Subsequent Cross-linking Research Articles

Thermal Degradation Behavior of Thermally‐Oxidized Hydroxyl‐Terminated Polybutadiene (HTPB): An Assessment of Thermal Stability

AbstractThermal analysis was performed on different thermally oxidized hydroxyl‐terminated polybutadiene (HTPB) samples, varying in molecular weights, polydispersities, and viscosities. The HTPB sample was subjected to thermal ageing at 65 °C for 10 weeks and periodically withdrawn for thermal analysis. During thermal ageing, HTPB undergoes chain rearrangements that may include scission and subsequent crosslinking, leading to a higher average molecular weight and viscosity. Differential scanning calorimeter (DSC) and thermogravimetric analyses were performed on thermally oxidized HTPB samples under inert heating conditions to investigate their degradation behavior. The DSC results revealed no significant correlations between the glass transition (Tg) and the samples' molecular weight, viscosity, and polydispersity. In TGA, all HTPB samples showed a two‐step thermal decomposition process characterized by two distinct mass loss stages. Notably, the first stage exhibited a lower total mass loss and a considerably lower peak rate of mass loss than the second stage. The thermal stability of HTPB is significantly compromised by thermal‐oxidative degradation, leading to a pronounced decrease in the initial degradation temperature (TIDT) values, from 372 °C (pristine or 0 week) to 228 °C (10 weeks). Furthermore, we measured the energy of activation (Ea) and the pre‐exponential factor (A) from TGA data using the Coats–Redfern integral equation. Notably, we observed a slight but systematic increase in both Ea and A as the molecular weight of the aged samples increased.

Peptide Bundlemer Networks or Lattices: Controlling Cross-Linking and Self-Assembly Using Protein-like Display of Chemistry.

Coiled-coil 'bundlemer' peptides were selectively modified with allyloxycarbonyl (alloc)-protected lysine, a non-natural amino acid containing an alkene on its side chain. The specific display of this alkene from the coiled-coil surface with protein-like specificity enabled this residue to be used as a covalent linkage for creating peptide networks with controllable properties or as a physical linkage for the self-assembly of bundlemers into unexpected, intricate lattices driven by the hydrophobic nature of the side chain. For network formation, peptides were modified with both alloc-protected lysine and cysteine amino acids for solution assembly into solvent-swollen films and subsequent covalent cross-linking via thiol-ene photo click reactions. The degree of network cross-linking, as determined by rheometry, was finely tuned by varying the specific spatial display of reactive groups on the bundlemer building block particles, transitioning between intrabundle and interbundle cross-linking. The designed display of alloc groups from the center of the bundlemer building block also prompted particle self-assembly into an unexpected intricate lattice with a porous morphology. The lattices were studied in a variety of solution conditions using transmission electron microscopy, cryotransmission electron microscopy, and small-angle X-ray scattering. The approximate particle arrangement in the lattice was determined by using coarse-grained modeling and machine learning optimization techniques along with experimental methods. The proposed truss-like face-centered cubic packing of the alloc-functionalized bundlemers agrees well with the experimental results.

Comparative Study of the Dehydrothermal Crosslinking of Electrospun Collagen Nanofibers: The Effects of Vacuum Conditions and Subsequent Chemical Crosslinking.

Collagen nanofibrous materials have become integral to tissue engineering due to their exceptional properties and biocompatibility. Dehydrothermal crosslinking (DHT) enhances stability and maintains structural integrity without the formation of toxic residues. The study involved the crosslinking of electrospun collagen, applying DHT with access to air and under vacuum conditions. Various DHT exposure times of up to 72 h were applied to examine the time dependance of the DHT process. The DHT crosslinked collagen was subsequently chemically crosslinked using carbodiimides. The material crosslinked in this way evinced elevated Young's modulus values and ultimate tensile strength values, a lower swelling rate and lower shrinkage ratio during crosslinking, and a higher degree of resistance to degradation than the material crosslinked solely with DHT or carbodiimides. It was shown that the crosslinking mechanism using DHT occupies different binding sites than those using chemical crosslinking. Access to air for 12 h or less did not exert a significant impact on the material properties compared to DHT under vacuum conditions. However, concerning longer exposure times, it was determined that access to air results in the deterioration of the properties of the material and that reactions take place that occupy the free bonding sites, which subsequently reduces the effectiveness of chemical crosslinking using carbodiimides.

Multifunctional Chitosan Nanofiber-Based Sponge Materials Using Freeze-Thaw and Post-Cross-Linking Method.

The fabrication of porous sponge materials with stable structures via cross-linking diverse polymers presents significant challenges due to the simultaneous requirements for phase separation as a pore-forming step and cross-linking reactions during the fabrication process. To address these challenges, we developed a sponge material solely from natural-based polymers, specifically chitosan nanofibers (CSNFs) and dialdehyde carboxymethyl cellulose (DACMC), employing a straightforward, eco-friendly technique. This technique integrates a facile freeze-thaw method with subsequent cross-linking between CSNFs and DACMC. This method effectively addresses the difficulties associated with pore formation in materials, which typically arise from the rapid formation and precipitation of polyionic complexes during the mixing of anionic and cationic polymers, using ice crystals as a rigid template. The resultant sponge materials exhibit remarkable shape recoverability in their wet state and maintain light, stable porosity in the dry state. Furthermore, in comparison to commonly used commercial foams, this composite porous material demonstrates superior fire retardancy and thermal insulation properties in its dry state. Additionally, it shows effective adsorption capacities for both cationic and anionic dyes and metal ions. This method of using biobased polymers to produce porous composites offers a promising avenue for creating multifunctional materials, with potential applications across various industries.

A dual crosslinking strategy to tailor rheological properties of gelatin methacryloyl

3D bioprinting is an emerging technology that enables the fabrication of three-dimensional organised cellular constructs. One of the major challenges in 3D bioprinting is to develop a material to meet the harsh requirements (cell-compatibility, printability, structural stability post-printing and bio-functionality to regulate cell behaviours) suitable for printing. Gelatin methacryloyl (GelMA) has recently emerged as an attractive biomaterial in tissue engineering because it satisfies the requirements of bio-functionality and mechanical tunability. However, poor rheological property such as low viscosity at body temperature inhibits its application in 3D bioprinting. In this work, an enzymatic crosslinking method triggered by Ca2+-independent microbial transglutaminase (MTGase) was introduced to catalyse isopeptide bonds formation between chains of GelMA, which could improve its rheological behaviours, specifically its viscosity. By combining enzymatic crosslinking and photo crosslinking, it is possible to tune the solution viscosity and quickly stabilize the gelatin macromolecules at the same time. The results showed that the enzymatic crosslinking can increase the solution viscosity. Subsequent photo crosslinking could aid in fast stabilization of the structure and make handling easy.

Chitosan-Alginate Gels for Sorption of Hazardous Materials: The Effect of Chemical Composition and Physical State.

Chitosan, alginate, and chitosan-alginate (50:50) mixed hydrogels were prepared by freeze casting, freeze-drying, and subsequent physical cross-linking. Chitosan was cross-linked with citrate and alginate with calcium ions, while the mixed gels were cross-linked with both cross-linking agents. Both cryogels and xerogels were obtained by lyophilization and drying of the hydrogels. We investigated the effect of the chemical composition and the physical state of gels on the gel structure and sorption of model dyes. Alginate and mixed gels cross-linked with Ca2+ ions sorbed 80-95% of cationic dye from the solutions. The chitosan gels are primarily capable of adsorbing anionic dyes, but at near-neutral pH, their capacity is lower than that of alginate gels, showing 50-60% dye sorption. In the case of alginate gels, the dye sorption capacity of xerogels, cryogels, and hydrogels was the same, but for chitosan gels, the hydrogels adsorbed slightly less dye than the dried gels.

Revealing the Impact of Viscoelastic Characteristics on Performance Parameters of UV-Crosslinked Hotmelt Pressure-Sensitive Adhesives: Insights from Time-Temperature Superposition Analysis.

This study emphasizes the influential role of rheology in decoding the viscoelastic properties of pressure-sensitive adhesives (PSAs) vital to predicting key application features such as shear, tack, and peel, depending on the flow characteristics of PSAs during bonding and debonding processes. By applying the principle of time-temperature superposition (TTS), we extend the scope of our frequency analysis, surpassing the technical constraints of the available apparatus. Our exploration aims to uncover the general correlations between PSAs' viscoelastic properties and their performance in end-use applications. Initially, the adhesive performance and viscoelastic properties of a UV-crosslinkable styrene-butadiene-styrene (SBS) model adhesive prior and subsequent to UV irradiation were examined. The subsequent crosslinking reaction increased cohesive strength and heat resistance, although tack and peel strength observed a substantial decline. We successfully demonstrated these effects by logging the viscoelastic properties, specifically the storage modulus G' at lower frequencies, which mirrors the shear strength at higher temperatures and the shift in the tan δ peak to represent each PSA's tack. These correlations were partially reflected in three commercial UV crosslinkable acrylic PSA products, although the effect of UV irradiation was less distinctive. This study also revealed the challenges in predicting tack and peel strength, which result from a complex interplay of bonding and debonding processes. Our findings reinforce the necessity for more sophisticated analysis techniques and models that can accurately predict the end-use performance of PSAs across different physical structures and chemical compositions. Further research is needed to develop these predictive models, which may reduce the need for labor-intensive testing under real-life conditions.

High-performance glued-bamboo through activation of chemical bonding interface

Bamboo glue products are widely used in decoration, construction and transportation. Bamboo is fast growing, strong and inexpensive, making it one of the ideal processing materials to replace steel and wood. Here we present a process for the production of high performance bamboo glue products. In this process, the conversion of natural bamboo surface (NBS) to oxidized bamboo surface (OBS) is a critical step prior to hot pressing, as it provides the bamboo interface with active sites (aldehyde groups) for chemical cross-linking with the adhesive. Subsequent covalent crosslinking with branched chain amine (PAXN) compounds is based on Schiff base chemistry. The improved properties of the oxidized bamboo specimens were attributed to chemical cross-linking within the oxidized bamboo-binder interface (OBI-PAXN) and further densification of the bamboo adhesive interface. The dry/hot/boiling water bond strength of OBI-PA6 N was increased by 130 % (7.5 MPa)/148 % (5.05 MPa)/130 % (3.26 MPa) compared to NBI-PA6 N (3.26 MPa, 2.04 MPa, 0.88 MPa). Its bonding strength and bending strength are superior to commercial PF resins. The combination of excellent mechanical properties with the rich, renewable and sustainable nature of bamboo makes it very attractive for engineering applications.

Ordered Transfer from 3D-Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns.

Films and patterns of 3D-oriented metal-organic frameworks (MOFs) afford well-ordered pore structures extending across centimeter-scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D-oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D-ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N3-functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide-alkyne cycloaddition on the Cu2(AzBPDC)2DABCO MOF. The micropatterning protocol exploits the X-ray sensitivity of azide groups in Cu2(AzBPDC)2DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N3-functionality, allowing for subsequent cross-linking through azide-alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro-patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D-oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications.

Zwitterion-functionalized nanofiber-based composite proton exchange membranes with superior ionic conductivity and chemical stability for direct methanol fuel cells

Proton exchange membranes with high ionic conductivity and good chemical stability are critical for achieving high power density and long lifespan of direct methanol cells (DMFCs). Herein, a zwitterionic molecule was grafted onto the surface of polyvinylidene fluoride (PVDF) nanofibers to obtain functionalized PVDF porous substrate (SBMA-PDA@PVDF). Then, sulfonated poly(ether ether ketone) (SPEEK) was filled into the pores of SBMA-PDA@PVDF, and further ionic cross-linked via H2SO4 to prepare the composite membrane (SBMA-PDA@PVDF/SPEEK). The basic groups on the zwitterionic interface could not only establish ionic cross-linking with SPEEK to increase chemical stability and reduce swelling, but also serve as the adsorption sites for subsequent H2SO4 cross-linking to significantly enhance proton conductivity. Super-high proton conductivity (165.34 mS cm−1, 80 °C) was achieved for the membrane, which was 2.12 times higher than that of the pure SPEEK. Moreover, the SBMA-PDA@PVDF/SPEEK membrane exhibited remarkably improved oxidative stability of 91.6 % mass retention after soaking in Fenton’s agent for 12 h, while pure SPEEK completely decomposed. Satisfactorily, the DMFC assembled with SBMA-PDA@PVDF/SPEEK exhibited a peak power density of 99.01 mW cm−2, which was twice as much as that of commercial Nafion 212 (48.88 mW cm−2). After 235 h durability test, only 11 % voltage loss was observed.

β-galactosidase immobilization on ceramic ultrafiltration membrane for simultaneous lactose hydrolysis and protein separation

Protein and lactose of cheese whey can be separated using ultrafiltration membranes and lactose can be hydrolyzed by β-galactosidase. This study investigated the integration of ultrafiltration and enzymatic hydrolysis for simultaneous protein concentration and lactose hydrolysis. β-galactosidase was immobilized on ceramic membrane via surface activation with gelatin and subsequent enzyme cross-linking with glutaraldehyde. Membrane geometries, buffer types, gelatin and enzyme concentrations were optimized. The optimal results yielded a 63 % enzyme immobilization efficiency and a 93 % lactose hydrolysis rate by using disc membrane, sodium acetate buffer (pH 4.8), sodium phosphate buffer (pH 7.5), 0.1 g/L gelatin concentration, and 5.0 g/L enzyme concentration. The optimized enzymatic membrane was evaluated with synthetic and real whey. In synthetic whey, 85 % lactose hydrolysis and 89 % protein rejection were achieved. While in real whey, 72 % lactose hydrolysis and 83 % protein recovery were obtained. This approach offers a single-step, efficient, and scalable method for whey valorization with potential for industrial applications.

An Ice‐Dissolving‐Crosslinking Method for Efficient and Large‐Scale Preparation of Polyelectrolyte Monoliths with Ultra‐Stability in Aqueous Environments

AbstractIce‐templating is a versatile method for constructing macro‐porous hydrophilic polymer materials. However, the ice‐templating method is generally limited by high energy cost and low efficiency for large‐scale fabrication. Further, due to its hydrophilic nature, the constructed materials are vulnerable to water swelling and have poor structural stability. Here, an Ice‐Dissolving‐Crosslinking (IDCr) method is developed for efficient and large‐scale preparation of polyelectrolyte monoliths with ultra‐stability in aqueous environment. Specifically, Ice‐Dissolving in water‐miscible organic solvent is responsible for pore creation, while subsequent Crosslinking ensures pore structures stabilization. The macro‐porous architecture of materials, taking sodium carboxymethyl cellulose (CMC) as a polyelectrolyte example and trimesoyl chloride (TMC) as the crosslinker, CMC‐TMCIDCr is made much stabler as compared with the case of conventional Lyophilization‐Crosslinking technique (CMC‐TMCLC). The IDCr method is applicable to various hydrophilic polyelectrolytes and hybrids for long‐time use in water and brines, as exemplified by CMC‐TMC‐carbon nanotubes monolith, which exhibits high performance in solar thermal desalination process. This novel approach opens up new opportunities for the construction of porous monoliths with efficient preparation and excellent water stability.

Synergistic enhancement of anthocyanin stability and techno-functionality of colored wheat during the steamed bread processing by selectively hydrolyzed soy protein

To improve the stability of anthocyanins and techno-functionality of purple and blue wheat, the selectively hydrolyzed soy protein (reduced glycinin, RG) and β-conglycinin (7S) were prepared and their enhanced effects were comparatively investigated. The anthocyanins in purple wheat showed higher stability compared to that of the blue wheat during breadmaking. The cyanidin-3-O-glucoside and cyanidin-3-O-rutincoside in purple wheat and delphinidin-3-O-rutinoside and delphinidin-3-O-glucoside in blue wheat were better preserved by RG. Addition of RG and 7S enhanced the quality of steamed bread made from colored and common wheat, with RG exhibited a more prominent effect. RG and 7S suppressed the gelatinization of starch and improved the thermal stability. Both RG and 7S promoted the unfolding process of gluten proteins and facilitated the subsequent crosslinking of glutenins and gliadins by disulfide bonds. Polymerization of α- and γ-gliadin into glutenin were more evidently promoted by RG, which contributed to the improved steamed bread quality.

Design, Construction, and Validation of a Yeast-Displayed Chemically Expanded Antibody Library.

In vitro display technologies, exemplified by phage and yeast display, have emerged as powerful platforms for antibody discovery and engineering. However, the identification of antibodies that disrupt target functions beyond binding remains a challenge. In particular, there are very few strategies that support identification and engineering of either protein-based irreversible binders or inhibitory enzyme binders. Expanding the range of chemistries in antibody libraries has the potential to lead to efficient discovery of function-disrupting antibodies. In this work, we describe a yeast display-based platform for the discovery of chemically diversified antibodies. We constructed a billion-member antibody library that supports the presentation of a range of chemistries within antibody variable domains via noncanonical amino acid (ncAA) incorporation and subsequent bioorthogonal click chemistry conjugations. Use of a polyspecific orthogonal translation system enables introduction of chemical groups with various properties, including photo-reactive, proximity-reactive, and click chemistry-enabled functional groups for library screening. We established conjugation conditions that facilitate modification of the full library, demonstrating the feasibility of sorting the full billion-member library in "protein-small molecule hybrid" format in future work. Here, we conducted initial library screens after introducing O-(2-bromoethyl)tyrosine (OBeY), a weakly electrophilic ncAA capable of undergoing proximity-induced crosslinking to a target. Enrichments against donkey IgG and protein tyrosine phosphatase 1B (PTP1B) each led to the identification of several OBeY-substituted clones that bind to the targets of interest. Flow cytometry analysis on the yeast surface confirmed higher retention of binding for OBeY-substituted clones compared to clones substituted with ncAAs lacking electrophilic side chains after denaturation. However, subsequent crosslinking experiments in solution with ncAA-substituted clones yielded inconclusive results, suggesting that weakly reactive OBeY side chain is not sufficient to drive robust crosslinking in the clones isolated here. Nonetheless, this work establishes a multi-modal, chemically expanded antibody library and demonstrates the feasibility of conducting discovery campaigns in chemically expanded format. This versatile platform offers new opportunities for identifying and characterizing antibodies with properties beyond what is accessible with the canonical amino acids, potentially enabling discovery of new classes of reagents, diagnostics, and even therapeutic leads.

Achieving a balance between permeability and selectivity in a ZIF-8-matrix nanocomposite membrane for desalination

Hybrid metal–organic framework (MOF)-polymer membranes are promising for addressing the permeability-selectivity tradeoff in membrane applications. The key challenges for achieving high-efficiency separation performance have been identified as increasing the MOF loading while maintaining interfacial compatibility with polymeric matrices. Herein, a novel design of ZIF-8 matrix nanocomposite membrane, with ZIF-8 nanoparticles (NPs) serving as the main matrix, was prepared by functionalizing the external surface of zeolitic imidazolate framework-8 (ZIF-8) NPs with polyethyleneimine and subsequent crosslinking into the selective layer using trimesoyl chloride as a crosslinking agent via confined interfacial polymerization. The content of ZIF-8 NPs in the selective layer was up to about 70 wt%, resulting in superior permeability (＞ 43.6 LMH bar−1) for desalination due to the large number of transport channels, which was several folds as compared to most of the reported membranes. Meanwhile, a reasonably high Na2SO4 rejection (∼95.1 %) was maintained as the polyamide fragments formed during interfacial polymerization, which filled defects among the ZIF-8 NPs. Overall, such strategy paves the way for the design of efficient MOF-based membranes for balancing between permeability and selectivity in desalination.

Thermadapt shape memory vitrimeric polymyrcene elastomer

Earlier studies of β-Myrcene (Myr)/ β-ketoester functional (acetoacetoxy)ethyl methacrylate (AAEMA) copolymers exhibited compositional drift, leading to ambiguity in microstructure/thermomechanical property correlations while shape memory recovery times were excessively long ~1 h. The terpene-based 1,3-diene Myr and AAEMA were copolymerized via nitroxide-mediated polymerization (NMP) with an initial Myr molar feed ratio ranging from 0.1 to 0.9. Reactivity ratios estimated by the Meyer-Lowry method were rMyr = 0.20 and rAAEMA = 0.22 with respective 95% confidence intervals of [0.13, 0.37] and [0.15, 0.23], suggesting alternating copolymerization. Bulk terpolymerization with styrene (Sty) afforded linear poly(Myr-stat-Sty-stat-AAEMA) prepolymers designed to modulate glass transition temperature Tg and stiffness. Subsequent cross-linking with isophorone diamine (IPDA) formed catalyst-free vinylogous urethane dynamic linkages. ATR-FTIR, dynamic mechanical analysis (DMA), and tensile measurements confirmed the recyclability of vitrimers through hot pressing at 110 °C, demonstrating minimal changes in rheological and mechanical properties even after four cycles. By heating the vitrimers to above their Tg (to ~45 °C), they exhibited a shape memory effect with high shape fixity and fast shape recovery (< 1 min). The vitrimers could undergo permanent shape reprogramming through reconfiguration of dynamic bonds at ~110 °C. This work shows the adaptability of Myr-based rubbers by vitrification and appropriate copolymerization for the synthesis of more sustainable elastomers with stimuli responsive properties.

Combined effect of polyelectrolyte assisted interfacial polymerization and tannic acid protective surface modification to boost organic solvent nanofiltration performance

Organic solvent nanofiltration (OSN) is an effective technology for separating solute with molecular weight of 200–1000 Da (Da) from organic solvents. However, as the core of this technology, most of OSN membranes exhibit a low solvent permeance. Herein, a highly permeable OSN membrane was prepared via a poly (sodium 4-styrenesulfonate) (PSSNa)-assisted interfacial polymerization reaction using ultra-low content of aqueous monomer solution, followed by a protective modification using tannic acid (TA) grafting onto the nascent polyamide surface, and a post chemical crosslinking treatment as well as an activation treatment. PSSNa manipulates the diffusion and distribution of the m-Phenylenediamine monomers, leading to a looser and thinner polyamide layer. TA molecules successfully reacted with the remaining acyl chloride groups on the nascent polyamide layer surface and formed ester, thus preventing the surface from subsequent crosslinking reaction and also making the selective layer looser, which is beneficial for solvent permeation. Moreover, the TA modification makes the surface more hydrophilic, thus further helps to improve the solvent permeance of OSN membrane. The optimal membrane possesses an excellent ethanol permeance of 71.5 L m−2 h−1 MPa−1, an increment of 41.6 % as compared with the baseline OSN membrane, while keeping a rejection of 98.2 % for rhodamine B (RDB). Meanwhile, the surface of optimal membrane is ultra-smooth, with an average roughness of 4.4 nm, which is much beneficial for antifouling. Moreover, the OSN membrane possesses a brilliant durability performance, with only a 1.5 % decrease of the RDB rejection after being immersed in N, N-Dimethylformamide (DMF) at room temperature for 115 d, and only a further 0.3 % decrease of the RDB rejection after being further immersed in DMF at 80 °C for another 11 d, indicating its superior solvent resistance, which makes it a promising candidate for treating organic solutions from pharmaceutical and textile industries.

Gradually Self-Strengthen DNA Supramolecular Hydrogels.

The dynamic mechanical strength of the extracellular matrix (ECM) has been demonstrated to play important role in determining the cell behavior. Growing evidences suggest that the gradual stiffening process of the matrix is particularly decisive during tissue development and wound healing. Herein, a novel strategy to prepare hydrogels with gradually enhanced mechanical strength is provided. Such hydrogels could maintain the dynamic properties at their initial states, such as self-healing and shear-thinning properties. With subsequent slow covalent crosslinking, the stability and mechanical properties would be gradually improved. This method is useful for sequence programmability and oxidation strategies, which has provided an alternated tool to study cell behavior during dynamic increase in mechanical strength of ECM.

Synthesis of Bottlebrush Polymers with Spontaneous Self-Assembly for Dielectric Generators.

Cross-linked bottlebrush polymers received significant attention as dielectrics in transducers due to their unique softness and strain stiffening caused by their structure. Despite some progress, there is still a great challenge in increasing their dielectric permittivity beyond 3.5 and cross-linking them to defect-free ultrathin films efficiently under ambient conditions. Here, we report the synthesis of bottlebrush copolymers based on ring-opening metathesis polymerization (ROMP) starting from a 5-norbornene-2-carbonitrile and a norbornene modified with a poly(dimethylsiloxane) (PDMS) chain as a macromonomer. The resulting copolymer was subjected to a postpolymerization modification, whereby the double bonds were used both for functionalization with thiopropionitrile and subsequent cross-linking via a thiol-ene reaction. The solutions of both bottlebrush copolymers formed free-standing elastic films by simple casting. DMA and broadband impedance spectroscopy revealed two glass transition temperatures uncommon for a random copolymer. The self-segregation of the nonpolar PDMS chains and the polynorbornane backbone is responsible for this and is supported by the interfacial polarization observed in broadband impedance spectroscopy and the scattering peaks observed in small-angle X-ray scattering (SAXS). Additionally, the modified bottlebrush copolymer was cross-linked to an elastomer that exhibits increased dielectric permittivity and good mechanical properties with significant strain stiffening, an attractive property of dielectric elastomer generators. It has a relative permittivity of 5.24, strain at break of 290%, elastic modulus at 10% strain of 380 kPa, a breakdown field of 62 V μm-1, and a small actuation of 5% at high electric fields of 48.5 V μm-1. All of these characteristics are attractive for dielectric elastomer generator applications. The current work is a milestone in designing functional elastomers based on bottlebrush polymers for transducer applications.

Degradable Nanogels Based on Poly[Oligo(Ethylene Glycol) Methacrylate] (POEGMA) Derivatives through Thermo-Induced Aggregation of Polymer Chain and Subsequent Chemical Crosslinking.

Polymer nanogels-considered as nanoscale hydrogel particles-are attractive for biological and biomedical applications due to their unique physicochemical flexibility. However, the aggregation or accumulation of nanoparticles in the body or the occurrence of the body's defense reactions still pose a research challenge. Here, we demonstrate the fabrication of degradable nanogels using thermoresponsive, cytocompatible poly[oligo(ethylene glycol) methacrylate]s-based copolymers (POEGMA). The combination of POEGMA's beneficial properties (switchable affinity to water, nontoxicity, non-immunogenicity) along with the possibility of nanogel degradation constitute an important approach from a biological point of view. The copolymers of oligo(ethylene glycol) methacrylates were partially modified with short segments of degradable oligo(lactic acid) (OLA) terminated with the acrylate group. Under the influence of temperature, copolymers formed self-assembled nanoparticles, so-called mesoglobules, with sizes of 140-1000 nm. The thermoresponsive behavior of the obtained copolymers and the nanostructure sizes depended on the heating rate and the presence of salts in the aqueous media. The obtained mesoglobules were stabilized by chemical crosslinking via thiol-acrylate Michael addition, leading to nanogels that degraded over time in water, as indicated by the DLS, cryo-TEM, and AFM measurements. Combining these findings with the lack of toxicity of the obtained systems towards human fibroblasts indicates their application potential.