Low , strongly segregated, ABA triblock copolymers: a rheological and structural study.

ABA triblock copolymers can form microphase separated structures where the B blocks form bridges between A domains, leading to reversible networks interesting for a variety of applications such as pressure sensitive adhesives or thermoplastic elastomers. However, a major drawback of these systems is their rapid loss of mechanical properties upon temperature increase. A potential way to circumvent this limitation would be to design ABA triblock copolymers that keep their microphase separation at high temperatures.

Phase behavior of medium-length hydrophobically associating PEO-PPO multiblock copolymers in aqueous media.

Hypothesis: The micellization of block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) is driven by the dehydration of PPO at elevated temperatures. At low concentrations, a viscous solution of isolated micelles is obtained, whereas at higher concentrations, crowding of micelles results in an elastic gel. Alternating PEO-PPO multiblock copolymers are expected to exhibit different phase behavior, with altered phase boundaries and thermodynamics, as compared to PEO-PPO-PEO triblock copolymers (Pluronics®) with equal hydrophobicity, thereby proving the pivotal role of copolymer architecture and molecular weight.

Real-Time Fluctuations in Single-Molecule Rotaxane Experiments Reveal an Intermediate Weak Binding State during Shuttling.

We report on the use of atomic force microscopy (AFM) to identify and characterize an intermediate state in macrocycle shuttling in a hydrogen bonded amide-based molecular shuttle. The [2]rotaxane consists of a benzylic amide macrocycle mechanically locked onto a thread that bears both fumaramide and succinic amide-ester sites, each of which can bind to the macrocycle through up to four intercomponent hydrogen bonds. Using AFM-based single-molecule force spectroscopy, we mechanically triggered the translocation of the ring between the two principal binding sites ("stations") on the axle.

Balancing Ligand Flexibility versus Rigidity for the Stepwise Self-Assembly of M L via M L Metal-Organic Cages.

Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal-organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd .

Linear and Nonlinear Dynamic Behavior of Polymer Micellar Assemblies Connected by Metallo-Supramolecular Interactions.

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene--poly(-butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model.

Integrating Proteins in Layer-by-Layer Assemblies Independently of their Electrical Charge.

Layer-by-layer (LbL) assembly is an attractive method for protein immobilization at interfaces, a much wanted step for biotechnologies and biomedicine. Integrating proteins in LbL thin films is however very challenging due to their low conformational entropy, heterogeneous spatial distribution of charges, and polyampholyte nature. Protein-polyelectrolyte complexes (PPCs) are promising building blocks for LbL construction owing to their standardized charge and polyelectrolyte (PE) corona.

Mechanisms of Crystalloid versus Colloid Osmosis across the Peritoneal Membrane.

Osmosis drives transcapillary ultrafiltration and water removal in patients treated with peritoneal dialysis. Crystalloid osmosis, typically induced by glucose, relies on dialysate tonicity and occurs through endothelial aquaporin-1 water channels and interendothelial clefts. In contrast, the mechanisms mediating water flow driven by colloidal agents, such as icodextrin, and combinations of osmotic agents have not been evaluated.

Photosensitizer localization in amphiphilic block copolymers controls photodynamic therapy efficacy.

Localization of the photosensitizer conjugation site in amphiphilic block copolymers is shown to have a great impact on photodynamic therapy efficiency. To this end, an asymmetric multifunctional derivative of the azadipyrromethene boron difluoride chelate (aza-BODIPY) was synthesized and inserted at specific locations in polypeptide-based rod-coil amphiphilic block copolymers. A study of the photophysical properties of the vesicle nanocarriers, obtained by self-assembly of these copolymers, as well as in vitro tests on two cancer cell lines were performed.

Influence of a Single Catenane on the Solid-State Properties of Mechanically Linked Polymers.

We report on mechanically linked polymers containing a single catenane in the middle of the chain. These polymers were synthesized by a simple procedure consisting in "clicking" polymer chains onto a functionalized palladium-templated [2]catenane, allowing the preparation of a variety of mechanically linked polymers. The flexibility of the catenane junction was modulated by removing the Pd ion from the catenane to unlock the macrocycles and increase their mobility.

Closer insight into the structure of moderate to densely branched comb polymers by combining modelling and linear rheological measurements.

Synthesis of combs with well-entangled backbones and long branches with high densities has always been a challenge. Steric hindrance frequently leads to coupling of chains and structural imperfections that cannot be easily distinguished by traditional characterization methods. Research studies have therefore tried to use a combination of different methods to obtain more information on the actual microstructures.

Orthogonal Control of the Dynamics of Supramolecular Gels from Heterotelechelic Associating Polymers.

One of the first examples of supramolecular gels presenting independent dual dynamics is built through a combination of hydrophobic and metal-ligand interactions. The associating building block consists in a water-soluble linear polymer terminated by a short hydrophobic sticker at one end, and a coordinating moiety at the other end. The distinct supramolecular nature of these noninterfering binding motifs allows the dynamics of the hydrogels to be finely tuned in an orthogonal fashion by the application of specific stimuli.

Correction: Catenane-based mechanically-linked block copolymers.

Correction for 'Catenane-based mechanically-linked block copolymers' by B. Nisar Ahamed et al., Chem.

Catenane-based mechanically-linked block copolymers.

An original strategy for the synthesis of diblock copolymers where the blocks are linked by a catenane junction is described. Starting from a functionalized catenane precursor, our strategy enables the preparation of a variety of copolymers by different techniques such as ROP, ATRP and CuAAC click reaction.

Precise Control over the Rheological Behavior of Associating Stimuli-Responsive Block Copolymer Gels.

"Smart" materials have considerably evolved over the last few years for specific applications. They rely on intelligent macromolecules or (supra-)molecular motifs to adapt their structure and properties in response to external triggers. Here, a supramolecular stimuli-responsive polymer gel is constructed from heterotelechelic double hydrophilic block copolymers that incorporate thermo-responsive sequences.

Revealing the supramolecular nature of side-chain terpyridine-functionalized polymer networks.

Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylamino)ethyl methacrylate) is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry.

Synthesis and self-assembly of terpyridine end-capped poly(N-isopropylacrylamide)-block-poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers.

At the basis of smart self-assembled materials are lying small building blocks that can hierarchically assemble in response to stimuli, e.g., temperature or chemical species.

Thermo-responsive properties of metallo-supramolecular block copolymer micellar hydrogels.

Metallo-supramolecular micellar hydrogels exhibiting thermo-mechanical responsiveness are prepared through the hierarchical assembly of a heterotelechelic associating copolymer. The copolymer consists of a linear thermo-sensitive water-soluble sequence terminated by a short hydrophobic sticker at one end, the other being functionalized by a chelating ligand. As the first level of assembly, the associating copolymer is dissolved in aqueous solution to yield micellar nanostructures, bearing coordinative motifs at the end of the coronal chains.

Pore-functionalized nanoporous materials derived from block copolymers.

This review deals with nanoporous materials made from the self-assembly of block copolymers with a special interest in the chemical functions covering the surface of their nanopores. A detailed overview of the existing methods and strategies to generate well-defined organic functional groups covering the surface of the pore walls is provided. This further enables to finely tune the affinity of the pore walls and to perform well-defined chemical reactions onto them, which is essential for further dedicated applications.

Multiresponsive Micellar Systems from Photocleavable Block Copolymers.

This contribution describes the synthesis and associating behavior in water of a multiresponsive amphiphilic diblock copolymer. This copolymer is composed of an hydrophobic photocleavable poly(-methoxyphenacyl methacrylate) block (PMPMA) and a hydrophilic thermosensitive poly[(oligo ethylene glycol)methacrylate] block (POEGMA). The PMPMA--POEGMA copolymer forms micelles with a PMPMA core and a POEGMA corona in water.

Functionalized nanoporous thin films from metallo-supramolecular diblock copolymers.

A polystyrene-[Ni(2+)]-poly(ethylene oxide) metallo-supramolecular block copolymer (PS-[Ni(2+)]-PEO), where -[ is a terpyridine, is used to create nanoporous thin films with free terpyridine ligands homogenously distributed on the pore walls. The PS-[Ni(2+)]-PEO block copolymer is synthesized by a two step assembly process, and is then self-assembled into a thin film in order to obtain PEO cylinders oriented perpendicularly to the film surface. The supramolecular junction is opened by exposing the film to an excess of a competing ligand, and the free PEO block is then rinsed away by a selective solvent.

Functionalized nanoporous thin films from photocleavable block copolymers.

A polystyrene-block-poly(ethylene oxide) block copolymer bearing a photocleavable junction between the blocks is used to form nanoporous thin films with carboxylic acid functions homogeneously distributed on the pore walls. The presence of the carboxylic acid groups is evidenced by fluorescence spectroscopy after their reaction with a diazomethane functionalized fluorescent dye. In addition, the initial light-responsive thin film, acting as a photoresist, can be easily patterned to selectively generate porosity in predetermined areas.

A single synthetic small molecule that generates force against a load.

Some biomolecules are able to generate directional forces by rectifying random thermal motions. This allows these molecular machines to perform mechanical tasks such as intracellular cargo transport or muscle contraction in plants and animals. Although some artificial molecular machines have been synthesized and used collectively to perform mechanical tasks, so far there have been no direct measurements of mechanical processes at the single-molecule level.