In nature, carrying out specific chemical reactions is often challenging due to the presence of numerous competing reactive groups and strong dilution. However, enzymes, as highly efficient biological catalysts, overcome this challenge by employing a proximity effect, where reactants are brought into close spatial arrangement within the active site, significantly accelerating reaction rates.
Inspired by this natural strategy, we present a supramolecular templating approach which enables to successfully carry out chemical transformation even under strong dilutions. For this purpose, we are utilizing a pyrene anchoring system [1] and polymersomes as supramolecular template. In this design, reactive functional groups conjugated to the pyrene anchor are positioned in close proximity upon binding to the supramolecular template, creating a dynamic and localized reaction environment that enhances reaction efficiency. This work demonstrates how supramolecular strategies can mimic enzymatic functions to control reactivity in complex chemical systems.

As more and more plastic waste accumulates in nature, new approaches to material manufacturing is required to tackle this. By using principles like "design to degrade" and "design to recycle", materials are tailored not only to specific properties but also with their end-of-life in mind.

Aliphatic polyesters are good candidates for the synthesis of both chemically recyclable and biodegradable plastics due to the presence of hydrolyzable bonds in the polymer backbone. However, chemical recycling can still require harsh conditions and harmful chemicals, while the biodegradation rate is highly dependent on physical factors, chemical structure and environmental parameters. [1] [2] To promote recyclability under mild conditions and to increase the biodegradation rate, while still keeping the stability of materials during service-life, double dynamics can be designed through incorporation of additional reversible bonds. These can be triggered to opened by external factors, like changes in pH or light irradiation.

With this thought in mind, our work has been focused on the development of double dynamic photocurable resins for digital light processing (DLP) 3D printing. Aliphatic polyester oligomers were end-functionalized with photoreactive groups that crosslink rapidly under UV. Under reductive conditions, this network can be reversibly de-crosslinked leading to the release of low molecular weight polyesters which are expected to be susceptible for further degradation. By varying the chemical structure of polyesters, the mechanical properties of the resin can be adjusted for different applications.

Dynamic Covalent Networks (DCNs) combine the best of thermosets and thermoplastics. The covalent crosslinks provide mechanical robustness and chemical stability, while their bond exchange imparts reprocessability. Our research focuses on networks in which the dynamic bonds exhibit an increased lifetime under applied force, thereby enhancing resistance to mechanical failure within a specific force regime. These force-responsive bonds, displaying counterintuitive behavior, are identified as catch bonds.

Our design strategy for synthetic catch bonds is based on providing mechanical hindrance to β-hydroxyl mediated transesterification reaction in phosphate triesters, which are susceptible to hydrolytic degradation. External stimuli, such as mechanical force or osmotic stress, make the trigonal bipyramidal transition state energetically less favorable, thereby extending bond lifetime. Previously, our group demonstrated the catch bond character in dynamic covalent networks based on 3-arm polyethylene glycol (PEG) crosslinked with ethylene glycol chlorophosphate, where the catch bond character was observed by varying the osmotic stress. The present work aims to investigate the pH-dependent degradation behavior of the catch bond network and compare it to phosphate triester network exhibiting potential slip bond characteristics, as well as a model system under similar conditions.

Hyperbranched Polymer Based Amphiphilic Crosslinked Networks
Hyperbranched polymers (HBPs) possess a unique branch-upon-branch topology that presents the numerous terminal groups on the molecular periphery of a dense globular conformation; some years ago, we developed a one-step melt-polymerization to prepare peripherally clickable HBPs carrying terminal propargyl esters groups.1,2 These clickable HBPs can be thermally crosslinked with PEG-diazides of different molecular weights to access amphiphilic crosslinked polymers, where the crosslink density can be varied by varying different input parameters, such as mole-ratio of propargyl:azide and the length of the PEG-diazide. Furthermore, the spacer segment in the HBP can be varied, which in turn will modify the compactness of the HBP, which serves as the multifunctional crosslinker; thus, modifying the conformational degrees of freedom of the HB crosslinker is also a unique strategy to change the mechanical properties of the crosslinked network. Although earlier studies have carefully examined the influence of various parameters of network structures, more recent studies using precision networks have revealed several new structural features that influence their final behavior.3
Recently, we have begun to examine alternate strategies to prepare photo-crosslinkable amphiphilic polymers based on suitably derivatized HBPs. The presentation will focus on correlating the various properties of these amphiphilic networks as a function of the some the input parameters outlined. Amphiphilic networks, such as the ones described in this study present some unique features, namely the presence of discrete hydrophobic (HBP) and hydrophilic (PEG) domains, which can be independently tailored for specific applications.

Solid polymer electrolytes (SPEs) are promising for high energy density Li-metal batteries (LMBs), offering safety advantages over traditional liquid electrolytes, which pose leakage, flammability, and stability issues.[1] Chemically crosslinked SPE enhance mechanical strength and thermal stability but lack reprocessability and self-healing capabilities. Vitrimer-based SPEs have emerged as a potential alternative to address these limitations. Vitrimers are a new class of crosslinked polymers that possess the ability to flow at high temperatures due to the presence of exchangeable covalent bonds.[2] This feature allows for reprocessability, recyclability, improved adhesion, and better ionic conductivity—key attributes for next generation SPEs.[1,3]

The objective of this project is to investigate the effective implementation of the vitrimer behavior to improve various properties of solid polymer electrolytes. This will be pursued through the synthesis of vitrimer-like SPE networks, in which properties are tuned by changing both the nature of the dynamic covalent bonds (DCBs) and the topology of the networks. The findings are expected to facilitate the development of the next generation of solid polymer electrolytes for sustainable solid-state LMBs with enhanced quality, reliability, and lifetime.

Here, we present two network topologies based on Poly(ethylene glycol) methacrylate (PEGMA) and two types of boronic ester as DCBs. The first network is made by reacting two polymers bearing complementary boronic ester functions. The second network is directly obtained by photopolymerization with a difunctional dioxazaborocane crosslinker. The resulting networks are further studied to evaluate their dynamic and electrochemical properties through rheology and ionic conductivity tests.

The use of diisocyanates in the synthesis of conventional polyurethanes raises significant environmental and health concerns due to their toxicity and the emission of harmful substances during production. Non-isocyanate polyurethanes (NIPUs) have emerged as a promising alternative, offering a more sustainable and safer route to polyurethane-based materials. In this study, a catalyst-free, bulk synthesis of a thiol containing NIPU is presented. To enhance functionality, a novel composite material was developed by incorporating 3 wt% multi-walled carbon nanotubes (MWCNTs) into the NIPU matrix. The resulting material exhibited enhanced electrical conductivity, making it suitable for a variety of electronic and energy applications. Furthermore, the NIPU/MWCNT composite demonstrated excellent recyclability due to the presence of dynamic sulphur-based linkages in its structure. These bonds enable reversible thiol-disulfide exchange reactions under moderated temperatures, allowing the polymer network to break and reform during reprocessing. Consequently, the material was successfully recycled up to three times in a hot-plate press with minimal loss in thermal and mechanical properties, highlighting the robust and sustainable nature of the NIPU-based system. This work not only addresses the challenges associated with conventional polyurethanes but also provides a promising pathway for the development of recyclable, conductive polymers for their use in sustainable electronics and other advanced material applications.

Liquid Polybutadienes (LPBDs) are low molecular weight, unsaturated oligomers in liquid form that offer numerous processing, performance, and environmental benefits across various rubber and elastomer applications. Conventional LPBDs undergo an irreversible curing reaction, making them non-recyclable waste at the end of their lifecycle. Additionally, reinforcing fillers are typically added to LPBDs to produce rubber composites with improved properties and stability. Enhancing the sustainability of these elastomeric materials can be achieved through two key strategies: modifying elastomers to enable reversible crosslinking,¹,² and developing fillers derived from biomass.³
This study modifies LPBDs and cellulosic bio-fillers to develop renewable, recyclable, and reprocessable composites using dynamic covalent Diels-Alder networks. Selected LPBDs varied in molecular weight and architecture (1,4-cis, 1,4-trans, 1,2 unsaturations). The modification process involved epoxidation via the Prilezhaev reaction, followed by furfuryl alcohol addition. Different bis-maleimides, varying in molecular structure and weight, were synthesized by reacting diamines with maleic anhydride to serve as the dienophile. Cellulose nanocrystals (CNCs) were extracted from hemp pulp via acidic hydrolysis and selected as a bio-filler. The extracted material was then modified through periodate oxidation followed by reductive amination with furfurylamine to introduce furan groups onto the CNC surface, ensuring filler-matrix compatibility and facilitating interfacial reactions during composite cross-linking.
Preliminary rubber composite films were prepared by Diels-Alder reaction using different furan/maleimide molar ratios, to optimize their cross-linking density and mechanical properties.

This study was carried out within the MadABio project – funded by European Union – Next Generation EU within the PRIN 2022 PNRR program.

Polyurethane-based thermoplastic elastomers (PU-TPEs) are used in many biomedical applications, among others. However, they are synthesized from highly harmful isocyanate compounds, and their bio- and hemocompatibility when used for medical devices in contact with blood remains insufficient, which can lead to high rates of thrombotic complications and risks of infection. In this work, the easy and up-scalable synthesis of a safer and greener isocyanate-free PU-TPE, called poly(hydroxy oxazolidone) (PHOx) is reported. Moreover, this new biomaterial can be (re)processed by various relevant manufacturing techniques, namely hot pressing, electrospinning, injection-molding, and additive manufacturing, that lead to a diversity of objects for multiple applications. The in vitro hemocompatibility tests performed with human blood exhibit better performance of PHOx than conventional medical grade PU-TPEs, in addition of triggering less platelet adhesion as well as less contact phase activation of coagulation. Interestingly, they also reduce the adhesion of Staphylococcus epidermidis compared to PU. Finally, this valuable PHOx is proven non-cytotoxic upon direct and indirect contact with fibroblasts and endothelial cells and its subcutaneous implantation in rabbits confirms its in vivo biocompatibility and non-degradation for a period of up to at least 4 weeks. This new polymer is therefore a highly promising isocyanate-free alternative to industrially produce PU-TPEs for the production of hemo-, biocompatible, durable and customizable blood-contacting devices.

Iodophors, polymer-iodine complexes, are crucial in pharmaceutical and antimicrobial applications [1-3]. This study explores the stability, binding mechanisms, and antimicrobial efficacy of iodophors formed with polyvinylpyrrolidone (PVP), poly(2-oxazolines) (poly(2-methyl-2-oxazoline) (PMOZ), poly(2-ethyl-2-oxazoline) (PEOZ), poly(2-propyl-2-oxazoline) (PPOZ)), and iodine in aqueous potassium iodide solutions. Using UV-Vis spectroscopy, viscometry, and dynamic light scattering (DLS) we characterised the structural and physicochemical properties of these complexes. Early in the work [4], we established that PEOZ forms complexes with iodine similarly to PVP, exhibiting stronger iodine binding, enhanced solution coloration, macromolecular compaction, and aggregation, yet iodophors based on both polymers demonstrate comparable antimicrobial activity.
In this study, UV-Vis analysis revealed bathochromic shifts upon complexation, with PPOZ showing the most pronounced interaction, followed by PEOZ and PVP, while PMOZ exhibited minimal binding. Partition coefficient studies demonstrated the highest iodine-binding affinity for PPOZ and PEOZ, indicating enhanced iodine stabilization. Intrinsic viscosity and Huggins constant measurements confirmed polymer chain collapse upon complex formation, reducing solvent quality. Antimicrobial studies against Staphylococcus aureus, Escherichia coli, Bacillus subtilis, and Candida albicans showed that PPOZ-iodine complexes exhibited the lowest minimal bactericidal concentrations (MBCs), highlighting their superior efficacy. A direct correlation was observed between the partition coefficient and antimicrobial activity, with lower partition values corresponding to increased iodine availability and enhanced bactericidal effects.
These findings provide a comprehensive understanding of iodophor formation, stability, and antimicrobial effectiveness, paving the way for the rational design of polymer-iodine formulations with optimized properties for biomedical and pharmaceutical applications.

Polyionenes are ion-containing polymers with quaternary nitrogen atoms integrated into the polymer chain, providing inherent cationic charge density [1]. This feature allows them to interact with negatively charged microbial membranes, disrupting membrane integrity and exhibiting antimicrobial effects. To evaluate their antimicrobial properties, among the traditional MTT assay and microbiological methods, the Galleria mellonella (wax moth larvae) model is increasingly used due to its cost-effectiveness, ease of handling, and immune system similarities to mammals, without the need for ethical approval.
This study reports the synthesis, characterization, and antimicrobial evaluation of new polyionic polymers. Two synthesis methods were used: one involved the hydrolysis of poly(2-ethyloxazoline) and subsequent quaternization with bromoethane, and the second utilized the Menshutkin reaction with N,N,N',N'-Tetramethylethylenediamine and 1,2-dibromoethane or bis(2-chloroethyl)amine hydrochloride.
The ionenes were characterized using 1H NMR, IR spectroscopy, and GPC to determine the composition and molecular weight. The Z-potential and electrophoretic mobility were measured as a function of pH, and hygroscopicity was evaluated using dynamic vapor sorption.
Antimicrobial and toxicological evaluations were performed with the MTT assay, microbiological methods (minimum inhibitory concentration and disk diffusion), and Galleria mellonella larvae. The experiments demonstrated that ionenes exhibited antimicrobial efficacy against Staphylococcus aureus based on concentration, and the best candidates were selected for further development.

Isotactic polypropylene (i-PP) is widely utilized in medical and laboratory applications, including syringes, pipette tips, microplates, and storage tubes, due to its high rigidity, good chemical resistance, and suitability for sterilization.[1] In addition to these properties, the gas penetration behavior of i-PP plays a crucial role in preserving the stability and integrity of biological samples, making it a valuable material for biobanking.[2]
A “biobank” is defined as an organized process for the long-term storage of biological samples and associated data to support diverse research purposes.[3] Optimizing biobanking processes—including sample collection, transportation, preservation, and storage—requires the selection of appropriate polymer materials for laboratory containers and devices. Since maintaining the stability of biological samples is essential, understanding the gas penetration behavior of i-PP is critical for its effective use in storage applications.
This study investigates the transport behavior of four different gas penetrate molecules including O₂, N₂, H₂, and CO₂, in i-PP using molecular dynamics (MD) simulations.
We considered the mean squared displacement (MSD) of the gas molecules as a function of time to describe the gas diffusion(D).[4] Also solubility(S) were determined through the test particle insertion (TPI) method.[5] The calculations have been studied in four temperatures: 300 K, 350 K, 400 K, and 500 K.
The results indicate that (D) correlates with molecular effective size and increases with temperature, whereas (S) is more closely related to the condensability and decreases as temperature rises. Finally, our findings suggest that i-PP can be considered an effective gas barrier within a specific temperature range.

Uranium load in groundwater is discussed as a topic of concern due to potential health risks, including kidney damage and increased cancer risk, particularly in regions lacking advanced water treatment facilities¹. Casein, a milk-derived protein, has a high affinity to bind heavy metal ions such as uranium²,³. However, its water solubility and susceptibility to microbial degradation limits practical applications in water purification. This study investigates the chemical crosslinking of casein with glyceraldehyde to synthesise a water-insoluble hydrogel that is resistant to microbial degradation during its intended use and complies with specifications for use in drinking water. A statistical design of experiments was used to analyse the effects of the synthesis parameters on the final product. These include reaction temperature and time, protein concentration in aqueous solution, concentrations of glyceraldehyde and glycerol (plasticiser) in relation to protein content and pH values. Once the reaction is complete, the solution is rapidly frozen with liquid nitrogen and then freeze-dried to obtain a solid material with a porous structure for good water permeability and a high surface area. It was shown that subsequent tempering has a positive effect on water insolubility.

The resulting bioplastic is intended to serve as a filter medium for water treatment, particularly in areas where further treatment is not possible or in crisis regions with uranium-contaminated groundwater. By modifying casein into a durable, water-insoluble adsorbent, this research contributes to the development of accessible and efficient solutions for the removal of heavy metal ions from wastewater.

Injectable porous hydrogels represent an advanced class of biomaterials for minimally invasive surgery, providing a supportive microenvironment for cell encapsulation, proliferation and tissue regeneration.
In this work, we present a fully synthetic and biodegradable hydrogel based on poly(α-amino acid) (PolyAA), a versatile polymeric biomaterial with tunable physicochemical properties and enzymatic degradability [1]. The polymeric precursor was functionalised with biocompatible tyramine groups allowing diphenol bond formation through enzymatic (horseradish peroxidase (HRP)/H₂O₂, in situ H₂O₂) or photoinitiated (Ru(II) complex/(NH₄)₂S₂O₈, 450 nm) cross-linking [1, 2]. Porous structures with interconnected pores were formed using an aqueous two-phase system (ATPS) with polyethylene oxide (PEO) as porogen. A novel single-step strategy incorporating a branched dihydroxyphenyl RGD peptide was employed to enhance cell adhesion while maintaining precise control over the peptide concentration.
Physicochemical characterization (NMR, UV-Vis, GPC) confirmed the successful synthesis of the polymer precursor. The gelation time, gel yield, swelling, and mechanical properties of the resulting hydrogels were compared between the different crosslinking methods. The resulting hydrogels exhibited gel yields above 80%, swelling capacities of 10–40 g/g, and tunable gelation times (5–300 s) depending on the cross-linking method. The compressive modulus can be adjusted in the range of 5 to 50 kPa, allowing various applications in tissue engineering. Finally, in vitro studies demonstrated the hydrogel's cytocompatibility with human mesenchymal stem cells (hMSCs), with encapsulated cells exhibiting long-term survival and adhesion modulated by RGD concentration and matrix stiffness.
These findings establish the PolyAA/ATPS/RGD hydrogel system as a versatile platform for next-generation injectable biomaterials in regenerative medicine.