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Bioceramics and Bioactive Glass-Based Composites

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced and Functional Ceramics and Glasses".

Deadline for manuscript submissions: closed (20 April 2023) | Viewed by 26530

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Dr. Tatiana Safronova

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Lomonosov Moscow State University, Moscow, Russia
Interests: inorganic materials science; solid-state chemistry; ceramics; biomaterials
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Dear Colleagues,

Biocompatible inorganic materials are most often used for the compensation and treatment of bone defects. Such materials are obtained using technologies of ceramics, cements, glasses, and glass–ceramics. Systems of oxides which are inert to the body's environment or oxide systems of metal and elements present in bone tissue are considered for the creation of biocompatible inorganic materials.

The phase composition of inorganic materials is a reliable tool for managing the key properties of composites in these systems. Biocompatible, inert, and nonresorbable materials are needed to replace lost bone tissue for a long period of time.

Biocompatible biodegradable materials are necessary for the development of modern regenerative methods of treatment involving the promotion of the self-healing of bone tissue. The development of advanced inorganic materials for medical purposes involves research related to the creation of powder precursors for bioceramics, bio-cement stone, and bioactive-glass-based composites.

Such a characteristic of inorganic biomaterials as osteoconductivity involves the creation of a material not only of an acceptable chemical and phase composition, but with a given porosity. Methods for creating a porous structure in inorganic materials for bone tissue engineering are in constant development. Evaluation of the applicability of new materials in medicine involves the use of in vitro and in vivo tests. Thus, this Special Issue will be devoted to various aspects of the creation of new materials designed to compensate and treat bone defects, including the synthesis and preparation of powder systems; the creation of dense and porous ceramic, cement, glass, and glass–ceramic materials; as well as the assessment of the biocompatibility and bioactivity of these materials and their ability to support bone regeneration.

Dr. Tatiana Safronova
Guest Editor

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Keywords

biocompatible inorganic materials
bioceramics
bone cements
bioglass
biocomposites
bone implants
osteoinductive materials
osteoconductive materials
bone tissue engineering

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Published Papers (10 papers)

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Research

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16 pages, 5237 KiB

Open AccessArticle

Zn-Doped Calcium Magnesium Phosphate Bone Cement Based on Struvite and Its Antibacterial Properties

by Polina A. Krokhicheva, Margarita A. Goldberg, Alexander S. Fomin, Dinara R. Khayrutdinova, Olga S. Antonova, Alexander S. Baikin, Aleksander V. Leonov, Ekaterina M. Merzlyak, Ivan V. Mikheev, Valentina A. Kirsanova, Irina K. Sviridova, Suraya A. Akhmedova, Natalia S. Sergeeva, Sergey M. Barinov and Vladimir S. Komlev

Materials 2023, 16(13), 4824; https://doi.org/10.3390/ma16134824 - 4 Jul 2023

Cited by 4 | Viewed by 2475

Abstract

The development of magnesium calcium phosphate bone cements (MCPCs) has garnered substantial attention. MCPCs are bioactive and biodegradable and have appropriate mechanical and antimicrobial properties for use in reconstructive surgery. In this study, the cement powders based on a (Ca + Mg)/P = 2 system doped with Zn²⁺ at 0.5 and 1.0 wt.% were obtained and investigated. After mixing with a cement liquid, the structural and phase composition, morphology, chemical structure, setting time, compressive strength, degradation behavior, solubility, antibacterial activities, and in vitro behavior of the cement materials were examined. A high compressive strength of 48 ± 5 MPa (mean ± SD) was achieved for the cement made from Zn²⁺ 1.0 wt.%-substituted powders. Zn²⁺ introduction led to antibacterial activity against Staphylococcus aureus and Escherichia coli strains, with an inhibition zone diameter of up to 8 mm. Biological assays confirmed that the developed cement is cytocompatible and promising as a potential bone substitute in reconstructive surgery. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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19 pages, 7467 KiB

Open AccessArticle

Three-Dimensional-Printed Molds from Water-Soluble Sulfate Ceramics for Biocomposite Formation through Low-Pressure Injection Molding

by Daniil Golubchikov, Pavel Evdokimov, Dmitry Zuev, Yaroslav Filippov, Tatiana Shatalova and Valery Putlayev

Materials 2023, 16(8), 3077; https://doi.org/10.3390/ma16083077 - 13 Apr 2023

Cited by 1 | Viewed by 1637

Abstract

Powder mixtures of MgSO₄ with 5–20 mol.% Na₂SO₄ or K₂SO₄ were used as precursors for making water-soluble ceramic molds to create thermoplastic polymer/calcium phosphate composites by low pressure injection molding. To increase the strength of the ceramic molds, 5 wt.% of tetragonal ZrO₂ (Y₂O₃-stabilized) was added to the precursor powders. A uniform distribution of ZrO₂ particles was obtained. The average grain size for Na-containing ceramics ranged from 3.5 ± 0.8 µm for MgSO₄/Na₂SO₄ = 91/9% to 4.8 ± 1.1 µm for MgSO₄/Na₂SO₄ = 83/17%. For K-containing ceramics, the values were 3.5 ± 0.8 µm for all of the samples. The addition of ZrO₂ made a significant contribution to the strength of ceramics: for the MgSO₄/Na₂SO₄ = 83/17% sample, the compressive strength increased by 49% (up to 6.7 ± 1.3 MPa), and for the stronger MgSO₄/K₂SO₄ = 83/17% by 39% (up to 8.4 ± 0.6 MPa). The average dissolution time of the ceramic molds in water did not exceed 25 min. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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21 pages, 2835 KiB

Open AccessEditor’s ChoiceArticle

Investigation of Multicomponent Fluoridated Borate Glasses through a Design of Mixtures Approach

by Kathleen MacDonald and Daniel Boyd

Materials 2022, 15(18), 6247; https://doi.org/10.3390/ma15186247 - 8 Sep 2022

Cited by 4 | Viewed by 1973

Abstract

Due to their enhanced dissolution, solubility and reaction speed, borate glasses offer potential advantages for the design and development of therapeutic ion-release systems. However, the field remains poorly understood relative to traditional phosphosilicate and silicate bioglasses. The increased structural complexity and relative lack of published data relating to borates, particularly borofluorates, also decreases the accuracy of artificial intelligence models, which are used to predict glass properties. To develop predictive models for borofluorate networks, this paper uses a design of mixtures approach for rapid screening of composition–property relationships, including the development of polynomial equations that comprehensively establish the predictive capabilities for glass transition, density, mass loss and fluoride release. A broad range of glass compositions, extending through the boron anomaly range, were investigated, with the inclusion of 45 to 95 mol% B₂O₃ along with 1–50 mol% MgO, CaO and Na₂O as well as 1–30% KF and NaF. This design space allows for the investigation of the impact of fluorine as well as mixed alkali–alkaline earth effects. Glass formation was found to extend past 30 mol% KF or NaF without a negative impact on glass degradation in contrast to the trends observed in phosphosilicates. The data demonstrates that fluoroborate materials offer an exceptional base for the development of fluoride-releasing materials. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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20 pages, 4669 KiB

Open AccessArticle

Mn-Containing Bioactive Glass-Ceramics: BMP-2-Mimetic Peptide Covalent Grafting Boosts Human-Osteoblast Proliferation and Mineral Deposition

by Leonardo Cassari, Paola Brun, Michele Di Foggia, Paola Taddei, Annj Zamuner, Antonella Pasquato, Adriana De Stefanis, Veronica Valentini, Vicentiu Mircea Saceleanu, Julietta V. Rau and Monica Dettin

Materials 2022, 15(13), 4647; https://doi.org/10.3390/ma15134647 - 1 Jul 2022

Cited by 10 | Viewed by 2106

Abstract

The addition of Mn in bioceramic formulation is gaining interest in the field of bone implants. Mn activates human osteoblast (h-osteoblast) integrins, enhancing cell proliferation with a dose-dependent effect, whereas Mn-enriched glasses induce inhibition of Gram-negative or Gram-positive bacteria and fungi. In an effort to further optimize Mn-containing scaffolds’ beneficial interaction with h-osteoblasts, a selective and specific covalent functionalization with a bioactive peptide was carried out. The anchoring of a peptide, mapped on the BMP-2 wrist epitope, to the scaffold was performed by a reaction between an aldehyde group of the peptide and the aminic groups of silanized Mn-containing bioceramic. SEM-EDX, FT-IR, and Raman studies confirmed the presence of the peptide grafted onto the scaffold. In in vitro assays, a significant improvement in h-osteoblast proliferation, gene expression, and calcium salt deposition after 7 days was detected in the functionalized Mn-containing bioceramic compared to the controls. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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23 pages, 7835 KiB

Open AccessArticle

Bioceramics Based on β-Calcium Pyrophosphate

by Tatiana Safronova, Andrey Kiselev, Irina Selezneva, Tatiana Shatalova, Yulia Lukina, Yaroslav Filippov, Otabek Toshev, Snezhana Tikhonova, Olga Antonova and Alexander Knotko

Materials 2022, 15(9), 3105; https://doi.org/10.3390/ma15093105 - 25 Apr 2022

Cited by 12 | Viewed by 2810

Abstract

Ceramic samples based on β-calcium pyrophosphate β-Ca₂P₂O₇ were prepared from powders of γ-calcium pyrophosphate γ-Ca₂P₂O₇ with preset molar ratios Ca/P = 1, 0.975 and 0.95 using firing at 900, 1000, and 1100 °C. Calcium lactate pentahydrate Ca(C₃H₅O₃)₂⋅5H₂O and monocalcium phosphate monohydrate Ca(H₂PO₄)₂⋅H₂O were treated in an aqua medium in mechanical activation conditions to prepare powder mixtures with preset molar ratios Ca/P containing calcium hydrophosphates with Ca/P = 1 (precursors of calcium pyrophosphate Ca₂P₂O₇). These powder mixtures containing calcium hydrophosphates with Ca/P = 1 and non-reacted starting salts were heat-treated at 600 °C after drying and disaggregation in acetone. Phase composition of all powder mixtures after heat treatment at 600 °C was presented by γ-calcium pyrophosphate γ-Ca₂P₂O₇ according to the XRD data. The addition of more excess of monocalcium phosphate monohydrate Ca(H₂PO₄)₂·H₂O (with appropriate molar ratio of Ca/P = 1) to the mixture of starting components resulted in lower dimensions of γ-calcium pyrophosphate (γ-Ca₂P₂O₇) individual particles. The grain size of ceramics increased both with the growth in firing temperature and with decreasing molar ratio Ca/P of powder mixtures. Calcium polyphosphate (t _melt = 984 °C), formed from monocalcium phosphate monohydrate Ca(H₂PO₄)₂⋅H₂O, acted similar to a liquid phase sintering additive. It was confirmed by tests in vitro that prepared ceramic materials with preset molar ratios Ca/P = 1, 0.975, and 0.95 and phase composition presented by β-calcium pyrophosphate β-Ca₂P₂O₇ were biocompatible and could maintain bone cells proliferation. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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12 pages, 2431 KiB

Open AccessArticle

Performance of Calcium Phosphate Cements in the Augmentation of Sheep Vertebrae—An Ex Vivo Study

by Raimund W. Kinne, Francesca Gunnella, Elke Kunisch, Sascha Heinemann, Berthold Nies, Stefan Maenz, Victoria Horbert, Bernhard Illerhaus, René Huber, Izabela Firkowska-Boden, Jörg Bossert, Klaus D. Jandt, André Sachse, Matthias Bungartz and Olaf Brinkmann

Materials 2021, 14(14), 3873; https://doi.org/10.3390/ma14143873 - 12 Jul 2021

Cited by 4 | Viewed by 2698

Abstract

Oil-based calcium phosphate cement (Paste-CPC) shows not only prolonged shelf life and injection times, but also improved cohesion and reproducibility during application, while retaining the advantages of fast setting, mechanical strength, and biocompatibility. In addition, poly(L-lactide-co-glycolide) (PLGA) fiber reinforcement may decrease the risk for local extrusion. Bone defects (diameter 5 mm; depth 15 mm) generated ex vivo in lumbar (L) spines of female Merino sheep (2–4 years) were augmented using: (i) water-based CPC with 10% PLGA fiber reinforcement (L3); (ii) Paste-CPC (L4); or (iii) clinically established polymethylmethacrylate (PMMA) bone cement (L5). Untouched (L1) and empty vertebrae (L2) served as controls. Cement performance was analyzed using micro-computed tomography, histology, and biomechanical testing. Extrusion was comparable for Paste-CPC(-PLGA) and PMMA, but significantly lower for CPC + PLGA. Compressive strength and Young’s modulus were similar for Paste-CPC and PMMA, but significantly higher compared to those for empty defects and/or CPC + PLGA. Expectedly, all experimental groups showed significantly or numerically lower compressive strength and Young’s modulus than those of untouched controls. Ready-to-use Paste-CPC demonstrates a performance similar to that of PMMA, but improved biomechanics compared to those of water-based CPC + PLGA, expanding the therapeutic arsenal for bone defects. O, significantly lower extrusion of CPC + PLGA fibers into adjacent lumbar spongiosa may help to reduce the risk of local extrusion in spinal surgery. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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17 pages, 22413 KiB

Open AccessArticle

Tetracalcium Phosphate/Monetite/Calcium Sulfate Hemihdrate Biocement Powder Mixtures Prepared by the One-Step Synthesis for Preparation of Nanocrystalline Hydroxyapatite Biocement-Properties and In Vitro Evaluation

by Lubomir Medvecky, Maria Giretova, Radoslava Stulajterova, Lenka Luptakova and Tibor Sopcak

Materials 2021, 14(9), 2137; https://doi.org/10.3390/ma14092137 - 22 Apr 2021

Cited by 10 | Viewed by 2737

Abstract

A modified one-step process was used to prepare tetracalcium phosphate/monetite/calcium sulfate hemihydrate powder cement mixtures (CAS). The procedure allowed the formation of monetite and calcium sulfate hemihydrate (CSH) in the form of nanoparticles. It was hypothesized that the presence of nanoCSH in small amounts enhances the in vitro bioactivity of CAS cement in relation to osteogenic gene markers in mesenchymal stem cells (MSCs). The CAS powder mixtures with 15 and 5 wt.% CSH were prepared by milling powder tetracalcium phosphate in an ethanolic solution of both orthophosphoric and sulfuric acids. The CAS cements had short setting times (around 5 min). The fast setting of the cement samples after the addition of the liquid component (water solution of NaH₂PO₄) was due to the partial formation of calcium sulfate dihydrate and hydroxyapatite before soaking in SBF with a small change in the original phase composition in cement powder samples after milling. Nanocrystalline hydroxyapatite biocement was produced by soaking of cement samples after setting in simulated body fluid (SBF). The fast release of calcium ions from CAS5 cement, as well as a small rise in the pH of SBF during soaking, were demonstrated. After soaking in SBF for 7 days, the final product of the cement transformation was nanocrystalline hydroxyapatite. The compressive strength of the cement samples (up to 30 MPa) after soaking in simulated body fluid (SBF) was comparable to that of bone. Real time polymerase chain reaction (RT-PCR) analysis revealed statistically significant higher gene expressions of alkaline phosphatase (ALP), osteonectin (ON) and osteopontin (OP) in cells cultured for 14 days in CAS5 extract compared to CSH-free cement. The addition of a small amount of nanoCSH (5 wt.%) to the tetracalcium phosphate (TTCP)/monetite cement mixture significantly promoted the over expression of osteogenic markers in MSCs. The prepared CAS powder mixture with its enhanced bioactivity can be used for bone defect treatment and has good potential for bone healing. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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23 pages, 11279 KiB

Open AccessFeature PaperArticle

The Influence of Co Additive on the Sintering, Mechanical Properties, Cytocompatibility, and Digital Light Processing Based Stereolithography of 3Y-TZP-5Al₂O₃ Ceramics

by Margarita Goldberg, Tatiana Obolkina, Sergey Smirnov, Pavel Protsenko, Dmitriy Titov, Olga Antonova, Anatoliy Konovalov, Egor Kudryavtsev, Irina Sviridova, Valentina Kirsanova, Natalia Sergeeva, Vladimir Komlev and Sergey Barinov

Materials 2020, 13(12), 2789; https://doi.org/10.3390/ma13122789 - 20 Jun 2020

Cited by 13 | Viewed by 3065

Abstract

Nanocrystalline 3 mol% yttria-tetragonal zirconia polycrystal (3Y-TZP) ceramic powder containing 5 wt.% Al₂O₃ with 64 m²/g specific area was synthesized through precipitation method. Different amounts of Co (0–3 mol%) were introduced into synthesized powders, and ceramic materials were obtained by heat treatment in the air for 2 h at 1350–1550 °C. The influence of Co addition on the sintering temperature, phase composition, microstructure, mechanical and biomedical properties of the obtained composite materials, and on the resolution of the digital light processing (DLP) printed and sintered ceramic samples was investigated. The addition of a low amount of Co (0.33 mol%) allows us to decrease the sintering temperature, to improve the mechanical properties of ceramics, to preserve the nanoscale size of grains at 1350–1400 °C. The further increase of Co concentration resulted in the formation of both substitutional and interstitial sites in solid solution and appearance of CoAl₂O₄ confirmed by UV-visible spectroscopy, which stimulates grain growth. Due to the prevention of enlarging grains and to the formation of the dense microstructure in ceramic based on the tetragonal ZrO₂ and Al₂O₃ with 0.33 mol% Co the bending strength of 720 ± 33 MPa was obtained after sintering at 1400 °C. The obtained materials demonstrated the absence of cytotoxicity and good cytocompatibility. The formation of blue CoAl₂O₄ allows us to improve the resolution of DLP based stereolithographic printed green bodies and sintered samples of the ceramics based on ZrO₂-Al₂O₃. The developed materials and technology could be the basis for 3D manufacturing of bioceramic implants for medicine. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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24 pages, 1048 KiB

Open AccessReview

Materials in the Na₂O–CaO–SiO₂–P₂O₅ System for Medical Applications

by Maksim R. Kaimonov and Tatiana V. Safronova

Materials 2023, 16(17), 5981; https://doi.org/10.3390/ma16175981 - 31 Aug 2023

Cited by 3 | Viewed by 1308

Abstract

Calcium phosphate materials and materials based on silicon dioxide have been actively studied for more than 50 years due to their high biocompatibility and bioactivity. Hydroxyapatite and tricalcium phosphate are the most known among calcium phosphate materials, and Bioglass 45S5 is the most known material in the Na₂O–CaO–SiO₂–P₂O₅ system. Each of these materials has its application limits; however, some of them can be eliminated by obtaining composites based on calcium phosphate and bioglass. In this article, we provide an overview of the role of silicon and its compounds, including Bioglass 45S5, consider calcium phosphate materials, talk about the limits of each material, demonstrate the potential of the composites based on them, and show the other ways of obtaining composite ceramics in the Na₂O–CaO–SiO₂–P₂O₅ system. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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16 pages, 1949 KiB

Open AccessReview

Resorbable Mg²⁺-Containing Phosphates for Bone Tissue Repair

by Gilyana Kazakova, Tatiana Safronova, Daniil Golubchikov, Olga Shevtsova and Julietta V. Rau

Materials 2021, 14(17), 4857; https://doi.org/10.3390/ma14174857 - 26 Aug 2021

Cited by 45 | Viewed by 4323

Abstract

Materials based on Mg²⁺-containing phosphates are gaining great relevance in the field of bone tissue repair via regenerative medicine methods. Magnesium ions, together with condensed phosphate ions, play substantial roles in the process of bone remodeling, affecting the early stage of bone regeneration through active participation in the process of osteosynthesis. In this paper we provide a comprehensive overview of the usage of biomaterials based on magnesium phosphate and magnesium calcium phosphate in bone reconstruction. We consider the role of magnesium ions in angiogenesis, which is an important process associated with osteogenesis. Finally, we summarize the biological properties of calcium magnesium phosphates for regeneration of bone. Full article

(This article belongs to the Special Issue Bioceramics and Bioactive Glass-Based Composites)

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