Molecular access to multi-dimensionally encoded information

Polymer scientist have only recently realized that information storage on the molecular level is not only restricted to DNA-based systems. Similar encoding and decoding of data have been demonstrated on synthetic polymers that could overcome some of the drawbacks associated with DNA, such as the ability to make use of a larger monomer alphabet. This feature article describes some of the recent data storage strategies that were investigated, ranging from writing information on linear sequence-defined macromolecules up to layer-by-layer casted surfaces and QR codes. In addition, some strategies to increase storage density are elaborated and some trends regarding future perspectives on molecular data storage from the literature are critically evaluated. This work ends with highlighting the demand for new strategies setting up reliable solutions for future data management technologies

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. Consequently, in the past 3 years, application-oriented papers based on discrete synthetic macromolecules emerged. Hence, material science applications such as macromolecular data storage and encryption, self-assembly of discrete structures and foldamers have been the object of many fascinating studies. Moreover, in the area of life sciences, such structures have also been the focus of numerous research studies. Here, it is aimed to highlight these recent applications and to give the reader a critical overview of the future trends in this area of research

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

Pressure-sensitive adhesives (PSAs) made from norbomene-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. The moduli at bonding and debonding frequencies of the obtained PSAs are plotted in the Chang classification system and are used to predict their adhesive performance. Tack and peel measurements indicate that the terpenoid-based norbornenate formulations show similar adhesive properties in comparison to the previously investigated acrylic counterparts

Sequence-defined oligoampholytes using hydrolytically stable vinyl sulfonamides : design and UCST behaviour

Polyampholytes, widely investigated for their distinct properties, are typically prepared via conventional polymerisation techniques. This results in an ensemble of polymer chains with variation in molecular parameters such as length, ratio of charged groups and monomer order, which could influence their behaviour. Here, uniform oligoampholytes with precisely positioned negatively charged carboxylate and positively charged ammonium side-chains were synthesised using an iterative solid-phase synthesis strategy based on thiolactone chemistry. The amine side-chains were initially introduced via an acrylate, resulting in an amino-functionalised beta-thioester that was shown to be susceptible to transesterification and hydrolysis, even under ambient conditions. While increasing the spacer length between the beta-thioester and amine functionality could slow down this undesired side-reaction, it could not be completely suppressed. On the other hand, a tertiary amine-bearing vinyl sulfonamide proved to be a viable, hydrolytically stable alternative to introduce this moiety. The resulting uniform oligoampholytes are soluble in water and show UCST-type thermoresponsive behaviour in 85 vol% isopropanol/water mixtures

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. This strategy allows to introduce two different coding monomers per synthetic cycle, rendering the resulting macromolecules especially attractive in the area of (macro)molecular data storage because of their increased data storage capacity. Subsequently, the efficiency of the herein reported synthesis route and the applicability of the dual-encoded sequence-defined macromolecules as a potential data storage platform have been demonstrated by unraveling the exact monomer order using tandem mass spectrometry techniques

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 miktoarm three-, four-, and five-arm star-shaped structures that were all characterized via LC-MS, MALDI-ToF, and NMR. This effective strategy drastically improves upon synthetic abilities of polymer chemists by enabling simultaneously sequence definition, precision insertion of branching points, as well as the orthogonal end-group functionalization of complex polymeric architectures. The presented approach, which can be translated to different platforms such as peptides and peptoids, is therefore particularly interesting in biomedical applications for which multiple different functional moieties on a single discrete macromolecule are needed