Melt‐stable poly(1,4‐dioxan‐2‐one) (co)polymers by ring‐opening polymerization via continuous reactive extrusion

Bulk polymerization of ?‐caprolactone (CL), 1,4‐dioxan‐2‐one (PDX), and mixtures of PDX and CL was carried out by initiation with Al(O^secBu)₃ in a co‐rotating twin‐screw extruder through a fast single‐step process. Both homopolymerizations and copolymerization of PDX and CL proceed very rapidly and reach almost complete (co)‐ monomer(s) conversion as soon as 8 mol% of CL are added in the feed. Even though poly(1,4‐dioxan‐2‐one) (PPDX) is known to thermally degrade mainly through unzipping depolymerization promoted from the hydroxyl end‐groups and yielding PDX monomer, it turns out that the thermal stability of PPDX chains is substantially improved by the copolymerization of PDX with limited amounts of CL. Interestingly, DSC analysis of the so‐obtained P(PDX‐co‐CL) copolymers has demonstrated that a CL molar fraction as high as 11 mol% does not prevent the crystallization of the resulting copolymer, which retains a melting temperature close to 95°C. This last observation has been explained by the formation of a blocky‐like copolymer structure, in which short PPDX and PCL sequences are randomly distributed. POLYM. ENG. SCI., 45:622–629, 2005. © 2005 Society of Plastics Engineers.     

NMR and EPR studies of room temperature highly fluorinated graphite heat-treated under fluorine atmosphere

Semi-ionic carbon fluoride obtained by reaction of graphite with a gaseous mixture of IF₅, HF and F₂ was modified by a post-fluorination at various temperatures in the range 100-680 °C. The resulting materials were studied by ¹⁹F-NMR and EPR both at room temperature and at different experimental temperatures from 200 to 360 K and from 100 to 473 K for NMR and EPR experiments, respectively. ¹⁹F-NMR gives information about the residual intercalated iodine fluoride species (IF₅, IF₆⁻ and IF₇) such as the temperature of their removal from the host fluorocarbon matrix and their mobility into the interlayer space. The nature of the C-F bonding was investigated by ¹⁹F-NMR, MAS/¹³C-NMR, FT-IR spectroscopy and X-ray diffraction. The C-F bonding changes from semi-ionic to a mainly covalent character at a fluorination post-treatment temperature close to 450 °C. This transformation coincides with the removal of the iodine fluoride species from the host structure. The densities of the paramagnetic dangling bonds were studied by EPR; this technique allows also to investigate the local environment of the dangling bonds in the fully fluorinated samples (obtained with fluorination post-treatment temperatures higher than 450 °C). As a matter of fact, an hyperfine structure was observed for these samples; it results from interaction of the dangling bond electron with six neighboring fluorine nuclei. The role of the intercalated species (iodine fluoride compounds and HF) on the mechanisms of the extra-fluorination is also discussed.     

Adaptability of competitive electricity reforms a modular analysis

Among the competitive electricity reforms that have been implemented in Europe and the US for the last 18 years, none has “survived” over several years without major changes. Their changing nature raises the question of their adaptability. Two characteristics of reforms play a key role on their adaptation properties. Firstly, they are “modular” objects in the sense of [Baldwin, C., 2008. Where do transactions come from? Modularity, transactions, and the boundaries of firms. Industrial and Corporate Change 17 (1), 155–195]. Secondly, they are produced in an institutional process which leads to “incomplete” rules and designs [Pistor, K., Xu, C., 2003. Incomplete law. International Law and Politics 35, 931–1013]. We propose a typology of adaptations based on the framework proposed by [Williamson, O.E., 1991. Comparative economic organization: the analysis of discrete structural alternatives. Administrative Science Quarterly 36 (2), 269–296] for contracts: (1) in case of small disturbances, adaptations are realized quasi-automatically, by autonomous decisions of the institutions governing the implementation of reforms; (2) in case of middle-range disturbances, adaption is made by Coasian bargaining; (3) finally, in case of strong disturbances, or when bargaining is not feasible, the adaptation of reforms is in the hands of legislative and executive institutions [North, D.C., 2005. Le processus du développement économique. Editions d’Organisation]. These institutions can reform the reforms [Joskow, P.L., 2006. Introduction to electricity sector liberalization: lessons learned from cross-country studies. In: Sioshansi, F.P. (Ed.), Electricity Market Reform: An International Perspective. Elsevier, Amsterdam, pp. 1–32; Hogan, W.W., 2002. Electricity market restructuring: reforms of reforms. Journal of Regulatory Economics 21, 103–132]. The role of these types of adaptations in each electricity reform is a consequence of the allocation of rights to the regulator, to stakeholders and to legislative and executive institutions.     

Experimental and numerical analysis of seat belt bunching phenomenon

In current cars, loops are commonly used to redirect the webbing which reels out from the retractor to the passenger's shoulder. Some types of pillar loops, also called D-rings, lead to a non-systematic instability. The webbing, which should scroll without hindrance through the D-ring, laterally shifts, bunches and produces the overturning of the ring.     

Young-type interferences using single-electron sources and an atomic-size two-center interferometer: Dependence with interferometer parameters

We present the realization of a Young-type double-slit experiment, in which single electrons, scattering on two protons, produce interference pattern. The electrons are produced by a Auger effect, following double capture process in low He²⁺ + H₂ collisions. Well-defined oscillations are visible in the angular distribution of the electrons emitted towards the receding protons. The presence of these oscillations is a clear demonstration that an electron interferes with itself. We also discuss the dependence of the interference pattern with interference parameters, such as the electron wavelength as well as the distance between the protons when the electron is ejected.     

Synthesis,Biological Evaluation of 1,1‐Diarylethylenes as a Novel Class of Antimitotic Agents

The cytotoxic activities of 23 new isocombretastatin A derivatives with modifications on the B‐ring were investigated. Several compounds exhibited excellent antiproliferative activity at nanomolar concentrations against a panel of human cancer cell lines. Compounds isoFCA‐4 ( 2 e ), isoCA‐4 ( 2 k ) and isoNH₂CA‐4 ( 2 s ) were the most cytotoxic, and strongly inhibited tubulin polymerization with IC₅₀ values of 4, 2 and 1.5 μM , respectively. These derivatives were found to be 10‐fold more active than phenstatin and colchicine with respect to growth inhibition but displayed similar activities as tubulin polymerization inhibitors. In addition, cell cycle arrest in the G₂/M phase and subsequent apoptosis was observed in three cancer cell lines when treated with these compounds. The disruptive effect of 2 e , 2 k and 2 s on the vessel‐like structures formed by human umbilical vein endothelial cells (HUVEC) suggest that these compounds may act as vascular disrupting agents. Both compounds 2 k and 2 s have the potential for further prodrug modification and development as vascular disrupting agents for treatment of solid tumors.     

Yardstick competition: which neighbours matter?

This paper aims at testing the existence of yardstick competition by estimating a fully specified vote-function on a panel data set of 104 French local governments from 1989 to 2001. When comparing the performance of their incumbent to the one of their “neighbours”, voters might consider their close geographical neighbours but also the nearby cities that are similar according to some socio-economic characteristics such as population size. The estimation results show that voters sanction their incumbent if their own local housing tax is high. Moreover, we find that voters reward their incumbent when neighbouring cities that are similar in terms of demographic characteristics have high local taxes.     

Gas migration properties through a bentonite/argillite interface

Among diversified industrial uses, see for instance Koch [Koch, Appl. Clay Sci., (21) 2002], and following positive in situ experiments, compacted bentonite blocks are potential candidates for sealing nuclear waste repositories, thanks to their swelling ability in a wet environment.As requested by Andra (French Agency for Nuclear Waste Management) and complementarily to in situ experiments, an original experimental laboratory set-up was designed in order to reproduce the introduction and swelling of bentonite plugs inside an argillite host rock. Once the argillite/bentonite interface is established, an increase in storage tunnel gas pressure is simulated and the interface gas migration pressure (or gas critical pressure) is evaluated. More precisely, a first experimental set-up provides bentonite swelling pressure and kinetics (i.e. mainly hydraulic cut-off, time to reach asymptotic swelling pressure and value of asymptotic swelling pressure) at given initial compaction and saturation rate. This phase is preparatory to reproducing the introduction and subsequent swelling of a bentonite plug inside the argillite host rock, which uses a similar test rig. Experimental results of water permeability and gas critical pressure are provided for MX80 compacted bentonite associated to Bure Callovo-Oxfordian argillite.