Dual-functional initiators containing both azo and per-ester groups enable efficient block copolymer synthesis by allowing polymerization under varying conditions. Since the 1980s, azo-peroxide initiators have been utilized for block copolymer production through thermal, redox, and UV-induced initiation. [1] Previous studies relied on thermal initiation, redox activation, and UV irradiation. [2] While previous studies explored multiple activation mechanisms, our research introduces a more direct approach by exclusively utilizing thermal initiation. The proposed one-pot polymerization strategy eliminates the need for intermediate purification, streamlining the synthesis process in contrast to traditional methods.
In this work, we employ di-tert-butyl 4,4ʹ-azobis(4-cyano peroxyl-valerate) (AIBN-PEN) as a dual-functional initiator for thermal free radical polymerization (FRP). The polymerization process occurs in two stages: first, at 70°C, poly (methyl methacrylate) (PMMA) macro-initiators are generated; then, at 110°C, polystyrene (PSt) block growth proceeds. A semi-batch approach ensures balanced monomer consumption, stabilizing the overall polymerization kinetics. Soxhlet extraction is applied to eliminate residual homopolymers and other impurities, yielding high-purity PSt-b-PMMA. The formation of block copolymers is confirmed through gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) analysis.

Polymer topology plays a crucial role in physical properties and determines potential material applications.1 The shape and interconnectedness of polymer chains significantly influence their behavior, such as solution and thermal properties. We explored advanced polymer architectures including a cyclic and 8-shaped with precise molecular designs in addition to the conventional linear polymer. By studying these polymer architectures, material properties can be fine-tuned at the molecular level as advanced new possibilities in materials design.
In this work, we synthesized poly(tert-butyl acrylate) with various shapes including linear, tetra-arm, cyclic, and 8-shaped polymers using ARGET-ATRP and click chemistry.2 This approach allowed us to control both the size and structure of the polymers. Comprehensive analysis using ¹H NMR, FT-IR, SEC, DSC, and MALDI-TOF mass spectrometry techniques confirmed the successful synthesis of these polymers. Our investigation revealed that the topologies significantly influenced the properties. Cyclic polymers exhibited higher glass transition temperatures compared to their linear precursors, attributing to their more compact rigid structures.3 Further, the intrinsic viscosity decreased with increasing structural compactness across different topologies. These findings demonstrate the profound impact of polymer topology on material properties, offering new avenues for fine-tuning polymer behavior in both solution and bulk states.4 This research covers the way for developing advanced materials with tailored properties, which can potentially revolutionize applications in fields such as drug delivery, smart coatings, and high-performance polymers.

Efficient and reliable energy storage systems are a key factor in transitioning from fossil fuel to renewable energy sources to reduce anthropogenic greenhouse emissions. Among well-established but limited hydropower storage, lithium-ion batteries (LIB) are increasingly used to store excess energy and to stabilize the grid. A drawback of current LIBs is their relatively low energy density and dependence on liquid volatile electrolytes as well as the formation of lithium dendrites during cycling, leading to capacity reductions and short circuits, especially in high-capacity lithium metal batteries (LMB).

A possible solution to these problems is the usage of solid polymer electrolytes (SPE) due to their adhesion to electrode interfaces, temperature stability, as well as their ease of handling. While polyethylene oxide (PEG) is a well-known system for lithium-ion conduction, it shows insufficient ionic conductivities (IC) below the melting point of PEG (Tm≈60 °C) due to its semi crystalline properties. Creating amorphicity in PEG-like systems through copolymerization thus provides higher IC, making amorphicity an important factor in SPE design. In turn mechanical stability of the SPE is lost promoting dendritic growth. This drawback can be compensated by employing blockcopolymers with a mechanically stable phaseas well as single ion conducting polymer electrolytes (SICPE) enabling lithium transference near unity.

This work showcases block copolymers combining glassy PS and modifiable amorphous polyether blocks. The macroinitiator PS-OH is synthesized via carbanionic polymerization and subsequent endcapping with EO. This is followed by anionic ring opening polymerization of EO and glycidyl ethers for amorphous modifiable SICPE polyethers.

(Co)polymers of N-isopropylacrylamide (NIPAM) are known for the thermosensitivity of their solutions in water. Such (co)polymers are non-toxic, therefore they are widely examined for drug delivery. Polylactides (PLAs) are also used in pharmacy and cell cultivation. Graft-copolymers of NIPAM and polyesters should have both thermosensitivity in water solutions, bioresorption and affinity for cells. Herein the graft-copolymers synthesis via macromonomer approach as well as lower critical solution temperature (LCST) behavior of copolymers water solutions are presented.
According to 1H NMR spectrometry data both methacrylate- and acrylate-terminated macromonomers were copolymerized with NIPAM resulting in random copolymers. LCST of copolymers varies from 32 °C to 14 °C depending on macromonomer content (from 3 % to 17 % by weight respectively). Interestingly, the end group (hydroxyl or butyl) of macromonomer units influences strongly on LCST of the copolymer: the presence of hydroxyl end group in a oligolactide chain reduced LCST to a lower extend (up to 23 °C) in comparison with hydrophobic butyl group (up to 14 °C).
This work was carried out within the framework of the State program for scientific research of Belarus «Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry» (assignment 2.2.02.04, state registration No. 20211517).

The synthesis of UV-responsive polymers is crucial for improving adhesion technologies. These polymers address the limitations of conventional adhesives, such as their irreversibility, lack of environmental adaptability, and limited spatial control. This work presents two approaches to developing innovative UV-responsive systems for adhesion applications. In the first approach, we employed initiated chemical vapor deposition (iCVD) to synthesize poly (allyl methacrylate) (PAMA) thin films as adhesion-promoting layers. iCVD, a solvent-free, substrate-independent technique, enables the deposition of conformal, tunable films on various surfaces without damaging thermally or chemically sensitive substrates. PAMA films exhibit strong adhesion to substrates while preserving surface allyl groups, which covalently bond with UV-curable thiol-ene adhesives via click chemistry. This mild and eco-friendly system enhances adhesion strength and expands the potential for using different substrates for varied applications.
The second approach focuses on introducing photochromic azobenzene molecules into the side chains of the polymer to achieve reversible adhesion. Azobenzene undergoes trans-to-cis isomerization under UV irradiation, reverting under visible light or thermal stimuli. This photo-induced conformational change modulates polymer properties such as polarity and mechanical behavior, enabling tunable adhesion strength and controlled detachment. In experiments, adhesion strength can be varied between 20% to 90% depending on the light exposure duration and different azobenzene contents.
These UV-responsive polymers demonstrate the potential to create eco-friendly, adaptive adhesives with reversible and dynamic properties, paving the way for advanced adhesion applications in industrial, biomedical, and electronics manufacturing fields.

Sodium metal batteries (SMBs) offer a promising alternative to lithium-ion batteries due to sodium’s abundance and cost-effectiveness[1]. However, the formation of sodium dendrites and the limited ion transport efficiency in solid polymer electrolytes hinder their commercial viability.
To address these challenges, we designed a self-healing single-ion conducting polymer electrolyte via reversible addition–fragmentation chain transfer (RAFT) polymerization. The electrolyte is based on a A–B–C copolymer architecture comprising three distinct functional parts: A is a poly(sulphopropyl acrylate-sodium), which anchors immobilized sulfonate groups for single-ion conduction and mechanical rigidity; B is a poly(oligo ethylene glycol acrylate), which enhances ion mobility via flexible ethylene glycol chains[2]; and C is a poly(ureido pyrimidinone acrylate), which enables autonomous self-healing through quadruple hydrogen bonds[3].
The self-assembly of the copolymer leads to microphase separation, forming continuous and efficient ion conducting channels, achieving high ion conductivity [4]. The single-ion conduction is expected to eliminate anion polarization, homogenizing Na⁺ flux and promoting the suppression of dendrite nucleation [5]. This design effectively mitigates sodium dendrite growth while ensuring mechanical stability and extended cycle life for SMBs.
This work pioneers a multifunctional electrolyte platform that simultaneously addresses SMBs’ key bottlenecks—dendrite growth, interfacial instability, and electrolyte degradation—while capitalizing on sodium’s inherent sustainability and scalability.

High-capacity lithium-ion batteries are essential for efficient energy storage and long-term operation. To achieve this, silicon (Si) is attracting attention as an anode material due to its superior theoretical capacity. However, a major challenge is the significant volume change of Si during charge–discharge cycles, which affects battery performance. Poly(acrylic acid) (PAA) is the most established binder for pure Si electrodes, primarily relying on abundant polar carboxylic groups that enable strong hydrogen bonding with the Si surface. [1] Despite these advantageous properties, the cycling performance of the fabricated Si anodes still far from meeting the standards required for practical applications.
Herein, we propose a reactive polyacrylate binder that can accommodate the volumetric expansion of Si anodes. The binder consists of a uniform mixture of PAA and polyacrylate crosslinker, which forms a network structure upon curing at high temperatures. In this network, PAA effectively maintains the integrity of the electrode through strong hydrogen bonding with Si particles, while crosslinking with polyacrylate crosslinker chains simultaneously enhances its mechanical strength (see Figure 1). The elasticity of the binder was carefully adjusted by controlling the ratio of monomers in the polyacrylate crosslinker to effectively accommodate Si volume changes. As a result, the binder demonstrates enhanced cycling stability and rate performance compared to conventional PAA binders. Moreover, its relatively simple synthesis and manufacturing processes improve its commercial viability.

In recent years, the potential and prospective uses of indoor photovoltaics in small-scale systems such as wireless sensors, the Internet of Things (IoT) and human-interactive machine-based actuators have drawn a lot of attention. They are perfect for indoor lighting applications because of their affordability, portability, low power consumption, and environmental friendliness[1]. Solution-processed organic photovoltaics (OPVs) present a viable path toward the production of low-cost, lightweight, and environmentally friendly solar energy. However, current high-efficiency OPVs often rely on low-bandgap donor polymers, which face challenges in stability and scalability, and fullerene-based acceptors, which suffer from high cost and limited spectral absorption [2].
In this work, the synthesis and characterization of a new non-fullerene acceptor (NFA) with excellent efficiency and stability for indoor photovoltaics are presented. We optimized performance and scalability by producing materials with low synthetic complexity from sustainable solvents using Stille cross-coupling polymerization [3]. Characterization techniques Proton Nuclear Magnetic Resonance Spectroscopy (H-NMR), Differential Scanning Calorimetry (DSC), Cyclic Voltammetry (CV), UV-Vis Spectroscopy, and Thermogravimetric Analysis (TGA), confirmed the structural integrity, thermal stability, and electronic properties of the materials [4]. The results demonstrate the potential of these polymers as electron acceptors, with promising performance for indoor light-harvesting applications.

Acknowledgements
The research project is implemented in the framework of H.F.R.I call: “Basic Research Financing (Horizontal Support of All Sciences)” under the National Recovery and Resilience Plan “Greece 2.0” funded by the European Union - NextGenerationEU (H.F.R.I. Project Number: 017007).

Block copolymers are the backbone of drug delivery in application and research ability to combine varying solubilities, enabling efficient drug transport.¹ Among these, biodegradable polyesters, such as the extensively studied poly(lactide) (PLA) and its copolymer with poly(glycolide), poly(lactide-co-glycolide) (PLGA), are widely employed.² Poly(2-oxazoline)s (POx) present a versatile platform for polymer therapeutics due to their peptide-like structure and biocompatibility. Additionally, their broad range of physical and chemical properties, facilitated by numerous available monomers and adaptable end-group designs, make them ideal candidates for advanced applications.³

We hereby present the synthesis of POx-PLGA-copolymers via organocatalyzed solvent polymerization from well-defined POx macroinitiators. This approach achieved high monomer conversion and narrow dispersities. Adjusting structural parameters, including block length ratios, block arrangements, microstructures, and the lactide-to-glycolide monomer ratio, allows for precise control over the resulting polymer properties. Notably, block copolymers with hydrophilic components demonstrated improved solubility and adjustable glass transition temperatures above 37 °C. These findings underline the potential of these materials in creating highly customizable matrices for PLGA nanoparticle coatings.

Their structural adaptability opens exciting opportunities for example in cancer therapy.⁴

In recent years, self-healing materials have garnered significant scientific interest, specifically focusing on
macromolecular chemistry to tailor functional polymers with desired healing properties. This study presents
the development of a hydrophobically modified, self-healable, UV-resistant smart polymer/metal-organic
framework (MOF) composite for coating applications. The P(GMA-co-LMA) copolymer was prepared for its
hydrophobicity, flexibility, self-cleaning, and heat-induced self-healing properties, while the MOF provided
antimicrobial and anti-UV capabilities. By incorporating MOF into the copolymer, a significant enhancement
in these functionalities is achieved, alongside increased surface roughness and improved water contact angle.
The copolymer was characterized using 1H-Nuclear Magnetic Resonance (1H-NMR), Fourier-transform
infrared (FTIR) spectroscopy, and Differential Scanning Calorimetry (DSC). Subsequently, the composite was
analysed via FTIR, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), UV-Vis spectroscopy,
water contact angle measurements, and antimicrobial tests. This innovative composite paints a promising
picture for multiple smart applications, particularly in sectors requiring advanced durability and protection,
such as military textiles, passport covers, and other high-performance coatings. The facile synthesis method
highlights the potential for scalable production of multifunctional fabrics, aligning with current industrial
needs for smart, robust materials with environmental resistance and self-repair capabilities.

Over the last couple of decades, metallopolymers with self-healing characteristic have emerged as preeminent smart materials. Despite being the fascinating natural occurrence of self-healing in mussel byssal threads,[1] the fabrication of intrinsic autonomous healable synthetic materials is a revolutionary and demanding area in modern material science. The combining properties of polymers with metallic components, enabling the metallopolymers to automatically heal the damaged like fractures or cracks, represent a notable advancement in the field of self-healing materials.[2] For instance, the self-healable materials are greatly favoured for using in sensors and shape memory devices, as well as in the domains of biomedicine, tissue engineering, biomaterials, and especially for applications where durability and longevity are critical, such as in aerospace and electronics.[3] In this work, we have developed novel copolymers following controlled radical polymerization mechanism, consisting of appended functionalized tridentate [2,6-bis(1,2,3-triazol-4-yl)pyridine] (btp) chelating ligands and alkyl acrylates in the backbone. The designed polymers are soluble in common organic solvents, allowing it to characterize easily by 1H NMR, GPC. The polymeric film can undergo self-healing through cross-linking by the Zn(II)-coordination to the appended chelating sites. Systematic study has been carried out using optical microscopy and it reveal remarkable ability to heal themselves within 24 hours at moderate temperature (<100 °C). Our attempt to develop novel smart self-healable metallopolymers will be presented.

Photocatalysis in polymer synthesis has rapidly advanced recently with significant progress in photocontrolled cationic polymerization [1]. The most promising approach to perform photocontrolled cationic polymerization involves using a suitable photoredox catalyst (PC) paired with a chain transfer agent (CTA), capable of mediating the polymerization via reversible-deactivation mechanism. However, despite the wide range of PCs and CTAs reported, this field remains limited to polymerization of highly reactive monomers such as vinyl ethers [2]. Recently, Yagci et al. developed alternative approach using a benzyl bromide/Mn₂(CO)₁₀/diphenyliodonium salt catalytic system for visible-light-induced living cationic polymerization of vinyl ethers [3]. The reaction occurs via radical oxidation/addition/deactivation mechanism, which can be potentially applied for the polymerization of less reactive monomers.
In this study, the visible-light-induced cationic polymerization of isobutylene using photoinitiating system PhCH₂Br/Mn₂(CO)₁₀/Ph₂IPF₆ was investigated in a mixture of CH₂Cl₂/n-hexane at −30°C [4]. Polyisobutylenes with a number-average molecular weight up to 3000g·mol⁻¹, relatively low polydispersity (Đ<1.7), and high content of exo-olefin end groups (>90%) were obtained. The possibility of controlling the molecular weight of synthesized polymers in the range of 2000 to 12,000g·mol⁻¹ by varying the concentration of diphenyliodonium salts was demonstrated. The influence of the oxidizing agent nature was investigated in detail. It was shown that substituents in the benzene ring of the diaryliodonium salt affect the rate of polymerization, while the nature of counterion influences significantly the molecular weight of polyisobutylene.
This work was supported by State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03).

Luminescent solar concentrators (LSCs) represent an interesting solution for light harvesting, management and conversion, efficiently operating under both direct and diffuse light conditions. In such devices, incident photons are absorbed and re-emitted by luminophore species embedded in a waveguide, and transported by total internal reflection towards solar cells for the light-to-electricity conversion. Conventional luminophores often exhibit diminished photoluminescence in concentrated solutions or at the solid state, negatively affecting the final performance of the devices.

To overcome these limitations, the present work investigates the enhanced emission properties associated with aggregation-induced emission (AIE) emitters. Specifically, newly synthesized macromolecules were employed as photonically active species through copolymerization between methyl methacrylate and a tetraphenyl ethylene based AIE-active monomer at varying molar concentrations. Two distinct radical polymerization methods were evaluated and explored: free radical polymerization (FRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization.

The resulting copolymers were comprehensively characterized in terms of their molecular, thermal, and optical properties, demonstrating the superiority of the RAFT method. This technique provided narrower molecular weight distribution (Đ~1.2) and yielded copolymers with more consistent glass transition temperatures, absorption features, and photoluminescence quantum yields. Subsequently, LSCs were fabricated by deposition of thin polymeric films onto optical glass substrates and their optical and photovoltaic characteristics were assessed under simulated sunlight conditions, with LSCs deriving from RAFT polymerization demonstrating improved performance.

This study illustrates a promising approach for enhancing the efficiency of LSCs through the manipulation of macromolecular architecture and the strategic incorporation of AIE-active species within polymer matrices.

Traditional synthesis methods for hyperbranched polymers often suffer from poor architectural control, leading to random branching structures. To address this limitation, we introduce a novel one-pot synthesis approach based on sulfoxide chemistry to achieve precise control over branch lengths. In this method, linear polystyrene was initially synthesized at temperatures below 40°C. The reaction temperature was then increased to 100°C, triggering the deprotection of sulfoxide-protected vinyl groups into reactive methacrylate functionalities. These newly generated vinyl groups underwent further polymerization, forming well-defined hyperbranched polystyrene structures. This approach enabled precise control over branch-point spacing by tuning structural parameters during polymerization. We successfully synthesized hyperbranched polymers with branch lengths of 5k, 10k, and 20k by adjusting the molecular weight of the linear polystyrene precursor, demonstrating excellent control over branch length and distribution.
The rheological behavior of these hyperbranched polymers was characterized through Small Amplitude Oscillatory Shear (SAOS) tests for linear viscoelastic properties and Extensional Viscosity Fixture (EVF) tests for nonlinear viscoelastic behavior. Branch length had a significant impact on relaxation time and strain hardening effects, with more pronounced effects in the nonlinear viscoelastic regime. This comprehensive analysis provides valuable insights into the structure-property relationships of hyperbranched polymers. The versatile and efficient synthesis method, combined with detailed rheological analysis, paves the way for innovative applications in materials science.

The use of petrochemical-based materials leads to significant environmental pollution and health issues. To address these challenges, it is crucial to develop methods aligned with the principles of green chemistry. Due to their high abundance and low cost, vegetable oils (VOs) are considered ideal renewable resources for the production of sustainable materials [1]. Introducing more reactive groups to vegetable oils is of great importance for achieving modularity, ease of modification, and faster reaction rates. The modification of vegetable oils can be readily achieved through "click chemistry," which aligns with the principles of green chemistry [2,3].
Michael addition reactions are the reactions that meet many criteria of "click" reactions. The Michael addition reaction of activated alkynes, in particular, proceeds under milder conditions and at faster reaction rates. These highly efficient and selective reactions are frequently employed in various applications and processes to achieve targeted outcomes [2,3].
In this study, we synthesized various phosphorus and silicone containing cross-linked thermosets by utilizing Michael addition reactions between propiolated castor oil, a bio-based platform previously developed by our group, and several nucleophiles (such as hydroxyls, amines, etc.) via nucleophilic-yne click reactions. The obtained thermosets were characterized by FTIR, DSC, TGA. Moreover, flammability tests and water repellency tests were also conducted on the relevant thermosets. We anticipate that the thermosets may find applications in various fields, particularly as hydrophobic coatings.

The growing ecological awareness of society and the need for environmental protection have fueled
increased interest in scientific research on developing biodegradable materials. In this context,
polylactide (PLA) has emerged as a promising, environmentally friendly option. However, despite its
numerous advantages, PLA exhibits properties that limit its broader applications. Since the repeating
units in the PLA chain do not have reactive side groups, further post-modification of the polymer is
significantly hindered. The aim of our study was to introduce acetal units equipped with functional
groups into the PLA backbone, enabling the functionalization of the resulting copolymers.
Importantly, acetal units, which are labile under acidic conditions, also enhance the degradability of
the polymer chain.[1]To obtain functionalized polylactide, we applied cationic copolymerization of
selected functional cyclic acetals (4-chloromethyl-1,3-dioxolane and 4-[(allyloxy)methyl]-1,3-
dioxolane) with lactide (Scheme 1). The presented results demonstrate the influence of reaction
temperature and time on the molecular weight and composition of the copolymers. Furthermore, the
ability of the resulting copolyesters to undergo post-modification was confirmed through reactions
with sodium azide and propane-1-thiol.

Polyethylene glycol (PEG) has long been regarded as the gold standard in pharmaceutical and biomedical applications due to its chemical inertness, biocompatibility, and unique stealth properties.[1] However, recent studies have demonstrated that PEGylated therapeutic agents can induce severe side effects, due to the formation of anti-PEG antibodies, including complement-activated pseudoallergic reactions, and accelerated blood clearance.[2,3] Frey and coworkers identified a random copolymer of ethylene oxide (EO) and racemic glycidyl methyl ether (GME) (randomized PEG isomer, “rPEG”) as a promising alternative to PEG.[4] Due to the lack of crystallinity, the purification of rPEG is challenging, making purification methods established for PEG, such as precipitation in diethyl ether, inapplicable.

This work presents an optimized purification process for rPEG using the ammonium sulfate precipitation method, a widely used technique for protein purification.[5] The method exploits the salting-out behavior of water-soluble polymers at high ionic strength, causing the polymer to precipitate while other substances remain dissolved in the solution. rPEGs of varying size and GME content, synthesized via anionic ring-opening copolymerization, were efficiently purified using ammonium sulfate precipitation, achieving high isolation yields of up to 97%. The resulting isolated polymers exhibited high purity, as confirmed by nuclear magnetic resonance spectroscopy, size exclusion chromatography, and mass spectrometry. Due to its cost-effectiveness and rapid execution, this method offers a compelling alternative to established purification techniques such as dialysis or preparative high-pressure liquid chromatography. Consequently, ammonium sulfate precipitation emerges as a promising method for the purification of water-soluble polyethers, with potential to expand its scope beyond rPEG.

Borane catalysis has proven to be an effective technology for epoxide polymerisation. We have investigated the ability of 13 different diborane catalysts with non-ionic backbones to facilitate oligomerisation and polymerisation of propylene oxide (PO), 1-butylene oxide (BO) and allyl glycidyl ether (AGE). From a structural point of view, particular attention has been paid to catalysts with different linker lengths and linker flexibilities. It is noteworthy that this screening could be carried out both under typical polymerisation conditions and under conditions relevant to large-scale production, characterised by the presence of alcohol chain transfer agents (CTAs) in excess. We reason that the pre-organisation of borane groups, as observed for biphenyl derivatives, provides a straightforward route to the development of high performance catalysts and the quantitative conversion of the epoxide monomers studied. Furthermore, diborane-catalysed oligomerisation can be sustained by repeated addition of monomer batches (14 steps) for up to six weeks, resulting in complete conversion and the production of well-defined oligoethers [1].