Porphyrin-based nanoporous network polymers

Network polymers exhibiting large surfaces areas (900-1000 m2g-1) are prepared by the highly efficient dibenzodioxane forming reaction between meso-tetrakis(pentafluorophenyl)porphyrin and a rigid bis(catechol) monomer.     

Phosphinoferrocenylaminophosphines as novel and practical ligands for asymmetric catalysis

[structure: see text] A new series of ligands with a novel phosphine-aminophosphine ligation design as depicted in structure 1 has been prepared on a ferrocenylethyl backbone. These BoPhoz ligands of structure 2 have afforded exceedingly high activity and enantioselectivity in the rhodium-catalyzed asymmetric hydrogenation of dehydro-alpha-amino acid derivatives, itaconic acids, and alpha-ketoesters. These air-stable ligands are readily prepared from cost-effective and non-pyrophoric intermediates.     

A hierarchy of coupled maps

A large number of logistic maps are coupled together as a mathematical metaphor for complex natural systems with hierarchical organization. The elementary maps are first collected into globally coupled lattices. These lattices are then coupled together in a hierarchical way to form a system with many degrees of freedom. We summarize the behavior of the individual blocks, and then explore the dynamics of the hierarchy. We offer some ideas that guide our understanding of this type of system. (c) 2002 American Institute of Physics.     

Diastereofacial selectivity in some 4‐substituted (X) 2‐adamantyl derivatives: electronic versus steric effects

π‐Facial selectivity data for the reduction and methylation of some 4^ax‐substituted (X) 2‐adamantanones ( 3 , Y = O) as well as the nucleophilic trapping of secondary and tertiary 4^ax‐substituted (X)‐2‐adamantyl cations ( 4 ; R = H and CH₃, respectively) and the 4‐methylene‐2‐adamantyl radical ( 8 ) are presented. The pronounced anti‐face selectivities observed for ( 3 , Y = O and 4 , R = CH₃) emphasize the importance of the steric factor as expected for systems with a strong steric bias. However, the dominant syn‐face capture of 4 (R = H) was completely unexpected and highlights a subtle interplay between steric and electronic effects. Finally, the very high anti‐face stereoselectivity for the trapping of ( 8 ) with the trimethylstannyl anion (Me₃Sn^?) is rationalized in terms of an electrostatic effect overwhelming the steric factor. Copyright © 2007 John Wiley & Sons, Ltd.     

ON THE CONVERGENCE OF THE PARABOLIC APPROXIMATION OF A CONSERVATION LAW IN SEVERAL SPACE DIMENSIONS

1.IntrodnctionWegiveaproofofthestrongconvergenceinofthesolutionoftheparabolicapproximationtowardstheentropicsolutiontothescalarconservationlawwhereuo(RN),udenotessomeapproximationofuosuchthatandthefluxfsatisfiesTheconvergenceoftheapproximatesolutions...     

Rates and mechanisms of the intermolecular cation-exchange reactions of sodium tetraphenylboron with sodium–nitrobenzene and with sodium–p-nitrobenzonitrile

The rates of the exchange of sodium ions between sodium tetraphenylborate and sodium–nitrobenzene or sodium–p-nitrobenzonitrile were measured from analysis of the line broadening effect on the ESR spectra off the paramagnetic ion pairs. The rate is significantly lower for the substituted nitro compound, and it is suggested that this reflects a difference in mechanism for the two systems.     

Dye-functionalized head-to-tail coupled oligo(3-hexylthiophenes)-perylene-oligothiophene dyads for photovoltaic applications

A series of novel donor-acceptor systems, consisting of head-to-tail coupled oligo(3-hexylthiophene)s covalently linked to perylenemonoimide, is described. These hybrid molecules, which differ by the length of the oligothiophene units from a monothiophene up to an octathiophene, were created via effective palladium-catalyzed Negishi and Suzuki cross-coupling reactions in good to excellent yields. The optical and electrochemical properties of these compounds were determined and based on this series structure-property relationships have been established which give vital information for the fabrication of photovoltaic devices. Because the synthesized perylenyl-oligothiophenes distinguish themselves by a high absorption between 300 and 550 nm and an almost complete fluorescence quenching of the perylene acceptor, they meet the requirements for organic solar cells.     

Investigating 3He diffusion NMR in the lungs using finite difference simulations and in vivo PGSE experiments

Finite difference simulations have been used to model (3)He gas diffusion in simulated lung tissue. The technique has the advantage that a wide range of structural models and diffusion-sensitizing gradient waveforms can be investigated, for which analytical methods would otherwise be virtually impossible. Results from simulations and in vivo pulsed-gradient-spin-echo (PGSE) experiments show that the apparent diffusion coefficient (ADC) is a function of diffusion time and gradient strength, and suggests diffusion is locally anisotropic. The simulations have been compared to recent work on an analytical model that characterizes lung tissue as a series of independent cylinders. The results presented may have clinical implications for (3)He ADC measurements in assessing lung diseases such as chronic-obstructive-pulmonary-disease.     

The design of bells with harmonic overtones

Musical bells have had limited application due to the presence of inharmonic partials in the lower part of their acoustic spectra. A series of bells has been designed that contains up to seven partial frequencies in the harmonic series beginning at the fundamental frequency. This was achieved by choosing geometries for finite-element analysis models in which as many purely circumferential bending modes as possible occurred at frequencies below any mode with an axial ring node. The bell models were then fine tuned using gradient projection method shape optimization and the resulting profiles were cast in silicon bronze. A range of bell geometries and timbres is analyzed using psycho-acoustic models and is discussed in relation to European carillon bells.