Anticoagulant, Antioxidant and Antitumor Activities of Heterofucans from the Seaweed Dictyopteris delicatula

In the present study, six families of sulfated polysaccharides were obtained from seaweed Dictyopteris delicatula by proteolytic digestion, followed by acetone fractionation and molecular sieving on Sephadex G-100. Chemical analyses demonstrated that all polysaccharides contain heterofucans composed mainly of fucose, xylose, glucose, galactose, uronic acid, and sulfate. The fucans F0.5v and F0.7v at 1.0 mg/mL showed high ferric chelating activity (～45%), whereas fucans F1.3v (0.5 mg/mL) showed considerable reducing power, about 53.2% of the activity of vitamin C. The fucan F1.5v presented the most prominent anticoagulant activity. The best antiproliferative activity was found with fucans F1.3v and F0.7v. However, F1.3v activity was much higher than F0.7v inhibiting almost 100% of HeLa cell proliferation. These fucans have been selected for further studies on structural characterization as well as in vivo experiments, which are already in progress.     

Electromagnetic modeling of waveguide amplifier based on Nd<Superscript>3+</Superscript> Si-rich SiO<Subscript>2</Subscript> layers by means of the ADE-FDTD method

By means of ADE-FDTD method, this paper investigates the electromagnetic modelling of a rib-loaded waveguide composed of a Nd³⁺ doped Silicon Rich Silicon Oxide active layer sandwiched between a SiO₂ bottom cladding and a SiO₂ rib. The Auxilliary Differential Equations are the rate equations which govern the levels populations. The Finite Difference Time Domain (FDTD) scheme is used to solve the space and time dependent Maxwell equations which describe the electromagnetic field in a copropagating scheme of both pumping (λ _pump = 488 nm) and signal (λ _signal = 1064 nm) waves. Such systems are characterized by extremely different specific times such as the period of electromagnetic field ~ 10^-15 s and the lifetimes of the electronic levels between ~ 10^-10s and ~ 10^-4 s. The time scaling method is used in addition to specific initial conditions in order to decrease the computational time. We show maps of the Poynting vector along the propagation direction as a function of the silicon nanograin (Si-ng) concentrations. A threshold value of 10²⁴ Si-ng m^-3 is extracted below which the pump wave can propagate so that a signal amplication is possible.     

Simulation of pH-controlled dissolution of aluminium based on a modified Scanning Electrochemical Microscope experiment to mimic localized trenching on aluminium alloys

Some constituent intermetallic (IMPs) particles at the surface of aluminium alloys are considered as preferential sites for the initiation of structural corrosion resulting in localized trenching around the particles and the surrounding Al matrix. In this work, a modified scanning electrochemical microscope (SECM) experiment was used to induce such phenomena via a local alcalinisation on 200 nm thick aluminium coatings promoting their local dissolution in an aerated 0.1 M NaCl electrolyte. The local alcalinisation was induced by the oxygen reduction reaction on the tip of a SECM which mimics the surface of an isolated IMP. From a phenomenological point of view, reproducible cylindrical damage develops in front of the platinum ultramicroelectrode (UME). Using a 2D finite element modelling to simulate the SECM experiments, the role of the local alcalinisation was validated and the calculated Al dissolution rate was found in agreement with the experimental evaluation.     

Influence of the counter-ion on the effective charge of polyacrylic acid in dilute condition

Osmotic pressure measurements were satisfactorily used to compute the effective charge of poly(acrylic) acid (PAA) at different pHs and with different monovalent and divalent counterions. This experimental method is sensitive to the osmotically active species (polymer and counterions). After correction for the polymer contribution to the total osmotic pressure (solvency and excluded volume), the remaining pressure can be attributed to the polyelectrolyte counterions and processed with Donnan and equation of state in order to compute the effective charge number per polymeric chain (Z^eff). The behavior of Z^eff against the chain concentration and pH was investigated after neutralization of PAA with LiOH, NaOH, and TMAOH. The results clearly indicate that the nature of the monovalent counterion has no effect on Z^eff leading to the conclusion that the interaction between monovalent counterions and the acrylate functionality is purely electrostatic in agreement with conductimetric and potentiometric results reported in the literature. The behavior of Z^eff against the degree of ionization of the polymer and its concentration is also in good agreement with the theoretical expectations of the theory of ionic condensation. Osmotic measurements were also used in order to understand the influence of divalent cations (Mg²⁺, Ca²⁺, Ba²⁺) on Z^eff of the sodium salt of PAA at pH 9 and at different divalent/acrylate molar ratio. All the divalent cations depress Z^eff each of one at different degrees, confirming a specific divalent/polymer interaction. The energy of hydration of cations can explain most of the observed results with divalents.     

Polyethylene-layered silicate nanocomposites prepared by the polymerization-filling technique: synthesis and mechanical properties

Polyethylene-layered silicate nanocomposites were prepared by the in situ intercalative polymerization of ethylene by the so-called polymerization-filling technique and analyzed by transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), differential scanning calorimetry, dynamic mechanical analysis and tensile testing. Non-modified montmorillonite and hectorite were first treated by trimethylaluminum-depleted methylaluminoxane before being contacted by a Ti-based constrained geometry catalyst. The nanocomposite was formed by addition and polymerization of ethylene. In the absence of a chain transfer agent, ultra high molecular weight polyethylene was produced. The tensile properties of these nanocomposites were poor and essentially independent of the nature and content of the silicate. Upon hydrogen addition, the molecular weight of the polyethylene was decreased with parallel improvement of the tensile and shear moduli, in relation to the filler content. The exfoliation of the layered silicates was confirmed by XRD analysis and TEM observation. The mechanical kneading of the molten nanocomposites resulted in the partial collapse of the exfoliated structure driven by the thermodynamic stability of the layered filler.     

Evolution of Chemistry,Morphology and Rheology of Various Polymer Systems along a Twin‐Screw Extruder

Intermeshing twin‐screw extruders have been recently identified as useful in special application niches such as the extrusion of PVC dry blends (counter‐rotating machines) and compounding operations (co‐rotating machines). Thus, it is of interest to study the mechanical and/or chemical effects that occur along the screw axis of the extruders, since they will dictate the characteristics and performance of the final material. This work aims at illustrating the usefulness of a simple experimental tool recently developed for the study of the physical, chemical and morphological evolution along the extruder of polymer based systems, data being presented and discussed for a number of composites and blends.     

State multiplicity in CSTR-separator-recycle polymerisation systems

This article continues earlier work (Comput. Chem. Eng. 24 (2000) 209) concerning the design and control of isothermal reactor-separator-recycle systems. The multiplicity behaviour of six reaction systems of increasing complexity, from one-reactant, first-order reaction to chain-growth polymerisation, is investigated. Below a critical value of the plant Damkohler number, Da<Da^cr, the only steady state involves infinite flow rates. Feasible steady states become possible if the critical value is exceeded, Da>Da^cr. For one-reaction systems, one stable steady state is born at a transcritical bifurcation. For consecutive-reaction systems, including polymerisation, a fold bifurcation can lead to two feasible steady states. Moreover, the transcritical bifurcation is destroyed when two reactants are involved. If the gel-effect is included, a maximum of four steady states are possible. When multiple steady states exist, the achievable conversion is constrained by the instability of the low-conversion branch. This has practical importance for polymerisation systems when the radicals’ quasi-steady state assumption is not valid or the gel effect is significant.     

Comparison of the wound-activated transformation of caulerpenyne by invasive and noninvasive Caulerpa species of the Mediterranean

The invasive green alga, Caulerpa taxifolia, that has spread rapidly after its introduction into the Mediterranean and the North American Pacific, reacts to wounding by transforming its major metabolite caulerpenyne (1). This wound-activated reaction involves the transformation of the bis-enol acetate moiety of 1, releasing reactive 1,4-dialdehydes. The ability to perform this transformation is found also in both the noninvasive Mediterranean C. prolifera and the invasive C. racemosa. Trapping experiments, as well as transformation of the model substrate geranyl acetate, suggest that all three investigated Caulerpa spp. rely on esterases that act upon wounding of the algae by subsequently removing the three acetate residues of caulerpenyne. The resulting reactive 1,4-dialdehyde oxytoxin 2 (9) can be identified by liquid chromatography–mass spectrometry and is unstable in the wounded tissue. Caulerpenyne transformation occurs rapidly, and severe tissue damage caused degradation of more than 50% of the stored caulerpenyne within 1 min in all three algae. Prevention of the enzymatic reaction before extraction, by shock freezing the tissue with liquid nitrogen, was used for the determination of the caulerpenyne content in intact algae. It gives about twofold higher values compared to an established methanol extraction protocol. The speed and mechanism of the wound-activated transformation, as well as the caulerpenyne content in intact tissue of invasive and noninvasive Caulerpa spp., are comparable. Thus, this enzymatic , transformation, despite being fast and efficient, is likely not the key for the success of the investigated invasive species.     

Modification of porous copolymers network based on acrylonitrile

Summary The preparation of a chelating ion-exchange network based on acrylonitrile was carried out by chemical modification with hydroxylamine. The beads of resin were synthesized by aqueous suspension copolymerization of acrylonitrile (AN), styrene (STY) and divinylbenzene (DVB). The influence of diluent used in the suspension polymerization on the structure of the resulting copolymers was evaluated. The diluents employed were heptane (HEP), toluene (TOL) and anisole (ANI). It was found that the AN incorporation into copolymer structure was dependent on the diluent used. Conversion of nitrile groups into the amidoxime was conducted by treatment with hydroxylamine under alkaline solution. The resins were characterized by apparent density, surface area, average pore diameter, elemental analysis (CHN), FTIR and optical microscopy. Based on the results obtained, it was possible to control the porosity by diluent employed in the synthesis and to modify chemically a resin containing nitrile groups by hydroxylamine reaction. Received: 6 October 2001/Revised version: 2 April 2002/ Accepted: 11 April 2002