Regioselective N-vinylation of cyclic thionocarbamates through a vinyl bis-sulfone methodology

A vinyl bis-sulfone Michael type approach towards heteroatom vinylation was applied on nitrogen derivatives. Cyclic thionocarbamates--mainly 1,3-oxazolidine-2-thiones--were converted into their N-vinyl counterparts; the procedure proved particularly efficient in the case of carbohydrate-derived complex structures.     

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.     

Long-term stability of InP MIS devices

Room-temperature bias stress measurements were performed on n-type InP MIS capacitors. A wide range of interface passivation processes and gate dielectrics was investigated. A generally observed behaviour under positive bias stress is a slow trapping - fast detrapping consistent with a trap distribution in the interfacial layer above the conduction band edge of InP. Large variations both in the magnitude and in the time dependence of the flat-band voltage shift ΔV_FB are observed. We discuss these drift behaviours in terms of interface traps - rather than bulk dielectric traps - in relation with the physico-chemical properties of the interface. It is shown that devices based on InP treated by annealing under arsenic pressure and controlled oxidation exhibit a very good stability. For any passivation procedure, the drift is strongly diminished if the device is stressed with AC voltage compared to DC voltage.     

Vibrational EELS studies of CO chemisorption on clean and carbided (111), (100) and (110) nickel surfaces

Room temperature adsorption of CO on bare and carbided (111), (100) and (110) nickel surfaces has been studied by vibrational electron energy loss spectroscopy (EELS) and thermal desorption. On the clean (100) and (110) surfaces two configurations of CO adsorbed species, namely “terminal” and bridge bonded CO, are observed simultaneously. On Ni(111), only two-fold sites are involved. The presence of superficial carbon lowers markedly the bond strength of CO on Ni(111)C and Ni(110)C surfaces, while no adsorption has been detected on the Ni(100)C surface. Moreover, on the carbided Ni(110)C surface, the adsorption mode for adsorbed CO is changed with respect to the clean surface; only “terminal” CO is then observed.     

Weak collision effects: Non-steady-state thermal unimolecular reactions

Bench-mark calculations for non-steady-state thermal systems are presented. Although the equations and calculations were modeled for the isomerization of cyclopropane in the single-pulse shock tube, the results are qualitatively and semiquantitatively correct for any experimental technique in which a finite time is required to energize the reactant to the reaction temperature. A useful parameter in describing this nonequilibrium behavior is the induction time τ₉₅; the log of τ₉₅ is linearly related to the collision frequency ω. For the model cyclopropane system a steady state is reached in ～1 msec when ω ≈ 10⁸ sec^?1 and T ≈ 1500 K.     

Experimental and modeling study of Newtonian and non-Newtonian fluid flow in pore network micromodels

The in situ rheology of polymeric solutions has been studied experimentally in etched silicon micromodels which are idealizations of porous media. The rectangular channels in these etched networks have dimensions typical of pore sizes in sandstone rocks. Pressure drop/flow rate relations have been measured for water and non-Newtonian hydrolyzed-polyacrylamide (HPAM) solutions in both individual straight rectangular capillaries and in networks of such capillaries. Results from these experiments have been analyzed using pore-scale network modeling incorporating the non-Newtonian fluid mechanics of a Carreau fluid. Quantitative agreement is seen between the experiments and the network calculations in the Newtonian and shear-thinning flow regions demonstrating that the 'shift factor,'alpha, can be calculated a priori. Shear-thickening behavior was observed at higher flow rates in the micromodel experiments as a result of elastic effects becoming important and this remains to be incorporated in the network model.