Controlling the Formation of Polyelectrolyte Complex Nanoparticles Using Programmable pH Reactions.

Enabling complexation of weak polyelectrolytes, in the presence of a programmable pH-modulation, offers a means to achieve temporal control over polyelectrolyte coassembly. Here, by mixing oppositely charged poly(allylamine hydrochloride) and poly(sodium methacrylate) in a (bi)sulfite buffer, nanoscopic complex coacervates are formed. Addition of formaldehyde initiates the formaldehyde-sulfite clock reaction, affecting the polyelectrolyte assembly in two ways.

Switchable Electrostatically Templated Polymerization.

We report a switchable, templated polymerization system where the strength of the templating effect can be modulated by solution pH and/or ionic strength. The responsiveness to these cues is incorporated through a dendritic polyamidoamine-based template of which the charge density depends on pH. The dendrimers act as a template for the polymerization of an oppositely charged monomer, namely sodium styrene sulfonate.

Chromonic nematic liquid crystals in a room-temperature ionic liquid.

Planar multiaromatic molecules hierarchically and selectively arrange into nematic chromonic liquid crystals in the room temperature ionic liquid 2-hydroxyethylammonium formate. In a proof of concept, these liquid crystals were used as reaction media to produce mesostructured silica materials under mild biomimetic conditions. Several other applications are envisaged.

Complex supramolecular fiber formed by coordination-induced self-assembly of benzene-1,3,5-tricarboxamide (BTA).

Hypothesis: In the quest for large but well-controlled supramolecular structures, the discotic benzene-1,3,5-tricarboxamide (BTA) has received quite some attention, because it can form hydrogen-bonded stacks that can be regarded as supramolecular polymers of which the single BTA molecule is the monomer. In this report, we consider a more complex BTA-based supramolecular polymer, namely one that is built up from supramolecular 'monomers'.

Experiments: We design a tris-ligand L consisting of a BTA core carrying three dipicolinic acid (DPA) groups.

Co-assembly of precision polyurethane ionomers reveals role of and interplay between individual components.

Industrial and household products, such as paints, inks and cosmetics usually consist of mixtures of macromolecules that are disperse in composition, in size and in monomer sequence. Identifying structure-function relationships for these systems is complicated, as particular macromolecular components cannot be investigated individually. For this study, we have addressed this issue, and have synthesized a series of five sequence-defined polyurethanes (PUs): one neutral-hydrophobic, one single-charged hydrophilic, one single-charged hydrophobic and two double-charged amphiphilic PUs (one symmetric and one asymmetric).

Fractal-like R5 assembly promote the condensation of silicic acid into silica particles.

Hypothesis: Despite advances in understanding the R5 (SSKKSGSYSGKSGSKRRIL) peptide-driven bio-silica process, there remains significant discrepancies regarding the physicochemical characterization and the self-assembling mechanistic driving forces of the supramolecular R5 template. This paper investigates the self-assembly of R5 as a function of monovalent (sodium chloride) and multivalent salt (phosphate) to determine if assembly is phosphate ion concentration dependent. Additionally, we hypothesize that the assembled R5 aggregates do not resemble a micelle or unimer structure as proposed in current literature.

Micellization of Sequence-Controlled Polyurethane Ionomers in Mixed Aqueous Solvents.

While the impact of compositional parameters such as block length and ionic content on the micellization of (polymeric) amphiphiles is widely investigated, the influence of monomer sequence has received far less attention until recently. Here, we report the synthesis of two sequence-controlled polyurethane ionomers (PUIs) prepared via a stepwise coupling-deprotection strategy, and compare their solution association in aqueous-organic mixtures. The two PUIs are highly similar in mass and overall composition, yet differ markedly in the sequence of building blocks.

Sequence of Polyurethane Ionomers Determinative for Core Structure of Surfactant-Copolymer Complexes.

The core of micelles self-assembled from amphiphiles is hydrophobic and contains little water, whereas complex coacervate core micelles co-assembled from oppositely charged hydrophilic polymers have a hydrophilic core with a high water content. Co-assembly of ionic surfactants with ionic-neutral copolymers yields surfactant-copolymer complexes known to be capable of solubilizing both hydrophilic and hydrophobic cargo within the mixed core composed of a coacervate phase with polyelectrolyte-decorated surfactant micelles. Here we formed such complexes from asymmetric () and symmetric (), sequence-controlled polyurethane ionomers and poly(-methyl-2-vinylpyridinium iodide)--poly(ethylene oxide) copolymers.

On Complex Coacervate Core Micelles: Structure-Function Perspectives.

The co-assembly of ionic-neutral block copolymers with oppositely charged species produces nanometric colloidal complexes, known, among other names, as complex coacervates core micelles (C3Ms). C3Ms are of widespread interest in nanomedicine for controlled delivery and release, whilst research activity into other application areas, such as gelation, catalysis, nanoparticle synthesis, and sensing, is increasing. In this review, we discuss recent studies on the functional roles that C3Ms can fulfil in these and other fields, focusing on emerging structure-function relations and remaining knowledge gaps.

Bioinspired Scaffolding by Supramolecular Amines Allows the Formation of One- and Two-Dimensional Silica Superstructures.

Silica materials attract an increasing amount of interest in (fundamental) research, and find applications in, for example, sensing, catalysis, and drug delivery. As the properties of these (nano)materials not only depend on their chemistry but also their size, shape, and surface area, the controllable synthesis of silica is essential for tailoring the materials to specific applications. Advantageously, bioinspired routes for silica production are environmentally friendly and straightforward since the formation process is spontaneous and proceeds under mild conditions.

Architecture-Dependent Interplay between Self-Assembly and Crystallization in Discrete Block Co-Oligomers.

Access to versatile and stable nanostructures formed by the self-assembly of block copolymers in water is essential for biomedical applications. These applications require control over the stability, morphology, and size of the formed nanostructures. Here, we study the self-assembly in water of a library of fully discrete and sequence-controlled AB-type block co-oligomers (BCOs) of oligo(l-lactic acid)--oligo(ethylene glycol).