Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines

Herein, we report the synthesis of specific silica-supported Co/Co₃O₄ core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.     

Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

Uniform bounds under increment conditions

We apply a majorizing measure theorem of Talagrand to obtain uniform bounds for sums of random variables satisfying increment conditions of the type considered in Gál-Koksma Theorems. We give some applications.

     

Quadrilateral surface meshes without self-intersecting dual cycles for hexahedral mesh generation

Several promising approaches for hexahedral mesh generation work as follows: Given a prescribed quadrilateral surface mesh they first build the combinatorial dual of the hexahedral mesh. This dual mesh is converted into the primal hexahedral mesh, and finally embedded and smoothed into the given domain. Two such approaches, the modified whisker weaving algorithm by Folwell and Mitchell, as well as a method proposed by the author, rely on an iterative elimination of certain dual cycles in the surface mesh. An intuitive interpretation of the latter method is that cycle eliminations correspond to complete sheets of hexahedra in the volume mesh.

Although these methods can be shown to work in principle, the quality of the generated meshes heavily relies on the dual cycle structure of the given surface mesh. In particular, it seems that difficulties in the hexahedral meshing process and poor mesh qualities are often due to self-intersecting dual cycles. Unfortunately, all previous work on quadrilateral surface mesh generation has focused on quality issues of the surface mesh alone but has disregarded its suitability for a high-quality extension to a three-dimensional mesh.

In this paper, we develop a new method to generate quadrilateral surface meshes without self-intersecting dual cycles. This method reuses previous b-matching problem formulations of the quadrilateral mesh refinement problem. The key insight is that the b-matching solution can be decomposed into a collection of simple cycles and paths of multiplicity two, and that these cycles and paths can be consistently embedded into the dual surface mesh.

A second tool uses recursive splitting of components into simpler subcomponents by insertion of internal two-manifolds. We show that such a two-manifold can be meshed with quadrilaterals such that the induced dual cycle structure of each subcomponent is free of self-intersections if the original component satisfies this property. Experiments show that we can achieve hexahedral meshes with a good quality.     

Pion correlations and resonance effects in \bar{p}p annihilation to 4\pi^0 at rest

We study correlations in the exclusive reaction at rest with complete reconstruction of the kinematics for each event. The inclusive distribution is fairly flat at small invariant mass of the pion pair while a small enhancement in the double differential distribution is observed for small invariant masses of both pion pairs. Dynamical models with resonances in the final state are shown to be consistent with the data while the stochastic HBT mechanism is not supported by the present findings. Received: 26 February 2002 / Revised version: 22 July 2002 / Published online: 30 August 2002