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Biomaterials Based on Calcium Phosphates and Their Modifications

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 31 March 2025 | Viewed by 8394

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Special Issue Editors

Prof. Dr. Aneta Zima

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Guest Editor

Department of Ceramics and Refractories, AGH University of Science & Technology, Al. Mickiewicza 30, 30-059 Krakow, Poland
Interests: bioceramics; calcium phosphates; bone cements; composites; hybrid materials; chitosan; pectins; tissue engineering
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Dr. Ewelina Cichoń

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Guest Editor

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Krakow, Poland
Interests: calcium phosphates; surfactants; biopolymers; functionalization; composites; biomaterials; bioceramics; polyhydroxyalkanoates

Dr. Joanna Czechowska

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Guest Editor

Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Mickiewicza 30, 30-059 Krakow, Poland
Interests: calcium phosphates; biopolymers; composites; hybrid materials; biomaterials; bioceramics; therapeutic ions

Special Issue Information

Dear Colleagues,

As Guest Editors of a Special Issue entitled ‘Biomaterials Based on Calcium Phosphates and Their Modifications‘ (IF=4.6; 140 points of Polish MNiSW), we encourage you to submit your review and original research articles.

In the last decade, the use of calcium phosphate bioceramics (CaPs) in clinical practice has significantly increased. Much attention is paid to the modification of such materials on both the chemical and physical level. Apart from the functionalization of CaPs with various biologically active ions and nanoparticles, their surface modifications have also been explored. Furthermore, many chemically bonded biomaterials, composites, scaffolds and hybrids based on calcium phosphates have been developed. Thus, this Special Issue is dedicated to research and review papers tackling the problems of novel calcium phosphate-based biomaterials for medical and biomedical engineering applications, as well as their modifications.

Prof. Dr. Aneta Zima
Dr. Ewelina Cichoń
Dr. Joanna Czechowska
Guest Editors

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Keywords

calcium phosphates
bone cements
scaffolds
hybrid materials
composites

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Published Papers (5 papers)

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Research

19 pages, 6461 KiB

Open AccessArticle

Effect of the Addition of Inorganic Fillers on the Properties of Degradable Polymeric Blends for Bone Tissue Engineering

by Stanisław Marecik, Iwona Pudełko-Prażuch, Mareeswari Balasubramanian, Sundara Moorthi Ganesan, Suvro Chatterjee, Kinga Pielichowska, Ravichandran Kandaswamy and Elżbieta Pamuła

Molecules 2024, 29(16), 3826; https://doi.org/10.3390/molecules29163826 - 12 Aug 2024

Viewed by 818

Abstract

Bone tissue exhibits self-healing properties; however, not all defects can be repaired without surgical intervention. Bone tissue engineering offers artificial scaffolds, which can act as a temporary matrix for bone regeneration. The aim of this study was to manufacture scaffolds made of poly(lactic acid), poly(ε-caprolactone), poly(propylene fumarate), and poly(ethylene glycol) modified with bioglass, beta tricalcium phosphate (TCP), and/or wollastonite (W) particles. The scaffolds were fabricated using a gel-casting method and observed with optical and scanning electron microscopes. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), wettability, and degradation tests were conducted. The highest content of TCP without W in the composition caused the highest hydrophilicity (water contact angle of 61.9 ± 6.3°), the fastest degradation rate (7% mass loss within 28 days), moderate ability to precipitate CaP after incubation in PBS, and no cytotoxicity for L929 cells. The highest content of W without TCP caused the highest hydrophobicity (water contact angle of 83.4 ± 1.7°), the lowest thermal stability, slower degradation (3% mass loss within 28 days), and did not evoke CaP precipitation. Moreover, some signs of cytotoxicity on day 1 were observed. The samples with both TCP and W showed moderate properties and the best cytocompatibility on day 4. Interestingly, they were covered with typical cauliflower-like hydroxyapatite deposits after incubation in phosphate-buffered saline (PBS), which might be a sign of their excellent bioactivity. Full article

(This article belongs to the Special Issue Biomaterials Based on Calcium Phosphates and Their Modifications)

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15 pages, 3410 KiB

Open AccessArticle

Physicochemical Properties of Inorganic and Hybrid Hydroxyapatite-Based Granules Modified with Citric Acid or Polyethylene Glycol

by Ewelina Cichoń, Karolina Kosowska, Piotr Pańtak, Joanna P. Czechowska, Aneta Zima and Anna Ślósarczyk

Molecules 2024, 29(9), 2018; https://doi.org/10.3390/molecules29092018 - 27 Apr 2024

Viewed by 932

Abstract

This study delves into the physicochemical properties of inorganic hydroxyapatite (HAp) and hybrid hydroxyapatite–chitosan (HAp-CTS) granules, also gold-enriched, which can be used as aggregates in biomicroconcrete-type materials. The impact of granules’ surface modifications with citric acid (CA) or polyethylene glycol (PEG) was assessed. Citric acid modification induced increased specific surface area and porosity in inorganic granules, contrasting with reduced parameters in hybrid granules. PEG modification resulted in a slight increase in specific surface area for inorganic granules and a substantial rise for hybrid granules with gold nanoparticles. Varied effects on open porosity were observed based on granule type. Microstructural analysis revealed increased roughness for inorganic granules post CA modification, while hybrid granules exhibited smoother surfaces. Novel biomicroconcretes, based on α-tricalcium phosphate (α-TCP) calcium phosphate cement and developed granules as aggregates within, were evaluated for compressive strength. Compressive strength assessments showcased significant enhancement with PEG modification, emphasizing its positive impact. Citric acid modification demonstrated variable effects, depending on granule composition. The incorporation of gold nanoparticles further enriched the multifaceted approach to enhancing calcium phosphate-based biomaterials for potential biomedical applications. This study demonstrates the pivotal role of surface modifications in tailoring the physicochemical properties of granules, paving the way for advanced biomicroconcretes with improved compressive strength for diverse biomedical applications. Full article

(This article belongs to the Special Issue Biomaterials Based on Calcium Phosphates and Their Modifications)

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17 pages, 4547 KiB

Open AccessArticle

New Nano-Crystalline Hydroxyapatite-Polycarboxy/Sulfo Betaine Hybrid Materials: Synthesis and Characterization

by Aránzazu Díaz-Cuenca, Kostadinka Sezanova, Rumiana Gergulova, Diana Rabadjieva and Konstans Ruseva

Molecules 2024, 29(5), 930; https://doi.org/10.3390/molecules29050930 - 21 Feb 2024

Viewed by 1465

Abstract

Hybrid materials based on calcium phosphates and synthetic polymers can potentially be used for caries protection due to their similarity to hard tissues in terms of composition, structure and a number of properties. This study is focused on the biomimetic synthesis of hybrid materials consisting of hydroxiapatite and the zwitterionic polymers polysulfobetaine (PSB) and polycarboxybetaine (PCB) using controlled media conditions with a constant pH of 8.0–8.2 and Ca/P = 1.67. The results show that pH control is a dominant factor in the crystal phase formation, so nano-crystalline hydroxyapatite with a Ca/P ratio of 1.63–1.71 was observed as the mineral phase in all the materials prepared. The final polymer content measured for the synthesized hybrid materials was 48–52%. The polymer type affects the final microstructure, and the mineral particle size is thinner and smaller in the synthesis performed using PCB than using PSB. The final intermolecular interaction of the nano-crystallized hydroxyapatite was demonstrated to be stronger with PCB than with PSB as shown by our IR and Raman spectroscopy analyses. The higher remineralization potential of the PCB-containing synthesized material was demonstrated by in vitro testing using artificial saliva. Full article

(This article belongs to the Special Issue Biomaterials Based on Calcium Phosphates and Their Modifications)

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15 pages, 6572 KiB

Open AccessArticle

Optimization of the Composition of Mesoporous Polymer–Ceramic Nanocomposite Granules for Bone Regeneration

by Marta Trzaskowska, Vladyslav Vivcharenko, Wojciech Franus, Tomasz Goryczka, Adrian Barylski and Agata Przekora

Molecules 2023, 28(13), 5238; https://doi.org/10.3390/molecules28135238 - 6 Jul 2023

Cited by 2 | Viewed by 1926

Abstract

Difficult-to-treat bone damage resulting from metabolic bone diseases, mechanical injuries, or tumor resection requires support in the form of biomaterials. The aim of this research was to optimize the concentration of individual components of polymer–ceramic nanocomposite granules (nanofilled polymer composites) for application in orthopedics and maxillofacial surgery to fill small bone defects and stimulate the regeneration process. Two types of granules were made using nanohydroxyapatite (nanoHA) and chitosan-based matrix (agarose/chitosan or curdlan/chitosan), which served as binder for ceramic nanopowder. Different concentrations of the components (nanoHA and curdlan), foaming agent (sodium bicarbonate—NaHCO₃), and chitosan solvent (acetic acid—CH₃COOH) were tested during the production process. Agarose and chitosan concentrations were fixed to be 5% w/v and 2% w/v, respectively, based on our previous research. Subsequently, the produced granules were subjected to cytotoxicity testing (indirect and direct contact methods), microhardness testing (Young’s modulus evaluation), and microstructure analysis (porosity, specific surface area, and surface roughness) in order to identify the biomaterial with the most favorable properties. The results demonstrated only slight differences among the resultant granules with respect to their microstructural, mechanical, and biological properties. All variants of the biomaterials were non-toxic to a mouse preosteoblast cell line (MC3T3-E1), supported cell growth on their surface, had high porosity (46–51%), and showed relatively high specific surface area (25–33 m²/g) and Young’s modulus values (2–10 GPa). Apart from biomaterials containing 8% w/v curdlan, all samples were predominantly characterized by mesoporosity. Nevertheless, materials with the greatest biomedical potential were obtained using 5% w/v agarose, 2% w/v chitosan, and 50% or 70% w/v nanoHA when the chitosan solvent/foaming agent ratio was equal to 2:2. In the case of the granules containing curdlan/chitosan matrix, the most optimal composition was as follows: 2% w/v chitosan, 4% w/v curdlan, and 30% w/v nanoHA. The obtained test results indicate that both manufactured types of granules are promising implantable biomaterials for filling small bone defects that can be used in maxillofacial surgery. Full article

(This article belongs to the Special Issue Biomaterials Based on Calcium Phosphates and Their Modifications)

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13 pages, 2731 KiB

Open AccessArticle

Monocyte Differentiation on Atomic Layer-Deposited (ALD) Hydroxyapatite Coating on Titanium Substrate

by Elina Kylmäoja, Faleh Abushahba, Jani Holopainen, Mikko Ritala and Juha Tuukkanen

Molecules 2023, 28(8), 3611; https://doi.org/10.3390/molecules28083611 - 21 Apr 2023

Cited by 1 | Viewed by 2430

Abstract

Hydroxyapatite (HA; Ca₁₀(PO₄)₆(OH)₂) coating of bone implants has many beneficial properties as it improves osseointegration and eventually becomes degraded and replaced with new bone. We prepared HA coating on a titanium substrate with atomic layer deposition (ALD) and compared monocyte differentiation and material resorption between ALD-HA and bone. After stimulation with macrophage colony-stimulating factor (M-CSF) and receptor activator of nuclear factor kappa-B ligand (RANKL), human peripheral blood monocytes differentiated into resorbing osteoclasts on bovine bone, but non-resorbing foreign body cells were observed on ALD-HA. The analysis of the topography of ALD-HA and bone showed no differences in wettability (water contact angle on ALD-HA 86.2° vs. 86.7° on the bone), but the surface roughness of ALD-HA (Ra 0.713 µm) was significantly lower compared to bone (Ra 2.30 µm). The cellular reaction observed on ALD-HA might be a consequence of the topographical properties of the coating. The absence of resorptive osteoclasts on ALD-HA might indicate inhibition of their differentiation or the need to modify the coating to induce osteoclast differentiation. Full article

(This article belongs to the Special Issue Biomaterials Based on Calcium Phosphates and Their Modifications)

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