Original Multivalent Gold(III) and Dual Gold(III)-Copper(II) Conjugated Phosphorus Dendrimers as Potent Antitumoral and Antimicrobial Agents.

Original metallophosphorus dendrimers (generation 3, 48 terminal groups) have been prepared via the complexation of phosphorus dendrimers bearing imino-pyridino end groups with Au(III) or with both Au(III) and Cu(II). The complexation of the dendrimer with Au(III), leading to 1G3-[Au48][AuCl4]48, strongly increased the antiproliferative activities against both KB and HL-60 tumoral cell lines, showing IC50s in the low nanomolar range. It can be noticed also that this gold conjugated phosphorus dendrimer displayed low activity on the quiescent cell line EPC versus its potent antiproliferative activity against actively dividing cells. In order to evaluate the potential synergistic effect between Au(III) and Cu(II) and the influence of the number of Au(III) moieties on the surface of dendrimer against the proliferative activities, nine other original dendrimers with several surface modifications have been prepared. Whatever the number of Au(III) moieties introduced on the surface of dendrimers, all the dendrimers prepared displayed similar potency (nanomolar range) to 1G3-[Au48][AuCl4]48 against KB and HL60. In marked contrast synergistic effects on the antimicrobial activity of some of these phosphorus dendrimers are observed when both Au(III) and Cu(II) are present on the dendritic structure.

Synthesis of onion-peel nanodendritic structures with sequential functional phosphorus diversity.

The preparation of novel families of phosphorus-based macromolecular architectures called "onion peel" phosphorus nanodendritic systems is reported. This construct is based on the versatility of methods of synthesis using several building blocks and on the capability of these systems to undergo regioselective reactions within the cascade structure. Sustainable metal-free routes such as the Staudinger reaction or Schiff-base condensation, involving only water and nitrogen as byproducts, allow access to several dendritic macromolecules bearing up to seven different phosphorus units in their backbone, each of them featuring specific reactivity. The presence of the highly aurophilic P=N-P=S fragment enables selective ligation of Au(I) within the dendritic framework.

Palladium-catalyzed direct C7-arylation of substituted indazoles.

A novel direct C7-arylation of indazoles with iodoaryls is described using Pd(OAc)2 as catalyst, 1,10-phenanthroline as ligand, and K2CO3 as base in refluxing DMA. Direct C7-arylation of 3-substituted 1H-indazole containing an EWG on the arene ring gave the expected products in good isolated yields. In addition, a one-pot Suzuki-Miyaura/arylation procedure leading to C3,C7-diarylated indazoles has been developed.

Review on palladium-containing perovskites: synthesis, physico-chemical properties and applications in catalysis.

This review reports on the recent advances in the synthesis and physico-chemical properties of palladium-containing perovskites. Initially, the perovskite structure is briefly reviewed, then palladium-containing perovskites synthesis and physico-chemical properties are detailed. The applications of palladium-containing perovskites in catalysis; namely, NO reduction, methane combustion, methanol as well as ethanol oxidation, are briefly highlighted. The involvement and the important contribution of palladium-containing perovskites in cross-coupling reactions, especially Suzuki-Miyaura, Sonogashira, Ulmann and Grignard, are discussed.

Recent progress in chitosan bio-based soft nanomaterials.

Polysaccharides are a new class of pervasive biopolymers that display many advantages including wide availability, sustainability, inherent inclusion of chemical functionality, biocompatibility and biodegradability. Current efforts are focused on the catalytic transformation of these macromolecules into fuels and platform chemicals. However, there is growing interest in using biopolymers directly to create functional materials. Particularly, the ability of some polysaccharides to form physical and chemical porous hydrogels has opened new avenues for material synthesis and has been the driving force for rethinking the strategies used to create value-added nanomaterials from naturally available biomass. Among them, chitosan is on the rise due to the presence of amino groups on the polymer backbone that distinguishes it as a unique natural cationic polymer. This contribution sheds light on the opportunities offered by engineering the secondary structure of chitosan fibrillar hydrogels. The optimization and stabilization of the open framework structure of these soft-materials are crucial to designing novel functional hybrid materials, dispersed chitosan-metal nanoparticles and hierarchical porous inorganic materials.

Original multivalent copper(II)-conjugated phosphorus dendrimers and corresponding mononuclear copper(II) complexes with antitumoral activities.

Novel multivalent copper(II)-conjugated phosphorus dendrimers and their corresponding mononuclear copper(II) complexes were synthesized, characterized, and screened for antiproliferative activity against human cancer cell lines. Selected copper ligands were grafted on the surface of phosphorus dendrimers of generation G(n) (n = 1 to 3): N-(pyridin-2-ylmethylene)ethanamine for dendrimers 1G(n), N-(di(pyridin-2-yl)methylene)ethanamine for dendrimers 2G(n), and 2-(2-methylenehydrazinyl)pyridine for dendrimers 3G(n). The results indicated that the most potent derivatives are 1G(n) and 1G(n)-Cu versus 2G(n), 2G(n)-Cu, and 3G(n), 3G(n)-Cu. A direct relationship between the growth inhibitory effect and the number of terminal moieties or the amount of copper complexed to the dendrimer was observed in copper-complexed 1 series and noncomplexed 1 series. These data clearly suggested that cytotoxicity increased with the number of terminal moieties available and was boosted by the presence of complexed Cu atoms. Importantly, no cytotoxic effect was observed with CuCl2 at the same concentrations. Finally, 1G3 and 1G3-Cu have been selected for antiproliferative studies against a panel of tumor cell lines: 1G3 and 1G3-Cu demonstrated potent antiproliferative activities with IC50 values ranging 0.3-1.6 µM. Interestingly, the complexation of the terminal ligands of 1G3 dendrimers by copper(II) metal strongly increased the IC50 values in noncancer cells lines referred to as "safety" cell lines.

Chitosan bio-based organic-inorganic hybrid aerogel microspheres.

Recently, organic-inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface-reactive organic-inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self-standing microspheres. Nanocasting of sol-gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO(2) supercritical drying provide high-surface-area organic-inorganic hybrid materials. Examples including chitosan-SiO(2), chitosan-TiO(2), chitosan-redox-clusters and chitosan-clay-aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption.

Nanosized vanadium, tungsten and molybdenum oxide clusters grown in porous chitosan microspheres as promising hybrid materials for selective alcohol oxidation.

The ability of chitosan biopolymer to coordinate vanadium, tungsten and molybdenum metallic species and to control their mineralisation growth provides a new family of surface-reactive organic-inorganic hybrid microspheres. Drying the resulting materials under supercritical conditions allowed the gel network dispersion to be retained, thereby leading to a macroporous catalyst with surface areas ranging from 253 to 278 m(2) g(-1). On account of the open framework structure of these microspheres, the redox species entangled within the fibrillar network of the polysaccharide aerogels were found to be active, selective and reusable catalysts for cinamylalcohol oxidations.

Color plasmons and trains of plasmons.

We show that a broadband surface plasmon can be excited in a thin metal film. A train of two plasmons can be excited at conditions near the condition of broadband surface plasmon excitation. Also, a method for independent multichannel checks of biochips by wavelength addressing is proposed.

Stretchable carbon nanosprings production by a catalytic growth process.

Due to their peculiar electromagnetic and mechanical properties, helical carbon nanotubes (HCNT) have important potential applications in micro and nanoelectromechanical fields where they can be used as springs, magnetic field detectors, electromagnets, inductors and actuators. We report here the synthesis of carbon nanosprings through a non-classical catalytic growth process using a nanoporous support, where the regular array of openings allows the control of the diameter and coil pitch of the nanosprings. Exposition of such carbon nanosprings to a laser beam beyond an energy threshold can induce a permanent deformation characterized by the decoiling of the spring. Such permanent deformation results from an internal stresses relief mechanism, where pentagon-heptagon defect pairs reverting back to hexagon rings reduce the curvature of the coiled nanotube. This is expected to have important potential therapeutic applications in which carbon nanosprings can be located specifically in artery channels to remove fatty substances. They can also be located within cancer cells through specific interactions, after which the cells would be destroyed through the use of a more energetic but not harmful laser light. Such energy application is expected to fragment HCNT into digestible carbon for assimilation by the human body.

Interfacial complexation driven three-dimensional assembly of cationic phosphorus dendrimers and graphene oxide sheets.

High content nitrogen, sulfur and phosphorus heteroatoms assembled in tree-like dendrimers (DG n ) are confined within the galleries of two-dimensional graphene oxide (GO). The presence of the ternary diethyl-N-ethyl-ammonium groups on the dendrimer peripheries ensures the exfoliation of graphene sheets thereby affording interfacially bridged, three-dimensional heteroatom-enriched graphene-based hybrid nanostructures (DG n -GO). Dendrimer generation (from 1 to 4) that reflects the bulkiness of these conceived nano-trees impacts increasingly the degree of dispersion-exfoliation and sheet desordering. The long-term stability of these aqueous suspensions associated with their handling flexibility allows uniform accommodation of the resulting hybrid materials as flame-retardants in bioplastics.

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites.

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.

Effect of shear on phase-separation in polystyrene/poly(vinyl methyl ether)/ organoclay nanocomposites.

Blends of polystyrene (PS)/poly(vinyl methyl ether) (PVME) modified with two types of organoclay were prepared by solution casting from toluene. The effect of clay addition on the phase separating morphology of PS/PVME blend with critical composition (25/75) was examined both under quiescent conditions and under shear flow. The variation in critical temperature of phase separation was assessed by rheology, small angle laser light scattering (SALLS) and by on-line laser light transmission during shearing at fixed shear rate during heating. Transmission electron microscopy and X-ray diffraction analyses were used to examine the state of delamination and distribution of clay nanoparticles with the blend matrix.

Aldehyde-functionalized chitosan-montmorillonite films as dynamically-assembled, switchable-chemical release bioplastics.

Temporal release of synergistic and/or complementary chemicals (e.g.: drugs) is recognized as extremely challenging because of their frequently intertwined kinetic delivery and presently, straightforward concepts enabling to circumvent this bottleneck are missing in the open literature. In this framework, we report herein on aldehyde-functionalized, transparent and flexible chitosan-montmorillonite hybrid films that act as a new generation of eco-friendly, controlled-chemical release bioplastics. These dynamically-assembled nanomaterials are designed by a ternary assembly from biowaste derived chitin biopolymer, aromatic aldehydes and layered clay nanoparticles. On the basis of their geometrical and conformational properties, the oxygenated groups on the grafted aromatics interact preferentially with either the base Schiff belonging to the carbohydrate (via intramolecular CNHO-Ar known as "imine clip") or with the hydroxyl groups belonging to the clay surface (via intermolecular Si-OHO-Ar). The exfoliated clay nanoparticles within the carbohydrate polymer enables either accelerating or slowing down of the imine (CN) hydrolysis depending on the interaction of the conjugated aromatics. This provides the driving force for fine tuning host-guest interactions at the molecular level and constitutes an entry toward subtle discrimination of different chemicals (e.g. complementary fertilizers, synergistic drugs) during their sequential release.

Dispersion characteristics and properties of poly(methyl methacrylate)/multi-walled carbon nanotubes nanocomposites.

The preparation, characterization, and properties of poly(methyl methacrylate) (PMMA)/multi-walled carbon nanotubes (MWCNTs) nanocomposites are described. Nanocomposites have been prepared by melt-blending in a batch mixer. Both unmodified and surface modified MWCNTs have been used for the nanocomposites preparation. Using both unmodified and modified MWCNTs, the effect of surface modification in nanocomposites is investigated by focusing on three major aspects: dispersion characteristics, mechanical properties, and electrical conductivity measurements. Dispersion of the MWCNTs in the PMMA matrix is examined by scanning and transmission electron microscopy that revealed a homogeneous distribution-dispersion of MWCNTs in the PMMA matrix for both unmodified and modified MWCNTs. Thermomechanical behavior is studied by dynamic mechanical analyzer and results showed a substantial improvement in the mechanical properties of PMMA in conjunction to an increase in the elastic behavior. The tensile properties of neat PMMA moderately improved after nanocomposites preparation with both modified and unmodified MWCNTs, however, electrical conductivity of neat PMMA significantly improved after nanocomposites preparation with 2 wt% unmodified MWCNTs. For example, the through plane conductivity increased from 3.6 x 10(-12) S x cm(-1) for neat PMMA to 3.6 x 10(-9) S x cm(-1) for nanocomposite. The various property measurements have been conducted and results have shown that, in overall, surface modifications have very little or no effect on final properties of neat PMMA.

Phase separation in PS/PVME thin and thick films.

Phase separation in both thin and thick films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) was studied by small-angle laser light scattering (SALLS), atomic force microscopy (AFM), optical microscopy, and X-ray photoelectron spectroscopy (XPS). Blend films with controlled thickness were obtained by spin-coating polymer-toluene solutions with various concentrations. Films with thicknesses smaller and larger than the maximum wavelength of concentration fluctuations were considered. Morphology of the blend films was characterized during and after phase separation. The obtained peculiar morphology was related to surface enrichment with the lower-surface-energy component, as was verified by XPS analyses.

Anticancer copper(II) phosphorus dendrimers are potent proapoptotic Bax activators.

A multivalent phosphorus dendrimer 1G3 and its corresponding Cu-complex, 1G3-Cu have been recently identified as agents retaining high antiproliferative potency. This antiproliferative capacity was preserved in cell lines overexpressing the efflux pump ABC B1, whereas cross-resistance was observed in ovarian cancer cell lines resistant to cisplatin. Theoretical 3D models were constructed: the dendrimers appear as irregularly shaped disk-like nano-objects of about 22 Å thickness and 49 Å diameter, which accumulated in cells after penetration by endocytosis. To get insight in their mode of action, cell death pathways have been examined in human cancer cell lines: early apoptosis was followed by secondary necrosis after multivalent phosphorus dendrimers exposure. The multivalent plain phosphorus dendrimer 1G3 moderately activated caspase-3 activity, in contrast with the multivalent Cu-conjugated phosphorus dendrimer 1G3-Cu which strikingly reduced the caspase-3 content and activity. This decrease of caspase activity is not related to the presence of copper, since inorganic copper has no or little effect on caspase-3. Conversely the potent apoptosis activation could be related to a noticeable translocation of Bax to the mitochondria, resulting in the release of AIF into the cytosol, its translocation to the nucleus and a severe DNA fragmentation, without alteration of the cell cycle. The multivalent Cu-conjugated phosphorus dendrimer is more efficient than its non-complexed analog to activate this pathway in close relationship with the higher antiproliferative potency. Therefore, this multivalent Cu-conjugated phosphorus dendrimer 1G3-Cu can be considered as a new and promising first-in-class antiproliferative agent with a distinctive mode of action, inducing apoptosis tumor cell death through Bax activation pathway.

Phase separation of polystyrene/poly(vinylmethylether)/organoclay nanocomposites.

The effect of addition of organically modified montmorillonite (OMMT) on the phase separation of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blend was examined. Using two types of OMMT modified with two different kinds of surfactants, the effect of organic modification on nanocomposites was investigated by focusing on three major aspects: phase transition, morphological study, and melt rheological behavior both below and above the critical transition temperature. X-ray diffraction (XRD) patterns revealed the formation of intercalated nanocomposites and transmission electron micrographic (TEM) observations showed that the ordering of silicate layers in blend matrix is well matched with the XRD patterns. The addition of clay was found to affect both the mechanism of phase separation and the final morphology. Such effects resulted in uncommon rheological behavior of the blend both below and above the critical transition temperature. Surface phase separation of thin films for virgin blend and nanocomposites was also examined by atomic force microscopy (AFM). Morphology resulting after phase separation was found to be dependent on the nature and the amount of OMMT added to the polymer blend.

Dispersion of multi-walled carbon nanotubes in biodegradable poly(butylene succinate) matrix.

This communication describes the preparation, characterization and properties of biodegradable poly(butylene succinate) (PBS)/multi-walled carbon nanotubes (MWCNTs) nanocomposite. Nanocomposite was prepared by melt-blending in a batch mixer and the amount of MWCNTs loading was 3 wt%. State of dispersion-distribution of the MWCNTs in the PBS matrix was examined by scanning and transmission electron microscopic observations that revealed homogeneous distribution of stacked MWCNTs in PBS matrix. The investigation of the thermomechanical behavior was performed by dynamic mechanical thermal analysis. Results demonstrated substantial enhancement in the mechanical properties of PBS, for example, at room temperature, storage flexural modulus increased from 0.64 GPa for pure PBS to 1.2 GPa for the nanocomposite, an increase of about 88% in the value of the elastic modulus. The tensile modulus and thermal stability of PBS were moderately improved after nanocomposite preparation with 3 wt% of MWCNTs, while electrical conductivity of neat PBS dramatically increased after nanocomposite formation. For example, the in plane conductivity increased from 5.8 x 10(-9) S/cm for neat PBS to 4.4 x 10(-3) for nanocomposite, an increase of 10(6) fold in value of the electrical conductivity.