Luminescent solar concentrators (LSCs) are emerging as valuable technologies for energy harvesting, prized for their transparent nature, aesthetic flexibility, and versatile application. This study advances LSC through the development of precursor copolymer architectures that incorporate aggregation-induced emission (AIE) luminophores to mitigate reabsorption losses and aggregation-caused quenching (ACQ).
To that end, we synthesized precursor copolymers of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) in both random and block configurations using controlled reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers, designed with free hydroxyl groups, were post-functionalized via esterification to integrate tailored AIEgens, enhancing LSC performance. Our research focused on how the spatial arrangement of these copolymers (random vs. block) affects the integration and effectiveness of AIEgens. We conducted a comprehensive chemical, physical and photophysical analysis to confirm their structural and thermal properties. Notably, block copolymers displayed enhanced thermal stability and superior optical properties, attributed to their ordered macromolecular architecture which facilitated more effective integration of AIE luminophores. In terms of luminescence, LSC devices fabricated with block copolymers exhibited increased efficiency and stability, particularly in formulations with higher concentrations of HEMA. These enhancements highlight the advantages of block configurations in improving luminescence output and reducing photon losses.
The strategic synthesis of functional polymers with free functional groups emerges as a promising route for developing versatile luminescent polymers based on AIE structures. This approach allows for the customization of polymer systems to optimize solar energy harvesting, significantly improving solar energy conversion efficiency and expanding the potential for innovative LSC designs.

Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) is a powerful technique that enables the synthesis of chain-end functionalized polymers with precise control over molecular weight distributions (MWDs). We previously contributed to this technique by exploring the use of inorganic bases combined with ascorbic acid, leveraging the ascorbate anion’s two orders of magnitude higher reduction rate toward the copper catalyst compared to the neutral form, thereby decreasing catalyst loading to ppm levels.[1,2,3] Recently, we improved the method’s versatility by employing ascorbic acid acetonide, a lipophilic derivative, with organic bases to achieve homogeneous polymerization of styrene.[4] By selecting appropriate ligands, solvents, and bases, the system accommodates the differing reactivity of exchanged halogens, yielding monomodal MWDs with low dispersities and predetermined number-average molar masses (Mn) from both chlorinated and brominated multifunctional initiators. The ease of post-functionalization, even for chloro-terminated polystyrenes, was demonstrated by targeting different chain-end functionalities. Furthermore, to assess the applicability of such products, trifunctional bromo-terminated polystyrenes were converted to amine-terminated analogs via azidation and subsequent Staudinger reduction. These well-defined trifunctional crosslinkers were incorporated into both traditional epoxy thermosets and covalent adaptable networks (CANs). By tuning the Mn of these macromolecular crosslinkers, the network’s crosslinking density could be tailored, enabling control over swelling degree, glass transition temperature, and, in the case of the obtained vinylogous urethane vitrimers, even reprocessability. The resulting materials exhibited excellent thermal resistance and rigidity, attributed to the high polystyrene content.

Amino-functionalized polyesters (APEs) are a remarkable class of polymeric materials with a wide range of applications, e.g. as antibacterial materials, gene delivery carriers, and biodegradable plastics. However, the current APE synthetic pathway poses significant challenges in terms of structural diversity and control over polymerization. In recent years, ring-opening alternating copolymerization (ROAC) of epoxides and cyclic anhydrides has been demonstrated to be a powerful and versatile method for polyester synthesis via varying the binary combination of monomers.[1] In this study, we successfully applied ROAC in APEs syntheses via utilizing cyclic anhydride with glycidylamine as an amino-functionalized epoxide, respectively (Figure).[2]
The ROAC of cyclic anhydride and glycidylamine was conducted with an alcohol initiator based on the conditions of our previous work.[1] The obtained products were characterized by ¹H and ¹³C nuclear magnetic resonance (NMR) and size elusion chromatography (SEC). The molecular weight of the poly(phthalic anhydride-alt-dibenzylglycidylamine) was easy to control up to ca. 21,000 by adjusting the initial monomer-to-initiator ratio, while retaining the narrow dispersity (Đ < 1.19). Moreover, the versatility of the present APEs syntheses was demonstrated by applying various alcohol initiators, cyclic anhydrides, and glycidylamines, which successfully produced APEs with functional terminal end-group or different properties.

In this work, the production of a more efficient and environmentally friendly emulsion to protect the automotive paint booth, robots and other equipment was developed to prevent the effect of “overspray”. The use of an innovative coating technology is intended to increase the service life of paint coatings on equipment/metal surfaces by ensuring resistance to corrosion, wear and cracking. In addition, no hazardous solvents need to be used for cleaning work. The use of long-chain acrylate monomers instead of fluorate monomers can make the process more environmentally friendly. Emulsions based on water, styrene and lauryl acrylate were prepared using acrylic acid as an auxiliary and ammonium persulphate as an initiator at 80ºC for 6 hours with mechanical stirring. Various emulsifiers were tested. A solids content of approx. 38-40% was achieved. The emulsion was also characterized in terms of surface tension, zeta potential, particle size and contact angle. Stable emulsions with a particle size within the expected values and contact angles around 100º were obtained. Overall, the emulsion was prepared in a simple and fast process and showed promising results.

With the aim to attain and regulate extraordinary functionalities exhibited in biological macromolecules, developments of a diverse chemical tool-box and methodologies have been made over the years to exert precise control over molecular parameters of synthetic macromolecules. These efforts have come to fruition in a novel class of polymers referred to as ‘sequence-defined polymers’, which exhibit a discrete molar mass and a perfectly controlled monomer structure, allowing for a thorough examination of structure–property relationships and applications in catalysis, self-assembly and data-storage.[1, 2]

In this work, a facile, two-step iterative protocol for the synthesis of sequence-defined oligourethanes[3] was optimised to synthesise uniform telechelic macromolecules in a scalable manner, via bidirectional growth of amino alcohols using a coupling agent. Molecular parameters including chemical functionalities, chirality and terminal moieties were controlled to produce a library of sequence-defined oligourethanes of diverse structure. Finally, a systematic study on their thermal properties were performed to gain an in-depth understanding of the impact of primary structure, thus emphasizing the design parameters that allow for the development of next-generation materials with tailor-made structures depending on their applications.[4]

Polypeptide-based nanoparticles have a wide range of applications, such as drug delivery, biosensing and bioimaging, due to their inherent biocompatibility and biodegradability.¹ These nanoparticles are typically synthesized from amphiphilic copolymers via the ring-opening polymerization (ROP) of N-carboxyanhydrides (NCAs) in organic solvents, followed by nanoprecipitation in water.²
A more promising approach involves the use of Polymerization Induced by Self-Assembly (PISA) combined with ROP of NCAs (ROPISA).³ In this process, a NH₂-terminal solvophilic polymer initiates the polymerization of a solvophobic NCA monomer to afford nanomaterials in one pot and at high solid content: while the polypeptide chain extends, the copolymer becomes amphiphilic and self-assembles as nanoparticles. Recently, our team described the first example of aqueous ROPISA⁴ ⁵ of NCA monomers (ɣ-benzyl-L-glutamate, L-leucine) using various macroinitiators including poly(ethylene glycol), poly(proline), polysarcosine or recombinant proteins. The resulting rod-shaped nanoparticles (~ 100 nm length) consist of a hydrophilic shell and a hydrophobic polypeptide core.
In this talk, I will provide a comprehensive overview of recent progress in the synthesis of fully peptidic core-shell nanoparticles via ROPISA. This method allows the use of hydrophilic NH₂-polyelectrolytes as initiators and the incorporation of reactive NCA monomers to create functional hydrophobic cores. These particles can be further functionalized with biomacromolecules, such as oligonucleotides, and the introduction of fluorescence into the core. The outcome of this research is the creation of advanced biodegradable nanoparticles with significant potential for use in biomedical applications.

Elemental sulfur, a waste product of the oil refinement process, contains preformed dynamic Sulfur-Sulfur bonds promising to impart dynamicity onto polymers obtained from this monomer. Yet robust methodologies to access linear polymers with tuneable properties and functionality are rare. Addressing these problems, we here report a rare sequence selective terpolymerisation of elemental sulfur with aromatic thioanhydrides and epoxides under simple lithium alkoxide catalysis yields semi-aromatic Poly(ester-alt-Sx). This enables access to terpolymers from a greatly improved range of epoxide comonomers compared to previous methodologies, including industrially relevant, flexible, rigid, functional and natural product derived variants allowing to tune glass transition temperatures across a Tg range of >150°C. Mechanistic investigations reveal that the insertion of S8 leads to an unusual rate acceleration via coordinative participation of the polyester links sitting adjacent to the propagating chain-end. The thermal stability of the polymers allows for post polymerisation backbone modification via -S-S- bond metathesis. After crosslinking these can be applied as thermally reprocessable and acid degradable adhesives, the performance of which can be enhanced via backbone editing. Our contribution paves the way for the rational buildup of diverse and functional polymer structures from elemental sulfur waste enabled by mechanistic understanding.

Controlled radical polymerization is highly desired to access well defined functional polymers.(1–3) Recently, photocatalyzed controlled radical polymerization by organic chromophore has become an exciting approach mediating visible light induced atom transfer radical polymerization (ATRP) with alkyl bromide initiator.(4) Inspired by this trend, we have investigated, N-substituted benzo[ghi]perylene (BPIm), as potential organocatalyst for polymerization under visible light irradiation. Interestingly, this catalyst system demonstrates excellent performance in the polymerization of various vinyl-containing monomers including MMA, BMA, LMA, styrene, and N-isopropylacrylamide (NIPAM) with good control over molecular weight and have low dispersity. Further, the polymerization can be paused and restarted by simply switching the light off/on which shows its excellent temporal control. Additionally, the polymerization strategy can be applied to broad variety of vinyl containing polypyridyl based monomers. Our effort to develop visible light driven controlled radical polymerization of functional monomers using organocatalysts will be presented.
Materials and methods: The reaction was performed under 35W Blue LED (λmax = 470 nm) with BPIm as organocatalyst, ethyl α-bromophenylacetate as initiator in DMF solvent. The reaction was performed in an inert atmosphere with ambient conditions. The polymerization was allowed to proceed as per the optimized time period (12h) after which it was poured in methanol and the polymer was isolated by filtration.

Due to their unique properties, fluorinated polymers are widely utilized in various industrial and consumer applications. In polyester synthesis via ring-opening alternating copolymerization (ROAC), fluorine incorporation into cyclic monomers is crucial in modulating polymerization reactivity. [1] Recent studies have demonstrated that fluorine-functionalized monomers can be leveraged to construct sequence-controlled block copolymers with high structural precision. [1-2] However, further exploration and chemical design are necessary to reveal the potential of high-performance fluorinated polyesters.
Herein, we present a systematic study on self-switchable polymerization using a cesium pivalate catalyst to elucidate the distinct effects of fluorinated epoxides and anhydrides on polymerization kinetics and monomer sequence control. Model reactions reveal that fluorinated epoxides introduce electronic effects that suppress chain propagation, whereas fluorinated anhydrides facilitate efficient incorporation, enabling a highly tunable alternating copolymerization system. This strategy allows for the rapid synthesis of block copolymers with precisely controlled architectures. Moreover, the resulting fluorinated block copolymers exhibit superior self-healing properties under ambient and aqueous conditions, significantly outperforming fluorinated homopolymers. This enhancement is attributed to strong dipolar interactions (H⋅⋅⋅H, F⋅⋅⋅F, and H⋅⋅⋅F) within the fluorinated segments. [3] These findings align with recent advancements in fluorinated polyester research, highlighting the potential of fluorine-mediated polymerization for achieving enhanced material performance and environmental responsiveness. This study provides valuable insights into fluorine-modulated polymerization strategies, offering a new pathway for designing advanced self-healing and sequence-controlled functional polymers.

Cationic polymers (CP) have emerged as promising vectors for gene delivery purposes, owing to their ability to facilitate lysosomal escape.[1] However, most highly transfecting CPs (such as poly(ethylene imine)) suffer from poor biocompatibility and cytotoxicity.[2] Furthermore, modifications to reduce cytotoxicity can lead to decreased transfection efficiency and complicated synthesis protocols.[2] In this respect poly(2-oxazoline)s (POx) offer a versatile platform to circumvent these issues. Not only do they benefit from increased biocompatibility, but they can also exhibit “stealth-behavior”, leading to prolonged blood retention time.[3] In addition, POx can be synthesized from a library of functional monomers and facile strategies for post-polymerization modifications are available. This enables the introduction of different functional moieties.
Yamaleyeva et al. previously presented a non-toxic, POx-based gene delivery system using diethylenetriamine-functionalized POx as the cationic block and poly(2-ethyl-2-oxazoline) as a hydrophilic solubilizing unit.[4] Based on their findings, we designed a set of copolymer structures as an optimized delivery platform. Our system is readily adaptable via polymerization conditions and can feature hydrophilic, hydrophobic and cationic units. For the latter we were able to introduce an additional guanidine group, which is hypothesized to enhance membrane penetrating properties in vivo.[5] Furthermore, click chemistry is accessible via a terminal azide group, allowing the coupling of more complex units, including targeting moieties and fluorescing agents. With its simplicity and flexibility our POx-based platform sets the stage for custom-made next generation gene delivery systems.

Emulsion styrene butadiene rubber (ESBR) is widely used in tire manufacturing due to its excellent physical properties and environmentally friendly water-based synthesis process. However, its free-radical mechanism leads to side reactions such as coupling and disproportionation, which terminate chain growth and complicate molecular weight distribution (MWD) control. The resulting broad MWD increases energy loss and negatively affects mechanical and viscoelastic properties. [1]
In this study, we report the first successful synthesis of SBR via ab initio reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization using poly(acrylic acid-b-styrene) with a trithiocarbonate end group as a reactive surfactant. By employing RAFT polymerization, we successfully synthesized ESBR with a narrow MWD. The polymerization was confirmed using FT-IR and NMR spectroscopy, while particle size was analyzed using dynamic light scattering (DLS). Additionally, we investigated the effect of the macro-RAFT agent structure, particularly the acrylic acid (AA) block length, on the polymerization process. Our results indicate that an increase in the AA block length led to a decrease in both polymerization rate and final monomer conversion, highlighting its critical role in controlling polymerization kinetics. (see Figure 1) The resulting SBR with a narrow MWD has the potential to enhance mechanical properties while its block structure enables its use as a filler dispersant, making it suitable for various applications.

Electron-deficient alkynes, i.e., terminal or internal alkynes connected to electron-withdrawing groups such as carbonyls are known to react with several nucleophiles easily and efficiently. The reaction between primary or secondary amines and electron-deficient alkynes, the amino-yne click reaction, is particularly of interest among other nucleophile-yne reactions since it may not require any catalysts, heat or extended reaction time[1]. The reaction proceeds under mild conditions to give the corresponding dynamic enamine products with high yields. Even though the reaction is well-studied in the polymer science, it was only recently used as a means of polymer-polymer conjugation and modification of amine-functional commercial polymers[2].
In this study, for the first time, the amino-yne click reaction was used to synthesize block copolymers and two commercial amine-functional polymers were modified using the amino-yne click reaction. For the polymer-polymer conjugation part, an electron-deficient alkyne end-functional methoxy poly(ethyelene glycol) (mPEG-alkyne) was synthesized and then reacted with two amine end-functional polymers, namely polystyrene-NH2 (PS-NH2), or poly(N-isopropylacrylamide)-NH2 (PNIPAM-NH2). Both reactions were conducted at room temperature without any catalysts to obtain the corresponding block copolymers efficiently. For the post-polymerization modification (PPM) part, a hyperbranched poly(ethyelene imine) (PEI) and an aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer (poly(AEAPMS-co-DMS)) were quantitatively modified using several electron-deficient alkyl propiolates or dialkyl acetylenedicarboxylates via the amino-yne click reaction. The PPM reactions also proceeded at room temperature and for only two minutes. The presented study offers an experimentally facile method for modification of amine-functional polymers and block copolymer synthesis in a greener and energy-saving way without any metal catalyst or heat.

Transitioning toward a sustainable and circular economy requires the development of alternative materials to replace non-degradable, fossil-derived plastics such as polyolefins. Among biodegradable polymers, poly(lactic acid) (PLA) has gained significant attention due to its increasing production and broad applicability. The development of materials aligned with circular economy principles is focusing on various cyclic esters (lactones) in both homo- and copolymerization. This approach enables the design of materials that can be chemically recycled to their monomers (CRM), a critical objective for sustainability (1). Recent studies have reported the synthesis of novel three-coordinate heteroleptic [N, N]Fe(II)(N(SiMe₃)₂) complexes featuring bidentate monoanionic pyridylamido ligands (Fig. 1a), which have demonstrated high efficiency and activity in the ring-opening polymerization (ROP) of lactide (LA) and ε-caprolactone (ε-CL) (2,3). These catalysts have recently been employed in the ROP of less reactive cyclic esters, such as δ-hexalactone (δ-HL), δ-nonalactone (δ-NL), and ε-decalactone (ε-DL). This study presents a preliminary computational investigation into the homopolymerization mechanisms of δ-HL and ε-CL (Fig. 1b) using density functional theory (DFT). The main goal is to explore the polymerization pathways facilitated by Fe(II) catalysts, with particular focus on the complexities introduced by the -N(SiMe₃)₂ group. We propose alternative mechanisms to the classical one reported in the literature (Fig. 1c). Our analysis incorporates experimental evidences to validate these mechanisms, providing insights into catalyst structure-reactivity relationships.

Oxidative chemical vapor deposition (oCVD) is a solvent-free method for synthesizing uniform, conformal thin films of conductive polymers with tunable properties. We investigated parameters involved in oCVD for synthesizing polypyrrole (PPy), which is well known for its versatility for many applications. We focused on the effects of nitrogen gas flow rate and deposition time on the structure and properties of PPy. The results show that increasing the nitrogen flow rate enhances the distribution of the oxidant, increasing the polaronic defects, which significantly deteriorate the polymeric structure and reduce electrical conductivity. Meanwhile, extending the deposition time increases the film thickness linearly due to longer reaction time and initially enhances the electrical conductivity until it reaches a plateau at approximately 75 S/cm [1].

Furthermore, we successfully deployed the PPy synthesized by oCVD for energy storage devices. We deposited a sub-micron-thick layer of PPy onto porous carbon fabric (CF) for supercapacitor electrodes. The resulting PPy coatings exhibit uniform, conformal, and retain the porosity of CF. The supercapacitive performance of the electrodes was then analyzed using electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charge-discharge measurements. Finally, the PPy/CF electrodes were used to fabricate a symmetric supercapacitor device, which exhibits ideal capacitive behavior, high rate capability (up to 2000 mV/s), and a stable operational voltage of 1 V. These findings highlight the ability of oCVD to precisely control the synthesis of conductive polymers, which advances the design of conductive polymer films for energy storage and a wide range of other applications.

While PEG remains the gold standard for biomedical applications, increasing reports of PEG-related allergies and anti-PEG antibodies necessitate the development of alternative polymer systems. Poly(2-oxazoline)s (POx) have emerged as promising alternatives to poly(ethylene glycol) (PEG) in drug delivery applications due to their stealth properties, lower immunogenicity, and tunable lower critical solution temperature (LCST) behavior. However, the functionalization of, in particular, hydrophobic POx with azide end groups for bioconjugation has posed significant synthetic challenges. Herein, we report the development of a novel initiator system for the cationic ring-opening-polymerization of 2-oxazolines that enables the direct incorporation of azide functionality at the α-terminus of various POx derivatives. This approach overcomes previous limitations in quenching reactions of hydrophobic POx variants and provides consistently high end group fidelity across a spectrum of POx hydrophilicity. Polymers with an azide end group exhibited excellent reactivity in azide-alkyne cycloaddition reactions. This versatile synthetic platform expands the potential applications of POx in drug delivery systems by providing a reliable method for bioconjugation while maintaining the favorable properties that position POx as a promising PEG alternative in biomedical applications.

When designing new stimuli-responsive features in sustainable coatings, the responsive
building blocks need to be compatible with green and naturally sourced monomers. One such
recently developed sustainable monomer is based on the alkoxybutenolide scaffold, which is
derived from biowaste, and can be functionalized through acetal groups. Polymers and
coatings from butenolides show excellent and tunable properties, which offer a more
sustainable alternative to conventional acrylates.

In this project, reactive molecular units will be designed and synthesized that can be
incorporated within such butenolide polymers. Post-modification on these molecular units
allows for straightforward incorporation of desired functionalities. Finally, incorporation of
responsive units into such polymers will allow for on-demand disassembly and recycling of the
coatings, as well as controlling surface structure and properties of the final coatings

In light of the COVID-19-crisis, antibacterial surfaces have gained relevance due to their application potential for medical devices[1]. A promising strategy is the coating of a surface with polymers because of their antifouling-behavior[2] as well as the addition of a positively charged functionality to gain bactericidal properties[3]. The combination of these antibacterial effects can be achieved by the coating with poly(2-methyl-2-oxazoline) (PMeOx) that is functionalized with a quarternary ammonium group[4].
This research aimed to synthesize block copolymers of the functionalized PMeOx and polylactide (PLA) to obtain a coating material for PLA-surfaces. Based on the work of REIF et al[5], the polymerization of 2-methyl-2-oxazoline (MeOx) was carried out with a bifunctional initiator. The resulting PMeOx was used as an initiator for the subsequent catalysed copolymerization with lactic acid. The optimization of several reaction-conditions enabled the successful synthesis of the PMeOx-PLA-copolymers containing a quarternary ammonium group. Therefore, an antibacterial coating material with the supposed combination of antifouling-behavior and bactericidal properties could be obtained.