Rheology/morphology/flow conditions relationships for polymethylmethacrylate/rubber blend

Viscoelastic behavior, phase morphology and flow conditions relationships in polymer/rubber blends have been investigated. The importance of such correlations is illustrated on polymethylmethacrylate (PMMA)/rubber blends subjected to different flow conditions both under small and large deformations. In small-amplitude oscillatory shear (the morphology does not change during the flow) the elastic modulus G of the concentrated blends shows a secondary plateau, G _p , in the low frequency region. This solid-like behavior appears for rubber particle contents beyond the percolation threshold concentration (15%). Morphological observations revealed that for concentrations higher than 15%, the particles are dispersed in a three-dimensional network-type structure.In capillary flow it was found that the network-type structure was destroyed and replaced by an alignment of particles in the flow direction. This morphological modification resulted in a decrease in both viscosity and post-extrusion swell of the blends. Morphological observations revealed that the ordered structure in the flow direction was concentrated only in the skin region of the extrudate, where the shear stress is higher than the secondary plateau, G _p . A simple kinetic mechanism is proposed to explain the observed morphology.Similarly, steady shear measurements performed in the cone-and-plate geometry revealed alignment of particles in the flow direction for shear stress values higher than G_p.Presented in part at the Symposium Recent Developments in Structured Continua Montréal (Canada) 26–28 May 1993 and at the 45th Canadian Chemical Engineering Conference, Quebec, October 15–18 (1995)     

Mean field calculation of effective permeability based on fractal pore space

Effective permeability for porous rocks is calculated using mean field theory. We make two simplifying assumptions about the internal conductances in a network representation of the porous rock: (i) Pore space is characterized by a uniform fractal scaling; (ii) the internal conductances depend only on the characteristic pore sizes. Within these approximations, it is possible to derive a simple probability density for the internal conductances which is used for calculating effective permeability. Good agreement between calculations and experimental data of permeability vs. porosity is achieved.     

Influence of biological media on the structure and behavior of ferrocene-containing cationic lipid/DNA complexes used for DNA delivery

Biological media affect the physicochemical properties of cationic lipid-DNA complexes (lipoplexes) and can influence their ability to transfect cells. To develop new lipids for efficient DNA delivery, the influence of serum-containing media on the structures and properties of the resulting lipoplexes must be understood. To date, however, a clear and general picture of how serum-containing media influences the structures of lipoplexes has not been established. Some studies suggest that serum can disintegrate lipoplexes formed using certain types of cationic lipids, resulting in the inhibition of transfection. Other studies have demonstrated that lipoplexes formulated from other lipids are stable in the presence of serum and are able to transfect cells efficiently. In this article, we describe the influence of serum-containing media on lipoplexes formed using the redox-active cationic lipid bis(n-ferrocenylundecyl)dimethylammonium bromide (BFDMA). This lipoplex system promotes markedly decreased levels of transgene expression in COS-7 cells as serum concentrations are increased from 0 to 2, 5, 10, and 50% (v/v). To understand the cause of this decrease in transfection efficiency, we used cryogenic transmission electron microscopy (cryo-TEM) and measurements of zeta potential to characterize lipoplexes in cell culture media supplemented with 0, 2, 5, 10, and 50% serum. Cryo-TEM revealed that in serum-free media BFDMA lipoplexes form onionlike, multilamellar nanostructures. However, the presence of serum in the media caused disassociation of the intact multilamellar lipoplexes. At low serum concentrations (2 and 5%), DNA threads appeared to separate from the complex, leaving the nanostructure of the lipoplexes disrupted. At higher serum concentration (10%), disassociation increased and bundles of multilamellae were discharged from the main multilamellar complex. In contrast, lipoplexes characterized in serum-free aqueous salt (Li(2)SO(4)) medium and in OptiMEM cell culture medium (no serum) did not exhibit significant structural changes. The zeta potentials of lipoplexes in serum-free media (salt medium and cell culture medium) were similar (e.g., approximately -35 mV). Interestingly, the presence of serum caused the zeta potentials to become less negative (about -20 mV in OptiMEM and -10 mV in Li(2)SO(4)), even though serum contains negatively charged entities that have been demonstrated to lead to more negative zeta potentials in other lipoplex systems. The combined measurements of zeta potential and cryo-TEM are consistent with the proposition that DNA threads separate from the lipoplex in the presence of serum, resulting in a decrease in the net negative charge of the surface of the lipoplex.     

Oxidation of 9-β-d-ribofuranosyl uric acid by one-electron oxidants versus singlet oxygen and its implications for the oxidation of 8-oxo-7,8-dihydroguanosine

Uric acid, a cellular antioxidant, undergoes oxidation in the presence of one-electron oxidants as well as singlet oxygen. In the present work, the oxidation pathways and products formed from oxidation of the uric acid nucleoside are compared to the more commonly studied uric acid free base. A wider distribution of products, including allantoin, urea, caffolide, and 5-carboxamido-5-hydroxyhydantoin nucleosides, are formed when the N9 position of uric acid is glycosylated. The oxidation pathways share some features in common with the oxidation of 8-oxo-7,8-dihydroguanosine, but the additional spectrum of products implies that the combination of oxidative and deaminative damage to guanosine may lead to a more complex set of DNA lesions than originally described.     

A new method to analyze copolymer based superplasticizer traces in cement leachates

Enhancing the flowing properties of fresh concrete is a crucial step for cement based materials users. This is done by adding polymeric admixtures. Such additives have enabled to improve final mechanicals properties and the development of new materials like high performance or self compacting concrete. Like this, the superplasticizers are used in almost cement based materials, in particular for concrete structures that can have a potential interaction with drinking water. It is then essential to have suitable detection techniques to assess whether these organic compounds are dissolved in water after a leaching process or not. The main constituent of the last generation superplasticizer is a PolyCarboxylate-Ester copolymer (PCE), in addition this organic admixture contains polyethylene oxide (free PEO) which constitutes a synthesis residue. Numerous analytical methods are available to characterize superplasticizer content. Although these techniques work well, they do not bring suitable detection threshold to analyze superplasticizer traces in solution with high mineral content such as leachates of hardened cement based materials formulated with superplasticizers. Moreover those techniques do not enable to distinguish free PEO from PCE in the superplasticizer.Here we discuss two highly sensitive analytical methods based on mass spectrometry suitable to perform a rapid detection of superplasticizer compounds traces in CEM I cement paste leachates: MALDI-TOF mass spectrometry, is used to determine the free PEO content in the leachate. However, industrial copolymers (such as PCE) are characterized by high molecular weight and polymolecular index. These two parameters lead to limitation concerning analysis of copolymers by MALDI-TOFMS. In this study, we demonstrate how pyrolysis and a Thermally assisted Hydrolysis/Methylation coupled with a triple-quadrupole mass spectrometer, provides good results for the detection of PCE copolymer traces in CEM I cement paste leachates.     

Summary of the CMS potential for the Higgs boson discovery

The European Physical Journal C - This work summarizes the studies for the Higgs boson searches in CMS at the LHC collider. The main discovery channels are presented and the potential is given for...     

Thermal stability of spin valve sensors using artificial Co/Ir based ferrimagnets

Hard-soft spin valve structures have been grown by molecular beam epitaxy on MgO(0 0 1) substrates. The hard magnetic layer consists of an artificial Co/Ir/Co ferrimagnet system (AFi), while a Fe/Co bilayer from the buffer has been used as a soft detection layer. The Fe layer has been grown at 600°C giving rise to a monocrystalline layer with a BCC structure. Consequently, this layer presents a hard and a easy magnetization axis, respectively, along the BCC [1 1 0] and the [1 0 0] directions. The AFi system presents dramatic differences after successive annealing steps up to 350°C. An increase of the GMR from 3% to 3.5% is observed after annealing at 250°C while the coercive field of the AFi and the GMR plateau are strongly reduced. After further annealing at higher temperature the GMR drops down accompanied with a strong decrease in the antiparallel alignment amount in the AFi system. Rutherford back scattering measurements have been performed to investigate the changes in the interface morphology and to correlate it to the magneto-transport properties.     

Les Systèmes B2O3?MO?MS Boracites M?S (M = Mg,Mn, Fe,Cd) et Sodalites M?S (M = Co,Zn)

In the B₂O₃? MO? MS (M = Mg, Mn, Fe, Co, Zn, Cd) systems six ternary phases have been isolated, four of them having the structure of the cubic variety of the boracite, Mg₃B₇O₁₃Cl, and two the structure of the sodalite, Na₄(SiAlO₄)₃Cl. Some properties of the new phases have been investigated.     

A microcomputer-controlled modulation technique for the detection of transient species in UV photoelectron spectroscopy

A microcomputer-controlled modulation method is described to measure UV photoelectron spectra of transient species generated in a microwave discharge. Spectra at low and high microwave power levels are simultaneously recorded and afterwards linearly combined in order to remove parent compound signals. The method is applied to discharged oxygen where the transition O₂⁺ (²Φ_u) ← O₂ (¹Δ_g) becomes visible without interference from the parent molecule O₂ (³Σ_g^?), and to discharged sulphur dioxide where SO (³Σ^?) and S (³P) photoelectron spectra are obtained free from SO₂ bands. Finally the build-up of transient bands as a function of time is recorded.     

Immobilization of dermatan sulphate on a silica matrix and its possible use as an affinity chromatography support for heparin cofactor II purification.

Dermatan sulphate (DS) is a glycosaminoglycan which catalyses specifically thrombin inhibition by a plasmatic inhibitor, Heparin cofactor II (HCII). DS was insolubilized on a silica matrix to study its interaction with HCII. The immobilization of DS was performed with a good yield on a silica previously coated with polysaccharides in order to neutralize the negatively charged silanol groups. The value of the affinity constant of insolubilized DS for HCII, measured by the adsorption isotherm, is consistent with the value obtained for soluble DS. The DS bound to the silica matrix was also tested as a chromatographic support for the purification of HCII from human plasma; the optimum conditions for HCII adsorption and desorption were determined. The eluted HCII was obtained with a good yield (21%) and with no contamination by antithrombin III, the other main plasmatic inhibitor of thrombin.