Acetylenic and diacetylenic liquid-crystalline monomers: towards ordered conjugated polymers

Abstract

Acetylenic and diacetylenic mesomorphic monomers have been prepared in order to obtain long conjugated polymers able to give high non-linear optical hyperpolarizabilities. Here we report the synthesis of such monomers incorporating cholesteryl and methoxybiphenyl groups; their structural and thermal behaviour are described. The occurrence of mesophases in the acetylenic and diacetylenic derivatives is discussed as a function of the spacer length and of the size of the mesogen moiety. The diacetylenic derivatives containing the methoxybiphenyl groups do not exhibit any liquid-crystalline behaviour but are able to polymerize under U.V. radiation.     

Investigation of NH–π (Ph) interaction in the 1:1[α:α-N-amino]mers using 1H NMR and FTIR absorption spectroscopy

¹H NMR and FTIR experiments performed on the 1:1[α:α-N-amino]mers series let us to point out a rare NH–π interaction between the carbamidic NH of the i residue and the phenyl group of a phenylalanine residue located at i+2.     

The evolution of catalytic function

It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells.Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”.In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution.We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.     

Helium- and argon-broadening coefficients of phosphine lines in the ν2 and ν4 bands

Pressure broadening of phosphine lines by helium and argon at room temperature has been experimentally investigated by high-resolution diode-laser spectroscopy. The broadening coefficients are measured for 38 transitions of PH₃ in the ^QR branch of the ν₂ band and in the ^PP and ^RP branches of the ν₄ band. The recorded lines with J values ranging from 3 to 14 and K from 0 to 10 are located between 1062 and 1094 cm⁻¹. The retrieval of the collisional widths is carried out by fitting each spectral line with a Voigt profile, a Rautian profile and a speed-dependent Rautian profile. The latter model provides larger broadening coefficients than the Voigt model. They are also calculated on the basis of a semiclassical model involving the atom-atom Lennard-Jones potential. The theoretical results are in reasonable agreement with the experimental data and reproduce the J and K dependencies of the broadenings.     

Pinning and depinning process of an incommensurate CDW as revealed by coherent X-ray diffraction

Experiments on the coherent X-ray diffraction, and their modeling, have been performed on the Charge Density Wave (CDW) system NbSe₃. The 2k_F$2k_F$ satellite reflection associated with the CDW has been measured with respect to external dc currents. Below the threshold current, reflection displays several fringes in the transverse direction which disappear when the threshold current is exceeded. In the sliding state, the transverse satellite profile has a form of two nonsymmetric peaks, one of them being centered at the same position as below the threshold and another one being shifted. The shift of the longitudinal peak position below the threshold current and the nonsymmetric peak in the transverse direction above the threshold one is interpreted as the influence of strong linear defect like a crystal step present on the sample surface, combined with induced arrays of dislocations. Coherent X-rays provide a new access to processes in a CDW driven by an external force in a random pinning potential.     

The Contribution of Raman Scattering to the Fluorescence of the Polyene Antibiotic Amphotericin B

Fluorescence has recently been applied to the analysis of the molecular organization state of the polyene antibiotic amphotericin B (AmB) in solution or in lipid membranes. The polyene chain of AmB monomer gives rise to two fluorescence emissions; S₁(2¹A_g) → S₀(1¹A_g) between 500 and 700 nm, S₂(1¹B_u) → S₀(1¹A_g) between 400 and 500 nm. However, Raman scattering might interfere with the S₂ → S₀ emission fluorescence due to the weak fluorescence quantum yield and close proximity to the exciting lines. In fact, we show here that a change in the excitation wavelength results in a shift of three emission bands, an effect which excludes their assignment to fluorescence. These bands originate from the water Raman at 3382 cm^-1and AmB resonance Raman at 1556 and 1153 cm^-1. As a consequence, some former conclusions on the molecular organization state of AmB should be reconsidered.     

Linear and nonlinear optical properties of carbon nanotube-coated single-mode optical fiber gratings

Single-wall carbon nanotube deposition on the cladding of optical fibers has been carried out to fabricate an all-fiber nonlinear device. Two different nanotube deposition techniques were studied. The first consisted of repeatedly immersing the optical fiber into a nanotube supension, increasing the thickness of the coating in each step. The second deposition involved wrapping a thin film of nanotubes around the optical fiber. For both cases, interaction of transmitted light through the fiber core with the external coating was assisted by the cladding mode resonances of a tilted fiber Bragg grating. Ultrafast nonlinear effects of the nanotube-coated fiber were measured by means of a pump-probe pulses experiment.     

Study of a fiber-optic LAN with a distributed controller

In this paper the performance of a fiber-optic LAN with spread spectrum multiplexing is discussed from the viewpoint of transmission parameters. Two architectures are considered. The first concerns a structure with cascade-connected Y-type fiber-optic couplers. The second concerns an architecture with cascade-connected active optoelectronic repeater-coupler (ORCA) devices.     

Existence of solutions to an anisotropic phase‐field model

We consider an anisotropic phase‐field model for the isothermal solidification of a binary alloy due to Warren–Boettinger ( Acta. Metall. Mater. 1995; 43 (2):689). Existence of weak solutions is established under a certain convexity condition on the strongly non‐linear second‐order anisotropic operator and Lipschitz and boundedness assumptions for the non‐linearities. A maximum principle holds that guarantees the existence of a solution under physical assumptions on the non‐linearities. The qualitative properties of the solutions are illustrated by a numerical example. Copyright © 2003 John Wiley & Sons, Ltd.