Polymerisation anionique du methacrylate de methyle par les organoalcalins—II. Polymerisation en milieu solvant protonique et influence de la temperature sur les tacticites des polymeres

Anionic polymerization of methylmethacrylate, initiated by fluorenyl-alkali metals in amine media, gives syndiotactic polymers.With amines having high dielectric constant (NH₃ and MeA) Li⁺, Na⁺ and K⁺ give approximately the same values of differential enthalpies and entropies of activation for iso- and syndiotactic placements.With primary amines having moderate dielectric constant (5 < ? < 7), influence of the nature of the counter-ion has been observed. The syndiotacticity increases with increasing alkali cation radius.For the same ion pair, the syndiotacticity of the propagation depends on the nature of the primary amine. From the absorption peak shifts detected by u.v. spectroscopy, it has been suggested that the living carbanion is solvated by amines. Because of this solvation, the coordination bond between the carboxy group of the living chain-end and the counter-ion is weakened; the syndiotactic placement is thus favoured.The strength of the solvation phenomenon depends on the steric hindrance of the amine molecule. Differences between the stereoconfiguration propagations have been observed for the bulky cyclohexylamine and the smaller and less rigid n-butylamine and ethylamine. With iso-propylamine, the behaviour of the anionic propagation is intermediate.Finally, with free ions or loose ion pairs, the anionic propagation is not affected by solvation of the living carbanion.     

A reversible polymorphic phase change which affects the luminescence and aurophilic interactions in the gold (I) cluster complex, [mu3-S(AuCNC7H13)3](SbF6)

Crystallographic examination of [mu3-S(AuCNC7H13)3](SbF6) shows that it undergoes a reversible phase change from orthorhombic to monoclinic upon cooling. At 190 K, the structure shows that two cations self-associate to form a pseudo-octahedral array of six gold atoms connected by both intra- and interionic aurophilic interactions. On cooling, the clusters become less symmetric, and in one, the interionic Au...Au separations increase, while they decrease in the second cluster. The luminescence of crystalline [mu3-S(AuCNC7H13)3](SbF6) shows corresponding changes in emission, with two emissions of similar lifetimes but with different excitations at 77 K, but only a single emission at 298 K. In contrast, [mu3-S(AuCNC6H11)3](PF6), which has a similar structure to that of the high-temperature form of [mu3-S(AuCNC7H13)3](SbF6), does not undergo a phase change or change in its luminescence upon cooling.     

Identification by 15N refocused INADEQUATE MAS NMR of intermolecular hydrogen bonding that directs the self-assembly of modified DNA bases

15N solid-state NMR refocused INADEQUATE spectra of two lipophilic deoxyguanosine derivatives unambiguously identify different intermolecular hydrogen-bonding arrangements that are indicative of either guanine ribbon or quartet self-assembly. The observation of guanine quartet formation in the absence of metal ions is a further example that challenges the accepted dogma that quartet formation requires metal ions.     

On the Asymptotic Behavior of Solutions of Differential Systems

There are many studies on the asymptotic behavior of solutions of differential equations. In the present paper, we consider another aspect of this problem, namely, the rate of the asymptotic convergence of solutions. Let ϕ (t) be a scalar continuous monotonically increasing positive function tending to ∞ as t → ∞. It is established that if all solutions of a differential system satisfy the inequality

Any nilpotence degree occurs in mod-<Emphasis Type="Italic">p</Emphasis> cohomology rings of <Emphasis Type="Italic">p</Emphasis>-groups

Let p be an odd prime number and let n be an arbitrary positive integer. We prove that there exists a p-group whose mod-p cohomology ring has a nilpotent element H²() satisfying ⁿ0,^n+p–1=0. As a corollary, we exhibit a p-group whose mod-p cohomology ring contains an element of nilpotency degree n+1.Mathematical Subject Classification (2000): 20J06, 20D15, 55R40To Phuong and Nin     

Polymerisation du methacrylate de methyle par le chlorure de tertio-butylemagnesium en solution dans le tetrahydrofuranne—III: Parametres thermodynamiques des propagations iso- et syndiotactique en fonction de la composition du magnesien

The thermodynamics of the polymerization of methylmethacrylate have been carefully studied for various MgCl₂/tBu₂Mg ratios. Assumptions have been made on the stereospecificity of the anionic propagation of MMA. The complex behaviour of the propagation mechanisms may result from possible (donor-acceptor) equilibria between monomer and ether on the one hand, and different magnesium compounds on the other.     

Inductions électromagnétiques en relativité générale et principe de Fermat

Sans résumé Mémoire transmis par A. Lichnerowicz     

Influence of ultrasonication and Fenton oxidation pre-treatment on rheological characteristics of wastewater sludge

The effect of ultrasonication and Fenton oxidation as physico-chemical pre-treatment processes on the change of rheology of wastewater sludge was investigated in this study. Pre-treated and raw sludges displayed non-Newtonian rheological behaviour with shear thinning as well as thixotropic properties for total solids ranging from 10 g/L to 40 g/L. The rheological models, namely, Bingham plastic, Casson law, NCA/CMA Casson, IPC Paste, and power law were also studied to characterize flow of raw and pre-treated sludges. Among all rheological models, the power law was more prominent in describing the rheology of the sludges. Pre-treatment processes resulted in a decrease in pseudoplasticity of sludge due to the decrease in consistency index K varying from 42.4 to 1188, 25.6 to 620.4 and 52.5 to 317.9; and increase in flow behaviour index n changing from 0.5 to 0.35, 0.62 to 0.55 and 0.63 to 0.58, for RS, UlS and FS, respectively at solids concentration 10–40 g/L. The correlation between improvement of biodegradability and dewaterability, decrease in viscosity, and change in particle size as a function of sludge pre-treatment process was also investigated. Fenton oxidation facilitated sludge filterability resulting in capillary suction time values which were approximately 50% of the raw sludges, whereas ultrasonication with high input energy deteriorated the filterability. Biodegradability was also enhanced by the pre-treatment processes and the maximum value was obtained (64%, 77% and 73% for raw, ultrasonicated and Fenton oxidized sludges, respectively) at total solids concentration of 25 g/L. Hence, pre-treatment of wastewater sludge modified the rheological properties so that: (1) the flowability of sludge was improved for transport through the treatment train (via pipes and pumps); (2) the dewaterability of wastewater sludge was enhanced for eventual disposal and; (3) the assimilation of nutrients by microorganisms for further value-addition was increased.