Effect of replacing Bis-GMA with a biobased trimethacrylate on the physicochemical and mechanical properties of experimental resin composites.

OBJECTIVES: To analyze the incorporation of cardanol trimethacrylate monomer (CTMA), derived from the cashew nut shell liquid, as a substitute for Bis-GMA in acrylic resins formulations and its effect on experimental resin composites' physicochemical and mechanical properties. MATERIALS AND METHODS: The intermediary cardanol epoxy was synthesized via cardanol epoxidation, followed by the synthesis of CTMA through methacrylic anhydride solvent-free esterification. Experimental resin composites were formulated with an organic matrix composed of Bis-GMA/TEGDMA (50/50 wt %) (control). CTMA was gradually added to replace different proportions of Bis-GMA: 10 wt % (CTMA-10), 20 wt % (CTMA-20), 40 wt % (CTMA-40), and 50 wt % (CTMA-50). The composites were characterized by degree of conversion, water sorption and solubility, viscosity, thermogravimetric analysis, dynamic mechanical analysis, flexural strength and elastic modulus. Data were analyzed with one-way ANOVA and Tukey's post-hoc test (α = 0.05), except for water sorption data, which were analyzed by Kruskall-Wallis and Dunn's method. RESULTS: CTMA-based and control composites did not show statistically significant differences regarding degree of conversion, flexural strength and elastic modulus. CTMA reduced the viscosity and solubility compared to the Bis-GMA-based composite. The CTMA-40 and CTMA-50 exhibited significantly lower water sorption compared to the control. Also, acceptable thermal stability and viscoelastic properties were obtained for safe use in the oral cavity. CONCLUSIONS: Incorporating CTMA into composites resulted in similar chemical and mechanical properties compared to Bis-GMA-based material while reducing viscosity, water sorption and solubility. CLINICAL RELEVANCE: CTMA could be used as a trimethacrylate monomer replacing Bis-GMA in resin composites, thereby minimizing BPA exposure.

Development of a Human Recombinant Collagen for Vat Polymerization-Based Bioprinting.

In light-based 3D-bioprinting, gelatin methacrylate (GelMA) is one of the most widely used materials, as it supports cell attachment, and shows good biocompatibility and degradability in vivo. However, as an animal-derived material, it also causes safety concerns when used in medical applications. Gelatin is a partial hydrolysate of collagen, containing high amounts of hydroxyproline. This causes the material to form a thermally induced gel at ambient temperatures, a behavior also observed in GelMA. This temperature-dependent gelation requires precise temperature control during the bioprinting process to prevent the gelation of the material. To avoid safety concerns associated with animal-derived materials and reduce potential issues caused by thermal gelation, a recombinant human alpha-1 collagen I fragment was expressed in Komagataella phaffii without hydroxylation. The resulting protein was successfully modified with methacryloyl groups and underwent rapid photopolymerization upon ultraviolet light exposure. The developed material exhibited slightly slower polymerization and lower storage modulus compared to GelMA, while it showed higher stretchability. However, unlike the latter, the material did not undergo physical gelation at ambient temperatures, but only when cooled down to below 10°C, a characteristic that has not been described for comparable materials so far. This gelation was not caused by the formation of triple-helical structures, as shown by the absence of the characteristic peak at 220 nm in CD spectra. Moreover, the developed recombinant material facilitated cell adherence with high cell viability after crosslinking via light to a 3D structure. Furthermore, desired geometries could be easily printed on a stereolithographic bioprinter.

Impact of refrigeration of different Resin composite restorative materials on the marginal adaptation in class II restorations.

BACKGROUND: The pre-polymerization temperature of resin composite restorative materials could influence their adaptation to cavity details. As a current debate is existing about the refrigeration of resin composite restorative materials, this study was designed to assess the effect of refrigeration of 3 types of resin composite restorative materials with different matrix systems on their marginal adaptation in Class II restorations. METHODS: Forty-two sound maxillary molars, each with two separated Class II cavities, were used in this study. The teeth were assigned into 3 main groups (n = 14) according to the restorative /adhesive system used; an Ormocer-based composite (Admira Fusion/Futurabond M+, Voco GmbH, Cuxhaven, Germany), a methacrylate modified Ormocer-based (Ceram.X SphereTEC One/Prime&Bond Universal, Dentsply Sirona GmbH Konstanz, Germany), and a methacrylate-based (Tetric N-Ceram/Tetric N-Bond Universal, Ivoclar Vivadent AG, Schaan, Liechtenstein). Each group was then divided into 2 subgroups (n = 14) according to the gingival margin location; 1 mm above and 1 mm below the cemento-enamel junction (C.E.J). Each subgroup was further divided into 2 categories (n = 7) according to the storage temperature; stored at room temperature or stored in refrigerator at 4°- 5° C. Epoxy resin replicas were observed under scanning electron microscope (SEM) to examine the marginal gaps. A gab scoring system was used to assess the marginal adaptation of each restoration by giving scores on the basis of measurements of the maximum marginal gaps. The data obtained were statistically analyzed using the Chi-square test at a significance level of p < 0.05. RESULTS: None of the tested groups exhibited 100% gap-free margins irrespective of margin location or storage temperature. For both storage temperatures, no statistically significant difference was observed among all tested groups either with margins located above or below C.E.J (p > 0.05). As well, there was no statistically significant difference when comparing both marginal locations for each material (p > 0.05). Regarding the effect of storage temperature, statistically significant difference was only observed between the room-temperature stored groups with margins located above C.E.J and their corresponding groups stored in refrigerator (p < 0.05). CONCLUSION: The refrigeration of resin composite restorative materials prior to the restorative procedures revealed a deleterious effect on marginal adaptation of the restorations with margins located in enamel regardless the type of material used.

Influence of light-polymerizing units and zirconia on the physical, chemical and biological properties of self-adhesive resin cements.

BACKGROUND: Self-adhesive resin cements (SARCs) are widely used for fixed prostheses, but incomplete cleaning near the gingival margin can cause inflammation. However, the factors influencing cement properties and the biological response of gingival fibroblasts to cement eluates are not well understood. This study examines the impact of two light-polymerizing units (LPUs) on the physical and chemical properties of two SARCs under simulated clinical conditions, as well as the subsequent response of human gingival fibroblasts (hGFs) to these eluates. METHODS: Dental cement discs of SARCs were polymerized using Kerr DemiPlus and 3 M Elipar DeepCure-S LED LPUs with or without a 2-mm thick zirconia screen. Physical properties (microhardness, surface roughness, residual monomers) were evaluated. hGFs' cell viability, wound healing potency, and gene expression were assessed. RESULTS: Both Maxcem and RelyX exhibited reduced microhardness and increased surface roughness when polymerized through zirconia or with DemiPlus LPU. Higher residual monomers (HEMA and GDMA in Maxcem; TEGDMA in RelyX) concentration was observed with DemiPlus and zirconia polymerization. Maxcem polymerized with DemiPlus exhibited lower cell viability, impaired healing, and altered gene expression in hGFs compared to those polymerized with Elipar LPU. Gene expression changes included downregulated NRF2 and HO-1 and upregulated CCR-3. CONCLUSIONS: Light-polymerizing Maxcem through zirconia with DemiPlus LPU compromised SARCs' properties, leading to higher residual monomers and negatively impacting hGFs' viability, healing, and gene expression. Careful material selection and polymerization techniques are crucial to minimize adverse effects on surrounding tissues. CLINICAL SIGNIFICANCE: Clinicians should exercise caution when using LPUs and SARCs, especially when polymerizing through zirconia. This will help optimize the physical and chemical properties of SARCs and minimize potential adverse effects on the surrounding gingival soft tissues.

A novel low shrinkage dimethacrylate monomer as an alternative to BisGMA for adhesive and resin-based composite applications.

The aim of this study was to develop a mixture of dimethacrylate isomers (PG6EMA) as a potential monomer for dental adhesives and composites. PG6EMA was synthesized de novo and characterized in the presence of ethanol (3%, 6% or 9%). BisGMA/TEGDMA (BTEG, 50/50 wt.%) was used as the resin control. Composites were formulated with 60 wt.% of either PG6EMA or BisGMA (40 wt.% TEGDMA and 70 wt.% filler). DMPA (0.2 wt.%) and DPI-PF6 (0.4 wt.%) were added as photoinitiators, irradiated with a mercury arc lamp (320-500 nm, 500 mW/cm2; Acticure). All materials were tested for polymerization kinetics (near-infrared), viscosity (η) and storage modulus (G', oscillatory rheometry). The composites were further characterized for water sorption/solubility, wet/dry flexural strength/modulus and polymerization stress. Data were analyzed with one-way ANOVA/Tukey's test (α = 0.05). The PG6EMA resins showed lower rates of polymerization compared with BTEG (p = 0.001) but high degrees of conversion (p = 0.002). Solvent concentration did not affect RPMAX but the 6% and 9% mixtures showed higher final DC, likely due to reduced viscosity. PG6EMA had much higher viscosity than BTEG (p <0.001) and lower G' (p = 0.003). Composites modified with PG6EMA have slower polymerization rates (p = 0.001) but higher final DC (p = 0.04) than the control. PG6EMA/TEGDMA showed lower dry/wet flexural strength and comparable dry modulus. The PG6EMA/TEGDMA composite showed a 18.4% polymerization stress reduction compared to the BTEG composite. Both base monomers had similar WS/SL and G'. Within its limitations, this study demonstrated that the newly synthesized PG6EMA was a viable alternative to BisGMA in dental composites.

3D bioprinting of fish skin-based gelatin methacryloyl (GelMA) bio-ink for use as a potential skin substitute.

Gelatin methacryloyl (GelMA), typically derived from mammalian sources, has recently emerged as an ideal bio-ink for three-dimensional (3D) bioprinting. Herein, we developed a fish skin-based GelMA bio-ink for the fabrication of a 3D GelMA skin substitute with a 3D bioprinter. Several concentrations of methacrylic acid anhydride were used to fabricate GelMA, in which their physical-mechanical properties were assessed. This fish skin-based GelMA bio-ink was loaded with human adipose tissue-derived mesenchymal stromal cells (ASCs) and human platelet lysate (HPL) and then printed to obtain 3D ASCs + HPL-loaded GelMA scaffolds. Cell viability test and a preliminary investigation of its effectiveness in promoting wound closure were evaluated in a critical-sized full thickness skin defect in a rat model. The cell viability results showed that the number of ASCs increased significantly within the 3D GelMA hydrogel scaffold, indicating its biocompatibility property. In vivo results demonstrated that ASCs + HPL-loaded GelMA scaffolds could delay wound contraction, markedly enhanced collagen deposition, and promoted the formation of new blood vessels, especially at the wound edge, compared to the untreated group. Therefore, this newly fish skin-based GelMA bio-ink developed in this study has the potential to be utilized for the printing of 3D GelMA skin substitutes.

Physicochemical properties of flowable composites using isobornyl methacrylate as diluent monomer.

OBJECTIVE: this study sought to evaluate the effect of isobornyl methacrylate (IBOMA) as a diluent monomer on the physicochemical properties of experimental flowable resin composites. METHODOLOGY: the organic resin matrix of a modal flowable resin composite was formulated with 50 wt.% of bisphenol-A-glycidyl methacrylate (Bis-GMA) and 50 wt.% of a diluent monomer, in which IBOMA was used as a combining or substituent diluent monomer to triethylene glycol dimethacrylate (TEGDMA). The resin matrices were filled with 55 wt.% particles, of which 10 wt.% was 0.05-µm fumed silica, and 45 wt.% was 0.7-µm BaBSiO2 glass. Polymerization shrinkage stress (PSS; n=10), degree of conversion (DC; n=3), maximum rate of polymerization (Rpmax; n=3), film thickness (FT; n=10), sorption (Wsp; n=10), solubility (Wsl; n=10), flexural strength (FS; n=10), flexural modulus (FM; n=10), Knoop microhardness (KH; n=10), and microhardness reduction after chemical softening (HR; n=10) were evaluated. Data were analyzed using one-way ANOVA, followed by Tukey's test (α=0.05; ß=0.2). RESULTS: the results showed that the substitution or addition of IBOMA reduced FT (p=0.001), PSS (p=0.013), Rpmax (p=0.001), DC (p=0.001), FM (p=0.006) Wsp (p=0.032), and Wsl (p=0.021). However, when used as a complete substituent, IBOMA demonstrated significantly lower FS (p=0.017) and KH (p=0.008), while TEGDMA demonstrated significantly lower HR (p=0.022). CONCLUSION: the flowable composite containing IBOMA combined with TEGDMA showed no effect in KH and FS and effectively reduced the PSS, RP, FT, Wsp, and Wsl. However, it showed a reduction in DC, FS, and an increase in HR.

The effect of a universal cleaning agent on the bonding performance of a self-adhesive cement to contaminated dentin surfaces.

PURPOSE: This study examined the effect of using KATANA Cleaner (KC) containing 10-methacryloyloxydecyl dihydrogen phosphate (MDP) salt on the micro-shear bond strength (µSBS) of a self-adhesive cement to uncontaminated and contaminated dentin. METHODS: Dentin samples were categorized into four contamination conditions (no contamination, saliva, blood, saliva/blood mixed) and subjected to two decontamination methods (water rinse and KC use), forming eight groups. Scanning electron microscope images representing each group were obtained. One sample representing each group was analyzed by Raman Spectroscopy. Composite resin was bonded to the sample dentin surfaces with a self-adhesive resin cement. After 5,000 thermal cycles, the µSBS test was performed. The data were analyzed statistically (α= 0.05). RESULTS: The lowest µSBS value was observed in the water-rinsed mixed contamination group, while the highest was in the KC-treated uncontaminated group. KC-treated groups exhibited significantly higher µSBS values compared to water-rinsed groups for each contamination type (P< 0.05), indicating the efficacy of KC in enhancing bond strength. CLINICAL SIGNIFICANCE: There are limited studies using the new MDP salt-containing cleaner on dentin. In this study, contamination of dentin tissue with saliva, blood, and saliva/blood mixture was simulated and the effects of water rinsing and MDP salt-containing cleaner (KATANA Cleaner) on bond strength were tested as decontamination methods. The results showed that the use of a cleaner containing MDP salt increased the bond strength to dentin tissue under both non-contaminated and contaminated conditions.

Highly precise strategy of polygalacturonic acid microcarriers functionalized with zwitterions and specific peptides for MSC screening.

Microcarriers for large-scale cell culture have a broader prospect in cell screening compared with the traditional high cost, low efficiency, and cell damaging methods. However, the equal biological affinity to cells has hindered its application. Therefore, based on the antifouling strategy of zwitterionic polymer, we developed a cell-specific microcarrier (CSMC) for shielding non-target cells and capturing mesenchymal stem cells (MSCs), which has characteristics of high biocompatibility, low background noise and high precision. Briefly, [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide and glycidyl methacrylate were grafted onto polygalacturonic acid, respectively. The former built a hydration layer through solvation to provide an excellent antifouling surface, while the latter provided active sites for the click reaction with sulfhydryl-modified cell-specific peptides, resulting in rapid immobilization of peptides. This method is applicable to the vast majority of polysaccharide materials. The accurate capture ratio of MSCs by CSMC in a mixed multicellular environment is >95 % and the proliferation rate of MSCs on microcarriers is satisfactory. In summary, this grafting strategy of bioactive components lays a foundation for the application of polysaccharide materials in the biomedical field, and the specific adhesive microcarriers also open up new ideas for the development of stem cell screening as well.

Effects of sodium copper- and sodium iron-chlorophyllin primers on resin bonding to dentin.

This study evaluated the effects of two chlorophyll derivatives, sodium copper chlorophyllin (Cu-Chl) and sodium iron chlorophyllin (Fe-Chl), on the bond strength between a self-curing luting agent (4-META/MMA-TBB resin) and dentin. Five aqueous primers containing 35% 2-hydroxyethylmethacrylate with 0.007% Cu-Chl, 0.07% Cu-Chl, 0.007% Fe-Chl, 0.07% Fe-Chl, or neither Cu-Chl nor Fe-Chl (no-Chl) were prepared. The extracted human dentin surfaces were etched with 10% phosphoric acid (10PA), primed, and bonded to a resin block using the 4-META/MMA-TBB resin. A conventional etching agent (10-3) and 10PA without primer (PA/no-primer) were used as controls. The microtensile bond strength was determined after 48 h. The arithmetic medians for 20 stick specimens were calculated and statistically analyzed using a nonparametric Steel-Dwass test (α = 0.05). The maximum bond strength was achieved in the 0.007% Cu-Chl group, followed by those in the 0.07% Cu-Chl, 0.07% Fe-Chl, 10-3, 0.007% Fe-Chl, no-Chl, and PA/no-primer groups. No significant difference was observed between 0.007% Fe-Chl, 0.07% Fe-Chl, and 10-3. The bond strength to dentin etched with 10PA was influenced by the type and concentration of the chlorophyll derivatives applied. Cu-Chl rather than Fe-Chl should be useful as a component of surface treatment agents for bonding 4-META/MMA-TBB resin to dentin.

Effects of the insecticide acetamiprid and the fungicide azoxystrobin on locomotion activity and mushroom bodies of solitary bee Centris analis.

Pesticide use is a major factor contributing to the global decline in bee populations. Sublethal effects, such as behavior alterations, are neglected in pesticide regulation for pollinators. However, these effects can bring important information to understanding the impacts of pesticides on bees' daily activities. In this study, we aimed to investigate the effects of the insecticide acetamiprid (7 ng/µL) and the fungicide azoxystrobin (10 ng/µL) on the behavior of the Neotropical solitary bee Centris analis. Female and male bees were exposed to these chemicals continuously for 48 h, followed by an additional 48 h without contaminated food, totaling 96 h of observation. We used five experimental groups: control, solvent control, insecticide, fungicide, and pesticide mixture (insecticide + fungicide). Behavioral alterations based on locomotion and light response were assessed by video tracking at 48 (end of pesticide exposure) and 96 h (end of bioassay). In addition, after recording bees at 96 h, the individuals were anesthetized for brain collection and histological evaluation of mushroom bodies to evaluate if pesticides can damage their neurons and impair the cognitive processes and responses of bees to sensory stimuli. Bees exposed to acetamiprid and pesticide mixture showed lethargic movements and impaired locomotion at 48 h. Notably, these behavioral effects were no longer evident after the bees consumed uncontaminated food for an additional 48 h, totaling 96 h from the start of pesticide exposure. Only fungicide exposure did not result in any behavioral or brain histological changes. Therefore, our study showed that acetamiprid at an estimated residual concentration, despite being classified as having low toxicity for bees, can cause significant initial locomotion disruption in solitary bees. These findings highlight the importance of considering sublethal effects in environmental risk assessment.

Antimicrobial hard denture reliners using quaternary ammonium methacryloxy silicate (K18 QAMS) and K18-functionalized filler.

OBJECTIVE: To determine the effects of adding a quaternary ammonium methacryloxy silicate (K18) and K18-functionalized filler (K18-Filler) on the material and antimicrobial properties of a hard denture reline material. MATERIALS AND METHODS: 30% K18 in methyl methacrylate (K18-MMA; 0-20 wt% of reliner) and K18-Filler (0-30 wt% of reliner) were incorporated into KoolinerTM hard denture reliner. KoolinerTM served as the control. The cure (Shore A hardness), hydrophilicity (contact angles), mechanical (3-point bend test), water sorption, and antimicrobial properties against Streptococcus mutans, S. sanguinis, and Candida albicans were determined. RESULTS: Most K18 groups cured well and had comparable Shore A hardness values (range ~52 to 70 DHN) to that of controls (67.2 ± 1.8 DHN; Bonferroni corrected p > 0.0003). Even the softest group had hardness values within the range of commercial products. Half of the K18 groups had comparable contact angles to that of controls (range ~75° to 80° vs 83.41° ± 2.66°; Bonferroni corrected p > 0.0003), and most were within the range of commercial liners. K18-MMA and K18-Filler increased modulus but decreased ultimate transverse strength (UTS). All experimental groups had comparable or higher moduli than controls (range ~966 to 2069 MPa vs 1340 ± 119 MPa; Bonferroni corrected p < 0.0003), but only half of the experimental groups had comparable UTS to that of controls (range ~41 to 49 MPa vs 55.8 ± 1.5 MPa; Bonferroni corrected p > 0.0003). The 15% and 20% K18-MMA with 30% K18-Filler groups had significant antimicrobial activity against all three microbes (p < 0.05). However, the 15% and 20% K18-MMA with 30% K18-Filler groups had significantly higher water sorption at early time points (p < 0.05). After 8 weeks, they were comparable to each other (p > 0.05). CONCLUSIONS: K18-MMA and K18-Filler are promising antimicrobial additives that produce hard denture liners with material properties within the range of commercial products and significant antimicrobial properties against S. mutans, S. sanguinis, and C. albicans. Further development is needed to reduce water sorption.

Sensitive Coatings Based on Molecular-Imprinted Polymers for Triazine Pesticides' Detection.

Triazine pesticide (atrazine and its derivatives) detection sensors have been developed to thoroughly check for the presence of these chemicals and ultimately prevent their exposure to humans. Sensitive coatings were designed by utilizing molecular imprinting technology, which aims to create artificial receptors for the detection of chlorotriazine pesticides with gravimetric transducers. Initially, imprinted polymers were developed, using acrylate and methacrylate monomers containing hydrophilic and hydrophobic side chains, specifically for atrazine, which shares a basic heterocyclic triazine structure with its structural analogs. By adjusting the ratio of the acid to the cross-linker and introducing acrylate ester as a copolymer, optimal non-covalent interactions were achieved with the hydrophobic core of triazine molecules and their amino groups. A maximum sensor response of 546 Hz (frequency shift/layer height equal to 87.36) was observed for a sensitive coating composed of 46% methacrylic acid and 54% ethylene glycol dimethacrylate, with a demonstrated layer height of 250 nm (6.25 kHz). The molecularly imprinted copolymer demonstrated fully reversible sensor responses, not only for atrazine but also for its metabolites, like des-ethyl atrazine, and structural analogs, such as propazine and terbuthylazine. The efficiency of modified molecularly imprinted polymers for targeted analytes was tested by combining them with a universally applicable quartz crystal microbalance transducer. The stable selectivity pattern of the developed sensor provides an excellent basis for a pattern recognition procedure.

Composition Tuning of Semi-Open Cell Carriers via Phase Freeze-Shrink Self-Molding.

Extracellular matrix (ECM)-mimicking microsized cell carriers featuring a semi-isolated chamber facilitate the study of cellular heterogeneity as well as intercellular communication. However, the semiopen shaping of the designated gel mixture remains unattainable with current methods. We report an oil-phase freeze-shrink self-molding mechanism for generating size- and composition-tunable cradle-shaped microgels (microcradles) from water-in-oil droplets. The universality of this shape transition principle is demonstrated with six types of polysaccharides dispersed in a poly(ethylene glycol) diacrylate (PEGDA) or methacrylate gelatin (GelMA) matrix. By doping the microcradles with the major ECM component, hyaluronic acid sodium, we demonstrate a label-free selective culture of CD44 receptor-rich cells and the formation of cell spheroids within 3 days. This cryo-induced cradle-shaping strategy enables the functionalization of microcarriers for selective cell culture, thereby allowing them to be used for intercellular communication, drug delivery, and the construction of structural units for osteogenesis and 3D printing.

3D printing/electrospinning of a bilayered composite patch with antibacterial and antiadhesive properties for repairing abdominal wall defects.

The application of patch methods for repairing abdominal wall wounds presents a variety of challenges, such as adhesion and limited mobility due to inadequate mechanical strength and nonabsorbable materials. Among these complications, postoperative visceral adhesion and wound infection are particularly serious. In this study, a bilayered composite patch with a gelatin methacryloyl (GelMA)/sodium alginate (SA)-vancomycin (Van)@polycaprolactone (PCL) (GelMA/SA-Van@PCL) antibacterial layer was prepared via coaxial 3D printing and a polycaprolactone (PCL)-silicon dioxide (SiO2) antiadhesive layer (PCL-SiO2) was prepared via electrospinning and electrostatic spray for hernia repair. The evaluation of the physicochemical properties revealed that the composite patch had outstanding tensile properties (16 N cm-1), excellent swelling (swelling rate of 243.81 ± 12.52%) and degradation (degradation rate of 53.14 ± 3.02%) properties. Furthermore, the composite patch containing the antibiotic Van exhibited good antibacterial and long-term drug release properties. Both in vivo and in vitro experiments indicated that the composite patch displayed outstanding biocompatibility and antiadhesive properties and could prevent postoperative infections. In summary, the bilayered composite patch can effectively prevent postoperative complications while promoting tissue growth and repair and holds significant application potential in hernia repair.

Laponite modified methacryloyl gelatin hydrogel with controlled release of vascular endothelial growth factor a for bone regeneration.

Reconstruction of bone defects has long been a major clinical challenge. Limited by the various shortcomings of conventional treatment like autologous bone grafting and inorganic substitutes, the development of novel bone repairing strategies is on top priority. Injectable biomimetic hydrogels that deliver stem cells and growth factors in a minimally invasive manner can effectively promote bone regeneration and thus represent a promising alternative. Therefore, in this study, we designed and constructed an injectable nanocomposite hydrogel co-loaded with Laponite (Lap) and vascular endothelial growth factor (VEGF) through a simplified and convenient scheme of physical co-mixing (G@Lap/VEGF). The introduced Lap not only optimized the injectability of GelMA by the electrostatic force between the nanoparticles, but also significantly delayed the release of VEGF-A. In addition, Lap promoted high expression of osteogenic biomarkers in mesenchymal stem cells (MSCs) and enhanced the matrix mineralization. Besides, VEGF-A exerted chemotactic effects recruiting endothelial progenitor cells (EPCs) and inducing neovascularization. Histological and micro-CT results demonstrated that the critical-sized calvarial bone defect lesions in the SD rats after treated with G@Lap/VEGF exhibited significant in vivo bone repairing. In conclusion, the injectable G@Lap/VEGF nanocomposite hydrogel constructed in our study is highly promising for clinical transformation and applications, providing a convenient and simplified scheme for clinical bone repairing, and contributing to the further development of the injectable biomimetic hydrogels.

Non-animal derived recombinant collagen-based biomaterials as a promising strategy towards adipose tissue engineering.

Adipose tissue engineering (ATE) has been gaining increasing interest over the past decades, offering promise for new and innovative breast reconstructive strategies. Animal-derived gelatin-methacryloyl (Gel-MA) has already been applied in a plethora of TE strategies. However, due to clinical concerns, related to the potential occurrence of immunoglobulin E-mediated immune responses and pathogen transmission, a shift towards defined, reproducible recombinant proteins has occurred. In the present study, a recombinant protein based on human collagen type I, enriched with arginine-glycine-aspartic acid was functionalized with photo-crosslinkable methacryloyl moieties (RCPhC1-MA), processed into 3D scaffolds and compared with frequently applied Gel-MA from animal origin using an indirect printing method applying poly-lactic acid as sacrificial mould. For both materials, similar gel fractions (>65%) and biodegradation times were obtained. In addition, a significantly lower mass swelling ratio (17.6 ± 1.5 versus 24.3 ± 1.4) and mechanical strength (Young's modulus: 1.1 ± 0.2 kPa versus 1.9 ± 0.3 kPa) were observed for RCPhC1-MA compared to Gel-MA scaffolds.In vitroseeding assays showed similar cell viabilities (>80%) and a higher initial cell attachment for the RCPhC1-MA scaffolds. Moreover, the seeded adipose-derived stem cells could be differentiated into the adipogenic lineage for both Gel-MA and RCPhC1-MA scaffolds, showing a trend towards superior differentiation for the RCPhC1-MA scaffolds based on the triglyceride and Bodipy assay. RCPhC1-MA scaffolds could result in a transition towards the exploitation of non-animal-derived biomaterials for ATE, omitting any regulatory concerns related to the use of animal derived products.

A carbon dot nanozyme hydrogel enhances pulp regeneration activity by regulating oxidative stress in dental pulpitis.

Preserving pulp viability and promoting pulp regeneration in pulpitis have attracted widespread attention. Restricted by the oxidative stress microenvironment of dental pulpitis, excessive reactive oxygen and nitrogen species (RONS) trigger uncontrolled inflammation and exacerbate pulp tissue destruction. However, modulating redox homeostasis in inflamed pulp tissue to promote pulp regeneration remains a great challenge. Herein, this work proposes an effective antioxidative system (C-NZ/GelMA) consisting of carbon dot nanozymes (C-NZ) with gelatin methacryloyl (GelMA) to modulate the pulpitis microenvironment for dental pulp regeneration by utilizing the antioxidant properties of C-NZ and the mechanical support of an injectable GelMA hydrogel. This system effectively scavenges RONS to normalize intracellular redox homeostasis, relieving oxidative stress damage. Impressively, it can dramatically enhance the polarization of regenerative M2 macrophages. This study revealed that the C-NZ/GelMA hydrogel promoted pulp regeneration and dentin repair through its outstanding antioxidant, antiapoptotic, and anti-inflammatory effects, suggesting that the C-NZ/GelMA hydrogel is highly valuable for pulpitis treatment.

Synthesis and biological applications of nanocomposite hydrogels based on the methacrylation of hydroxypropyl methylcellulose and lignin loaded with alpha-pinene.

Oral conditions, such as recurrent aphthous stomatitis, are chronic inflammatory disorders that significantly affect the life quality. This study aims to develop a novel buccal mucoadhesive based on methacrylate hydroxypropyl methylcellulose (M-HPMC) and methacrylate lignin (M-SLS) encapsulated with nanostructured lipid carriers (NLCs) for controlled release of alpha-pinene (α-pinene). NLCs with particle sizes of 152 ± 3 nm were prepared by using stearic acid and oleic acid as solid and liquid lipids, respectively. Following the successful synthesis of M-HPMC and M-SLS, various concentrations of α-pinene loaded NLCs (0, 18, 38, and 50 wt%) were encapsulated in M-HPMC/M-SLS hydrogel. It was demonstrated that the physiological and mechanical performances of hydrogels were changed, depending on the NLC content. Remarkably, the incorporation of 18 wt% NLC improved the compressive strength (143 ± 14 kPa) and toughness (17 ± 1 kJ/m3) of M-HPMC/M-SLS hydrogel. This nanocomposite hydrogel considerably decreased dissipated energy from 1.64 kJ/m3 to 0.99 kJ/m3, after a five-cycle compression test. The nanocomposite hydrogel exhibited controlled α-pinene release for up to 96 h which could significantly improve the antioxidant activity of M-HPMC/M-SLS matrix. Moreover, the reinforcing M-HPMC/M-SLS hydrogel with α-pinene-loaded NLCs resulted in increased adhesive strength (113.5 ± 7.5 kPa) to bovine buccal mucosa and cytocompatibility in contact with fibroblasts.

Preparation and application of a pseudo-templated multi-monomer aflatoxins imprinted polymer.

A functional material was developed with specific recognition properties for aflatoxins for pre-processing enrichment and separation in the detection of aflatoxins in Chinese herbal medicines. In the experiment, ethyl coumarin-3-carboxylate, which has a highly similar structure to the oxonaphthalene o-ketone of aflatoxin, was selected as a pseudo-template, zinc acrylate, neutral red derivative, and methacrylic acid, which have complementary functions, were selected as co-monomers to prepare a pseudo-template multifunctional monomer molecularly imprinted polymer (MIP). The MIP obtained under the optimal preparation conditions has a maximum adsorption capacity of 0.036 mg/mg and an imprinting factor of 3.67. The physical property evaluation of the polymers by Fourier infrared spectrometer, scanning electron microscopy, pore size analyzer, thermogravimetric analyzer, and diffuse reflectance spectroscopy showed that the MIP were successfully prepared and porous spherical-like particles were obtained. The synthesized polymer was used as a solid-phase extraction agent for the separation of aflatoxins from the extract of spina date seed. The linear range of the developed method was 10-1000 ng/mL, the limit of detection was 0.36 ng/mL, the limit of quantification was 1.19 ng/mL, and the recoveries of the extracts at the concentration level of 0.2 µg/mL were in the range 88.0-93.4%, with relative standard deviations (RSDs) of 1.97% (n). The results showed that the preparation of MIPs using ethyl coumarin-3-carboxylate as a template was simple, economical, and convenient. It is expected to become a promising functional material for the enrichment and separation aflatoxins from complex matrices.