Decoding of complex isothermal chromatograms recovered from space missions. Identification of molecular structure

A chemometric approach, based on the study of the autocovariance function, is described to study isothermal GC chromatograms of multicomponent mixtures: isothermal GC analysis is the method of choice in space missions since it is, to date, the only method compatible with flight constraints. Isothermal GC chromatograms look inhomogeneous and disordered with peak density decreasing at higher retention times: a time axis transformation is proposed to make retention an homogeneous process so that CH2 addition in terms of an homologous series yields a constant retention increment. The time axis is transformed into a new scale based on the retention times of n-alkanes, as they are the basis of the universal Kovats indices procedure. The order introduced into the chromatogram by retention time linearization can be simply singled out by the experimental autocorrelation function (EACF) plot: if constant inter-distances are repeated in different regions of the chromatogram, well-shaped peaks are evident in the EACF plot. By comparison, with a standard mixture it is possible to identify peaks diagnostic of specific molecular structures: study of the EACF plot provides information on sample chemical composition. The procedure was applied to standard mixtures containing compounds representative of the planetary atmospheres that will be investigated in the near future: in particular, those related to Titan's atmosphere (Cassini-Huygens mission) and cometary's nucleus (Rosetta mission). The employed experimental conditions simulated those applied to GC instruments installed on space probes and landers in space missions. The method was applied to two specific investigations related to space research, i.e., a comparison of retention selectivity of different GC columns and identification of the chemical composition of an unknown mixture.     

Studies of a nickel-based single-molecule magnet

A cyclic complex [Ni(12)(chp)(12)(O(2)CMe)(12)(thf)(6)(H(2)O)(6)] (1) has been synthesised and studied (chp=6-chloro-2-pyridonate). Complex 1 exhibits ferromagnetic exchange between the S=1 centres, giving an S=12 spin ground state. Detailed studies demonstrate that it is a single-molecule magnet with an energy barrier of approximately 10 K for reorientation of magnetisation. Resonant quantum tunnelling is also observed. The field between resonances allows accurate measurement of D, which is 0.067 K. Inelastic neutron scattering studies have allowed exchange parameters to be derived accurately, which was impossible from susceptibility data alone. Three exchange interactions are required: two ferromagnetic nearest neighbour interactions of approximately 11 and 2 cm(-1) and an anti-ferromagnetic next nearest neighbour interaction of -0.9 cm(-1).     

Cyclodextrins containing an acetone bridge. Synthesis and study as epoxidation catalysts

Three cyclodextrine derivatives (6A,6D-di-O-(prop-2-one-1,3-dienyl)-alpha-cyclodextrin (1), 6-O-(prop-2-one-1-yl)-alpha-cyclodextrin (2) and 6A,6D-di-O-(prop-2-one-1,3-dienyl)-beta-cyclodextrin (3)) were synthesised and investigated as epoxidation catalysts. The three compounds were synthesised from the corresponding perbenzylated cyclodextrins which were mono- or didebenzylated in the 6-position using Sina?'s method. Reaction with NaH and methallyl chloride in the case of 2, or methallyl dichloride in the case of 1 and 3, followed by dihydroxylation, periodate cleavage and protection group removal gave the target compounds. All three compounds catalysed, in the presence of oxone, the epoxidation of a series of alkenes. Epoxidation was compared to the reaction catalysed by simple ketones and inhibition was studied.     

Liquid-crystalline octopus dendrimers: block molecules with unusual mesophase morphologies

The synthesis and the mesomorphic properties of several new main-chain liquid-crystalline dendrimers, thereafter designated as octopus dendrimers in accordance with their eight sidearms, are reported. In these dendritic systems, the arborescence is ensured by anisotropic segments, acting as branching cells with a double multiplicity, which are incorporated at every node of the dendritic architecture. In such a way, these compounds radically differ from the classical end-functionalized liquid-crystalline dendrimers, the most commonly reported systems. Following our previous report on purely homolithic systems, that is, the building blocks constituting the dendritic matrix are all identical, several heterolithic systems made of different anisotropic blocks have been prepared. The dendritic branches and corresponding dendrimers were synthesized using a modular construction. Polarized optical microscopy and X-ray diffraction studies showed that all of these new octopus dendrimers exhibit either smectic-like or columnar phases with novel morphologies, the nature of the mesophases depending on the number of terminal chains attached to the peripheral groups. The mesomorphism of these heterolithic dendrimers is discussed in terms of their intrinsic architecture and compared to the analogous homolithic octopus systems. Models for the molecular organizations within both the smectic and the columnar phases are proposed on the basis of small Bragg angle X-ray diffraction studies and are supported by molecular modelizations. Moreover, this study showed that the mesophase stability is very sensitive to the nature and to the mutual arrangement (the spatial location) of the mesogenic segments within the dendritic matrix, illustrating the intimate relationships existing between the mesomorphic properties and the molecular architecture of these dendrimers.     

Synthesis of 2-(2′,3′-dihydroxypropyl)-5-amino-2H-1,2,4-thiadiazol-3-one and 3-(2′,3′-dihydroxypropyl)-5-amino-3H-1,3,4-thiadiazol-2-one

The synthesis of two new acyclic nucleoside analogs, 2-(2′,3′-dihydroxypropyl)-5-amino-2H-1,2,4-thiadiazol-3-one (1) and 3-(2′,3′-dihydroxypropyl)-5-amino-3H-1,3,4-thiadiazol-2-one (2), is reported. The first compound, 1, was obtained by reaction of 3-chloro-1,2-propanediol with the sodium salt of 5-amino-2H-1,2,4-thiadiazol-3-one (3) in anhydrous dimethylformamide. Similarly, 5-amino-3H-1,3,4-thiadiazol-2-one (4) reacted with 3-chloro-1,2-propanediol to give 2. The thiadiazole 4 was prepared by condensation-cyclization of hydrazothiodicarbonamide (9).     

Exponential Mixing for the 3<Emphasis Type="Italic">D</Emphasis> Stochastic Navier–Stokes Equations

We study the Navier–Stokes equations in dimension 3 (NS3D) driven by a noise which is white in time. We establish that if the noise is at the same time sufficiently smooth and non-degenerate in space, then the weak solutions converge exponentially fast to equilibrium. We use a coupling method. The arguments used in dimension two do not apply since, as is well known, uniqueness is an open problem for NS3D. New ideas are introduced. Note however that many simplifications appear since we work with non degeneratenoises.     

Bismuth‐Coated Screen‐Printed Microband Electrodes for On‐Field Labile Cadmium Determination

Performances of a screen‐printed microband electrode prepared by ex situ bismuth deposition are reported. According to the low bismuth toxicity, this electrode represents an environmentally friendly alternative to mercury modified sensors, particularly for on‐field measurements. The electrochemical behaviour of the microband electrode has been studied and is in agreement with microelectrode theory before and after bismuth modification. Sensitive cadmium analysis achieved in nondeaerated and unstirred solutions leads to a detection limit of 1.3 μg L^?1 using SWASV for 120 s deposition time. This sensor has been successfully applied to a nontreated river water sample.     

Second-order elliptic integro-differential equations: viscosity solutions' theory revisited

The aim of this work is to revisit viscosity solutions' theory for second-order elliptic integro-differential equations and to provide a general framework which takes into account solutions with arbitrary growth at infinity. Our main contribution is a new Jensen–Ishii's lemma for integro-differential equations, which is stated for solutions with no restriction on their growth at infinity. The proof of this result, which is of course a key ingredient to prove comparison principles, relies on a new definition of viscosity solution for integro-differential equation (equivalent to the two classical ones) which combines the approach with test-functions and sub-superjets.     

Simulation of 2-D lateral light propagation in nematic-liquid-crystal cells with tilted molecules and nonlinear reorientational effect

In the general case the optical tensor of a nematic liquid crystal consists of nine nonzero elements, which makes it difficult to calculate light propagation in a liquid-crystal cell. For a two-dimensional (2-D) problem with TM polarization and a parallel liquid-crystal orientation where the molecules are only tilted and not twisted, the full problem can be calculated by using one magnetic field component, thus reducing the problem to a scalar one. This geometry is used to simulate the self-focusing effect which can lead to the generation of spatial optical solitary waves. This self-focusing occurs due to the optical nonlinear effect of field-induced director reorientation. Due to nondiagonal elements of the optical tensor, however, it is expected that the Poynting vector will deviate from the original propagation direction. Our simulations reveal that, in this case, the deviation will not cause the loss of the soliton-like beam propagation regime, but will rather give rise to a transverse undulating behaviour.