The effect of solvents on the propagation rate coefficient, kp, in radical polymerization was described for the first time in sixties of the last century. Since then, solvents are used to tune the reactivity of monomers and growing radicals involved in propagation step. The solvent effects on kp have been described for a number of monomers polymerized in organic [1] and aqueous [2] solutions.

In this work, we determined kp values of acrylic acid (AA) by pulsed-laser polymerization in combination with size-exclusion chromatography in different environments involving hydrogen bonding organic solvents, saturated carboxylic acids, inert solvents with respect to the hydrogen bonding, water, and bulk. This work complements the existing knowledge on kp for AA polymerized in aqueous solutions [3] and in bulk [4].

The kp values for AA are governed by the presence of cyclic dimers. The conjugation between C=O and C=C electrons results in activation of double bond for the radical attack. Then, kp decreases upon addition of any solvent disturbing these dimers (hydrogen bonding organic solvents, saturated carboxylic acids). The inert solvents support dimer formation and kp is similar to that in bulk. The highest kp values are in aqueous solutions due to strong hydrogen bonding interactions with molecules of water.

Data obtained in this work, in combination with existing data in the literature, enabled us to generalize the kp behavior in different environments by classification of monomers into self-associating and non-self-associating monomers.

Acknowledgment. This work was supported by the Slovak Scientific Grant Agency VEGA 2/0143/23.

Developing sustainable plastics derived from renewable carbon sources, such as plant-based biomass or
captured carbon dioxide, presents a significant challenge in transitioning away from traditional petrochemical based
materials. Overcoming these challenges requires significant research and development on both the
fundamental and applied level. Herein, we present three distinct oxanorbornene based monomers
generated via Diels-Alder reactions from bio-derived furanics building blocks. The monomers’ architecture is
built upon a tricyclic core, presenting bifunctionality through an unsaturated olefin and a lactone site.
The former enables Ring Opening Metathesis Polymerisation, while the latter allows for Ring Opening
Polymerisation , offering various materials from one bio-based building block. Utilizing ROMP, we achieved
well-controlled polymerizations, yielding exceptionally high glass transition temperatures and excellent
thermal stability. Our study explored the translation from micro- to macrostructures, through complementary
in-depth NMR studies on these materials, scrutinising the influence of the presence or absence of the
lactone functionality on the final material properties. We were able to observe rare reactivity by using a vinyl
ether as a chain-transfer agent, giving access to monotelechelic polymers. These novel polyenes, with
adjustable functionalities, offer sustainable alternatives to traditional plastics and valuable insights into
monomer design.

Electronically conductive polymers are critical enablers for next-generation electrochemical devices. While π-conjugated semiconducting polymers have demonstrated exceptional performances, they face persistent challenges with compatibility and reliance on chemical doping to achieve sufficient conductivities. Additionally, todays’ materials design must address mounting electronic waste concerns. One route is to deliberately incorporate degradation pathways, enabling responsible lifecycle management and reduced end-of-life environmental impact.

Non-conjugated, redox-active polymers have emerged as promising electronic conductors, particularly, TEMPO-containing polymers, which facility electron transport through hopping conduction via radical moieties appended to the polymer backbone. These materials offer advantages including ambient stability, optical transparency, and impressive solid-state electrical conductivity – with poly(thio)ether materials achieving up to ca. 0.3 S/cm at narrow channel lengths. Applications span batteries and other energy storage technologies, memristive devices, organic light-emitting diodes, and chemical sensors. Despite their technological promise, most current redox-active polymers lack built-in end-of-life degradation pathways, creating a critical sustainability gap in an era demanding circular materials approaches.

Herein, we present a library of non-conjugated redox-active polyesters designed with intrinsic solvolytic degradability. These polymers are synthesised via controlled, metal-free ring-opening copolymerisation (ROCOP) of a TEMPO-containing epoxide with various cyclic anhydrides. Our approach enables precise control of backbone compositions through anhydride selection, yielding a series of polymers with modular flexibility. The mechanical properties and electrochemical performance of these degradable polyesters demonstrate a holistic approach to polymer design that addresses both functionality and sustainability in next-generation electronic materials.

Developing well-defined antifouling coatings remains a challenge in biomaterials research. This study presents an optimized protocol for the surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization of poly(N-(2-hydroxypropyl) methacrylamide) (poly(HPMAm)) brushes, employing a mixed-chain transfer agent (CTA) approach. By systematically evaluating different combinations of surface-tethered and free CTAs, we demonstrate that utilizing structurally distinct CTA classes simultaneously; dithiobenzoate (DTB) and trithiocarbonate (TTC), enhances polymerization control and brush growth rates. Our optimized conditions enable the fabrication of poly(HPMAm) brushes exceeding 70 nm in thickness within only 4 hours at 50 °C, and in aqueous media. Spectroscopic ellipsometry confirmed that the mixed-CTA approach significantly outperforms single-CTA systems, yielding higher polymerization efficiency and greater brush thickness. X-ray photoelectron spectroscopy (XPS) analysis revealed that the enhanced surface coverage achieved with DTB-based CTAs plays a crucial role in facilitating rapid brush growth. Additionally, size exclusion chromatography (SEC) confirmed that the solution-born polymers exhibited narrow dispersity (Ð = 1.05–1.15), ensuring well-defined polymer structures. Our findings highlight the advantages of combining different CTAs in a single polymerization system, leading to a more efficient and scalable method for fabricating antifouling poly(HPMAm) coatings. This approach offers a significant potential for biomedical applications, including biosensors, blood-contacting devices, and implantable materials.

DNA has been storing our genetic code since the beginning of life on Earth. The industrial process of storing data in DNA has been studied for decades but many problems still remain. For over ten years, the Lutz group has demonstrated that it is possible to store information in abiological polymers. Coded polyphosphodiesters are synthesized using phosphoramidite chemistry. Each step of the iterative cycle has been optimized for decades however, the general cycle can be improved by removing one step. Indeed, pioneers of this technique worked with Phosphorus (III) because it was the most reactive phosphorus species at this time. Nowadays, new synthesis of nucleic acids are growing by using Phosphorus (V) chemistry. This chemistry could be promising for increasing the writing speed of digital polymers.
Phosphorodiamidate oligomers with a morpholino scaffold were synthesized by Summerton & Weller at the beginning of the century to create antisens molecules. They replaced the ribose of the nucleotide with a morpholine core. The hydroxyl group is functionalized with the dichlorophosphoramidate reagent (P(V)). To synthesize the nucleotide derivatives, they used the solid support strategy : the amine has to be deprotected first to couple with the new monomer. The aim of this project is to transfer this technology to abiological digital morpholinos to store data.

This research project focuses on a new generation of thermoplastic elastomers (TPEs) with tunable and scalable thermomechanical properties, addressing the growing demand for sustainable and high-performance polymeric materials. TPEs uniquely combine the elasticity of rubbers with the processability and recyclability of thermoplastics. Traditionally based on di- or tri-block copolymers, TPEs rely on a rubbery block for elasticity and one or two rigid blocks for thermal stability and stiffness1.
Our innovative approach involves side-chain-functionalized triblock copolymers, enabling independent, covalent, and reversible crosslinking of the blocks, as illustrated in Figure 1. This strategy allows precise fine-tuning of thermomechanical properties by exploiting orthogonal stimuli: the hard block undergoes thermal crosslinking, while the soft block is UV-crosslinkable. This dual-stimuli system not only facilitates local and selective property tuning but also enables the design of functionally graded materials. Furthermore, the TPEs are formed through self-assembly of the blocks via metallo-supramolecular chemistry, providing exceptional flexibility in macromolecular design and precise control over block synthesis. In addition, these heteroleptic Metal-Ligands Complexes (MLCs) are also thermally responsive and can be assembled/disassembled upon heating conferring to these TPEs a healing behavior.
This communication will focus on the synthesis, assembly, structure and thermomechanical characterizations of these materials, with a particular attention on the reversible crosslinking processes and their influence on thermal properties. Our results highlight the potential of this approach to expand the application scope of TPEs in advanced engineering and functional materials.