Methacrylate Moieties Research Articles

Exploring Methacrylated Gellan Gum 3D Bioprinted Patches Loaded with Tannic Acid or L-Ascorbic Acid as Potential Platform for Wound Dressing Application.

To improve wound healing, advanced biofabrication techniques are proposed here to develop customized wound patches to release bioactive agents targeting cell function in a controlled manner. Three-dimensional (3D) bioprinted "smart" patches, based on methacrylated gellan gum (GGMA), loaded with tannic acid (TA) or L-ascorbic acid (AA) have been manufactured. To improve stability and degradation time, gellan gum (GG) was chemically modified by grafting methacrylic moieties on the polysaccharide backbone. GGMA patches were characterized through physicochemical, morphological and mechanical evaluation. Kinetics release and antioxidant potential of TA and AA as well as antimicrobial activity against common pathogens Pseudomonas aeruginosa, Staphylococcus aureus and Escherichia coli in accordance with ISO 22196:2011 are reported. The cytocompatibility of the patches was demonstrated by direct and indirect tests on human dermal fibroblasts (HDF) as per ISO 10993. The positive effect of GGMA patches on cell migration was assessed through a wound healing assay. The results highlighted that the patches are cytocompatible, speed up wound healing and can swell upon contact with the hydration medium and release TA and AA in a controlled way. Overall, the TA- and AA-loaded GGMA patches demonstrated suitable mechanical features; no cytotoxicity; and antioxidant, antimicrobial and wound healing properties, showing satisfactory potential for wound dressing applications.

In-situ halloysite functionalization of anionic hybrid gels possessing easily implemented site-specific (alkyl)amide and carboxyl groups

Design of functional materials with tunable properties based on anionically-modified copolymer network of poly (N-isopropyl acrylamide-co-methacrylic acid) P(NIPA-co-MA) containing linear polyacrylamide and various amounts of Halloysite nanotubes (Hal) was presented using a facile route of solution casting. The organic/inorganic nanostructures based on thermo-responsive PNIPA were constructed to create hybrid materials via in situ polymerization with different Hal-loading and then used for the removal of cationic methylene blue (MB) dye from aqueous solutions. To achieve the desired mechanical property, the optimum composition of hybrids was determined following a simple and cost-effective synthesis procedure. In situ one-pot polymerization was promoted by semi-IPN formation, following a much simpler route than traditional preparation approaches for stable cross-linked hybrid formation. The swelling of hybrids decreased by 2.9-fold with loading of 5.40 % Hal, confirming the hydrogen bonding interactions between Hal and PAAm/P(NIPA-co-MA) network. The mechanical properties of Hal-doped hybrid gels showed an increase–decrease tendency with increase of Hal-content from 0.80 to 5.40 % (w/v) due to the high aspect ratio of Hal and strong secondary interactions between Hal and PAAm/P(NIPA-co-MA) chains. The effective cross-link density for Hal-doped hybrids was expressed by a cubic polynomial as a function of Hal concentration. Temperature-sensitive swelling results showed that the advantage of sustained release property of Hal can be combined with excellent controllability of PNIPA-based network. Adsorption results of MB onto Hal-doped hybrids bearing methacrylic acid moieties demonstrated their potential as efficient adsorbents for the removal of cationic dyes. A new route offered by the proposed procedure for design of hybrids containing “green” one-dimensional nanofillers creates an innovative perspective on robust hybrid structures for practical applications.

Developing double-crosslinking 3D printed hydrogels for bone tissue engineering

Bone defects are one of the main causes of disability worldwide. Due to the disadvantages associated with autografts, the latest advances have been focused on tissue regeneration approaches that use injectable hydrogels or 3D printed hydrogel-based structures that could refill appropriately the bone gap area without the need for external fixatives, leading to bone formation in the long term. Injectable hydrogels could be applied in extrusion-based 3D printing as inks; in this sense, double-crosslinking hydrogels appear as ideal candidates. In this work, injectable and printable double crosslinkable hydrogels based on oxidized xanthan gum (XGox) and methacrylate polyaspartylhydrazide (PAHy-MA) were produced. The formation of dynamic hydrazone bonds, occurring between aldehyde groups on the polysaccharide backbone and hydrazine moieties of PAHy-MA, induced an instant gelation, conferring, also, injectability and self-healing properties to the hydrogels. The presence of methacrylic moieties on the synthetic polymer allowed further crosslinking upon UV irradiation that stabilized the hydrogel shape and mitigated its susceptibility to hydrolytic degradation. Obtained hydrogels showed pseudoplastic behaviour and good recovery of viscoelastic properties over time. The physicochemical and rheological characterization highlighted increased stability and higher viscoelastic moduli after photo-crosslinking. The hydrogels also showed good printability, cytocompatibility and the early formation of a bone-like matrix when osteosarcoma-derived cells (MG-63) were cultured in the scaffolds for 21 days, with an increased collagen I deposition, mineralization and the expression of characteristic osteogenic markers.

Salivary levels of eluents during Invisalign™ treatment with attachments: an in vivo investigation

BackgroundThe aim of the present study was to investigate qualitatively and quantitatively the elution of substances from polyester-urethane (Invisalign™) aligners and resin composite attachments (Tetric EvoFlow) in vivo.MethodsPatients (n = 11) treated with the aligners and attachments (16 per patient, without other composite restorations) for an average of 20 months, who were planned for attachment removed were enrolled in the study. Patients were instructed to rinse with 50 mL of distilled water upon entry and the rinsing solution was collected (before removal). Then, the attachments were removed with low-speed tungsten carbide burs for adhesive residue removal, a thorough water rinsing was performed immediately after the grinding process to discard grinding particle residues, and subsequently, after a second water-rinsing the solution was collected for analysis (after removal). The rinsing solutions were analyzed for targeted (LC-MS/MS: Bis-GMA, DCDMA, UDMA, BPA) and untargeted (LC-HRMS: screening of leached species and their degradation products) compounds.ResultsTargeted analysis revealed a significant reduction in BPA after attachment removal (4 times lower). Bis-GMA, DCDMA, UDMA were below the detection limit before removal but were all detectable after removal with Bis-GMA and UDMA at quantifiable levels. Untargeted analysis reviled the presence of mono-methacrylate transformation products of Bis-GMA (Bis-GMA-M1) and UDMA (UDMA-M1), UDMA without methacrylate moieties (UDMA-M2), and 4-(dimethylamino) benzoic acid (DMAB), the degradation product of the photo-initiator ethyl-4-(dimethylamino) benzoate (EDMAB), all after attachment removal. Several amino acids and endogenous metabolites were also found both before and after removal.ConclusionsElevated levels of BPA were traced instantaneously in patients treated with Invisalign™ and flowable resin composite attachments for the testing period. BPA was reduced after attachment removal, but residual monomers and resin degradation products were found after removal. Alternative resin formulations and attachment materials may be utilized to reduce eluents.

Photocrosslinked gelatin/chondroitin sulfate/chitosan-based composites with tunable multifunctionality for bone tissue regeneration

Novel hydrogel-based multifunctional systems prepared utilizing photocrosslinking and freeze-drying processes (PhotoCross/Freeze-dried) dedicated for bone tissue regeneration are presented. Fabricated materials, composed of methacrylated gelatin, chitosan, and chondroitin sulfate, possess interesting features including bioactivity, biocompatibility, as well as antibacterial activity. Importantly, their degradation and swellability might be easily tuned by playing with the biopolymeric content in the photocrosllinked systems. To broaden the potential application and deliver the therapeutic features, mesoporous silica particles functionalized with methacrylate moieties decorated with hydroxyapatite and loaded with the antiosteoporotic drug, alendronate, (MSP-MA-HAp-ALN) were dispersed within the biopolymeric sol and photocrosslinked. It was demonstrated that the obtained composites are characterized by a significantly extended degradation time, ensuring optimal conditions for balancing hybrids removal with the deposition of fresh bone. We have shown that attachment of MSP-MA-HAp-ALN to the polymeric matrix minimizes the initial burst effect and provides a prolonged release of ALN (up to 22 days). Moreover, the biological evaluation in vitro suggested the capability of the resulted systems to promote bone remodeling. Developed materials might potentially serve as scaffolds that after implantation will fill up bone defects of various origin (osteoporosis, tumour resection, accidents) providing the favourable conditions for bone regeneration and supporting the infections' treatment.

Structure-properties relationships of defined CNF single-networks crosslinked by telechelic PEGs

The high structural anisotropy and colloidal stability of cellulose nanofibrils' enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

Renewable Methacrylate Resins for 3D Printing Containing Dynamic Hydroxyester Linkages for Reprocessability

AbstractTo facilitate the ongoing transition toward a circular economy, renewable 3D print materials that are both sustainable and competitive must be accessible. However, the growing demand for bio‐based thermosetting resins, which are used as ink for vat photopolymerization, gives rise to environmental concerns in terms of plastic waste management. Therefore, photocurable materials that are renewable and recyclable at the same time are needed. In this work, a mechanically robust and reprocessable 3D printed photopolymer is developed from renewable feedstock. Reaction of malic acid with glycidyl methacrylate introduces both methacrylate moieties that can undergo photopolymerization in the 3D printer, and β‐hydroxyester linkages that can act as dynamic crosslinks via bond exchange reactions. By combining modified malic acid with reactive diluents, a photoinitiator, and phosphate catalyst, three distinct resins are formulated, resulting in bio‐based contents ranging from 43% to 49%. The formulations demonstrate good layer fusion and accurate print quality, while the 3D printed specimens are robust and thermally stable. Notably, the printed object with shortest relaxation time displayed Arrhenius flow behavior with an activation energy of 36.0 kJ mol−1, and its mechanical performance is maintained after being recycled three times. This contributes to the end‐of‐life perspective of photocurable resins in additive manufacturing.

Copolymerization kinetics of hydrogels based on oligo(ethylene glycol) methacrylates and acrylic acid using isoconversional methods

Monomers consisting of a methacrylate moiety attached to a short poly(ethylene glycol) (PEG) chain can be polymerized to form hydrogels with several applications such as the removal of dyes and heavy metals from wastewater. In this study, the radical copolymerization kinetics of oligo(ethylene glycol) methyl methacrylate (OEGMMA), and oligo(ethylene glycol) hydroxyethyl methacrylate (OEGHEMA), with acrylic acid (AAc) was investigated. In both cases, hydrogels were formed with cross-linked structure. The rate of polymerization and degree of conversion were measured using differential scanning calorimetry (DSC) operating under non-isothermal conditions, at several constant heating rates, or under isothermal conditions, at different constant reaction temperatures. Isoconversional kinetics were employed to estimate the effective activation energy of the polymerization. It was found that, in the homopolymer (POEGHEMA) bearing hydroxyl groups, polymerization under both isothermal and non-isothermal conditions proceeds faster compared to the polymer with methoxy groups (POEGMMA). This behavior is attributed to the interaction between the hydrogen in the hydroxyl group with the carbonyl oxygen of the methacrylic ester, which results in a reduction of the electron density at the double bond and therefore increases its reactivity. Monomer–monomer association through hydroxyl groups results in initially lower activation energy of POEGHEMA. As polymerization proceeds, the existence of aggregated hydroxyl structures in the POEGHEMA macromolecular chains result in higher activation energies and a more abrupt increase in the conversion time curve. The addition of acrylic acid results in higher copolymerization rates for both methacrylates, with P(OEGMMA-AAc) affected more, since in the case of OEGHEMA specific functional (i.e. hydroxyl) groups already exist in the macromolecules. The association of monomer-AAc through hydroxyl‑carbonyl groups, results in lower activation energies for both copolymers compared to the corresponding homopolymers. The significant contribution of isoconversional methods in the study of polymerization kinetics of hydrogels it was thus verified.

Dual Cross-Linked Stimuli-Responsive Alginate-Based Hydrogels.

Sodium alginate with different molecular weights (55, 170, and 320 kg mol-1) were chemically modified by grafting methacrylic moieties onto the hydroxyl groups of the alginate backbone. The methacrylation was optimized to obtain different degrees of modification. Chemically cross-linked hydrogels were obtained following UV-light irradiation in the presence of a photoinitiator. The swelling behavior and the mechanical properties were observed to depend on both the degree of methacrylation and the alginate molecular weight. Due to the chain entanglement present in high-viscosity sodium alginate, lower degrees of modification were required to tune the hydrogel properties. Moreover, in the presence of Ca2+, secondary cross-linking was introduced by the coordination of the alginate guluronate moieties with the Ca2+ ions. The addition of this secondary cross-linking caused fast volume shrinkage and a reinforcement of the mechanical properties. The secondary cross-linking was reversible, and the hydrogels regained their original shape for at least three cycles. Additionally, the dual cross-linked network can be used to induce adhesion between hydrogels and serve as a building block for self-folding actuators.

Rapid UV-curable preparation of durable soybean oil-based superhydrophobic anti-icing surfaces with excellent photothermal deicing property

Photothermal superhydrophobic coatings are promising for anti-icing/deicing. However, preparing such coatings from environmentally friendly and sustainable strategies is challenging. Herein, a bio-based and durable photothermal superhydrophobic coating is prepared via layer-by-layer strategy. Bio-based methacrylic acid epoxidized soybean oil oligomers are synthesized as an alternative to petroleum-based binders. Meanwhile, efficient photothermal conversion of hydrophobic particles are enabled by oxidative self-polymerization of dopamine to decorate hydrophobic silica particles grafted with hydrophobic long-chain alkanes and photo-curable methacrylic acid moieties. Ultimately, the superhydrophobic coating is achieved by spraying photothermal hydrophobic particles onto an oxygen-inhibited layer of pre-cured bio-based binder followed by thorough photocuring treatment. The coating exhibits powerful water repellency (WCA of 158.2 ± 1.6°, SA of 4.6 ± 0.8°), good robustness, chemical and UV irradiation resistance. Moreover, under NIR laser irradiation (808 nm, 1 W/cm2), the coating features excellent photothermal conversion efficiency (ΔT of 41.0 °C at 30 s) and stable photothermal conversion performance. And in frigid conditions (-15 °C, ∼73 ± 5 % RH), the coating delivers rapid defrosting (few seconds) and deicing (20 μL water droplet melts in 42 s) performance under NIR irradiation of 1 W/cm2. Therefore, the as-prepared coating provides valuable insight into global anti-icing/deicing action.

Triple physical cross-linking cellulose nanofibers-based poly(ionic liquid) hydrogel as wearable multifunctional sensors

A novel triple physical cross-linking poly(ionic liquid) hydrogel, composed of poly(acrylamide-co-dodecyl methacrylate-co-1-vinyl-3-methyluracil-imidazolium chloride)/cellulose nanofibers-Ca2+ (PADV/CNFs-Ca2+), was synthesized through micellar-copolymerization followed by a solvent-soaked procedure. The synergistic interactions in polymer network (i.e. the hydrophobic association of dodecyl methacrylate moiety in surfactant micelles, the hydrogen bondings between imidazolium monomer segments and other monomer segments in polymers, and the ionic coordination between Ca2+ and -COO− on cellulose nanofibers surface) endowed the hydrogel with excellent mechanical properties, including high strength (754 kPa of tensile strength and 1905 kPa of compressive strength), outstanding stretchability (1963 %), elastic modulus (56.5 kPa) and remarkable mechanical durability (200 cycles with 500 % deformations and 100 cycles at 50 % compression strain). Besides, this hydrogel exhibited other advantages, such as satisfied conductivity (28.7 mS/cm), high strain/pressure/temperature-sensitive behavior, precise and stable signal transmission, varying degrees of antibacterial activity, and biocompatibility. Owing to the exceptional comprehensive performance, the hydrogel was then assembled as a multifunctional sensor to monitor the joint motion, vocal cord vibration, tactile sensation and body temperature with remarkable sensitivity in real time. This work offered a new strategy for the fabrication of durable, biocompatible, antibacterial and conductive materials for wearable multifunctional electronic devices.

Visible light-mediated cross-linking of injectable gellan gum hydrogels embedding human chondrocytes

Gellan gum, a polysaccharide with structural similarities to glycosaminoglycans, is gaining attention in cartilage tissue engineering. It can be chemically modified with methacrylic moieties to produce a photo-crosslinkable formulation, called methacrylated gellan gum (GGMA), envisaging the injection and the in situ cross-linking through light on the cartilage surface.This study aimed to investigate the visible light cross-linking of GGMA, underlying the impact of steam sterilization on its chemical and rheological properties and cross-linking efficiency. After an initial assessment of the sterilization effects, we evaluated a combination of hydrogel concentrations (1 and 2 % w/v), ruthenium/sodium persulfate concentrations (0.1/1, 0.2/2 and 0.5/5 mM ratios), and light exposure times (30, 60 and, 120 s). The formulations with the lowest sol fraction were characterized for mechanical and showed self-healing properties. Biological characterization on encapsulated chondrocytes in hydrogels showed high cell viability with increased metabolic activity over two weeks. The expression of genes encoding collagen type II and cartilage oligomeric matrix protein was upregulated in the softer formulation (E = 0.95 ± 0.48 kPa) composed of 2 % w/v GGMA, 0.1/1 mM Ru/SPS, and photo-crosslinked for 60 s. These findings represent an interesting overview of the potential application of visible-light crosslinked GGMA in the clinical scenario to treat cartilage defects.

Designing functionalized polymers through post-polymerization modification of side chain leucine-based polymer

The opportunity to modify the chemical functionality of the incorporated amino acid moiety in side chain amino acid-based polymers provides access to tailor their optical, mechanical, and biological properties. Methacrylate monomers from C-terminus modified amino acids and their subsequent polymerization leads to the formation of polymethacrylate polymers with pendant amine (-NH2) groups. To this end, the post-polymerization reactions on the amine groups offer a facile route to prepare functionalized side chain amino acid-based polymeric materials. Herein, we synthesized side chain L-leucine pendant homopolymer using reversible addition-fragmentation chain transfer (RAFT) polymerization of Boc-L-leucine methacryloyloxyethyl ester (Boc-leu-HEMA) and subsequently the Boc group is deprotected to prepare P(H3N+-leu-HEMA). Post-polymerization modifications on the pendant amine groups were performed to incorporate fluorescent probe, propargyl group, methacrylic moiety, hydrophobic fatty acid, anionic pendant, and hydrophilic polyethylene glycol (PEG) units; which demonstrates an efficient platform to build a library of functionalized polymers from a single polymeric backbone. We have studied the solvatochromic behavior of fluorescence probe bearing polymers using fluorescence spectroscopy. The ability of the pendent methacrylic unit containing polymers to undergo crosslinking and the mechanical properties of the synthesized gel are investigated by the rheological study.

Inducing an LCST in hydrophilic polysaccharides via engineered macromolecular hydrophobicity

Thermoresponsive polysaccharide-based materials with tunable transition temperatures regulating phase-separated microdomains offer substantial opportunities in tissue engineering and biomedical applications. To develop novel synthetic thermoresponsive polysaccharides, we employed versatile chemical routes to attach hydrophobic adducts to the backbone of hydrophilic dextran and gradually increased the hydrophobicity of the dextran chains to engineer phase separation. Conjugating methacrylate moieties to the dextran backbone yielded a continuous increase in macromolecular hydrophobicity that induced a reversible phase transition whose lower critical solution temperature can be modulated via variations in polysaccharide concentration, molecular weight, degree of methacrylation, ionic strength, surfactant, urea and Hofmeister salts. The phase separation is driven by increased hydrophobic interactions of methacrylate residues, where the addition of surfactant and urea disassociates hydrophobic interactions and eliminates phase transition. Morphological characterization of phase-separated dextran solutions via scanning electron and flow imaging microscopy revealed the formation of microdomains upon phase transition. These novel thermoresponsive dextrans exhibited promising cytocompatibility in cell culture where the phase transition exerted negligible effects on the attachment, spreading and proliferation of human dermal fibroblasts. Leveraging the conjugated methacrylate groups, we employed photo-initiated radical polymerization to generate phase-separated hydrogels with distinct microdomains. Our bottom-up approach to engineering macromolecular hydrophobicity of conventional hydrophilic, non-phase separating dextrans to induce robust phase transition and generate thermoresponsive phase-separated biomaterials will find applications in mechanobiology, tissue repair and regenerative medicine.

α-Substituted ketones as reagent for Passerini modification of carboxymethyl cellulose: Toward dually functionalized derivatives and thermo-sensitive chemical hydrogels

The present works describes the Passerini modification of carboxymethyl cellulose (CMC) by using a library of nine α-substituted ketones derivatives, differing in their hydrophobicity and reactivity, conjointly with cyclohexyl isocyanide. The Passerini ligation, achieved in aqueous and mild conditions, was shown to be successful, leading to a large panel of dually functionalized CMC derivatives, in an eco-friendly manner. A particular attention was dedicated to the influence of the experimental parameters such as the stoichiometry, the nature of a co-solvent or the temperature, which allowed to tune the extent of modification. The reactivity of the ketone was proven to be governed by its i) compatibility with water, ii) sterical accessibility, and by iii) the presence of neighboring electron-withdrawing group. The resulting Passerini CMC products modified by methacrylate moieties (CMC-MA) were used as reactive macromonomer under a “grafting through” approach. The copolymerization of CMC-MA with oligoethylene glycol methacrylate (OEGMA) and diethylene glycol methacrylate (DEGMA) upon thermal radical reaction conditions enabled to generate tightly cross-linked chemical hydrogels, with a thermo-sensitive and thermo-reversible behavior, reflected by a macroscopical shrinkage/swelling response, and confirmed by SAXS analysis. Such chemical strategy paves the way toward multifunctional polysaccharide-based networks with potential utilizations as drug delivery devices, dye removals or actuators.

Blood compatible, fog-, frost- and bacterial-resistant dopamine-enabled zwitterionic glass interfaces

BackgroundHydration is at the core of the mechanisms rationalizing the ability of hydrophilic interfaces to resist fogging, frosting and biofouling, and to be hemocompatible. Although essential, very few biomedical interfaces and devices possess this set of properties. MethodsThis study sheds light on this combination of properties imparted to glass by a dopamine-enabled grafting of poly(sulfobetaine methacrylate) moieties. Water contact angle (WCA), fogging, frost resistance antifouling and blood compatibility tests were then conducted. Significant FindingsThe very low WCA measured on the glass surface (8.4°) permitted to inhibit condensation and maintain optical transparency, whereas other hydrophilic graftings prepared using hydroxyethylmethacyrlate (HEMA) or poly(ethylene glycol) methyl ether acrylate (PEGMA) lost 15% of their optical transparency. The strong hydration layer provided by the zwitterionic grafting almost entirely inhibited frost formation. While the virgin glass suffered from severe biofouling by various types of cells found in the medical field including Pseudomonas aeruginosa and whole blood, the grafted glass materials resisted biofouling efficiently (90% and 99% decrease using bacteria and whole blood, respectively). Hemocompatibility was supported by negligible haemolyis activity, and activated partial thromboplastin time (APTT, 32.1 s) and prothrombin time (PT, 10.4 s) comparable to those measured with whole blood. Stability was also proven by carrying out antifouling tests after 1 month-immersion in an ultrasonic bath. Thus, these zwitterionic glass materials have potential for application in the biomedical field.

Bioactive Composite Methacrylated Gellan Gum for 3D-Printed Bone Tissue-Engineered Scaffolds

Gellan gum (GG) was chemically modified with methacrylic moieties to produce a photocrosslinkable biomaterial ink, hereinafter called methacrylated GG (GGMA), with improved physico-chemical properties, mechanical behavior and stability under physiological conditions. Afterwards, GGMA was functionalized by incorporating two different bioactive compounds, a naturally derived eumelanin extracted from the black soldier fly (BSF-Eumel), or hydroxyapatite nanoparticles (HAp), synthesized by the sol-gel method. Different ink formulations based on GGMA (2 and 4% (w/v)), BSF-Eumel, at a selected concentration (0.3125 mg/mL), or HAp (10 and 30% wHAp/wGGMA) were developed and processed by three-dimensional (3D) printing. All the functionalized GGMA-based ink formulations allowed obtaining 3D-printed GGMA-based scaffolds with a well-organized structure. For both bioactive signals, the scaffolds with the highest GGMA concentration (4% (w/v)) and the highest percentage of infill (45%) showed the best performances in terms of morphological and mechanical properties. Indeed, these scaffolds showed a good structural integrity over 28 days. Given the presence of negatively charged groups along the eumelanin backbone, scaffolds consisting of GGMA/BSF-Eumel demonstrated a higher stability. From a mechanical point of view, GGMA/BSF-Eumel scaffolds exhibited values of storage modulus similar to those of GGMA ones, while the inclusion of HAp at 30% (wHAp/wGGMA) led to a storage modulus of 32.5 kPa, 3.5-fold greater than neat GGMA. In vitro studies proved the capability of the bioactivated 3D-printed scaffolds to support 7F2 osteoblast cell growth and differentiation. BSF-Eumel and HAp triggered a different time-dependent physiological response in the osteoblasts. Specifically, while the ink with BSF-Eumel acted as a stimulus towards cell proliferation, reaching the highest value at 14 days, a higher expression of alkaline phosphatase activity was detected for scaffolds consisting of GGMA and HAp. The overall findings demonstrated the possible use of these biomaterial inks for 3D-printed bone tissue-engineered scaffolds.

Dual-Crosslinked Degradable Elastomeric Networks With Self-Healing Properties: Bringing Multi(catechol) Star-Block Copolymers into Play

In the biomedical field, degradable chemically crosslinked elastomers are interesting materials for tissue engineering applications, since they present rubber-like mechanical properties matching those of soft tissues and are able to preserve their three-dimensional (3D) structure over degradation. Their use in biomedical applications requires surgical handling and implantation that can be a source of accidental damages responsible for the loss of properties. Therefore, their inability to be healed after damage or breaking can be a major drawback. In this work, biodegradable dual-crosslinked networks that exhibit fast and efficient self-healing properties at 37 °C are designed. Self-healable dual-crosslinked (chemically and physically) elastomeric networks are prepared by two methods. The first approach is based on the mix of hydrophobic poly(ethylene glycol)-poly(lactic acid) (PEG-PLA) star-shaped copolymers functionalized with either catechol or methacrylate moieties. In the second approach, hydrophobic bifunctional PEG-PLA star-shaped copolymers with both catechol and methacrylate on their structure are used. In the two systems, the supramolecular network is responsible for the self-healing properties, thanks to the dynamic dissociation/reassociation of the numerous hydrogen bonds between the catechol groups, whereas the covalent network ensures mechanical properties similar to pure methacrylate networks. The self-healable materials display mechanical properties that are compatible with soft tissues and exhibit linear degradation because of the chemical cross-links. The performances of networks from mixed copolymers versus bifunctional copolymers are compared and demonstrate the superiority of the latter. The biocompatibility of the materials is also demonstrated, confirming the potential of these degradable and self-healable elastomeric networks to be used for the design of temporary medical devices.

Synthesis and Properties of Polyol Copolymer with Alternating Methacrylate-Vinyl Ether Backbone.

Radical polymerization of a tailored diphenylsilane-bridged bi-functional monomer consisting of methacrylate and vinyl ether moieties is conducted in diluted monomer concentration, in which both two moieties are consumed at almost the same rate despite their huge difference in monomer reactivity ratio. The vinyl ether content in the backbone is quantified as 45% by 1 H NMR after removal of the silane bridge. Since vinyl ether alone cannot be polymerized in such radical polymerization, it should be incorporated in an alternating fashion with methacrylate into the copolymer main chain. The cleavage of silane bridge also yields a series of polyol materials composed of ethylene glycol monovinyl ether (EGVE) and hydroxyethyl methacrylate (HEMA), and the EGVE content in the backbone can be regulated from 45% to 18% by increasing the bi-functional monomer concentration. Interestingly, although containing more than 50% HEMA units, the alternating copolymer exhibits new properties totally different from poly(HEMA), but more similar to poly(EGVE), e.g., good water solubility and a markedly low glass transition temperature (Tg ) of -31°C, which is attributed to the major HEMA-EGVE repeating unit that replaced HEMA-HEMA consecutive segments so that the properties of poly(HEMA) such as 95°CTg are completely altered.

Evaluation of allyl sulfides bearing methacrylate groups as addition-fragmentation chain transfer agents for low shrinkage dental composites

Polymerization shrinkage and the consequential shrinkage stress in methacrylate-based dental composites are crucial drawbacks for restorative dentistry. An effective way for the reduction of shrinkage stress is the incorporation of addition fragmentation chain transfer agents (AFCT agents). In this contribution, four novel polymerizable allyl sulfides were synthesized and evaluated in dental composites. Photo-DSC and DMTA measurements were performed to evaluate their influence on the polymerization rate and on the network homogeneity. Good to excellent shrinkage force values and mechanical properties were obtained for all AFCT based composites. Especially, the incorporation of AFCT agents containing multiple urethane and methacrylate moieties improved the mechanical properties. Hence, the incorporation of polymerizable and urethane-based allyl sulfides in dental composite is a promising strategy to obtain low shrinkage materials exhibiting high flexural strength and modulus.