Search Results (46)

Developing materials that simultaneously exhibit bulk elasticity and a durable, self-renewing surface is a persistent challenge, as traditional fillers often impair flexibility and sacrificial coatings fail under repeated strain. This paper presents an innovative thiol–ene/polyurethane hybrid system, fabricated via a sequential thermal–UV curing process, which decouples the properties of the highly elastic bulk from those of the robust surface layer. The resulting bulk elastomer achieves an outstanding combination of high strength (20.9 MPa) and exceptional extensibility (990% elongation at break). Crucially, the UV-crosslinked surface forms a dense, abrasion-resistant shield that reduces friction-induced mass loss by 81% compared to the bulk material. This surface layer also exhibits a unique self-renewing capability, effectively restoring its protective function over at least three abrasion cycles and reducing mass loss by 57% after the first recovery cycle relative to an unprotected control. Dynamic mechanical analysis validates the distinct dual-network structure, evidenced by two well-separated glass transition temperatures, which underpin the material’s pronounced shape memory effect. This work provides a design paradigm for creating flexible and durable polymer systems with independently tailored bulk and surface properties, offering significant potential for applications in artificial skin and demanding flexible components. Full article

Background/Objectives: The development of stimuli-responsive hydrogels for biomedical uses is an intense field of research. The use of dendritic crosslinkers can enhance the control over the structure and properties of the networks. This work presents a comparative study on the design and evaluation of Pluronic L35 thermogels, incorporating either hydrophobic carbosilane dendrimers (CBS, generations 1 to 3) or hydrophilic dendritic polyglycerols (dPG, 10 k) as crosslinkers. Methods: The thermogels were synthesized via UV-initiated thiol–ene click chemistry. Additionally, they were characterized through swelling studies, mechanical properties, degradation kinetics as well as loading and release studies of the antitumor drug doxorubicin as poorly soluble model cargo. Results: The incorporation of dendritic crosslinkers allowed higher control over the crosslinking process, while the amphiphilic polymer imparted temperature-responsive properties to the resulting networks. Remarkable differences were observed in swelling behavior, mechanical properties and degradation kinetics, depending on the nature of the dendritic crosslinker. Additionally, regarding doxorubicin loading and release in water, CBS hydrogels produced a sustained release over one week, led by network swelling, while dPG hydrogels exhibited a burst release in 4–24 h but were limited by the stronger interaction of DOX with the dPG scaffold. Conclusions: The study provided useful insight for the tailoring of dendritic thermogels for specific biomedical uses such as controlled drug delivery. Full article

Click chemistry is highly valued in the design of polymeric biomaterials due to its ability to generate complex structures and localized surface modifications. However, prominent mechanisms in click chemistry, such as copper-catalyzed azide-alkyne cycloaddition (CuAAC), are inefficient for the synthesis and/or modification of biomaterials because they present significant limitations for in vivo applications. The presence of residual copper in the material is toxic and requires extensive purification, increasing production costs and hindering scalability and availability for in vivo applications. To overcome these limitations and ensure the safety and biocompatibility of materials, biorthogonal reactions such as strain-promoted azide-alkyne cycloaddition (SPAAC) have been developed. Thiol-ene/thiol-yne and Diels–Alder mechanisms are also relevant for the formation of robust polymer networks with specific characteristics and attractive advantages for generating biocompatible materials. These reactions not only improve cell integration and reduce fibrosis in in vivo applications but also enable the creation of functional structures for tissue regeneration. This review provides a comprehensive analysis of advances in the synthesis of biomaterials for tissue regeneration using hydrogels designed via click chemistry, as well as the various mechanisms and structural considerations. Full article

Protein phosphorylation is a crucial post-translational modification that regulates protein activity, cellular signaling, transcriptional regulation, and cell cycle control. However, the analysis of phosphoproteins in biological samples is often compromised by complex sample matrices and interference from high-abundance proteins. While the top-down phosphoproteomics strategy enables comprehensive analysis of post-translational modifications based on intact proteins, its requirement for higher protein purity due to low protein ionization efficiency poses stern challenges. Consequently, developing appropriate enrichment methods for phosphoproteins in practical samples becomes essential. Immobilized metal ion affinity chromatography (IMAC) represents a common strategy for phosphorylated protein separation and enrichment. Among metal ions, Ti⁴⁺ has gained widespread application as IMAC chelating ligands due to its capacity to form multiple coordination networks and its high selectivity for phosphorylated protein enrichment, leveraging the strong chelating ability of phosphate groups toward metal ions. This paper presents the design and preparation of a novel magnetic Ti-IMAC nanocomposite, MNP@MPTMS–VPA–Ti(IV). The material is modified with phosphate groups via facile thiol-ene click chemistry and then immobilizes Ti⁴⁺, enabling selective enrichment of intact phosphoproteins through IMAC affinity. The efficiency of enrichment was evaluated using subsequent matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for detection and analysis. This Ti-IMAC material-based magnetic solid-phase extraction (MSPE)-MALDI-TOF MS protocol has been successfully applied to enrich intact phosphoproteins in milk and eel mucus with high selectivity, sensitivity, and suitability. Full article

In this work, a multifunctional surface engineering strategy was developed to impart both flame-retardant and hydrophobic properties to cotton fabrics. In the first stage, cellulose fibers were modified with poly(methylvinyl)siloxane containing trimethoxysilyl groups, 2,4,6,8-tetramethyl-divinyl-bis(trimethoxysilylpropyltioethyl)cyclotetrasiloxane, or tetrakis(vinyldimethylsiloxy)tetrakis(trimethoxysilylpropyltioethyl)octasilsesquioxane (POSS). All modifiers contained alkoxysilyl groups capable of forming covalent bonds with cellulose hydroxyl groups. The modification was performed using a dip-coating process followed by thermal curing. This procedure enabled the formation of Si-O-C linkages and the generation of a reactive organosilicon layer on the cotton surface. In the second step, O,O′-diethyl dithiophosphate was grafted directly onto the vinyl-functionalized fabrics via a thiol-ene click reaction. This process resulted in the formation of a phosphorus- and sulfur-containing protective layer anchored within the siloxane-based network. The obtained hybrid coatings were characterized using Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and SEM-EDS. These analyses confirmed the presence and uniform distribution of the modifiers on the fiber surface. Microscale combustion calorimetry demonstrated a substantial reduction in the heat release rate. Thermogravimetric analysis (TG/DTG) revealed increased char formation and altered thermal degradation pathways. The limiting oxygen index (LOI) increased for all modified fabrics, confirming enhanced flame resistance. Water contact angle measurements showed values above 130°, indicating effective hydrophobicity. As a result, multifunctional textile surfaces were obtained. In addition, the modified fabrics exhibited partial durability toward laundering and retained measurable flame-retardant and hydrophobic performance after repeated washing cycles. Full article

Although covalently crosslinked gelatin hydrogels have been investigated for use in 3D cell culture due to inherent bioactivity and proliferation within the denatured collagen precursor, the stability of the matrix, and relatively inexpensive synthesis, current systems lack precise control over mechanical properties, including homogeneity, stiffness, and efficient diffusion of nutrients to embedded cells. Difficulties in modifying gel matrix composition and functionalization have limited the use of covalently crosslinked gelatin hydrogels as a three-dimensional (3D) cell culture medium, lacking the ability to tailor the microenvironment for specific cell types. In addition, the currently utilized chain-growth photopolymerization mechanism for crosslinking hydrogels has a potential for side reactions between the matrix backbone and components of the cell surface, requires a high concentration of radicals for initiation, and only cures with long irradiation times, which could lead to cytotoxicity. To overcome these limitations, a superfast curing reaction mechanism, in which a thiol monomer reacts efficiently with non-homopolymerizable alkenes, is suggested. This mechanism reliably produces a well-defined matrix that does not require a high radical concentration for photoinitiation. Mechanical customization of the hydrogel is largely achievable through variation in degree of functionalization of the gelatin backbone, dependent on reaction conditions such as pH, allyl concentration, and time. This work provides a mechanistic framework for GelAGE hydrogel fabrication by elucidating the molecular mechanism of gelatin functionalization with AGE and the thiol-ene crosslinking reactions controlling network stiffness. These insights provide the foundation for engineering hydrogels that mimic the viscoelastic and structural characteristics of cartilage, enabling advanced in vitro models for osteoarthritis research. Full article

This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. Full article

A new topological material, the [c2]daisy-chain rotaxane network, was successfully synthesized via a thiol-ene reaction between a [c2]daisy-chain rotaxane, which consists of a host–guest compound (H–G compound) where a crown ether and a secondary ammonium salt are linked, and a multi-branched thiol compound. The resulting network polymer exhibited higher compressive strength compared to one without the [c2]daisy-chain rotaxane. Additionally, the neutralized [c2]daisy-chain rotaxane network, in which the ammonium salt was neutralized and there was no interaction with the crown ether, showed increased rigidity compared to its state before neutralization. Furthermore, a gel electrolyte was prepared by impregnating the [c2]daisy-chain rotaxane network with an organic electrolyte containing dissolved lithium salts, and its ionic conductivity was investigated. As a result, high ionic conductivity was achieved despite the high polymer content. Full article

A covalent adaptable network (CAN) of semicrystalline polyolefin blends with triple-shape memory effects was fabricated by the reactive melt blending of maleated polypropylene (mPP) and maleated polyolefin elastomer (mPOE) (50 wt/50 wt) in the presence of a small amount of a tetrafunctional thiol (PETMP) and 1,5,7-triazabicyclo [4,4,0]dec-5-ene (TBD). The polymer blend formed a chemically crosslinked network via the reaction between the thiol group of PETMP and maleic anhydride of both polymers in the blend, which was confirmed by FTIR, the variation of torque during the melt mixing process, a solubility test, and DMA. DSC analysis revealed that the crosslinked polyolefin blends show two distinct crystalline melting transitions corresponding to each component polymer. Improved tensile strength as well as elongation at break were observed in the crosslinked blend as compared to the simple blend, and the mechanical properties were maintained after repeated melt processing. These results suggest that thermoplastic polyolefin blends can be transformed into a high-performance and value-added material with good recyclability and reprocessability. Full article

The thermo-responsive behavior of Poly(N-isopropylacrylamide) makes it an ideal candidate to easily embed cells and allows the polymer mixture to be injected. However, P(NiPAAm) hydrogels possess minor mechanical properties. To increase the mechanical properties, a covalent bond is introduced into the P(NIPAAm) network through a biocompatible thiol-ene click-reaction by mixing two polymer solutions. Co-polymers with variable thiol or acrylate groups to thermo-responsive co-monomer ratios, ranging from 1% to 10%, were synthesized. Precise control of the crosslink density allowed customization of the hydrogel’s mechanical properties to match different tissue stiffness levels. Increasing the temperature of the hydrogel above its transition temperature of 31 °C induced the formation of additional physical interactions. These additional interactions both further increased the stiffness of the material and impacted its relaxation behavior. The developed optimized hydrogels reach stiffnesses more than ten times higher compared to the state of the art using similar polymers. Furthermore, when adding cells to the precursor polymer solutions, homogeneous thermo-responsive hydrogels with good cell viability were created upon mixing. In future work, the influence of the mechanical micro-environment on the cell’s behavior can be studied in vitro in a continuous manner by changing the incubation temperature. Full article

Dendritic hydrogels based on carbosilane crosslinkers are promising drug delivery systems, as their amphiphilic nature improves the compatibility with poorly water-soluble drugs. In this work, we explored the impact of the complementary polymer on the amphiphilic properties of the dendritic network. Different polymers were selected as precursors, from the highly lipophilic propylene glycol (PPG) to the hydrophilic polyethylene glycol (PEG), including amphiphilic Pluronics L31, L35 and L61. The dithiol polymers reacted with carbosilane crosslinkers through UV-initiated thiol–ene coupling (TEC), and the resultant materials were classified as non-swelling networks (for PPG, PLU_L31 and PLU_L61) and high-swelling hydrogels (for PEG and PLU_L35). The hydrogels exhibited thermo-responsive properties, shrinking at higher temperatures, and exhibited an intriguing drug release pattern due to internal nanostructuring. Furthermore, we fine-tuned the dendritic crosslinker, including hydroxyl and azide pendant groups in the focal point, generating functional networks that can be modified through degradable (ester) and non-degradable (triazol) bonds. Overall, this work highlighted the crucial role of the amphiphilic balance in the design of dendritic hydrogels with thermo-responsive behavior and confirmed their potential as functional networks for biomedical applications. Full article

In this work, a thiol–ene coupling reaction was employed to prepare the semi-interpenetrating polymer network AEMs. The obtained QP-1/2 membrane exhibits high hydroxide conductivity (162.5 mS cm⁻¹ at 80 °C) with a relatively lower swelling ratio, demonstrating its mechanical strength of 42 MPa. This membrane is noteworthy for its improved alkaline stability, as the semi-interpenetrating network effectively limits the attack of hydroxide. Even after being treated in 2 M NaOH at 80 °C for 600 h, 82.5% of the hydroxide conductivity is maintained. The H₂/O₂ fuel cell with QP-1/2 membrane displays a peak power density of 521 mW cm⁻². Alkaline water electrolyzers based on QP-1/2 membrane demonstrated a current density of 1460 mA cm⁻² at a cell voltage of 2.00 V using NiCoFe catalysts in the anode. All the results demonstrate that a semi-interpenetrating structure is a promising way to enhance the mechanical property, ionic conductivity, and alkaline stability of AEMs for the application of alkaline fuel cells and water electrolyzers. Full article

A series of poly(thiourethanes) (PTUs) from biobased monomers have been synthesized. Limonene and squalene were transformed into polyfunctional thiols by thiol-ene reaction with thioacetic acid and further saponification. They were then reacted in different proportions with hexamethylene diisocyanate (HDI) in the presence of a catalyst to prepare bio-based poly(thiourethane) vitrimer-like materials. The different functionalities of squalene and limonene thiols (six and two, respectively) allow for changing the characteristics of the final material by only varying their relative proportions in the reactive mixture. The proportions of thiol and isocyanate groups were stoichiometric in all the formulations tested. An acidic and a basic catalyst were tested in the preparation of the networked polymers. As the acidic catalyst, we selected dibutyltin dilaurate (DBTDL), and as the basic catalyst, a tetraphenylborate salt of 1,8-diazabicyclo(5.4.0)undec-7-ene (BGDBU), which has the advantage of only releasing the base at high temperatures. The materials obtained were characterized by thermogravimetry and thermomechanical analysis. The vitrimeric-like behavior was evaluated, and we could see that higher proportions of the limonene derivative in the formulations led to faster stress relaxation of the material. The use of the base catalyst led to a much shorter relaxation time. The materials obtained demonstrated good self-healing efficiency. Full article

Temperature and light responsiveness are widely exploited stimuli to tune the physico-chemical properties of double network hydrogels. In this work, new amphiphilic poly(ether urethane)s bearing photo-sensitive moieties (i.e., thiol, acrylate and norbornene functionalities) were engineered by exploiting the versatility of poly(urethane) chemistry and carbodiimide-mediated green functionalization procedures. Polymers were synthesized according to optimized protocols maximizing photo-sensitive group grafting while preserving their functionality (approx. 1.0 × 10¹⁹, 2.6 × 10¹⁹ and 8.1 × 10¹⁷ thiol, acrylate and norbornene groups/g_polymer), and exploited to prepare thermo- and Vis-light-responsive thiol-ene photo-click hydrogels (18% w/v, 1:1 thiol:ene molar ratio). Green light-induced photo-curing allowed the achievement of a much more developed gel state with improved resistance to deformation (ca. 60% increase in critical deformation, γL). Triethanolamine addition as co-initiator to thiol-acrylate hydrogels improved the photo-click reaction (i.e., achievement of a better-developed gel state). Differently, L-tyrosine addition to thiol-norbornene solutions slightly hindered cross-linking, resulting in less developed gels with worse mechanical performances (~62% γL decrease). In their optimized composition, thiol-norbornene formulations resulted in prevalent elastic behavior at lower frequency compared to thiol-acrylate gels due to the formation of purely bio-orthogonal instead of heterogeneous gel networks. Our findings highlight that exploiting the same thiol-ene photo-click chemistry, a fine tuning of the gel properties is possible by reacting specific functional groups. Full article

An increase in resistance to key antibiotics has made the need for novel treatments for the gastric colonization of Helicobacter pylori (H. pylori) a matter of the utmost urgency. Recent studies tackling this topic have focused either on the discovery of new compounds to ameliorate therapeutic regimes (such as vonoprazan) or the synthesis of gastroretentive drug delivery systems (GRDDSs) to improve the pharmacokinetics of oral formulations. The use of semi-interpenetrating polymer networks (semi-IPNs) that can act as super-porous hydrogels for this purpose is proposed in the present work, specifically those displaying low ecological footprint, easy synthesis, self-floating properties, high encapsulation efficiency for drugs such as amoxicillin (AMOX), great mucoadhesiveness, and optimal mechanical strength when exposed to stomach-like fluids. To achieve such systems, biodegradable synthetic copolymers containing acid-labile monomers were prepared and interpenetrated with guar gum (GG) in a one-pot polymerization process based on thiol-ene click reactions. The resulting matrices were characterized by SEM, GPC, TGA, NMR, and rheology studies, and the acidic hydrolysis of the acid-sensitive polymers was also studied. Results confirm that some of the obtained matrices are expected to perform optimally as GRDDSs for the sustained release of active pharmaceutical ingredients at the gastrointestinal level, being a priori facilitated by its disaggregation. Therefore, the optimal performance of these systems is assessed by varying the molar ratio of the labile monomer in the matrices. Full article