Generalized Jansen's perturbation theory for exchange interactions between aroms or molecules

The theory for treating exchange interactions between atoms or molecules as a perturbation, which was first propoed by Jansen, is extended to general cases by the use of the group algebraic technique and a nonorthogonal basis set. As a result, a new expresion for the perturbation ket and energy of each order is obtained. A comparion of the expression with those presented by other investigators is made.     

Surface reaction of alkynes and alkenes with H-Si(111): a density functional theory study

Recent experiments on the addition of alkene and alkyne molecules to H-terminated silicon surfaces have provided evidence for a surface chain reaction initiated at isolated Si dangling bonds and involving an intermediate carbon radical state, which, after abstraction of a hydrogen atom from a neighboring Si-H unit, transforms into a stable adsorbed species plus a new Si dangling bond. Using periodic density functional theory (DFT) calculations, together with an efficient method for determining reaction pathways, we have studied the initial steps of this chain reaction for a few different terminal alkynes and alkenes interacting with an isolated Si dangling bond on an otherwise H-saturated Si(111) surface. Calculated minimum energy pathways (MEPs) indicate that the chain mechanism is viable in the case of C(2)H(2), whereas for C(2)H(4) the stabilization of the intermediate state is so small and the barrier for H-abstraction so (relatively) large that the molecule is more likely to desorb than to form a stable adsorbed species. For phenylacetylene and styrene, stabilization of the intermediate state and decrease of the H-abstraction barrier take place. While a stable adsorbed species exists in both cases, the overall heat of adsorption is larger for the alkyne molecules.     

Chiral norbornadienes as efficient ligands for the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds

[reaction: see text] A rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds has been developed. While phosphorus-based chiral ligands fail to induce high stereoselectivity, chiral norbornadiene ligands have proved to be uniquely effective to achieve high enantioselectivity in these 1,4-addition reactions.     

Oligocyclization of 2-(hydroxymethyl)pyrroles with electron-withdrawing groups at beta-positions: formation and structural elucidation of porphyrinogens and hexaphyrinogens

Acid-catalyzed oligomerization of 2-(hydroxymethyl)pyrroles bearing C6F5, 2,6-Cl2C6H3, CF3 and CO2Et groups at beta-positions was examined. The reaction of ethyl pyrrole-3-carboxylates gave a mixture of oligomers and type I isomers of porphyrinogens and hexaphyrinogens were isolated when the other beta-substituents were sufficiently bulky, for example, mesityl, 2,6-Cl2C6H3 and C6F5 groups. On the other hand, the pyrroles having other electron-withdrawing groups afforded porphyrinogens as the only isolable products.     

A chiral chelating diene as a new type of chiral ligand for transition metal catalysts: its preparation and use for the rhodium-catalyzed asymmetric 1,4-addition

As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.     

The role of mammalian autophagy in protein metabolism

Autophagy is in principle a non-selective degradation system within cells, which is conserved in all eukaryotic cells. Autophagy is usually suppressed at low levels but can be upregulated during periods of nutrient starvation, which facilitates cell survival. In addition to this fundamental role, basal autophagy was recently revealed to be important for constitutive turnover of intracellular proteins and organelles. Autophagy has been considered to be involved also in presentation of endogenous antigens, degradation of invasive bacteria, tumor suppression, cell death and development. This review will discuss the biological significance of autophagy, particularly focusing on its implications in protein metabolism in mammals.     

First principles calculations of the adsorption of acetylene on the Si(0 0 1) surface at low and full coverage

The adsorption of acetylene on the Si(0 0 1)-c(2 × 4) surface at low and full coverage is studied by first principles density functional calculations using the generalized gradient approximation. For a single acetylene molecule, the most stable configuration corresponds to the di-σ site, on-top of a silicon dimer. This configuration is 0.36 eV more stable than the end-bridge site between two adjacent Si dimers. However, if there are two acetylene molecules, the paired end bridge configuration becomes the most stable. We have also studied the kinetics of the adsorption of a single acetylene molecule. Our calculations show that the reaction is barrier-free for adsorption in the di-σ configuration, while there is an energy barrier of 0.19 eV for adsorption in the end-bridge site. At monolayer coverage, the most stable configuration corresponds to acetylene molecules in the pair-end bridge configuration, in agreement with previous calculations. We have found a noticeable coverage dependence only for the end-bridge site, but not for the di-σ. Our results show that to have an accurate picture of the adsorption of acetylene on the Si(0 0 1) surface, a large unit cell is needed.     

Design of an Optimal Grid for Finite Element Methods

ABSTRACT Finite element solutions of improved quality are obtained by optimizing the location of nodes of the finite element grid, while keeping the number of degrees of freedom fixed. The formulation of the grid optimization problem is based on the reduction of error associated with interpolation of the exact solution, using functions from the finite element space. Element sizes are selected as design variables: length in R1 and area in R2. Analytically derived optimality conditions are presented and an approximation to these conditions is introduced to obtain a set of operationally useful equations that can be used as guidelines for construction of improved grids. Example problems are given for illustration.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.