Fe or FeNO Catalysis? A Quantum Chemical Investigation of the [Fe(CO)3(NO)]−‐Catalyzed Cloke–Wilson Rearrangement

A quantum chemical investigation of the Bu₄N[Fe(CO)₃(NO)]‐catalyzed Cloke–Wilson rearrangement of vinyl cyclopropanes is reported. It was found that allylic C?C bond activation can proceed through a S_N2′ or S_N2‐type mechanism. The application of the recently reported intrinsic bond orbital (IBO) method for all structures indicated that one Fe?N π bond is directly involved. Further analysis showed that during the reaction oxidation occurs at the NO ligand exclusively.     

Functionalized Membranes for Photocatalytic Hydrogen Production

Functionalized vesicles for photocatalytic hydrogen production in water have been prepared by co‐embedding of amphiphilic photosensitizers and a hydrogen‐evolving catalyst in phospholipid membranes. The self‐assembly allows a simple two‐dimensional arrangement of the multicomponent system with close spatial proximity, which gave turnover numbers up to 165 for the incorporated amphiphilic cobaloxime water reduction catalyst 3 b under optimized conditions in purely aqueous solution. Superior photocatalytic activity in fluid membranes indicates that mobility and dynamic reorganization of catalytic subunits in the membrane promote the visible‐light‐driven hydrogen production. The functionalized membranes represent nanostructured assemblies for hydrogen production in aqueous solution mimicking natural photosynthesis.     

A molecular modeling study of pentanol solubilized in a sodium octanoate micelle

In order to study the structural and dynamical aspects of the solubilization process of pentanol within a sodium octanoate micelle a molecular dynamics simulation is presented. In this initial study we discuss the results and detailed insights into the interactions between sodium octanoate, pentanol, and water. The total micellar radius and the hydrophobic core radius were determined. The calculated values are in fairly good agreement with experimental results. In contrast to pure sodium octanoate micelles the aggregate with dissolved pentanol attained a more spherical shape related to the time interval of the simulation. It is clear that the results of a molecular dynamics computer simulation are always limited by its total length and the total time used for data analysis. Nevertheless, from our simulation study it turned out that a part of the pentanol hydroxyl groups were located within the micellar core and some alcohol molecules were also observed at the surface region of the micelle. The corresponding partition coefficient was calculated and agreed well with the experiment. The evaluated radial distribution functions of the sodium ions, the octanoate oxygens, and the hydroxyl hydrogens reveal details of the interface region of the micelle and the bulk phase. Additionally, it was possible to calculate the trans-to-gauche ratios of the alkyl chains and to compare these results with the simulation of a pure octanoate micelle.     

On Indecomposable and Imprimitive Modules for Finite Groups - A G-Algebra Approach

One of the most useful results in modular representation theoryof finite groups is Green's indecomposability theorem [4]. Inorder to state it in a simple form, let us fix a complete discretevaluation ring O of characteristic 0 with algebraically closedresidue field F of characteristic p0. Unless stated otherwise,all our modules will be free of finite rank over O or F, respectively.In its most popular form, Green's theorem says the following.     

Partial match retrieval

The study of partial match file designs is continued. This study is concerned with a class of file designs which properly contains theABD designs of Rivest. A new family of partial match files is presented, the worst case performance is determined, and the implementation of these files is discussed.     

Determination of the lattice vibrations of imidazole by neutron scattering

The external molecular vibrations of deuterated imidazole have been investigated at 12 K for wave vectors along the three principal directions of the Brillouin zone by neutron scattering and by Raman scattering at the zone center. A complete symmetry assignment is obtained. The dominant role of the N-H … N hydrogen bond within the intermolecular interactions is reflected in a relatively simple manner in the shape of the dispersion curves because of the chain-like arrangement of hydrogen bonds. The experiment yields directly a stretching force constant of 0.33 mdyn Å^?1 for this bond. This value is compatible with monopole-dipole and dipole-dipole interactions as major contributions to the attractive interactions of the hydrogen bond of this length (2.86 Å). Relatively strong static monopoles and dipoles are confirmed by a $\text{CNDO}\text{2}$ calculation and are consequently incorporated into the interaction model.     

Construction of universal rotations from point-to-point transformations

For a desired range of offsets, universal rotations of arbitrary flip angle can be constructed based on point-to-point rotations of I(y) with half the flip angle. This approach allows, for example, creation of broadband or bandselective refocusing pulses from broadband or bandselective excitation pulses. Furthermore, universal rotations about any axis can be obtained from point-to-point transformations that can easily be optimized using optimal control algorithms. The construction procedure is demonstrated on the examples of a broadband refocusing pulse, a broadband 120(x) degrees rotation and a z-rotation with offset pattern.