Preparation of 5-hydroxy-1-alkenyboronates from 1-alkynylboronates, Cp2ZrCl2/2EtMgBr, and aldehydes

1-Alkynylboronates form five-membered zirconacycles with Cp(2)ZrCl(2)/2-EtMgBr as indicated by deuterium labeling. The zirconacycles add aldehydes to form seven-membered zirconacycles. Hydrolysis of the latter provides 5-hydroxy-1-alkenylboronates in fair to good isolated yields. Both aliphatic and aromatic aldehydes undergo insertion.     

Influence of the coulomb interaction on the liquid-gas phase transition and nuclear multifragmentation

The liquid-gas phase transition is analyzed from the topologic properties of the event distribution in the observables space. A multicanonical formalism allows one to directly relate the standard phase transition with neutral particles to the case where the nonsaturating Coulomb interaction is present, and to interpret the Coulomb effect as a deformation of the probability distributions and a rotation of the order parameter. This formalism is applied to a statistical multifragmentation model and consequences for the nuclear multifragmentation phase transitions are drawn.     

Raising the Coefficient of Turbulent Diffusion in the Reaction Zone as Means To Improve Technical and Economical Parameters of Polymer Production

Use of a new type of apparatus, high-output small-size tubular turbulent reactors of mainly dif- fuser-confuser design, in very fast processes, including polymerization, is considered. The turbulent diffusion coefficient D _t and its distribution over the apparatus volume were calculated as functions of the confuser divergence angle . The calculations were confirmed by experimental data. New reactor designs for a number of processes of large-tonnage polymer production were proposed and put into practice.     

Dislocation dynamics in pulse-loaded NaCl crystals

The mean path l of freshly introduced dislocations in NaCl crystals under the effect of triangular loading pulses τ(t) is shown to depend only on the pulse amplitude τ_m and be insensitive to the rate of stress growth. The replacement of triangular pulses with trapezoidal ones with a constant-load plateau (τ=const) extension of up to 60 min only insignificantly changes the l(τ_m) dependence. The data obtained are interpreted on the basis of the concept of quasi-static relaxation in a nonequilibrium system of dislocations subject to a combined effect of time-dependent applied stresses τ(t), coordinate-dependent internal stresses τ_i(x), and “dry friction” τ_p due to the pinning of dislocations by point defects. In such a model, the l(τ_m) dependence should saturate at τ_m<2τ_p; this is in fact observed in the range of 0.2τ_m<τ_m<0.3τ_y (here, τ_y is the yield stress), which gives an estimate for the pinning stress τ_p≈0.1τ_y. Based on the model suggested, a series of experimentally confirmed predictions were obtained, e.g., a recipe of “switching-off” of anomalies. Thus, a preliminary treatment of the samples by a series of stress pulses or holding in a magnetic field, which transforms the system of fresh dislocations into a more equilibrium state, sharply decreases the density of mobile dislocations quasi-statically responding to a pulsed load. It is shown that the discussed anomalies of dislocation mobility should be observed only in sufficiently pure crystals, where , and should be absent in contaminated crystals, where τ_p ～ τ_y.     

Observations of the collapse of dilute lyotropic lamellar phases under shear flow

Experimental evidence of the collapse of dilute lamellar phases due to shear flow is presented. Two systems are used: one composed of brine and an ionic surfactant, and another composed of water, a nonionic surfactant, and cosurfactant. We observe this transition for a range of lamellar spacings and brine salinity. The results are in reasonable agreement with recent theory in which the suppression of fluctuations by shear plays an important role.     

Surface activity and thermodynamic properties of water‐soluble polyester surfactants based on 1,3‐dicarboxymethoxybenzene used for enhanced oil recovery

The surface activity and thermodynamic properties for eight low molecular weight nonionic co‐polyester (PE) surfactants have been investigated. Surface and interfacial tensions (IFT) of surfactants in aqueous solutions were measured using the spinning drop technique. From these measurements, the critical micelle concentration (CMC), the surface pressure at CMC (Y_CMC), the maximum surface concentration (Γ_max), the minimum area/molecule at the aqueous solution/air interface (A_min), the effectiveness of surface tension reduction (Π_CMC), the alkane carbon number (n_min) and the IFT at n_min (Y_min) were determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic and ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad and ΔS_ad) for these polymeric surfactants were also calculated. Structural effects on micellization and adsorption are discussed in terms of these parameters. The results show that the ΔG_ad values were more negative than ΔG_mic values for these compounds, so that they favored adsorption before the micellization process. They exhibited IFT in the order of 10⁻³ to 10⁻⁴ mN/m against the thin alkane carbon number range 6–9. This range seemed to be prefered for enhanced oil recovery. Copyright © 2000 John Wiley & Sons, Ltd.     

New notions in derived categories of local rings

In the derived category of a local commutative noetherian ring, we define irreducible chain complexes, atomic chain complexes, minimal atomic chain complexes and chain complexes having no mod m detectable homology. Also, we define nuclear chain complexes and core of chain complexes. After defining these notions, we establish the connection between them.     

Synthesis of well‐designed polymers carrying saccharide moieties via RAFT miniemulsion polymerization

Two hydrophobic vinyl saccharide monomers based on D ‐glucose and D ‐fructose were polymerized by employing the reversible addition‐fragmentation transfer (RAFT) miniemulsion polymerization technique to prepare well‐designed glycopolymers. Three dithiobenzoate‐RAFT agents [S?C(Ph)S? R], 1‐phenylethyl dithiobenzoate (PED), 2‐phenylprop‐2‐yl dithiobenzoate (PPD), and 2‐cyanoprop‐2‐yl dithiobenzoate (CPD), were used to control the growth of polymer chains. The best results were obtained in the presence of the PPD‐RAFT agent and the formed polymers have polydispersity index's (PDI) lower than 1.15. Under adequate miniemulsion polymerization conditions, a glycopolymer with PDI of 1.1 and molecular weight of 5 × 10⁴ g/mol has been successfully synthesized in a short reaction time of 100 min. Furthermore, some block copolymers containing saccharide segment with butyl or methyl methacrylate were prepared. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis, structure and magnetic properties of chiral and nonchiral transition-metal malates

Carboxylate-bridged complexes of transition metals, M(II)=Mn(II), Fe(II), Co(II), Ni(II), Zn(II), were synthesised by reaction of M(II) salts with dl-malate and L-malate under hydrothermal conditions. These complexes form four series of compounds, which have been fully characterised structurally, thermally and magnetically. The crystal structures of the new chiral compounds, [Mn(L-mal)(H(2)O)] (1), [Fe(L-mal)(H(2)O)] (2), [Co(L-mal)(H(2)O)] (3) and [Zn(L-mal)(H(2)O)] (4) as well as those of the bimetallic analogues [Mn(0.63)Co(0.37)(L-mal)(H(2)O)] (5) and [Mn(0.79)Ni(0.21)(L-mal)(H(2)O)] (6) have been solved by single-crystal X-ray diffraction. The six L-malate monohydrates crystallise in the chiral space group P2(1)2(1)2(1) and consist in a three-dimensional network of metal(II) centres in octahedral sites formed by oxygen atoms. These structures were compared to those of the chiral trihydrate compounds [Co(L-mal)(H(2)O)]2 H(2)O (7), [Ni(L-mal)(H(2)O)]2 H(2)O (8) and [Co(0.52)Ni(0.48)(L-mal)(H(2)O)]2 H(2)O (9), which exhibit helical chains of M(II) centres, and those of dl-malate dihydrates [Co(dl-mal)(H(2)O)]H(2)O (10) and [Ni(dl-mal)(H(2)O)H(2)O (11) and trihydrate [Mn(L-mal)(H(2)O)]2 H(2)O (12) highlighting the great flexibility of the coordination by the malate ligand. UV/Vis spectroscopic results are consistent with octahedral coordination geometry of high-spin transition-metal centres. Extensive magnetic characterisation of each homologous series indicates rather weak coupling interaction between paramagnetic centres linked through carboxylate bridges. Curie-like paramagnetic, antiferromagnetic, ferromagnetic or weak ferromagnetic behaviour is observed and discussed on the basis of the structural features. The bimetallic compounds 5 and 6 represent new examples of chiral magnets.     

Une formulation hybride du modèle de coque de Naghdi

We present a new version of the Naghdi model for shells with curvature discontinuities. The unknowns – the displacement and the rotation of the normal to the shell midsurface – are described respectively in Cartesian and local covariant or contravariant basis. Our purpose here is to consider a constraint-free formulation instead of the one introduced by Blouza et al. (Two finite element approximation of Naghdi?s shell model in Cartesian coordinates, SIAM J. Numer. Anal. 44 (2) (2006) 636–654), where the tangency character of the rotation is enforced by penalization or by duality. This new version enables us, in particular, to approximate by conforming finite elements the solution with less degrees of freedom compared to the method of Blouza et al.