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Biomaterials Science Jun 2024This study details the design, fabrication, clinical trials' evaluation, and analysis after the clinical application of 3D-printed bone reconstruction implants made of...
This study details the design, fabrication, clinical trials' evaluation, and analysis after the clinical application of 3D-printed bone reconstruction implants made of nHAp@PLDLLA [nanohydroxyapatite@poly(L-lactide--D,L-lactide)] biomaterial. The 3D-printed formulations have been tested as bone reconstruction in 3 different medical cases, including frontal lobe, mandibular bone, and cleft palate reconstructions. Replacing one of the implants after 6 months provided a unique opportunity to evaluate the post-surgical implant obtained from a human patient. This allowed us to quantify physicochemical changes and develop a spatial map of osseointegration and material degradation kinetics as a function of specific locations. To the best of our knowledge, hydrolytic degradation and variability in the physicochemical and mechanical properties of the biomimetic, 3D-printed implants have not been quantified in the literature after permanent placement in the human body. Such analysis has revealed the constantly changing properties of the implant, which should be considered to optimize the design of patient-specific bone substitutes. Moreover, it has been proven that the obtained composition can produce biomimetic, bioresorbable and bone-forming alloplastic substitutes tailored to each patient, allowing for shorter surgery times and faster patient recovery than currently available methods.
Topics: Humans; Printing, Three-Dimensional; Durapatite; Absorbable Implants; Bone Substitutes; Skull; Polyesters; Male; Prosthesis Design; Biocompatible Materials; Female
PubMed: 38787753
DOI: 10.1039/d3bm01826a -
Journal of Biomedical Materials... Jun 2024The challenge of integrating hydroxyapatite nanoparticles (nHAp) with polymers is hindered by the conflict between the hydrophilic and hygroscopic properties of nHAp and...
The challenge of integrating hydroxyapatite nanoparticles (nHAp) with polymers is hindered by the conflict between the hydrophilic and hygroscopic properties of nHAp and the hydrophobic properties of polymers. This conflict particularly affects the materials when calcium phosphates, including nHAp, are used as a filler in composites in thermal processing applications such as 3D printing with fused filament fabrication (FFF). To overcome this, we propose a one-step surface modification of nHAp with calcium stearate monolayer. Moreover, to build the scaffold with suitable mechanical strength, we tested the addition of nHAp with diverse morphology-spherical, plate- and rod-like nanoparticles. Our analysis showed that the composite of polycaprolactone (PCL) reinforced with nHAp with rod and plate morphologies modified with calcium stearate monolayer exhibited a significant increase in compressive strength. However, composites with spherical nHAp added to PCL showed a significant reduction in compressive modulus and compressive strength, but both parameters were within the applicability range of hard tissue scaffolds. None of the tested composite scaffolds showed cytotoxicity in L929 murine fibroblasts or MG-63 human osteoblast-like cells, supporting the proliferation of the latter. Additionally, PCL/nHAp scaffolds reinforced with spherical nHAp caused osteoactivation of bone marrow human mesenchymal stem cells, as indicated by alkaline phosphatase activity and COL1, RUNX2, and BGLAP expression. These results suggest that the calcium stearate monolayer on the surface of the nHAp particles allows the production of polymer/nHAp composites suitable for hard tissue engineering and personalized implant production in 3D printing using the FFF technique.
Topics: Printing, Three-Dimensional; Tissue Scaffolds; Durapatite; Tissue Engineering; Mice; Animals; Humans; Nanoparticles; Cell Line; Polyesters; Osteoblasts; Osteogenesis; Materials Testing
PubMed: 38786580
DOI: 10.1002/jbm.b.35409 -
Cell Biochemistry and Function Jun 2024We aimed to evaluate the materials based on 4-methacryloxyethyl trimellitate anhydride/methyl methacrylate tri-n-butylborane (Super-bond [SB]) and nano hydroxyapatite...
We aimed to evaluate the materials based on 4-methacryloxyethyl trimellitate anhydride/methyl methacrylate tri-n-butylborane (Super-bond [SB]) and nano hydroxyapatite (naHAp) for the repair of perforation at pulp chamber floor (PPF) in vitro and in vivo models. SB and naHAp were mixed in the mass ratio of 10% or 30% to produce naHAp/SB. Human periodontal ligament stem cells (HPDLSCs) were cultured on resin discs of SB or naHAp/SB to analyze the effects of naHAp/SB on cell adhesion, proliferation, and cementoblastic differentiation. A rat PPF model was treated with SB or naHAp/SB to examine the effects of naHAp/SB on the healing of defected cementum and periodontal ligament (PDL) at the site of PPF. HPDLSCs were spindle-shaped and adhered to all resin discs. Changing the resin from SB to naHAp/SB did not significantly alter cell proliferation. Both 10% and 30% naHAp/SB were more effective than SB in promoting cementoblastic differentiation of HPDLSCs. In the rat PPF model, 30% naHAp/SB was more effective than SB in promoting the formation Sharpey's fiber-like structures with expression of the PDL-related marker and cementum-like structures with expression of cementum-related markers. In conclusion, 30% naHAp/SB can be the new restorative material for PPF because it exhibited the abilities of adhering to dentin and healing of defected periodontal tissue.
Topics: Animals; Rats; Humans; Durapatite; Periodontal Ligament; Boron Compounds; Methacrylates; Cell Differentiation; Wound Healing; Male; Cell Proliferation; Dental Pulp Cavity; Stem Cells; Cells, Cultured; Rats, Sprague-Dawley; Methylmethacrylates; Cell Adhesion
PubMed: 38783647
DOI: 10.1002/cbf.4058 -
International Journal of Biological... Jun 2024Cyclic olefin copolymer (COC) has emerged as an interesting biocompatible material for Organ-on-a-Chip (OoC) devices monitoring growth, viability, and metabolism of...
Cyclic olefin copolymer (COC) has emerged as an interesting biocompatible material for Organ-on-a-Chip (OoC) devices monitoring growth, viability, and metabolism of cells. Despite ISO 10993 approval, systematic investigation of bacteria grown onto COC is a still not documented issue. This study discusses biofilm formations of the canonical wild type BB120 Vibrio campbellii strain on a native COC substrate and addresses the impact of the physico-chemical properties of COC compared to conventional hydroxyapatite (HA) and poly(dimethylsiloxane) (PDMS) surfaces. An interdisciplinary approach combining bacterial colony counting, light microscopy imaging and advanced digital image processing remarks interesting results. First, COC can reduce biomass adhesion with respect to common biopolymers, that is suitable for tuning biofilm formations in the biological and medical areas. Second, remarkably different biofilm morphology (dendritic complex patterns only in the case of COC) was observed among the examined substrates. Third, the observed biofilm morphogenesis was related to the interaction of COC with the conditioning layer of the planktonic biological medium. Fourth, Level Co-occurrence Matrix (CGLM)-based analysis enabled quantitative assessment of the biomass textural fractal development under different coverage conditions. All of this is of key practical relevance in searching innovative biocompatible materials for pharmaceutical, implantable and medical products.
Topics: Biocompatible Materials; Biofilms; Vibrio; Bacterial Adhesion; Cycloparaffins; Polymers; Durapatite; Biomass
PubMed: 38782326
DOI: 10.1016/j.ijbiomac.2024.132550 -
Arthritis Research & Therapy May 2024To perform a detailed morphological analysis of the inorganic portion of two different clinical presentations of calcium-based deposits retrieved from subjects with SSc...
BACKGROUND
To perform a detailed morphological analysis of the inorganic portion of two different clinical presentations of calcium-based deposits retrieved from subjects with SSc and identify a chemical dissolution of these deposits suitable for clinical use.
METHODS
Chemical analysis using Fourier Transform IR spectroscopy ('FTIR'), Raman microscopy, Powder X-Ray Diffraction ('PXRD'), and Transmission Electron Microscopy ('TEM') was undertaken of two distinct types of calcinosis deposits: paste and stone. Calcinosis sample titration with ethylenediaminetetraacetic acid ('EDTA') assessed the concentration at which the EDTA dissolved the calcinosis deposits in vitro.
RESULTS
FTIR spectra of the samples displayed peaks characteristic of hydroxyapatite, where signals attributable to the phosphate and carbonate ions were all identified. Polymorph characterization using Raman spectra were identical to a hydroxyapatite reference while the PXRD and electron diffraction patterns conclusively identified the mineral present as hydroxyapatite. TEM analysis showed differences of morphology between the samples. Rounded particles from stone samples were up to a few micron in size, while needle-like crystals from paste samples reached up to 0.5 µm in length. Calcium phosphate deposits were effectively dissolved with 3% aqueous solutions of EDTA, in vitro. Complete dissolution of both types of deposit was achieved in approximately 30 min using a molar ratio of EDTA/HAp of ≈ 300.
CONCLUSIONS
Stone and paste calcium-based deposits both comprise hydroxyapatite, but the constituent crystals vary in size and morphology. Hydroxyapatite is the only crystalline polymorph present in the SSc-related calcinosis deposits. Hydroxyapatite can be dissolved in vitro using a dosage of EDTA considered safe for clinical application. Further research is required to establish the optimal medium to develop the medical product, determine the protocol for clinical application, and to assess the effectiveness of EDTA for local treatment of dystrophic calcinosis.
Topics: Edetic Acid; Humans; Calcinosis; Spectroscopy, Fourier Transform Infrared; Microscopy, Electron, Transmission; X-Ray Diffraction; Spectrum Analysis, Raman; Female; Durapatite; Middle Aged; Male; Calcium Chelating Agents
PubMed: 38778407
DOI: 10.1186/s13075-024-03324-7 -
Journal of the Mechanical Behavior of... Aug 2024This study aimed to produces and characterize bovine hydroxyapatite (HA) bioceramic with 3Y-TZP addition and analyze different sintering curves. HA was extracted from...
This study aimed to produces and characterize bovine hydroxyapatite (HA) bioceramic with 3Y-TZP addition and analyze different sintering curves. HA was extracted from bovine bones and nanoparticulated. HA discs (0, 1, 5 and 10 wt% 3Y-TZP) were subjected to uniaxial and isostatic pressing. Dilatometry analysis was performed and the groups were sintered using 3 different firing curves (conventional, 1300 °C; 2-step, 1292 °C; 2-step, 1420 °C). The samples were analyzed by X-ray diffraction (XRD), biaxial flexural strength (BFS), Vickers microhardness (VH) and Field emission scanning electron microscopy (FE-SEM). The dilatometry results signaled the need for sintering optimization in groups added with 3Y-TZP. XRD demonstrated the characteristic crystallographic peaks of HA in the pure groups and with 1% 3Y-TZP, and decomposition of HA into β-TCP and formation of calcium zirconate in the groups with 5 and 10% 3Y-TZP. Considering each composition, the groups of pure HA (131.3 ± 13.5 MPa; 401 ± 12.7 GPa) sintered by the conventional curve and HA+1%3Y-TZP (145 ± 8.6 MPa; 507 ± 47.9 GPa), HA+5%3Y-TZP (68.1 ± 14.2 MPa; 183 ± 9.8 GPa) and HA+10%3Y-TZP (55.6 ± 5.1 MPa; 96.1 ± 7.64 GPa) sintered by the 2-step curve at 1420 °C, combined the best BFS and VH results. The addition of 1 wt% 3Y-TZP and optimization in the sintering process improved the mechanical and microstructural properties of HA bioceramics and maintenance of its crystalline characteristics. Refinement in material processing is necessary for the future use of this bioceramic in dentistry.
Topics: Animals; Durapatite; Zirconium; Cattle; Yttrium; Ceramics; Materials Testing; Hardness; Biocompatible Materials; Mechanical Phenomena
PubMed: 38776741
DOI: 10.1016/j.jmbbm.2024.106569 -
Brazilian Dental Journal 2024This study aimed to evaluate the osteogenic potential of hydroxyapatite (HA), Alginate (Alg), and Gelatine (Gel) composite in a critical-size defect model in rats....
This study aimed to evaluate the osteogenic potential of hydroxyapatite (HA), Alginate (Alg), and Gelatine (Gel) composite in a critical-size defect model in rats. Twenty-four male rats were divided into three groups: a negative control with no treatment (Control group), a positive control treated with deproteinized bovine bone mineral (DBBM group), and the experimental group treated with the new HA-Alg-Gel composite (HA-Alg-Gel group). A critical size defect (8.5mm) was made in the rat's calvaria, and the bone formation was evaluated by in vivo microcomputed tomography analysis (µCT) after 1, 15, 45, and 90 days. After 90 days, the animals were euthanized and histological and histomorphometric analyses were performed. A higher proportion of mineralized tissue/biomaterial was observed in the DBBM group when compared to the HA-Alg-Gel and Control groups in the µCT analysis during all analysis periods. However, no differences were observed in the mineralized tissue/biomaterial proportion observed on day 1 (immediate postoperative) in comparison to later periods of analysis in all groups. In the histomorphometric analysis, the HA-Alg-Gel and Control groups showed higher bone formation than the DBBM group. Moreover, in histological analysis, five samples of the HA-Alg-Gal group exhibited formed bone spicules adjacent to the graft granules against only two of eight samples in the DBBM group. Both graft materials ensured the maintenance of defect bone thickness, while a tissue thickness reduction was observed in the control group. In conclusion, this study demonstrated the osteoconductive potential of HA-Alg-Gel bone graft by supporting new bone formation around its particles.
Topics: Animals; Alginates; Gelatin; Bone Regeneration; Durapatite; Skull; Rats; Male; X-Ray Microtomography; Biocompatible Materials; Glucuronic Acid; Rats, Wistar; Hexuronic Acids; Osteogenesis; Bone Substitutes
PubMed: 38775590
DOI: 10.1590/0103-6440202405461 -
Journal of Biomedical Materials... Jun 2024This study reports the synthesis and characterization of hydroxyapatite (HA)-based bio-composites reinforced with varying amounts (by weight, 1-15 wt.%) of bio-medium...
This study reports the synthesis and characterization of hydroxyapatite (HA)-based bio-composites reinforced with varying amounts (by weight, 1-15 wt.%) of bio-medium entropy alloy (BioMEA) for load-bearing implant applications. BioMEA powders consisting of Ti, Nb, Zr, and Mo were mechanically alloyed for 100 h and subsequently added to HA using powder metallurgy techniques. To show the effect of BioMEA, the microstructure, density, and mechanical tests have been conducted and the synthesized BioMEA was characterized by scanning electron microscope (SEM), x-ray diffractometer (XRD), and Fourier-transform infrared spectroscopy (FTIR) analysis. In addition, in vitro degradation behavior and bioactivity analyses of bio-composites have been conducted. XRD analysis revealed the formation of BioMEA after 20 h of mechanical alloying. The highest density value of 2.47 g/cm was found in 15 wt.% BioMEA-reinforced bio-composite. The addition of BioMEA reinforcement led to a significant increase in hardness and tensile strength values, with the highest values observed at 15 wt.% reinforcement. Compression tests demonstrated a significant increase in compressive strength and deformation capability of the bio-composites with the highest values observed at 15 wt.% BioMEA addition. The highest toughness of 7.68 kJ/m was measured in 10 wt.% MEA-reinforced bio-composites. The produced bio-composite materials have an elastic modulus between 3.5-5.5 GPa, which may provide a solution to the stress shielding problems caused by the high elastic modulus of metallic implant materials. The most severe degradation occurred in 15 wt.% MEA-reinforced bio-composites, and the effect of degradation caused a decrease in Ca and an increase in Ti-Ni-Zr-Mo in all bio-composites. These findings suggest that HA/BioMEA bio-composites have the potential to be developed as advanced biomaterials with moderate mechanical and biological properties for load-bearing implant applications.
Topics: Materials Testing; Zirconium; Durapatite; Alloys; Titanium; Entropy; Niobium; Biocompatible Materials
PubMed: 38773744
DOI: 10.1002/jbm.b.35415 -
International Journal of Biological... Jun 2024The salient gelling feature of alginate via forming the egg-box structure with calcium ions has received extensive interests for different applications. Owing to the...
The salient gelling feature of alginate via forming the egg-box structure with calcium ions has received extensive interests for different applications. Owing to the interfacial incompatibility of rigid inorganic solids with soft polymers, the requirement of overall stereocomplexation with calcium released from uniformly distributed solids in alginate remains a challenge. In this study, a novel alginate-incorporated calcium source was proposed to tackle the intractable dispersion for the preparation of injectable alginate hydrogels. Calcium phosphate synthesis in alginate solution yielded CaP-alginate hybrids as a calcium source. The physicochemical characterization confirmed the CaP-alginate hybrid was a nano-scale alginate-hydroxyapatite complex. The colloidally stable CaP-alginate hybrids were uniformly dispersed in alginate solutions even under centrifugation. The calcium-induced gelling of the CaP-alginate hybrids-loaded alginate solutions formed soft yet tough hydrogels including transparent sheets and knittable threads, confirming the homogeneous gelation of the hydrogel. The gelation time, injectability and mechanical properties of the hydrogels could be adjusted by changing preparation parameters. The prepared hydrogels showed uniform porous structure, excellent swelling, wetting properties and cytocompatibility, showing a great potential for applications in different fields. The present strategy with organic/inorganic hybridization could be exemplarily followed in the future development of functional hydrogels especially associated with the interface integration.
Topics: Hydrogels; Alginates; Durapatite; Biocompatible Materials; Injections; Animals; Mechanical Phenomena; Mice
PubMed: 38772458
DOI: 10.1016/j.ijbiomac.2024.132458 -
Biomaterials Advances Jul 2024This study investigates the safety and efficacy of 3D-printed polycaprolactone/hydroxyapatite (PCL/HA) scaffolds for patient-specific cranioplasty surgeries, employing...
A comprehensive bench-to-bed look into the application of gamma-sterilized 3D-printed polycaprolactone/hydroxyapatite implants for craniomaxillofacial defects, an in vitro, in vivo, and clinical study.
This study investigates the safety and efficacy of 3D-printed polycaprolactone/hydroxyapatite (PCL/HA) scaffolds for patient-specific cranioplasty surgeries, employing liquid deposition modeling (LDM) technology. This research is pioneering as it explores the impact of gamma radiation on PCL/HA scaffolds and utilizes printing ink with the highest content of HA known in the composite. The mechanical, morphological, and macromolecular stability of the gamma-sterilized scaffolds were verified before implantation. Subsequent research involving animal subjects was conducted to explore the effects of sterilized implants. Eventually, three clinical cases were selected for the implantation studies as part of a phase 1 non-randomized open-label clinical trial. It was shown that a 25 kGy gamma-ray dose for sterilizing the printed implants did not alter the required geometrical precision of the printed implants. The implants exhibited well-distributed HA and strength comparable to cancellous bone. Gamma radiation reduced hydrophobicity and water uptake capacity without inducing pyrogenic or inflammatory responses. Personalized PCL/HA substitutes successfully treated various craniomaxillofacial defects, including trauma-induced facial asymmetry and congenital deformities. HA nanoparticles in the ink stimulated significant osteoconductive responses within three months of implantation. Moreover, the results revealed that while larger implants may exhibit a slower bone formation response in comparison to smaller implants, they generally had an acceptable rate and volume of bone formation. This clinical trial suggests the application of a sterilized PCL/HA composite for craniomaxillofacial surgery is safe and could be considered as a substitute for autologous bone.
Topics: Printing, Three-Dimensional; Durapatite; Gamma Rays; Humans; Polyesters; Animals; Sterilization; Male; Female; Tissue Scaffolds; Prostheses and Implants; Adult; Bone Substitutes
PubMed: 38772132
DOI: 10.1016/j.bioadv.2024.213900