Emilie Brulé

Synthesis of biodegradable polymers from renewable resources

The vast majority of commodity materials are obtained from fossil fuels. However, many studies predict that all fossil resources will be depleted within a few centuries. Biomass represents an abundant carbon-neutral renewable resource for the production of materials. Using biomass for the production of new polymers can have both economic and environmental benefits. This review focuses on the use of biomass for the synthesis of biodegradable polymers.

Synthesis and structure-activity relationships of the first ferrocenyl-aryl-hydantoin derivatives of the nonsteroidal antiandrogen nilutamide.

We present here the first synthesis of organometallic complexes derived from the nonsteroidal antiandrogen nilutamide, bearing a ferrocenyl substituent at position N(1) or at C(5) of the hydantoin ring; for comparison, we also describe the C(5) p-anisyl organic analogue. All of these complexes retain a modest affinity for the androgen receptor. The N-substituted complexes show a weak or moderate antiproliferative effect (IC 50 around 68 microM) on hormone-dependent and -independent prostate cancer cells, while the C(5)-substituted compounds exhibit toxicity levels 10 times higher (IC 50 around 5.4 microM). This strong antiproliferative effect is probably due to a structural effect linked to the aromatic character of the ferrocene rather than to its organometallic feature. In addition, it seems connected to a cytotoxic effect rather than an antihormonal one. These results open the way toward a new family of molecules that are active against both hormone-dependent and hormone-independent prostate cancer cells.

Metal-Catalyzed Synthesis of Alternating Copolymers

The creation of polymers with a high degree of sequence and/or stereocontrol represents an exciting frontier in materials science. In order to obtain alternating polymers, coordination polymerization using well-defined metal complexes has played a leading role in the last two decades. In the following paper, we will describe selected published efforts to achieve these research goals using discrete, structurally well-characterized metal complexes.

Supported metalloporphyrin catalysts for alkene epoxidation

This review is devoted to the recent advances in the preparation of immobilised metalloporphyrins and their use as heterogeneous catalysts for alkene epoxidation. The wide range of supports, nature of attachments, and metalloporphyrins that have been reported is detailed and a comparison is made between the activities of the resulting catalysts in the epoxidation of different alkenes. The important issue of recyclability of the metalloporphyrins is also covered.

Zinc and cobalt complexes based on tripodal ligands: synthesis, structure and reactivity toward lactide.

The coordination chemistry of a series of pro-ligands ([L¹]-[L⁶]) with cobalt and zinc derivatives has been studied. All complexes have been characterized by multinuclear NMR, elemental analysis, and by single-crystal X-ray diffraction studies. Polymerization of rac-lactide takes place at 130 °C in the presence of cobalt and zinc complexes to yield polymers under solvent free conditions with controlled molecular masses and narrow polydispersities.

Supported neodymium catalysts for isoprene and rac-β-butyrolactone polymerization: modulation of reactivity by controlled grafting.

A series of hybrid materials, bearing neodymium silylamide initiating groups, have been shown to mediate isoprene polymerization when combined with alkyl aluminum activators [methylaluminoxane, AlEt(2)Cl, Al(iBu)(3)]. The surface species nature and relative distribution were correlated with isoprene polymerization activity and selectivity. This approach to stereocontrol modulation has been extended to racemic β-butyrolactone isoselective ring opening polymerization.

Functional and electrophysiological characterization of four non-truncating mutations responsible for creatine transporter (SLC6A8) deficiency syndrome

Intellectual disability coupled with epilepsy are clinical hallmarks of the creatine (Cr) transporter deficiency syndrome resulting from mutations in the SLC6A8 gene. So far characterization of pathogenic mutations of SLC6A8 has been limited to Cr uptake. The aim of our study was to characterize the electrogenic and pharmacological properties of non truncating SLC6A8 mutations identified in patients presenting variable clinical severity. Electrophysiological and pharmacological properties of four mutants (including two novel ones) were studied in X. laevis oocyte expression system. Creatine uptake was assessed with [14C]-Cr in X. laevis and patients’ fibroblasts. Subcellular localization was determined by immunofluorescence and western blot. All mutants were properly targeted to the plasma membrane in both systems. Mutations led to the complete loss of both electrogenic and transport activities in X. laevis and Cr uptake in patients’ fibroblasts. Among the Cr analogs tested, guanidinopropionate induced an electrogenic activity with the normal SLC6A8 transporter similar to creatine whereas a phosphocreatine derivative, PCr-Mg-CPLX, resulted in partial activity. SLC6A8 mutants displayed no electrogenic activity with all Cr analogs tested in X. laevis oocytes. Although the mutations altered various domains of SLC6A8 Cr uptake and electrogenic properties were completely inhibited and could not be dissociated. Besides the metabolic functions of Cr, the loss of SLC6A8 electrogenic activity, demonstrated here for the first time, may also play a role in the altered brain functions of the patients.

A joint experimental/theoretical investigation of the MMA polymerization initiated by yttrium phenoxyamine complexes

A joint experimental/theoretical study has been carried out on the putative MMA polymerization catalyzed by an yttrium isopropyloxide complex. Despite its high activity in lactone polymerization, this catalyst is found to be unreactive on methyl methacrylate (MMA) polymerization. This surprising result is rationalized using a computational approach at the DFT level. Indeed, the endothermicity of the initiation step explains this lack of reactivity. The theoretical proposal of yttrium amido complexes as catalysts allows overcoming this initiation problem.