Topological modification of block copolymer (BCP) conformations offers a promising approach for developing self-assembled periodic nanostructured materials with smaller domain sizes, which are essential for a range of technological applications. Cyclic polymers, with their inherently more compact conformations, present an effective strategy for achieving this miniaturization. In this work, through a combination of analytical theory and coarse-grained molecular dynamics simulations, we establish a relationship between different nonlinear topologies and the corresponding domain size of lamella-forming BCPs. Our investigations includes BCP architectures with one or two cyclic segments such as tadpoles, diblock and triblock 8-shaped polymers, and diblock nonconcatenated and concatenated rings. We demonstrate that the primary reduction in lamellar domain size is driven by the more compact arrangement of monomers in the cyclic architectures, with an additional contribution from the non-concatenation of cyclic segments. This is corroborated by theoretical predictions for both domain size reduction and BCP conformations across different architectures. Moreover, consistent with theoretical expectations, the non-concatenation of rings reduces the interpenetration of opposing brushes, thereby lowering friction between lamellae.

Rare earth metal-mediated group transfer polymerization (REM-GTP) enables the synthesis of high-precision polymers, e.g., polyvinylphosphonates.^1 By activating the initiator sym-collidine with Cp2Y(CH2TMS)(THF) (Cp = C5H6; TMS = Si(CH3)4), a variety of polymers with tailored architectures can be produced.^2
Vinylphosphonates have been exclusively amorphous polymers, offering versatile applications, e.g., dental adhesives or flame retardants, due to their water solubility and biocompatibility.^3 They exhibit thermoresponsiveness and possess a low critical solution temperature, classifying them as smart materials.^4

However, synthesizing these polymers is demanding due to the high sensitivity and instability of the activated catalyst species towards hydrolysis, requiring meticulous and clean handling. This challenge is particularly pronounced when attempting to reproduce identical polymers with the same molecular weight, as slight variations can result in significant differences in polymer structure. Achieving perfect reproducibility is crucial for post-polymer modification processes, as it enables precise comparison of the physical properties of the modified polymers.^5

To address these challenges and ensure consistent polymer synthesis, a universally applicable robot was developed, capable of autonomously performing any homogeneously catalyzed reaction. The robot precisely doses water- and oxygen-sensitive reactants into a self-designed reactor. Using the robotic setup led to the discovery of a new vinylphosphonate polymer that exhibits the properties of amorphous polymers and possesses crystalline characteristics – the first of its kind. This breakthrough opens new possibilities in materials research and application.

Shortly, artificial intelligence will be integrated into the setup, automatically monitoring the reactions using in situ NMR measurements and adjusting the reaction conditions accordingly in real-time.

Complex coacervation is the phase separation of oppositely charged polyelectrolytes resulting in a polymer-dense coacervate phase and a polymer-depleted supernatant phase. Coacervation is crucial for many biological processes and novel synthetic materials, where the environment is often filled with other neutral molecules (crowders). Yet, the complex role of crowders on complex coacervation has not been studied systematically in controlled conditions. We performed coarse-grained molecular dynamics simulations of coacervation in the presence of polymeric crowders of varying concentration and chain length. While short crowders do not have any significant effect on coacervation, larger crowders stabilise the coacervate against added salt, increasing its critical salt concentration. The change in critical salt concentration saturates for long crowders to a value determined by the crowder concentration. Rescaling all phase diagrams by their critical salt concentration leads to a collapse of the data that demonstrates a universal phase behaviour. Our simulation indicates that the inability of crowder chains to mix with the polyelectrolytes is the driving force behind crowding effects. These testable predictions provide a first step towards a comprehensive understanding of crowding effects in complex coacervation.

In recent years, the disposal of large quantities of polymeric materials has become a serious environmental problem，highlighting the need for enhancing their durability and longevity. One effective approach to toughening polymer materials is the incorporation of energy dissipation mechanisms, which can be achieved through supramolecular crosslinking, topological crosslinking, and sacrificial bonds. In particular, polymer materials with non-covalent bonds introduced as reversible cross-linking points show excellent toughness due to efficient energy dissipation, since bond dissociation occurs easily when stress is applied.
In this study, the mechanical properties of polymeric materials with reversible crosslinks consisting of a ring-shaped host molecule, β-cyclodextrin (β-CD), and a cage-shaped guest molecule, adamantane (Ad), were investigated using molecular dynamics simulations.
First, a local model of the host-guest complex was used to confirm the stability of the reversible bridge formation, showing good agreement with experimental results.
Next, reversible crosslinks were introduced into polymers with polymethyl methacrylate (PMMA) as the base material, and differences in interfacial interdiffusion coefficients and interfacial layer thicknesses were investigated from the glass transition temperature, and the experimental trends were explained consistently.
Finally，the formation of complexes at the polymer interface and the effect of β-CD/Ad complexes on the mechanical properties of the materials were quantified by uniaxial tensile analysis.
These results of this study provide valuable insights into the design of tough and sustainable polymer materials with reversible crosslinking structures.

In recent years, a novel crosslinking approach based on cyclic macromolecular monomers, known as "mobile crosslinking," has attracted significant attention as an alternative to traditional chemical and physical crosslinking methods. This method enhances flexibility and impact resistance through dynamic structural adjustments but may also lead to reduced stiffness and strength. Therefore, achieving a balance between toughness and strength has become a critical challenge in this field. To address this issue, researchers have explored polymer composites reinforced with cellulose nanocrystals (CNC).
In this study, we focused on polymer matrix composites with mobile crosslinking, using cyclodextrin (CD) as the cyclic macromolecular monomer and CNC as the reinforcing agent. Through multiscale simulations, we systematically investigated the mechanical mechanisms of these composites. Specifically, we employed multiscale finite element analysis to quantify the reinforcing effects of CNC fibers based on strain energy and proposed a design strategy to optimize the mechanical performance of the composite. Furthermore, to elucidate the molecular mechanism of mobile crosslinking, full-atom molecular dynamics simulations were conducted to analyze the role of cyclodextrin in the composite. We examined how cyclodextrin influences the structural changes and interactions of the polymer backbone. The simulation results demonstrated that the introduction of cyclodextrin significantly enhances material performance, with the maximum tensile strength increased by 487%.

Bottlebrush polymers are emerging as promising materials for soft biomimetic applications due to their unique mechanical properties. In this study, we investigate how polydispersity in architectural parameters of bottlebrush
polymer influence the conformation of individual bottlebrush polymers in polymer melts.
Molecular dynamics simulations reveal that increasing polydispersity significantly alters polymer stiffness and persistence length, resulting in a broader distribution of structural conformations and enhanced variability in mechanical properties. Furthermore, a machine learning-based Gaussian process model efficiently predicts the structure–property relationships across various architectures. These findings underscore the crucial role of nanoscale heterogeneities in determining the macroscopic behaviour of bottlebrush-based elastomers, paving the way for designing ultra-soft, tuneable materials with potential applications in tissue engineering and soft robotics.

Keywords: Polydispersity, Bottlebrush Polymers, Structure–Property Relationships, Molecular Dynamics, Gaussian Process Model, Elastomers, Biomimetic Materials, Tissue Engineering, Soft Robotics

Polyether polyols are important building blocks for many consumer and industrial polymer formulations, including polyurethanes.(1) Among the most important polyether is polypropylene glycol (PPG), commonly made through the ring opening polymerization (ROP) of propylene oxide (PO) using heterogeneous catalysts such as double metal cyanide (DMC). There are reports of supported DMC catalysts used in copolymerizations with supports such as zeolite MCM-41 (2), titanium dioxide (TiO2) (3), silicium dioxide (SiO2) (4), and aluminium oxide (2) (Al2O3). It was shown in a patent that especially DMC on hydrophobic supports provide highly active catalysts (5). This work aims to compare supported DMC via the rate constant from the ring-opening polymerization of PO which is highly exothermic and was therefore done in semi-batch reactor. Hydrophilic and hydrophobic variants of alumina, silica, and titania were used as supports with loadings of each 16 wt.-% and 6 wt.-%. It was found that next to the support material and loading, the wettability plays an important role in the tuning of the catalyst activity. However, these support characteristics influence the catalyst activity in unexpected patterns.

We have conducted a computational study on the self-assembly behavior of cylinder-forming block copolymers, directed by a guide pattern of hexagonally or tetragonally arrayed pillars, using mesoscale density functional theory simulations. By adjusting the spacing (L) and diameter (D) of the pillars in relation to the intrinsic cylinder-to-cylinder distance (L₂) of the cylinder-forming block copolymer (Fig 1 a-c), we investigated the effectiveness of replicating cylinders formed by the block copolymer multiple times through this pillar-directed self-assembly process. The simulations demonstrated that at specific values of normalized parameters L~=L/L₂ and D~=D/L₂ coupled with suitable surface fields, triple and quadruple replication are achievable with a hexagonally arrayed pillar pattern, while only double replication is attainable with a tetragonally arrayed pillar pattern. This work, offering an extensive structure map encompassing a wide range of possible parameter spaces, including L~ and D~, serves as a valuable guide for designing contact hole patterning essential in nanoelectronics applications.

Methods such as Density Function Theory (DFT) can be successfully applied to studying polymers and their composites. Polyvinylidene halides (PVDX, X = F, Cl, Br, I) have gained attention as potential materials for solid polymer electrolytes, particularly for energy storage applications due to the presence of atoms with increasing electronegativity. Understanding the interactions between polymer chains and lithium salts, such as lithium perchlorate (LiClO₄), is crucial for optimizing their ion conduction properties and reactivity.
Models reflecting the structure of a composite composed of different varieties of polyhalides with the addition of LiClO₄ were optimized and characterized using DFT methods. The stability and reactivity of PVDX composites were analyzed and compared. Cluster models for both PVDX-α and PVDX-β were investigated, considering geometry, electrostatic potentials, electron density, Gibbs free energy difference, and the HOMO-LUMO gap. Structural modifications, including changes in the energetic gap, geometric distortions, and reactivity, were observed upon interaction with LiClO₄. Theoretical results were compared with experimental data, particularly FTIR spectra, which showed that the crystalline form of PVDF significantly influences the ionic conductivity and functionality of polymer electrolytes. The analysis revealed that PVDF-β and PVDC-β exhibited favorable dissociation of LiClO₄ due to weaker interactions with lithium ions in the β form. Additionally, a decrease in the HOMO-LUMO gap with increasing atomic number of halogens suggests easier electronic transitions in heavier halogens [1].
Calculated data provided valuable insights into the conductive properties of solid polymer electrolytes, particularly in the PVDF and PVDC-β forms, highlighting their potential for energy storage applications.

Additive manufacturing (AM) techniques, also known as 3D-printing, have been widely recognised as promising technology for rapid production of novel personalised drug-delivery systems, scaffolds for bio-fabrication, and food applications (1). Rapid advancements in AM technology demand the development of advanced polymeric materials for personalised 3D-printed devices to enter clinical use. Although there has been promising progress in identifying new materials for 3D-printing, the range of resins/polymers available is still limited, (2) with big reliance on petroleum-derived materials.

Therefore, new materials that are renewably sourced and biodegradable are desirable for expanding applicability and recyclability. (3) Polymer synthesis and manufacturing processes based on molecules derived from bio-renewable resources has soared steadily with varied attempts to reduce waste of final products. Specifically, glycerol, a readily available waste product from biodiesel processing that is highly functionalised since bearing three hydroxyl groups. Glycerol global production has been predicted to exceed 4 billion litres by 2026 (4).

We previously reported that an acrylated glycerol-based oligomer, polyglycerol-6-acrylate, fulfils all the necessary criteria for volumetric printing (transparency, photo-reactivity, viscosity) and was successfully used to print a variety of models with intricate geometries and good resolution. (2) In the present work, we want to expand the use of (meth)acrylated-polyglycerols (4 and 6 units of glycerol) and their blends in Stereolithography (SLA), as this technique presents numerous advantages. SLA has the capability to generate thin features (≃ 10 µm), can reach intricate geometries, with high reliability (5) and reduced waste production.

Fluorescent chemosensors stand out for their ease of use, real-time imaging, and rapid response capabilities. While various fluorophore materials have been widely utilized in the literature, most applications rely on solution-phase or solid support for analysis. However, this dependency limits their practicality for gas-phase applications, which are crucial in diverse fields such as industrial and environmental monitoring, civilian security, and indoor/outdoor air quality assessment. For that purpose, nano-fibres of pyrene, which have significant potential for sensor applications due to its ability to respond sensitively, it is aimed to develop over pyrenylstyrene homopolymer. With that in mind, this study aims to develop pyrene-based polymeric materials that can be directly used as sensors. Furthermore, considering the ease of derivatization of aromatic structures, functional groups such as oxime, aldehyde, diamine, and nitrile can be utilized in the structure after the synthesis of either the monomer or polymer, enabling the design of smart sensors capable of target recognition. The incorporation of these functional groups will enhance the specificity of the sensors, allowing for more precise and targeted detection.

Polyethylene (PE) with disperse in-chain functional groups (such as ester- or keto-groups) represent promising materials for supporting a more sustainable plastics economy. Such polymers retain the desirable properties and performance of PE while being more amenable to degradation processes with the functional groups acting as “pre-determined breaking points”. Thereby, external biotic (e.g., enzymatic) or abiotic (e.g., hydrolytic or photochemical) degradation processes can break the polymer down at these disperse in-chain functional groups, yielding lower molecular weight segments which may be more accessible for ultimate biodegradation.[1],[2] In order to obtain polyethylene-like properties of such polymers, the predetermined breaking points must be present in a small amount and isolated. For this reason, the degradation intermediates are expected to consist of long linear methylene chains with a small number of functional groups; the amenability of such compounds to ultimate biodegradation has not yet been clarified. To elucidate the ultimate biodegradability of these materials, model degradation intermediates of PE-like polymers are synthesized using advanced catalytic chain-growth systems to enable control over the molecular weight and distributions as well as the possibility of introducing functional groups.[3],[4] These polymers are subjected to biodegradation studies in laboratory incubations with natural soil samples to determine the relationship between structure and biodegradability.

Due to its hazardous nature, Cr(VI) discharge into water bodies is strictly limited to a maximum of 0.05 mg/L. Adsorption emerges as a highly effective wastewater treatment method due to its affordability, simplicity, and eco-friendliness (Wakshum et al., 2024). The development of a composite adsorbent integrating chitosan (Cs), lignin nanoparticles (LNPs), and graphene oxide (GO) offers a promising approach for Cr(VI) removal. Chitosan is widely recognized for its abundance of functional groups, such as −OH and −NH₂, which facilitate heavy metal adsorption (Maroulas et al., 2023). Its limited mechanical strength and acid stability necessitate modification for optimal performance. Lignin, natural polymer, derived from the paper industry, complements chitosan by providing mechanical reinforcement and diverse functional groups that enhance chemical affinity and electrostatic interactions. Graphene oxide adds high surface area and exceptional mechanical strength, further enhancing the composite’s performance and structural integrity (Bashir et al., 2024). The composite’s adsorptive efficiency was tested via batch adsorption experiments, with its morphology and structure analyzed using FT-IR, SEM, BET, and XRD techniques. Experimental equilibrium data were modeled using Langmuir and Freundlich isotherms, demonstrating that the Cs/GO@LNPs composite effectively removes Cr(VI) from aqueous environments.

Acknowledgment: We acknowledge support of this work by the project “Advanced Nanostructured Materials for Sustainable Growth: Green Energy Production/Storage, Energy Saving and Environmental Remediation” (TAEDR-0535821) which is implemented under the action “Flagship actions in interdisciplinary scientific fields with a special focus on the productive fabric” (ID 16618), Greece 2.0 – National Recovery and Resilience Fund and funded by European Union NextGenerationEU.

A phenothiazine-derived diamine monomer, namely 3,7-bis-[4-aminophenyl(4'- methoxyphenyl)amino]-10-(4-methoxyphenyl)phenothiazine, was synthesized and led to new electroactive aromatic polyamides and polyimides. The resulting polymers were readily soluble in polar organic solvents and could afford strong and flexible film by solution casting. These polymers displayed a pink color change at their first-stage oxidation and blue color change at their second-stage oxidation. Cyclic voltammetry results indicated that the polymers showed two reversible oxidation redox couples at 0.47－0.61 V and 0.73－0.85 V. These polymers exhibited excellent electrochemical and electrochromic stability with good coloration efficiency.

The increasing global water crisis necessitates advanced treatment systems to safely reuse water, especially in the presence of persistent emerging contaminants (ECs). This study presents an innovative heterogeneous Fenton system that generates H₂O₂ in situ through the basic hydrolysis of CaO₂. To counteract the alkalinity that inhibits the Fenton reaction (pH > 4), various polymeric and biopolymeric materials were evaluated for pH control. Additionally, condensed tannins (TAN) from Pinus radiata bark were incorporated as natural chelating agents, utilizing their catechol units to enhance Fe³⁺ to Fe²⁺ reduction and accelerate the reaction’s rate-limiting step.

Experimental optimization aimed to maximize the degradation of ethylparaben (EtP), a model EC, monitored via HPLC-UV-Vis. Under optimal conditions, 95% EtP degradation was achieved with [Fe³⁺] = 50 μM, [CaO₂] = 1.4 mM, TAN = 1200 mg/L, and pH control material = 0.112 g. HS-SPME-GC/MS analysis confirmed the formation of aromatic and aliphatic oxidation products, validating the system’s effectiveness.

This is the first study testing this hypothesis, highlighting the potential of functionalized biopolymers, synthetic resins, CaO₂, and tannins in Fenton applications. The results pave the way for sustainable polymer-based water treatment technologies, offering an effective alternative for EC removal.

Cross-linked multi-crystalline polymer networks can be effectively designed to have thermo-sensitive reversible shape-memory properties (SMPs)1,2. However, for certain applications, direct heating should be avoided. Instead, an indirect increase in temperature can be achieved through photo-thermal or plasmonic resonance3 in a polymeric matrix that contains chromophores or metallic nanoparticles when it is exposed to light.
Our research focuses on developing a novel photo-activable reversible shape-memory polymer realized starting from a triblock-copolymers: poly(caprolactone)-polybutylene succinate- poly(caprolactone), possessing different semicrystalline domains. After functionalization of terminal hydroxy groups with a methacrylate isocyanate, the photo-polymerizable copolymer was embedded with commercial Titanium Nitride (TiN) nanoparticles, that present plasmonic resonance peak in near-infrared region (NIR) inside the biological window4 and promising features as agent for Photo-Thermal Treatment5. The nanoparticle formulation has been optimized, and the material managed to reach the required activation temperature (55-60 °C, corresponding to the melt of PCL phase) for reversible shape-shifts when exposed to NIR light sources (figure 1a). Moreover, an evaluation on the feasibility of extrusion based 4D-printing has been conducted studying rheological and thermal properties of the prepared material to optimize printing and cross-linking process. First printing trials were performed (figure 1b and 1c) to study the feasibility of 4D-printing process for photo-sensitive artifacts.

The textile and packaging industries are among the largest contributors to environmental pollution due to their heavy reliance on fossil-based plastics. The widespread production and consumption of these materials, combined with low recyclability rates, have led to significant waste accumulation, particularly in landfills. Consequently, developing sustainable alternatives that retain the functionality of conventional plastics has become a priority at national and international levels[1].
The ”From Fossil to Fossil” project aims to develop cellulose-based raw materials that can adequately be used to replace fossil resources in packaging solutions. Cellulosic fibres, when combined with other materials (thermoplastic matrices, preferentially bioplastics) can give rise to new biocomposites that can be processed through injection/moulding, thermomoulding, extrusion, lamination or 3D printing. These biocomposites have the potential to be applied in a wide range of applications such as rigid packaging, films and filaments. Additionally, in the form of monofilaments, they can also be combined with/originate sustainable textile products and create new products for flexible or rigid packaging solutions.
This study investigates the incorporation of cellulose fiber and microcrystalline cellulose at varying loadings in a poly(lactic acid) (PLA) matrix, focusing on their impact on the mechanical, thermal, and rheological behavior of the resulting composites. Understanding these effects will support the optimization of PLA-cellulose composites for melt spinning applications, paving the way for more sustainable textile and packaging solutions.
Work developed within Agenda “From Fossil to Forest” [C644920945-00000036| Project nº 8], financed by RRP - Recovery and Resilience Plan under the Next Generation EU from the European Union.

Polymers in liquid formulations (PLFs) are integral components of numerous consumer and industrial products, including adhesives, agricultural solutions, household care, lubricants, personal care items and cosmetics, and water treatment solutions. These formulation polymers play a critical role in delivering technical performance, functionality, and a multitude of other applications for many fast-moving consumer goods.1,2

The PLF industry currently relies on fossil-derived feedstocks, but rising costs, competition with other industries, and increasing environmental pressures pose significant challenges for the PLF industry.3 Furthermore, the current methods of production, use, and disposal of PLFs are unsustainable. Transitioning to natural polymers or those derived from bio-based feedstocks presents a viable solution.4 However, as we move away from non-degradable and fossil-derived polymers, it is essential to ensure that their replacements are genuinely sustainable. This requires a thorough assessment of resource use, biodegradability, biocompatibility and their performance in formulations.5

Herein, our current research is focused on the synthesis of bio-derived monomers and polymers that are known to biodegrade through hydrolysis. We aim to gain a deeper understanding of how to control their performance and degradability, with the goal of developing these polymers as additives in beauty and personal care products. These bio-based alternatives have the potential to replace petroleum-based, non-degradable PLFs currently in use.