Montmorillonite-reinforced methacrylated collagen/methacrylated silk fibroin hydrogel-based inks: rheological and physicochemical characterization for bone scaffold applications.
Aug 2026· International Journal of Biological Macromolecules· Vol 380, pp.
154129
· 0 citations· 72 references
Medicine
TL;DR
Montmorillonite-reinforced ColMA/SFMA systems are promising hydrogel-based inks for bone scaffold applications and demonstrate that montmorillonite-reinforced ColMA/SFMA systems are promising hydrogel-based inks for bone scaffolds.
Abstract
Collagen is widely used in bone tissue engineering due to its biocompatibility; however, its poor mechanical properties, limited print fidelity restrict its use in extrusion-based bioprinting. Collagen methacrylate (ColMA) improves structural stability via photopolymerization but remains prone to enzymatic degradation. In this study, methacrylated silk fibroin (SFMA) and montmorillonite clay (MMT) were incorporated into ColMA-based systems to enhance mechanical performance and mimic aspects of the bone extracellular matrix. Successful methacrylation of ColMA and SFMA was confirmed by 1H NMR and TNBS assay, while FTIR analysis indicated interactions between the polymeric network and the clay phase. Rheological characterization, before and after UV exposure, revealed increased viscosity and a transition to predominantly elastic behavior after photopolymerization, indicating effective network formation. Extrusion-based 3D printing of SFMA/ColMA +3.0% MMT enabled the fabrication of porous grid structures with good shape fidelity, followed by rapid curing under UV light (365 nm, 40 s). These results demonstrate that montmorillonite-reinforced ColMA/SFMA systems are promising hydrogel-based inks for bone scaffold applications.
Objectives: The development of biomaterials for bone tissue engineering requires a combination of suitable mechanical properties, bioactivity, and cytocompatibility. In this study, photocrosslinked polymer-ceramic composites based on poly(vinylpyrrolidone) (PVP), poly(ethylene glycol) (PEG), and pullulan were developed and reinforced with dicalcium phosphate dihydrate (DCPD, brushite) to obtain bioactive materials with enhanced biological performance. Methods: DCPD was synthesized via a wet precipitation method and incorporated into polymer matrices through UV-induced photopolymerization. The resulting composites were characterized in terms of swelling behavior, hardness, degradation in physiological conditions, surface morphology, and biological response. Cytocompatibility was assessed using direct and indirect cytotoxicity assays, proliferation studies, and scanning electron microscopy (SEM) evaluation of MC3T3-E1 preosteoblast adhesion and morphology. Results: The composition of the polymer matrix significantly affected the physicochemical properties of the materials. Increased PVP content resulted in higher hardness and more developed surface morphology, whereas DCPD incorporation reduced swelling and increased surface roughness. All materials exhibited satisfactory cytocompatibility, with cell viability remaining above the threshold specified by ISO 10993-5. Proliferation studies demonstrated progressive cell growth over time, particularly on DCPD-containing composites. SEM observations confirmed successful cell attachment and favorable cell-material interactions, with the most pronounced response observed for balanced PVP/PEG formulations reinforced with DCPD. Conclusions: The developed PVP/PEG/pullulan-DCPD composites demonstrated promising physicochemical and biological properties and may serve as preliminary bone-facing materials for future osteochondral tissue engineering applications. Further studies are required to investigate their osteogenic potential and long-term biological performance.
Karina Niziołek, Dagmara Słota, Katarzyna Haraźna et al.· European Cells & Materia...· 0 citations
The developed scaffold showed higher cell viability value than control groups than control groups, and confirmed cells proliferation potential of the scaffold at prolonged times, and future studies should explore in vivo performance and long-term functionality of the scaffold.
Ali Khalaji, Soheila Zare, Faranak Aghaz et al.· Scientific Reports· 0 citations
Results highlight the critical interplay between macromolecular composition, 3D microenvironment, and cell response, demonstrating that GelMA+TA systems represent a promising preliminary platform for the development of tunable bioactive scaffolds for wound-related applications.
Leonor Resina, M. M. Pérez‐Madrigal, Carlos Alemán· International Journal of Bio...· 0 citations
Biomedical devices for bone tissue repair require materials with a balanced combination of printability, structural integrity, and biological performance. Their fabrication is increasingly shifting toward additive manufacturing, in which thermoplastic biodegradable polymers, particularly poly(lactic acid) (PLA), serve as matrices. In this study, PLA composite filaments with varying hydroxyapatite (HAp) contents (0, 5, 10, 20, and 30 wt%) were fabricated via a solvent-assisted non-solvent-induced precipitation method and evaluated for extrusion-based bone tissue engineering applications. HAp content significantly influenced the physicochemical, rheological, mechanical, and biological performance of the composites: increasing HAp loading reduced filler dispersion homogeneity and, at 30 wt%, pronounced agglomeration and microvoid formation. Thermal analysis demonstrated that the incorporation of HAp did not significantly affect the glass transition temperature of PLA, which remained nearly constant regardless of HAp content. However, the presence of HAp shifted the cold crystallization temperature to higher values, suggesting delayed cold crystallization during heating. Intermediate HAp incorporation (5-10 wt%) provided the most favourable balance between homogeneous filler dispersion, mechanical reinforcement, and osteoblastic response, with PLA-HAp10 showing enhanced ALP activity and osteogenic gene expression together with reliable filament formation and scaffold printability. In contrast, 20 wt% HAp approached the upper composition-processing threshold of the system, while 30 wt% HAp compromised structural homogeneity and extrusion reliability. These findings highlight the importance of controlling HAp loading to achieve a balanced combination of processability, structural integrity, and osteogenic performance in PLA-based biomaterials.
Lukošiūnas Jokūbas, Šaparajavaitė Gabrielė, Dambrauskas Tadas et al.· International Journal of Bio...· 0 citations
Poly(ε-caprolactone) (PCL) is a biodegradable and biocompatible polyester widely used in biomedical scaffolds. However, its relatively low mechanical strength and limited cell adhesion properties remain major challenges for bone tissue engineering applications. This study developed a 3D-printed PCL mesh enhanced with calcium carbonate (CaCO3) to improve mechanical strength and cytocompatibility. PCL was synthesized via ring-opening polymerization at 120 °C for 72 h using 0.015 mol % of Sn(OnBu)2 as the initiator, resulting in a high molecular weight polymer of 189 kg/mol. The addition of 5 wt % CaCO3 into the PCL matrix enhanced the flexural performance of the biocomposite mesh compared to pure PCL, with flexural strength increasing from 2.11 ± 0.46 to 4.17 ± 1.15 MPa and Young’s modulus increasing from 81 ± 14 to 130 ± 33 MPa, a value within the range reported for native trabecular bone. Cytocompatibility was evaluated using L929 fibroblasts and the MTT assay, following ISO 10993-5 guidelines, and demonstrated noncytotoxic behavior, with cell viability ranging from 80% to 110% over 28 days. Additionally, MG-63 osteoblast-like cells showed increased proliferation on the PCL-CaCO3 mesh. These results demonstrate the feasibility of the 3D-printed PCL-CaCO3 mesh as a mechanically reinforced, cytocompatible scaffold candidate for bone tissue engineering applications, warranting further evaluation of osteogenic potential and in vivo performance.
Injectable fillers that combine immediate volume restoration with a sustained biological response remain of considerable interest in minimally invasive aesthetic medicine. In this study, a hydroxyapatite-loaded methacrylated recombinant type III collagen microgel (HAp@rhCol III-MA) was prepared by in situ coprecipitation and photocrosslinking. Recombinant type III collagen (rhCol III) was functionalized with methacryloyl groups to obtain rhCol III-MA, after which a calcium phosphate phase was mineralized in the presence of the modified collagen and the collagen phase was crosslinked under ultraviolet irradiation. More than 80% of the microgel particles prepared at 900 rpm were 20–80 μm in diameter. Spectroscopic, elemental, thermal, and diffraction analyses supported the incorporation of a poorly crystalline, HAp-compatible calcium phosphate phase, while rheological measurements showed higher storage and loss moduli than those of rhCol III-MA gel. HAp@rhCol III-MA did not reduce NIH-3T3 cell viability at the tested concentrations and enhanced HUVEC scratch closure and tube-network formation in vitro. Following subcutaneous implantation in rats, the microgel retained more volume than rhCol III-MA during the early and intermediate observation periods, with residual volumes of 56.58 ± 3.03 mm3 for HAp@rhCol III-MA and 52.80 ± 1.79 mm3 for rhCol III-MA at day 59; the commercial type I collagen comparator retained 123.23 ± 2.80 mm3. The composite caused no evident tissue injury and was associated with progressive collagen deposition and a low, declining CD68-positive response. These findings support further investigation of HAp@rhCol III-MA as an injectable dermal-filling material, while long-term persistence and clinical injection performance remain to be established.
Qian-Qian Zhu, Cui-Cui Wu, Xi Luo et al.· Gels· 0 citations
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