Physically crosslinked polyacrylates by quadruple hydrogen bonding side chains.

Dynamic polymer materials can be obtained by introducing supramolecular interactions between the polymer chains. Here we report on the preparation and mechanical properties of poly(methyl acrylate) (PMA) and poly(-butyl acrylate) (PBA) funcionalized with ureidopyrimidinone (UPy) in the side chains. In contrast to the traditional UPy with a methyl group, the selected UPy motif contained a branched alkyl side chain, which enhances solubility, compatibility with the polymer matrix and potentially prevents stacking of UPy dimers.

Sequence-defined antibody-recruiting macromolecules.

Antibody-recruiting molecules represent a novel class of therapeutic agents that mediate the recruitment of endogenous antibodies to target cells, leading to their elimination by the immune system. Compared to single-ligand copies, macromolecular scaffolds presenting multiple copies of an antibody-binding ligand offer advantages in terms of increased complex avidity. In this study, we describe the synthesis of sequence-defined macromolecules designed for antibody recruitment, utilising dinitrophenol (DNP) as a model antibody-recruiting motif.

Ring-Opening Metathesis Polymerization for the Synthesis of Terpenoid-Based Pressure-Sensitive Adhesives.

Pressure-sensitive adhesives (PSAs) made from norbornene-functionalized terpenoid-based monomers are reported as a possible alternative to the conventional petrochemically based PSAs. For this, tetrahydrogeranyl, menthyl, and isobornyl norbornenate monomers, with a renewable carbon content up to 72%, are synthesized and copolymerized via ring-opening metathesis polymerization (ROMP) with cyclooctadiene and 5-norbornene-2-carboxylic acid. ROMP enables a much faster and controlled polymerization process in comparison to free radical polymerization techniques when targeting high molecular weights and therefore unlocks a potential to design a unique class of PSA materials.

Sequence-Encoded Macromolecules with Increased Data Storage Capacity through a Thiol-Epoxy Reaction.

Sequence-encoded oligo(thioether urethane)s with two different coding monomers per backbone unit were prepared via a solid phase, two-step iterative protocol based on thiolactone chemistry. The first step of the synthetic cycle consists of the thiolactone ring opening with a primary amine, whereby the in situ released thiol is immediately reacted with an epoxide. In the second step, the thiolactone group is reinstalled to initiate the next cycle.

Sequence-Defined Mikto-Arm Star-Shaped Macromolecules.

The synthesis of sequence-defined, discrete star-shaped macromolecules is a major challenge due to the lack of straightforward and versatile approaches. Here, a robust strategy is proposed that allows not only the preparation of sequence-defined mikto-arm star-shaped macromolecules but also the synthesis of a series of unprecedented discrete, multifunctional complex architectures with molar masses above 11 kDa. The iterative approach reported makes use of readily available building blocks and results in asymmetrically branched macromolecules with high purity and yields, which is showcased with monodisperse mikto-arm three-, four-, and five-arm star-shaped structures that were all characterized via LC-MS, MALDI-ToF, and NMR.

Applications of Discrete Synthetic Macromolecules in Life and Materials Science: Recent and Future Trends.

In the last decade, the field of sequence-defined polymers and related ultraprecise, monodisperse synthetic macromolecules has grown exponentially. In the early stage, mainly articles or reviews dedicated to the development of synthetic routes toward their preparation have been published. Nowadays, those synthetic methodologies, combined with the elucidation of the structure-property relationships, allow envisioning many promising applications.

Effect of Arm Number and Length of Star-Shaped Glycopolymers on Binding to Dendritic and Langerhans Cell Lectins.

Many cell types in Nature are covered by glycans with a sugar shell on their surface. Synthetic glycopolymer-based materials can mimic these glycans in terms of their variety of biological processes, such as cell growth regulation, adhesion, inflammation by bacteria and viruses, and immune responses. However, the complexity of glycans is still very challenging to be mimicked completely to obtain specific and selective binding ability.

Transformation of Thioester-Initiated Star Polymers into Linear Arms via Native Chemical Ligation.

The synthesis of a new class of Cu-mediated polymerization initiators with thioester functionality is demonstrated and their polymerization kinetics via single-electron transfer living radical polymerization is reported. From periodic sampling, it is found that thioester- or ester-based initiators can be employed interchangeably, resulting in very similar polymerization rates. Furthermore, a multifunctional thioester initiator is employed for the preparation of a well-defined four-arm star-shaped polymer.