Material order‐independent interface reconstruction using power diagrams

We have developed a new, multi‐material, piecewise linear interface reconstruction method that correctly locates the position of each material in the mesh cell and matches the required volume fractions with no material ordering required. This is different from other volume tracking interface reconstruction methods in which an improper material ordering may result in materials being incorrectly located within the cell. The new method utilizes a type of weighted Voronoi diagram, known as a power diagram, to reconstruct the interface from approximate material locations derived either from a particle model or quadrature formula. It works on structured and general polygonal grids, for an arbitrary number of materials and can be naturally extended to three dimensions. Published in 2007 by John Wiley & Sons, Ltd.     

Three-dimensional modelling of micromachined-ultrasonic-transducer arrays operating in water

We report on the 3-D modelling of periodic arrays of capacitive micromachined ultrasonic transducers (cMUTs) operating in fluid. Specific developments have been performed to model biperiodic transducer arrays and to take into account radiation into any stratified media at the front-side as well as the back-side of the device. The model is based on a periodic finite-element-analysis/boundary-element-method (FEA/BEM). It is applied to micromachined ultrasonic transducers (MUTs), based on silicon-nitride-circular-membrane arrays on a silicon substrate, and operating in water. The spectrum characteristics of MUTs excited in phase are investigated, showing that very-large-band emission is achievable as previously demonstrated by many authors. However, other contributions are also found, depending on the excitation conditions, that do not radiate in the fluid. These contributions are identified as guided modes that could generate significant cross-talk effects. The origin and the nature of these modes is analyzed to gain insight in the actual operation of MUTs.     

Self-equivalences of stable module categories

Let P be an abelian p-group, E a cyclic -group acting freely on P and k an algebraically closed field of characteristic . In this work, we prove that every self-equivalence of the stable module category of comes from a self-equivalence of the derived category of . Work of Puig and Rickard allows us to deduce that if a block B with defect group P and inertial quotient E is Rickard equivalent to , then they are splendidly Rickard equivalent. That is, Broué's original conjecture implies Rickard's refinement of the conjecture in this case. All of this follows from a general result concerning the self-equivalences of the thick subcategory generated by the trivial module. Received January 22, 1998; in final form June 23, 1998     

Modular Construction of Dynamic Nucleodendrimers

Isoguanosine‐containing dendritic small molecules self‐assemble into decameric nucleodendrimers as observed by 1D NMR spectroscopy, 2D DOSY, and mass spectrometry. In particular, apolar building blocks readily form pentameric structures in acetonitrile while the presence of alkali metals promotes the formation of stable decameric assemblies with a preference for cesium ions. Remarkably, co‐incubation of guanosine and isoguanosine‐containing nucleodendrons results in the formation of decameric structures in absence of added salts. Further analysis of the mixture indicated that guanosine derivatives facilitate the formation, but are not involved in decameric structures; a process reminiscent of molecular crowding. This molecular system provides a powerful canvas for the rapid and modular assembly of polyfunctional dendritic macromolecules.     

Reactions of silyl-stabilised sulfur ylides with organoboranes: enantioselectivity, mechanism, and understanding

The reaction of trimethylsilyl-substituted sulfonium ylides with organoboranes (Ph(3)B, Et(3)B) has been studied and although homologated products were obtained in good yield (after oxidation to the corresponding alcohols), the enantiomeric excesses were low with our camphor-based chiral sulfide (up to 40% ee, cf. corresponding phenyl-substituted sulfonium ylides gave >95% ee). Cross-over experiments were conducted to ascertain the nature of this difference in selectivity. Thus, aryl- and silyl-substituted sulfonium ylides (1 equiv.) were (separately) reacted with Et(3)B (1.5 equiv.) followed by Ph(3)B (1.5 equiv.) The experiments were repeated changing the order of addition of the two boranes. It was found that the aryl-substituted sulfonium ylide only trapped the first borane that was added indicating that ate complex formation was non-reversible and so was the selectivity determining step. In contrast the silyl-substituted sulfonium ylide only trapped Ph(3)B (it is more reactive than Et(3)B) indicating that ate complex formation was reversible and so 1,2-migration was now the selectivity determining step. The reactions have been studied computationally and the experimental observations have been reproduced. They have further revealed that the cause of reversibility in the case of the silyl-substituted sulfonium ylides results from ate complex formation being less exothermic and a higher barrier to 1,2-migration.     

A novel small molecule that alters shelterin integrity and triggers a DNA-damage response at telomeres

We describe a novel synthetic small molecule which shows an unprecedented stabilization of the human telomeric G-quadruplex with high selectivity relative to double-stranded DNA. We report that this compound can be used in vitro to inhibit telomerase activity and to uncap human POT1 (protection of telomeres 1) from the telomeric G-overhang. We also show that the small molecule G-quadruplex binder induces a partial alteration of shelterin through POT1 uncapping from telomeres in human HT1080 cancer cells and the presence of gammaH2AX foci colocalized at telomeres.     

Triarylpyridines: a versatile small molecule scaffold for G-quadruplex recognition

The triarylpyridines are potent G-quadruplex ligands that are highly discriminating against duplex DNA and show promising selectivity between intramolecular quadruplexes.     

Cyclen-based bismacrocycles for biological anion recognition. A potentiometric and NMR study of AMP, ADP and ATP nucleotide complexation

The behaviour of two cyclen-based bismacrocycles linked by aromatic spacers as receptors of adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) anions is explored. The two bismacrocycles differ from one another by the nature of their spacers, which are respectively 1,3-dimethylbenzene (BMC), or 2,6-dimethylpyridine (BPyC). Potentiometric investigations supported by (1)H and (31)P NMR measurements were performed over a wide pH range to characterize and understand the driving forces implicated in the supramolecular assemblies. A comparison is also carried out with the results presented in this work and those obtained previously with these two ligands and inorganic phosphates. The comparison exhibits the importance of pi-stacking capability of the organic anions in the binding and hydrogen-bonding network. For BPyC, NMR studies highlight two coordination schemes depending on the protonation of the nitrogen atom of the pyridinyl spacer, which acts in acidic media as a supplementary anchoring point.     

Palladium-catalyzed C-allylation of benzoins and an NHC-catalyzed three component coupling derived thereof: compatibility of NHC- and Pd-catalysts

A large range of benzoins was successfully applied as C-nucleophiles in the palladium-catalyzed allylic alkylation with several allyl acetates, resulting in functionalized tertiary homoallylic alcohols. A number of unsymmetrical benzoins can be coupled with high levels of regio- and chemoselectivity. Finally, the challenging compatibility of free N-heterocyclic carbenes with a palladium catalyst has been utilized in a number of metal- and organocatalyzed three-component coupling reactions.