Interactions in water-alcohol mixtures: Conductance of lithium picrate in solutions of water and isomeric pentanols at 25°C

Conductance measurements of lithium picrate in solutions of water in n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol have been carried out at 25°C. Ionic association and conductance were found to change with water content and with the molecular structure of the alcohols (i.e. position of the OH group and degree of branching of the alkyl chain). These results indicate that both conductance and ion pair formation are not the consequence of the simple motion of ions in the electrical field as required by the continuum model. A more realistic approach, involving the internal structure of the solvent mixtures, has been considered.     

Spin–rotation couplings: spinning test particles and Dirac field

The hypothesis of coupling between spin and rotation introduced long ago by Mashhoon is examined in the context of “1 + 3” and “3 + 1” space-time splitting techniques, either in special or in general relativity. Its content is discussed in terms of classical (Mathisson–Papapetrou–Dixon–Souriou model) as well as quantum physics (Foldy–Wouthuysen transformation for the Dirac field in an external field), reviewing and discussing all the relevant theoretical literature concerning the existence of such effect. Some original contributions are also included. Dedicated to Bahram Mashhoon for his 60th birthday.     

Long‐Lived Charge‐Transfer State Induced by Spin‐Orbit Charge Transfer Intersystem Crossing (SOCT‐ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (³CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the ³NI* state. Then the slow secondary CS (125 ns) gives the long‐lived ³CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as ¹NI*→¹CT→³NI*→³CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory.     

Long-Lived Charge-Transfer State Induced by Spin-Orbit Charge Transfer Intersystem Crossing (SOCT-ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long-lived triplet charge-transfer (³CT) state, based on the electron spin control using spin-orbit charge transfer intersystem crossing (SOCT-ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT-ISC takes 8 ns to produce the ³NI* state. Then the slow secondary CS (125 ns) gives the long-lived ³CT state (0.94 μs in deaerated n-hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as ¹NI*→¹CT→³NI*→³CT. With time-resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron-spin polarization pattern was observed for the naphthalimide-localized triplet state. Our spiro compact dyad structure and the electron spin-control approach is different to previous methods for which invoking transition-metal coordination or chromophores with intrinsic ISC ability is mandatory.     

Multistep Methods for Conservative Problems

We discuss the use of linear multistep methods for the solution of conservative (in particular Hamiltonian) problems. Despite the lack of good results concerning their behaviour, linear multistep methods have been satisfactorily used by researchers in applicative fields. We try to elucidate the requirements that a linear multistep method should fulfill in order to be suitable for the integration of such problems, relating our analysis to their use as boundary value methods. We collect a number of results obtained for the linear autonomous case and also consider some numerical tests on the Kepler problem.Work supported by GNCS and MIUR.     

Periodic unfolding and Robin problems in perforated domains

The periodic unfolding method was introduced in 2002 by D. Cioranescu et al. for the study of classical periodic homogenization. In this Note, we extend this method to perforated domains introducing also a boundary unfolding operator. As an application, we study the homogenization of some elliptic problems with Robin condition on the boundary of the holes. To cite this article: D. Cioranescu et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Isolation,Structure Determination and Synthesis of New Acetylenic Steroids from the Sponge Calyx nicaaensis

Two acetylenic steroids, cholest-5-en-23-yn-3β-ol ( 5 ) and 26,27-dinorcholest-5-en-23-yn-3β-ol ( 3 ), and another unsaturated steroidalcohol, stigmasta-5,23-dien-3β-ol ( 7 ), were isolated from the sponge Calyx nicaaensis. The structures of these two acetylenic steroids were established by synthesis. Several attempts to synthesize the marine steroids alcohol calysterol ( 1 ), with a cyclopropene-containing side chain, starting from cholest-5-en-23-yn-3β-ol are also recorded. Addition of ethyl-diazo-acetate to the triple bond was performed, but the reduction to the methyl derivative yielded decomposition products.