Search Results (118)

The development of new photoinitiators for photocurable systems has gained increasing interest in response to regulatory and environmental requirements, including efficient absorption in the UV/Vis range and reduced toxicity. Among emerging light-sensitive compounds, oxime esters have attracted growing attention as efficient radical photoinitiators. In this paper, five series of oxime esters based on carbazole, coumarin, carbazole–coumarin, phenothiazine, and triphenylamine scaffolds were described. Their high performance in photopolymerization processes was presented, demonstrating their ability to act as both type I and type II photoinitiators, as confirmed by high monomer conversion degrees. These data highlight oxime esters as versatile photoinitiating systems and provide a basis for further structural optimization aimed at improving water solubility and enabling comprehensive cytotoxicity assessment. 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

Hydrogels have attracted considerable attention as biomedical materials owing to their distinctive properties; however, improvements in mechanical strength, biodegradability, and biocompatibility remain essential for advanced clinical applications. This study developed a new dual-crosslinked hydrogel based on gelatin (Gel) and dextran (Dex) via sequential aldimine condensation and photopolymerization. Natural Gel and Dex were functionalized to synthesize methacrylated Gel (GelMA) and oxidized Dex (ODex), respectively. An imine-linked network was initially formed between GelMA and ODex via aldimine condensation, followed by a second crosslinked network generated through blue-light-induced free-radical polymerization of GelMA, yielding dual-crosslinked hydrogels (GMODs). ¹H NMR and FT–IR analyses confirmed the successful functionalization and formation of dual-crosslinked structure. The dual-crosslinked network enhanced the thermal stability and water-retaining capacity of the freeze-dried hydrogels (DGMODs) while reducing the surface wettability and equilibrium swelling ratio of GMODs. The maximum compressive strength (σₘ) increased with crosslinking density; GMOD−2, with moderate crosslinking density, remained intact under 85% compressive strain and achieved σₘ of 108.0 kPa. The degradation rate of GMODs was tunable by adjusting the crosslinking density, thereby modulating their drug-release behavior. GMOD−3, possessing the highest crosslinking density, exhibited effective drug-sustained release for up to five weeks. Biological evaluations, including cytotoxicity assays, live/dead cell staining, and hemolysis tests, verified excellent cytocompatibility (cell survival rate > 92%) and minimal hemolysis ratio (<5%). Furthermore, inhibition zone tests preliminarily revealed moderate antibacterial activity for GMOD−1. The GMOD hydrogels exhibited superior compressive robustness, adjustable biodegradability, and excellent biocompatibility, holding great potential for biomedical applications such as sustained drug-delivery system. Full article

The photoinitiation properties of two porphyrins were evaluated for the free-radical photopolymerization (FRP) of a bio-based acrylated monomer, i.e., soybean oil acrylate (SOA). Their combination with various co-initiators, such as a tertiary amine as electron donor (MDEA), an iodonium salt as electron acceptor (Iod), as well as two biosourced co-initiators used as H-donors (cysteamine and N-acetylcysteine), makes them highly efficient photoinitiating systems for FRP under visible light irradiation. Electron paramagnetic resonance spin trapping (EPR ST) demonstrated the formation of highly reactive radical species, and fluorescence and laser flash photolysis highlighted the chemical pathways followed by the porphyrin-based systems under light irradiation. High acrylate conversions up to 96% were obtained with these different systems at different irradiation wavelengths (LEDs@385 nm, 405 nm, 455 nm, and 530 nm), in laminate or under air. The final crosslinked and bio-based porphyrin-based materials were used for the full photo-oxidation in water of an azo-dye (acid red 14) and under UV irradiation. These materials have been involved in three successive depollution cycles without any reduction in their efficiency. 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

The oxygen inhibition and migration of micromolecules which stem from photoinitiators (PIs) remain two critical challenges to address in radical photocuring. In this work, we reported a one-step ternary copolymerization strategy to construct a one-component macromolecular photoinitiator (PPI) using polymerizable thioxanthone (TX), amine (N), and fluorinated alkane (F) as monomers. Then, we utilize the low surface energy of F unit and macromolecular skeleton to reduce oxygen inhibition and migration. Compared to micromolecule TX, PPI also exhibits a broad absorption in the 250–430 nm range, and a higher molar extinction coefficient. The effects of the TX, N, and F component ratios on the photoinitiation efficiency of PPI were systematically investigated, and the photopolymerization kinetics revealed that the increased content of F unit can eliminate the oxygen inhibition of PPI. As a result, PPI demonstrates the more superior photoinitiation efficiency compared to the traditional TX/N two-component macromolecule photoinitiation system. Migration experiments indicated that there is a 60% reduction in the migration rate for PPI compared to the TX/N photoinitiation system. This work provides an effective strategy to address oxygen inhibition and micromolecule migration issues in radical photocuring, showing potential applications in food and pharmaceutical packaging fields. Full article

The electrochromic naphthalenediimide (NDI) based monomer containing styrene pedant groups, which are capable of polymerization, was prepared, and the formation of its polymer via a photopolymerization reaction was described. Both the monomer and polymer exhibited a color change in the visible range from transparent or slightly yellow, respectively, followed by brown-red to green. This was the result of a two-step reduction reaction of NDI core to radical anion and dianion, respectively. The device constructed using the polymer as an active material was found to exhibit good electrochromic stability over 500 redox cycles. The switching times were calculated to be 18 s and 6 s for the coloration and bleaching steps, respectively. The presented results showed the usability of the photopolymerization of styrene-based monomers in the generation of the stable electrochromic layers of polymers. Full article

In this work, cellulose nanocrystals (CNCs) were obtained from the wood of Acacia farnesiana L. Willd (Huizache) via acid hydrolysis; then, they were used to reinforce polyacrylic acid–co-acrylamide (AAc/AAm) hydrogels synthesized in a solution process via in situ free radical photopolymerization. The nanomaterials were characterized using atomic force microscopy, dynamic light scattering (DLS), and the residual charge on the CNCs; the nanohydrogels were characterized using infrared spectroscopy, scanning electron microscopy, swelling kinetics, and Young’s modulus. Soluble-grade cellulose presented 94.6% α-cellulose, 0.5% β-cellulose, and 2.7% γ-cellulose, as well as a viscosity of 8.25 cp and a degree of polymerization (DP) of 706. The CNCs averaged 180 nm in length and 20 nm in width. In the nanohydrogels, it was observed that the swelling kinetic behavior followed the Schott kinetic model, at times lower than 500 h; after that, it became linear. The results show that the hydrogel swelling capacity depended on the crosslinking agent and CNC concentration, as well as the CNC chemical and morphological properties, rather than the CNC source. The hydrogels with CNCs exhibited a decreased swelling degree compared to the hydrogels without CNCs. Young’s modulus increased with CNC presence and depended on the concentration and characteristics of the CNC as a crosslinking agent. Full article

The study addresses the challenge of temperature sensitivity in pristine gelatin hydrogels, widely used in biomedical applications due to their biocompatibility, low cost, and cell adhesion properties. Traditional gelatin hydrogels dissolve at physiological temperatures, limiting their utility. Here, we introduce a novel method for creating stable hydrogels at 37 °C using pristine gelatin through photopolymerization without requiring chemical modifications. This approach enhances consistency and simplifies production and functionalization of the gelatin with bioactive molecules. The stabilization mechanism involves the partial retention of the triple-helix structure of gelatin below 25 °C, which provides specific crosslinking sites. Upon activation by visible light, ruthenium (Ru) acts as a photosensitizer that generates sulphate radicals from sodium persulphate (SPS), inducing covalent bonding between tyrosine residues and “locking” the triple-helix conformation. The primary focus of this work is the characterization of the mechanical properties, swelling ratio, and biocompatibility of the photopolymerized gelatin hydrogels. Notably, these hydrogels supported better cell viability and elongation in normal human dermal fibroblasts (NHDFs) compared to GelMA, and similar performance was observed for human pluripotent stem cell-derived cardiomyocytes (hiPSC-CMs). As a proof of concept for functionalization, gelatin was modified with selenous acid (GelSe), which demonstrated antioxidant and antimicrobial capacities, particularly against E. coli and S. aureus. These results suggest that pristine gelatin hydrogels, enhanced through this new photopolymerization method and functionalized with bioactive molecules, hold potential for advancing regenerative medicine and tissue engineering by providing robust, biocompatible scaffolds for cell culture and therapeutic applications. Full article

Diglycidylether of vanillyl alcohol (DGEVA), in combination with mechanically recycled carbon fibers (RCFs), was used to make, via Radical-Induced Cationic Frontal Photopolymerization (RICFP), fully sustainable and bio-based conductive composites with good electrical conductivity and consequent Joule effect proprieties. Three different fiber lengths, using three different sieve sizes during the mechanical recycling process (0.2, 0.5, and 2.0 mm), were used in five different amounts (ranging from 1 to 25 phr). The samples were first characterized by dynamic mechanical thermal analysis (DMTA), followed byelectrical conductivity and Joule heating tests. More specifically, the mechanical properties of the composites increased when increasing fiber content. Furthermore, the composites obtained with the longest fibers showed the highest electrical conductivity, reaching a maximum of 11 S/m, due to their higher aspect ratio. In this context, the temperature reached by Joule effect was directly related to the electrical conductivity, and was able to reach an average and maximum temperatures of 80 °C and 120 °C, respectively, just by applying 6 V. Full article

The aim of the study was to investigate the effect of ethanol on the properties of acrylic-urethane resin products obtained by vat photopolymerization using the masked stereolithography method. The effect of alcohol at concentrations of 15, 25, and 35% in the resin on the chemical structure, weight, thickness of the samples, and mechanical properties in static tabltensile tests performed immediately after printing and one month later were studied. The results obtained were evaluated in terms of the use of ethanol as a cosolvent to help load the resin with agomelatine for the potential of obtaining microneedle transdermal systems. It was shown that in terms of stability of properties, the most favorable system was resin with the addition of alcohol at a concentration of 15%. The greatest changes induced by the presence of the solvent in the resin were observed in the case of tensile properties, where the alcohol caused a decrease in the plasticity of the material, reducing the relative elongation at break from 14% for the pure resin to 4% when the alcohol concentration was 35%. Young’s modulus and tensile strength also decreased with the addition of alcohol by 18% and 31%, respectively, for testable samples with the maximum amount of alcohol in the resin. The deterioration in properties is most likely related to the effect of the solvent on the radical polymerization process of the resin, particularly the phenomenon of chain transfer to the solvent, which is important in view of the intended application of the developed material. Full article

Driven by environmental considerations, the scientific community has directed great effort towards the synthesis of new materials derived from renewable resources. However, for photocurable resins, most commercially available building blocks still rely on petroleum-based precursors. Herein, we present a simple synthesis route for bio-based acrylate-modified polyester resins, whose viscosity is sufficiently low for processing them with vat photopolymerization 3D printing. The established synthesis route enables the gradual substitution of fossil-based raw materials with bio-based alternatives. The acid number, color and viscosity of the bio-based acrylic resins are characterized and photocurable formulations are prepared by adding a radical photoinitiator. The photopolymerization kinetics, and thermomechanical and mechanical properties of the photopolymers are investigated as a function of the resin structure and benchmarked against a commercially available petroleum-based counterpart. Finally, the processability of the new bio-based resins via digital light processing 3D printing is demonstrated and test specimens are successfully 3D printed with a resolution in the millimeter range. Full article

Hybrid epoxide–acrylate photopolymerization enables the temporal structuring of polymer networks for advanced material properties. The ability to design polymer network architectures and to tune mechanical properties can be realized through the control of the cationic active center propagation reaction (active chain end mechanism) relative to the cationic chain transfer reaction (activated monomer mechanism). Grafted polymer networks (GPNs) can be developed through the covalent bonding of epoxide chains to acrylate chains through hydroxyl substituents, making hydroxyl-containing acrylates a promising class of chain transfer agents. This work demonstrates the formation of these GPNs and explores the physical properties obtained through the control of hydroxyl content and hybrid formulation composition. The GPNs exhibit a lower glass transition temperature than the neat epoxide network and result in a more homogeneous network. Further investigations of hydroxyl-containing acrylates as chain transfer agents will generate a wider range of physical property options for photopolymerized hybrid coatings, sealants, and adhesives. Full article

In this investigation, a multifunctional visible-light TX-based photosensitizer containing a siloxane moiety (TXS) was designed with a good overall yield of 54%. The addition of a siloxane moiety enabled the incorporation of a TX photosensitizer into a siloxane network by photoinduced sol–gel chemistry, thus avoiding its release. Both liquid ¹H and solid-state ²⁹Si NMR measurements undeniably confirmed the formation of photoacids resulting from the photolysis of the TXS/electron acceptor molecule (Iodonium salt), which promoted the photoinduced hydrolysis/condensation of the trimethoxysilane groups of TXS, with a high degree of condensation of its inorganic network. Notably, the laser flash photolysis, fluorescence, and electron paramagnetic resonance spin-trapping (EPR ST) experiments demonstrated that TXS could react with Iod through an electron transfer reaction through its excited states, leading to the formation of radical initiating species. Interestingly, the TXS/Iod was demonstrated to be an efficient photoinitiating system for free-radical (FRP) and cationic (CP) polymerization under LEDs@385, 405, and 455 nm. In particular, whatever the epoxy monomer mixtures used, remarkable final epoxy conversions were achieved up to 100% under air. In this latter case, we demonstrated that both the photoinduced sol–gel process (hydrolysis of trimethoxysilane groups) and the cationic photopolymerization occurred simultaneously. Full article

The development of thermo-responsive shape-memory polymers has attracted attention due to their ability to undergo reversible deformations based on temperature changes. Vegetable oils are confirmed to be an excellent biorenewable source of starting materials for the synthesis of polymers. Therefore, the objective of this research was to synthesize thermo-responsive shape-memory polymers based on vegetable oils by using the dual-curing technique and obtaining polymers with tailorable properties. Acrylated epoxidized soybean oil and two epoxidized vegetable oils, linseed oil and camelina oil, were chosen for dual curing with m-xylylenediamine. Rheological tests were used to analyze the curing kinetics of systems undergoing radical photopolymerization, thermal cationic polymerization, and dual-curing processes. The rheological, mechanical, and thermal characteristics of the polymers were enhanced by the second curing stage. Dual-cured vegetable oil-based polymers had shape-memory properties with a recovery ratio of 100%, making them suitable for a variety of applications, including electronics, biomedical devices, and robotics. Full article