Characterization of free radicals from vitamin K1 and menadione by 2 mm-band EPR,ENDOR and ESEEM

The anion and cation radicals of vitamin K₁ and its analog menadione were characterized using the magnetic resonance techniques of Electron Nuclear Double Resonance (ENDOR), Electron Spin Echo Envelope Modulation (ESEEM), and Electron Paramagnetic Resonance (EPR) at X-band and 2 mm-band. Theg-factor anisotropy of the radicals at 2 mm-band allow them to be distinguished from each other in the solid state. Theg-factor matrix of the radical anion of vitamin K₁ is virtually identical with that reported for the reduced A₁ acceptor in green plant photosystem I thus demonstrating that reduced A₁ is the anion radical of vitamin K₁.     

Incidence of apparent restricted diffusion in three different models of cerebral infarction

High speed magnetic resonance imaging (MRI) and short diffusion times are used to investigate the appearance of restricted diffusion in three different models of cerebral infarction. The models are: the middle cerebral artery occlusion (MCAO) model in the rat, the carotid occlusion model in the gerbil, and the Rose Bengal microvascular occlusion model in the rat. All three were investigated for 16 b-values equally spaced between 10 and 1510 s/mm² using two distinct experiments. In the ct (constant time) experiment, the diffusion time was held constant at 11.7 ms while the b-value was varied with the gradient strength. In the cg (constant gradient) experiment, the gradient strength was held constant and the b-value increased by varying the diffusion time from 4.4 to 11.7 ms. A monoexponential decay of the signal intensity with b-value in the ct experiment accompanied by nonmonoexponential (NME) decay in the cg experiment is indicative of restricted diffusion. As this phenomenon is detectable only at short diffusion times, it cannot be due to restriction by impermeable membranes, and we have thus termed this apparent restriction. For the MCAO model and the carotid occlusion model, apparent restriction was found both inside the infarct territory and in some regions outside it. No definite evidence for restriction was found for the Rose Bengal model, which was, however, only studied from 24 h post-insult.     

A Flexible, Fast, and Optimal Modeling Approach Applied to Crew Rostering at London Underground

We present a general modeling approach to crew rostering and its application to computer-assisted generation of rotation-based rosters (or rotas) at the London Underground. Our goals were flexibility, speed, and optimality, and our approach is unique in that it achieves all three. Flexibility was important because requirements at the Underground are evolving and because specialized approaches in the literature did not meet our flexibility-implied need to use standard solvers. We decompose crew rostering into stages that can each be solved with a standard commercial MILP solver. Using a 167 MHz Sun UltraSparc 1 and CPLEX 4.0 MILP solver, we obtained high-quality rosters in runtimes ranging from a few seconds to a few minutes within 2% of optimality. Input data were takes from different depots with crew sizes ranging from 30–150 drivers, i.e., with number of duties ranging from about 200–1000. Using an argument based on decomposition and aggregation, we prove the optimality of our approach for the overall crew rostering problem.     

The energy of a growing elastic surface

The potential energy of the elastic surface of an elastic body which is growing by the coherent addition of material is derived. Several equivalent expressions are presented for the energy required to add a single atom, also known as the chemical potential. The simplest involves the Eshelby stress tensors for the bulk medium and for the surface. Dual Lagrangian/Eulerian expressions are obtained which are formally similar to each other. The analysis employs two distinct types of variations to derive the governing bulk and surface equations for an accreting elastic solid. The total energy of the system is assumed to comprise bulk and surface energies, while the presence of an external medium can be taken into account through an applied surface forcing. A detailed account is given of the various formulations possible in material and current coordinates, using four types of bulk and surface stresses: the Piola-Kirchhoff stress, the Cauchy stress, the Eshelby stress and a fourth, called the nominal energy-momentum stress. It is shown that inhomogeneity surface forces arise naturally if the surface energy density is allowed to be position dependent.     

Reactions of several monosaccharide-derived alcohols with p-acetamidobenzenesulfonyl azide and DBU

Attempted diazo transfer to 1-O-(2-phenylacetyl)-2,3;5,6-di-O-isopropylidene-α-d-mannofuranose using p-acetamidobenzenesulfonyl azide (p-ABSA) and DBU as base affords 1-O-(2-diazo-2-phenylacetyl)-2,3;5,6-di-O-isopropylidene-α-d-mannofuranose in low yield along with 2,3;5,6-di-O-isopropylidene-α-d-mannofuranose, 1-azido-2,3;5,6-di-O-isopropylidene-β-d-mannofuranose, as well as the unreacted starting material. The azido sugar likely arises from α-mannofuranosyl sulfonate ester formation, through displacement of azide from p-ABSA by the sugar lactol, followed by stereospecific displacement by azide anion on the furanosyl sulfonate ester. This outcome has been studied further with the conditions being applied to several common monosaccharide derivatives. Accessible substrates afford the azido sugar in an overall one-pot alcohol-to-azide conversion, while hindered substrates yield the sulfonate esters.     

Facile synthesis of silver chalcogenide (Ag2E; E=Se, S, Te) semiconductor nanocrystals

A general, one-pot, single-step method for producing colloidal silver chalcogenide (Ag(2)E; E = Se, S, Te) nanocrystals is presented, with an emphasis on Ag(2)Se. The method avoids exotic chemicals, high temperatures, and high pressures and requires only a few minutes of reaction time. While Ag(2)S and Ag(2)Te are formed in their low-temperature monoclinic phases, Ag(2)Se is obtained in a metastable tetragonal phase not observed in the bulk.     

Nuclear coherences in photosynthetic reaction centers following light excitation

Transient electron paramagnetic resonance is used to study the secondary radical pair in plant photosystem I. Nuclear coherences are observed in the transverse magnetization at lower temperatures following light excitation. Comparative studies of deuterated and deuterated¹⁵N-substituted cyanobacteriaS. lividus indicate assignment of these coherences to nitrogen nuclei in the primary donor and deuterons in the secondary acceptor. The modulation amplitude of a deuteron matrix line, as a function of the microwave power, reveals a distinct resonance behavior. The maximum amplitude is obtained when the Rabi frequency equals the nuclear Zeeman frequency.     

New geometrical approach to Rainich-Misner-Wheeler theory

We introduce a new principal fiber bundle, the bundle of biframes, associated with the geometry of bivectors on spacetime. It is shown that the biframe bundle is a natural geometric arena for modeling the already unified theory of Rainich, Misner, and Wheeler (RMW). The structure equations for the bitorsion inherent in the biframe bundle lead to a generalization of Rainich's algebraic conditions for electromagnetic-type stress tensors which includes sources in a natural way. Besides the usual complexion vector of the RMW theory, an additional new complexion-type vector is found. The generalized algebraic conditions reduce to the usual RMW conditions in the special case of no sources.     

Steric and electronic limitations of the SRN1 reaction between p-nitrobenzylic substrates and tertiary carbanions

The S_RN1 reaction between sterically hindered p-nitrobenzylic substrates and tertiary carbanions gives C-alkylated products whose yields depend on the steric bulk of both the benzylic substrate and the carbanion, and on the nature of the groups in the carbanion.