Easy reversible clustering of gold nanoparticles via pH-Induced assembly of PVP-b-PAA copolymer.

The growing demand of novel hybrid organic/inorganic systems with exciting properties has contributed to an increasing need for simplifying production strategies. Here, we report a simple method to obtain controlled three-dimensional hybrid architectures, in particular hybrid supracolloids (hSC), formed by gold nanoparticles and a double hydrophilic block copolymer, specifically the poly(acrylic acid)-block-poly(N-vinyl-2-pyrrolidone) (PAA-b-PVP), directly in aqueous medium. The ubiquitous pH-sensitive poly(acrylic acid) (PAA) block initiates the assembly through pH changes, while the poly(N-vinyl-2-pyrrolidone) block assures the close affinity with the AuNPs.

Iron-based hybrid polyionic complexes as chemical reservoirs for the pH-triggered synthesis of Prussian blue nanoparticles.

Hypothesis: Hybrid polyion complexes (HPICs) obtained from the complexation in aqueous solution of a double hydrophilic block copolymer and metal ions can act as efficient precursors for the controlled synthesis of nanoparticles. In particular, the possibility to control the availability of metal ions by playing on the pH conditions is of special interest to obtain nanoparticles with controlled size and composition.

Experiments: HPICs based on Fe ions were used to initiate the formation of Prussian blue (PB) nanoparticles in presence of potassium ferrocyanide in reaction media with varying pH values.

Assemblies of poly(-vinyl-2-pyrrolidone)-based double hydrophilic block copolymers triggered by lanthanide ions: characterization and evaluation of their properties as MRI contrast agents.

Because of the formation of specific antibodies to poly(ethylene glycol) (PEG) leading to life-threatening side effects, there is an increasing need to develop alternatives to treatments and diagnostic methods based on PEGylated copolymers. Block copolymers comprising a poly(-vinyl-2-pyrrolidone) (PVP) segment can be used for the design of such vectors without any PEG block. As an example, a poly(acrylic acid)--poly(-vinyl-2-pyrrolidone) (PAA--PVP) copolymer with controlled composition and molar mass is synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization.

Double-hydrophilic block copolymer-metal ion associations: Structures, properties and applications.

Hybrid polyionic complexes (HPICs), constructed from double-hydrophilic block copolymers and metal ions, have been largely developed with increasing interest in the past decade in the fields of catalysis, materials science and biological applications. The chemical natures of both blocks are very versatile, but one block should be able to interact with ions, and the second one should be neutral. Many metals have been used to form HPICs, which have, in their simplest architectural form, a core-shell structure of a few tens of nanometers in radius with an external shell made of the neutral block of the copolymer.

Hybrid polymeric micelles stabilized by gallium ions: Structural investigation.

The addition of gallium ions to a solution of a double-hydrophilic block copolymer, i.e. poly(ethylene oxide)-block-poly(acrylic acid), leads to the spontaneous formation of highly monodisperse micelles with a Hybrid PolyIon Complexes (HPICs) core.

Effect of the microstructure of n-butyl acrylate/N-isopropylacrylamide copolymers on their thermo-responsiveness, self-organization and gel properties in water.

Hypothesis: Polymer composition, microstructure, molar mass, architecture… critically affect the properties of thermoresponsive polymers in aqueous media.

Experiments: The behaviour of n-isopropylacrylamide and n-butyl acrylate-based copolymers of variable composition and structure (statistical, diblock or triblock) was studied in solution at different temperatures and concentrations with turbidimetry measurements, differential scanning calorimetry, electronic microscopy, rheology and scattering experiments.

Findings: This study illustrates how it is possible through chemical engineering of the microstructure of amphiphilic thermoresponsive polymers to modulate significantly the self-assembly, morphological and mechanical properties of these materials in aqueous media.

Frit inlet field-flow fractionation techniques for the characterization of polyion complex self-assemblies.

Polymer self-assemblies joining oppositely charged chains, known as polyion complexes (PICs), have been formed using poly(ethyleneoxide - b - acrylic acid)/poly(l-lysine), poly(ethyleneoxide-b-acrylic acid)/dendrigraft poly(l-lysine) and poly[(3-acrylamidopropyl) trimethylammonium chloride - b - N - isopropyl acrylamide]/poly(acrylic acid). The self-assemblies have been first characterized in batch by Dynamic Light Scattering. In a second step, their analysis by Flow Field-Flow Fractionation techniques (FlFFF) was examined.

Pickering emulsions: what are the main parameters determining the emulsion type and interfacial properties?

We synthesized surface-active lipophilic core-hydrophilic shell latex particles, and we probed their efficiency as emulsion stabilizers. The relative weight percentage of the shell, RS/P, was varied to trigger the balance between lipophilicity and hydrophilicity of the particles. Particle wettability could concomitantly be tuned by the pH of the aqueous phase determining the surface charge.

Investigation of the reversibility of the unimer-to-aggregate transition in block copolymers by surface tension-measurements.

Two DNA-block copolymers, poly(caprolactone)-DNA and poly(methyl metacrylate)-DNA, were synthesized by conjugation of a short single strand of DNA (12 or 22mer) to a single reactive group at one end of the synthetic polymer. These polymers self-assemble in water, without the need of any cosolvent, forming micelle-like aggregates that were imaged by TEM. The solution behavior of the bioconjugated polymers was investigated by surface tension measurements.

Biphenyl bicelle disks align perpendicular to magnetic fields on large temperature scales: a study combining synthesis, solid-state NMR, TEM, and SAXS.

A phosphatidylcholine lipid (PC) containing a biphenyl group in one of its acyl chains (1-tetradecanoyl-2-(4-(4-biphenyl)butanoyl)-sn-glycero-3-PC, TBBPC) was successfully synthesized with high yield. Water mixtures of TBBPC with a short-chain C(6) lipid, dicaproyl-PC (DCPC), lead to bicelle systems formation. Freeze-fracture electron microscopy evidenced the presence of flat bilayered disks of 800 A diameter for adequate composition, hydration, and temperature conditions.

Bicelle membranes and their use for hydrophobic peptide studies by circular dichroism and solid state NMR.

Mixtures of dicaproyl- (DC), dimyristoyl- (DM) and 1-tetradecanoyl-2-biphenylbutanoyl-(TBB) phosphatidylcholine (PC) in water produce bicelle membranes that are oriented by magnetic fields. DMPC/DCPC systems orient such that their membrane plane is parallel to the magnetic field, whereas for TBBPC/DCPC, the plane is perpendicular to the field. Partial temperature-composition-hydration diagrams are established using solid-state 31P-NMR.