A new approach to A,B-difunctionalisation of cyclodextrins using bulky 1,3-bis[bis(aryl)chloromethyl]benzenes as capping reagents

1,3-Bis[bis(4-tert-butylphenyl)chloromethyl]benzene and 1,3-bis[bis(4-anisyl)chloromethyl]benzene were employed as regioselective capping reagents for the preparation of C-6A,C-6B-bridged, permethylated alpha- and beta-CD derivatives; isolated yields up to 55% of proximally capped, methylated CDs were obtained, thus opening the way to the straightforward preparation of a wide range of A,B-functionalised CDs. As revealed by a single crystal X-ray diffraction study, the benzene-1,3-bis[bis(4-tert-butylphenyl)methyl] spacer is perfectly suited for A,B-capping of beta-cyclodextrin.     

Ni(N2)4 revisited: an analysis of the Ni-N2 bonding properties of this benchmark system on the basis of UV/Vis, IR and Raman spectroscopy

Matrix isolation of Ni atoms in an N2 matrix leads to the formation of Ni(N2)4. This compound, being isoelectronic with the well known Ni(CO)4, represents an important bench-mark system. It has been characterised experimentally by UV/Vis, IR and Raman spectra. The vibrational spectra give evidence for both a1 modes, three of the four t2 modes, and one of the two e modes of the Td symmetric molecule. The experimental data obtained for Ni(14N2)4 and Ni(15N2)4 were used to determine the valence force constants f(Ni-N) and f(N-N), which are compared with those derived for Ni(N2) and for the corresponding carbonyl complexes Ni(CO) and Ni(CO)4. In addition, several overtones and combination modes of Ni(N2)4 were observed for the first time, providing further valuable information about the bond properties. The data allow for the first time a direct estimate of the Ni-N2 bond energy in Ni(N2)4 (120 kJ mol(-1)), that compares with a value of 148 kJ mol(-1) determined by the same method for Ni(CO)4.     

Experimental evidence of spontaneous symmetry breaking in intracavity type II second-harmonic generation with triple resonance

We describe a spontaneous symmetry-breaking phenomenon between the intensities of the ordinary and extraordinary components of the fundamental field in intracavity type II harmonic generation. It is based on a triply resonant cavity containing a type II chi(2) crystal pumped at fundamental frequency omega0. The pump beam generates a second-harmonic mode at frequency 2omega0 that acts as a pump for frequency-degenerate type II parametric downconversion. Under operating conditions symmetric with respect to the ordinary and extraordinary components of the fundamental wave, we show a breaking of the symmetry of the intensities of these two waves.     

Suppression of radiative losses of surface polaritons on nanostructured thin metal films

The strong electromagnetic coupling between surface plasmon polariton modes on opposite interfaces of a finite thickness periodically nanostructured metal film has been studied. Surface polariton dispersion and associated electromagnetic field distributions have been analyzed. It was shown that at a frequency that corresponds to the crossing of film Bloch modes of different symmetries, the radiative losses of surface polaritons that are related to the polaritons' coupling to light during propagation on the structured surface are suppressed.     

Reconstruction method for weak-phase optical interferometry

Current optical interferometers are affected by unknown turbulent phases on each telescope. We account for this lack of phase information by introducing system aberration parameters, and we solve the image reconstruction problem by minimizing an original joint criterion in the aberrations and in the object. We validate this method by means of simulations. Tests on experimental data are under way.     

Chaotic breathers in delayed electro-optical systems

We show that in integro-differential delayed dynamical systems, a hybrid state of simultaneous fast-scale chaos and slow-scale periodicity can emerge subsequently to a sequence of Hopf bifurcations. The resulting time trace thereby consists in chaotic oscillations "breathing" periodically at a significantly lower frequency. Experimental evidence of this type of dynamics in delayed dynamical systems is achieved with a Mach-Zehnder modulator optically fed by a semiconductor laser and is subjected to a delayed nonlinear electro-optical feedback. We also propose a theoretical understanding of the phenomenon.     

Godunov-type approximation for a general resonant balance law with large data

We consider the Cauchy problem for the 2×2 nonstrictly hyperbolic system

     

Construction of some families of 2-dimensional crystalline representations

We construct explicitly some analytic families of étale (,)-modules, which give rise to analytic families of 2-dimensional crystalline representations. As an application of our constructions, we verify some conjectures of Breuil on the reduction modulo p of those representations, and extend some results (of Deligne, Edixhoven, Fontaine and Serre) on the representations arising from modular forms.Mathematics Subject Classification (2000): 11F80, 11F33, 11F85, 14F30