Synthesis of the trans-fusarinine scaffold

The trans-fusarinine backbone is a common feature encountered in many fungal siderophores. This monomer is notably the structural base of N^α-methyl coprogen B and dimerumic acid. Both siderophores are known to be secreted by Scedosporium apiospermum, an emerging pathogenic fungus studied for its high involvement in invasive infections of immunocompromised patients. The strategy developed here for the synthesis of the trans-fusarinine scaffold relies on the preparation of both N-hydroxyornithine and 3-anhydroxymevalonic acid subunits starting from l-ornithine and 3-butyn-1-ol, respectively. The coupling of these two building blocks led to the expected protected backbone.     

High-pressure NMR study of water exchange on magnetic resonance imaging contrast agents

Abstract

The knowledge of water exchange reaction mechanism in aqueous solutions of Gd³⁺ polyaminocarboxylates is important for the understanding of the relatively slow water exchange rates measured for these complexes. Variable ressure measurements show a change of mechanism from associatively activated on [Gd(H₂O)₈]³⁺ and [Gd(PDTA)(H₂O₂)₂]^? to probably limiting dissociative on the MRI contrast agents [Gd(DOTA)(H₂O)]^?, [Gd(DTPA)(H₂O)]^2? and [Gd(DTPA-BMA)(H₂O)].     

Macromolecule Loading into Spherical,Elliptical, Star‐Like and Cubic Calcium Carbonate Carriers

We fabricated calcium carbonate particles with spherical, elliptical, star‐like and cubical morphologies by varying relative salt concentrations and adding ethylene glycol as a solvent to slow down the rate of particle formation. The loading capacity of particles of different isotropic (spherical and cubical) and anisotropic (elliptical and star‐like) geometries is investigated, and the surface area of such carriers is analysed. Potential applications of such drug delivery carriers are highlighted.     

Kinetic study of nickel(II) complexation by pteroylglutamic acid

The kinetics of the complexation of NiII by pteroylglutamic acid have been studied in the 545 ∘C range, the ionic strength (0.6 M) being regulated with KNO3, in the 5.5–7.0pH range, using the stopped-flow method. Under the experimental conditions two processes were observed. The faster process was detected in the millisecond range and is associated with the reaction between NiII and the ligand. The slower is observed within a few seconds. Complementary equilibrium studies were made at 25 ∘C. The results are consistent with the formation of a 1:1 complex between the reactants, and a mechanism is proposed to account for the observed behaviour. Equilibrium constants for the NiII plus pteroylglutamic acid system, as well as activation parameters, are reported. This revised version was published online in June 2006 with corrections to the Cover Date.     

Chemical kinetics at high pressure

Abstract

Numerous studies have demonstrated the importance to include pressure as a kinetic parameter in the elucidation of inorganic reaction mechanisms. These studies have specially led to a better understanding and a systematic classification of solvent exchange and ligand substitution reactions of octahedral complexes of transition metal elements. The mechanistic picture for substution reactions on square planar complexes is well established and involves a concurrent bimolecular attack by solvent and the nucleophile on the substrate with a considerable discrimination among different entering groups. The search for factor promoting the conversion of the normal associative mode of activation into a dissociative process has then attracted much attention. Two attempts to induce dissociation, as studied by high-pressure NMR, are presented: one is to prevent the formation by means of sterically hindered ligands, the other one is to promote bond weakening at the leaving group.     

Engineering of a two-step purification strategy for a panel of monoclonal immunoglobulin M directed against undifferentiated human embryonic stem cells

A two-step purification strategy comprising of polyethylene glycol (PEG) precipitation and anion-exchange chromatography was developed for a panel of monoclonal immunoglobulin M (IgM) (pI 5.5–7.7) produced from hybridoma cultures. PEG precipitation was optimized with regards to concentration, pH and mixing. For anion-exchange chromatography, different resins were screened of which Fractogel EMD, a polymer grafted porous resin had the highest capacity. Despite its significantly slower mass transfer, the binding capacity was still higher compared to a convection driven resin (monolith). This purification strategy was successfully demonstrated for all 9 IgMs in the panel. In small scale most antibodies could be purified to >95% purity with the exception of two which gave a lower final purity (46% and 85%). The yield was dependent on the different antibodies ranging from 28% to 84%. Further improvement of recovery and purity was obtained by the digestion of DNA present in the hybridoma supernatant using an endonuclease, benzonase. So far this strategy has been applied for the purification of up to 2 l hybridoma supernatants.     

Optimization of capacity expansion planning for gas transportation networks

This paper presents techniques for solving the problem of minimizing investment costs on an existing gas transportation network. The goal of this program is to find, first, the optimal location of pipeline segments to be reinforced and, second, the optimal sizes (among a discrete commercial list of diameters) under the constraint of satisfaction of demands with high enough pressure for all users.     

Kinetics of partly diffusion-controlled reaction XXI: A simple algorithm for computing the apparent rate of reaction

Starting from Smoluchowski's hypothesis, a simple algorithm is developed in order to obtain the apparent rate constant at large values of time, t, with some physical and chemical processes, as in the case of diffusion controlled reactions. Some practical examples are illustrated, assuming nonuniform distribution function, space-dependent diffusion coefficient or short-range interaction leading to an asymptotic analytical expression of the form α + β/√t, where α and β are constants function of the system of interest.