Rigid oligonaphthalenediimide rods as transmembrane anion-pi slides

We report the design, synthesis, and evaluation of rigid oligonaphthalenediimide (O-NDI) rods that are expected to act as transmembrane anion-pi slides. Studies in fluorogenic large unilamellar egg yolk phosphatidylcholine vesicles reveal that rigid O-NDI rods mediate anion-selective transport with a rare halide VI selectivity sequence (Cl- > F- > Br- > I-). This and decreasing activity, selectivity, and halide sequence with increasing positive charge of the rod termini support the occurrence of anion-pi interactions. A strong anomalous mole fraction effect in Cl-/I- mixtures is in agreement with the existence of multiple active sites along the anion-pi slide and multi-anion hopping as a mechanism of transport. The strong inverted NDI quadruple moment found by DFT calculations is in excellent agreement with these results.     

Enhanced photochemical [6π] electrocyclization within the lipophilic protein binding site

Photocyclization of N-methyldiphenylamine to N-methylcarbazole is achieved within the microenvironment provided by site I of serum albumins. Quantum yield determinations, combined with transient absorption spectroscopic detection of the dihydrocarbazole intermediate, demonstrate that protein encapsulation provides a subtle control of the kinetic parameters, leading to optimized efficiencies.     

Reactivity of nucleosides with a hydroxyl radical in non-aqueous medium

DNA damage: The reactivity of HO(.) with silylated 2'-deoxyribonucleosides was investigated in acetonitrile by means of a time-resolved technique. The obtained rate constants were in general slightly lower than those reported for the natural nucleosides in water. Analysis of the reaction mixture by UPLC-MS revealed that HO(.) attack occurred at the nucleobase (see scheme).     

Enantioselective metallo-organocatalyzed preparation of cyclopentanes bearing an all-carbon quaternary stereocenter

Enantioselective metallo-organocatalyzed carbocyclizations of formyl-alkynes have been developed. The cooperation between aminocatalysis and a chiral copper(I) complex granted access to enantio-enriched cyclopentanes through the challenging formation of all-carbon quaternary stereocenters.     

Suzuki coupling of potassium cyclopropyl- and alkoxymethyltrifluoroborates with benzyl chlorides

Efficient Csp(3)-Csp(3) Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols.     

Closed time-like curves in flat Lorentz space–times

We consider the region of closed time-like curves (CTCs) in three-dimensional flat Lorentz space–times. The interest in this global geometrical feature goes beyond the purely mathematical one. Such space–times are lower-dimensional toy models of sourceless Einstein gravity or cosmology. In three dimensions all such space–times are known: they are quotients of Minkowski space by a suitable group of Poincaré isometries. The presence of CTCs would indicate the possibility of “time machines”, a region of space–time where an object can travel along in time and revisit the same event. Such space–times also provide a testbed for the chronology protection conjecture, which suggests that quantum back reaction would eliminate CTCs. In particular, our interest in this note will be to find the set free of CTCs for , where is modeled on Minkowski space and γ is a Poincaré transformation. We describe the set free of CTCs where γ is hyperbolic, parabolic, and elliptic.     

Gender Differences in Attitudes toward Environmental Science

This study examined the role of gender in the areas of environmental education that included environmental knowledge, attitudes, behaviors, and comfort levels in the outdoors. The current study was part of a larger study designed to explore the effects of a treatment that consisted of 14 weeks of outdoor lessons conducted in the schoolyard as compared with a control group of students who had 14 weeks of traditional classroom environmental education lessons. This follow‐up study focused on gender and its effect on each of the areas studied. Researchers found significance in boys' and girls' attitudes toward the environment. Quantitative and qualitative data were used to offer an in‐depth view of students' environmental attitudes. The results from this study can have implications for science educators in an effort to capitalize on boys' and girls' interests in science to help them learn about environmental issues and to recruit both boys and girls into science careers.     

The affine deformation space of a rank two Schottky group: a picture gallery

The Margulis invariant of an affine hyperbolic element measures the signed Lorentzian displacement along the unique closed geodesic in its class. Given a group of affine transformations of Minkowski spacetime whose linear part is Schottky, the Margulis invariant is a useful tool in determining properness of its action. This paper, based on a presentation given at CGG IV Oostende 2005, describes the affine deformation space of a rank two Schottky group. Several illustrations are included, contrasting the difference between the case of a three-holed sphere and that of a one-holed torus. Paper based on a presentation given at CGG IV Oostende 2005. Attendance of the conference and the subsequent writing of this paper was made possible by an NSERC Discovery Grant.