical/hydroperoxide in a weakly exothermic process with modest barriers in the range of 64-92 kJ mol-1.

Stable hydrogen isotope ratios of lignin methoxyl groups as a palaeoclimate proxy

• Stable isotope ratios of organic compounds are valuable tools for determining the geographical origin, identity, authenticity or history of samples from a vast range of sources such as sediments, plants and animals, including humans. • Hydrogen isotope ratios (d2H values) of methoxyl groups in lignin from wood of trees grown in different geographical areas were measured using compound-specificpyrolysis isotope ratio mass spectrometry analysis. • Lignin methoxyl groups were depleted in 2H relative to both meteoric water andwhole wood. A high correlation (r2=0.91) was observed between the d2 H valuesof the methoxyl groups and meteoric water, with a relatively uniform fractionation of –216±19 recorded with respect to meteoric water over a range of d2H values from –110 in northern Norway to + 20‰ in Yemen. Thus, woods from northernlatitudes can be clearly distinguished from those from tropical regions. By contrast, the d2H values of bulk wood were only relatively poorly correlated (r 2 = 0.47) with those of meteoric water. • Measurement of the d 2H values of lignin methoxyl groups is potentially a powerful tool that could be of use not only in the constraint of the geographical origin of lignified material but also in paleoclimate, food authenticity and forensic investigations.

Decay measures on locally compact abelian topological groups

Source: PROCEEDINGS OF THE ROYAL SOCIETY OF EDINBURGH SECTION A-MATHEMATICS Volume: 131 Pages: 1257-1273 Part: Part 6 Published: 2001 Times Cited: 5 References: 23 Citation MapCitation Map beta Abstract: We show that the Banach space M of regular sigma-additive finite Borel complex-valued measures on a non-discrete locally compact Hausdorff topological Abelian group is the direct sum of two linear closed subspaces M-D and M-ND, where M-D is the set of measures mu is an element of M whose Fourier transform vanishes at infinity and M-ND is the set of measures mu is an element of M such that nu is not an element of MD for any nu is an element of M \ {0} absolutely continuous with respect to the variation \mu\. For any corresponding decomposition mu = mu(D) + mu(ND) (mu(D) is an element of M-D and mu(ND) is an element of M-ND) there exist a Borel set A = A(mu) such that mu(D) is the restriction of mu to A, therefore the measures mu(D) and mu(ND) are singular with respect to each other. The measures mu(D) and mu(ND) are real if mu is real and positive if mu is positive. In the case of singular continuous measures we have a refinement of Jordan's decomposition theorem. We provide series of examples of different behaviour of convolutions of measures from M-D and M-ND.

Universal Abelian topological groups

A topological group G is said to be universal in a class K of topological groups if G is an element of K and if for every group H is an element of K there is a subgroup K of G that is isomorphic to H as a topological group. A group is constructed that is universal in the class of separable metrizable topological Abelian groups.

Huddling in groups leads to daily energy savings in free-living African Four-Striped Grass Mice, Rhabdomys pumilio

1. Free-living animals make complex decisions associated with optimizing energy and nutrient intake. In environments where ambient temperatures fall below the thermoneutral zone, homeotherms must choose whether or not to forage, how long and what to forage for, and whether or not to perform activities that conserve energy.