Applications of Calcium Phosphates-Based Nanostructured Materials and Coatings

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Inorganic Materials and Metal-Organic Frameworks".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 6604

Special Issue Editors


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Guest Editor
Department of Chemistry “Giacomo Ciamician”, Via F. Selmi 2, University of Bologna, I-40126 Bologna, Italy
Interests: biomaterials; biomimetic materials chemistry; bioceramics; nanocrystals; hydroxyapatite; octacalcium phosphate; metal nanoparticles; bioactive coatings
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Guest Editor
Dipartimento di Chimica, Materiali ed Ingegneria Chimica "Giulio Natta", Politecnico di Milano, Via Luigi Mancinelli, 7, 20131 Milan, Italy
Interests: calcium phosphates; nanostructured coatings; biomaterials; infection; 3D printing and bioprinting; orthopaedics; orthopaedic oncology; tissue models; cultural heritage; stone consolidants
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Calcium phosphates have been widely studied in recent decades because they have peculiar properties that make them suitable for a variety of applications.

Furthermore, calcium phosphate-based nanostructured materials have a significant relevance and in addition, they can be easily functionalized with ions, small molecules, polyelectrolytes or drugs, which can significantly alter their physico-chemical, mechanical and/or biological properties. Nanostructuration itself is also important, as it permits the regulation of the dissolution profile, microbial/cells adhesion and (eventually) drug delivery profile.

The aim of this Special Issue is to document the current advances and the future perspectives in the field of calcium phosphates-based nanostructured materials, and their fields of application.

The topics of interest include, but are not limited to, the following:

  • Calcium phosphates in biomedicine and cultural heritage conservation;
  • Synthesis or deposition of calcium phosphate nanostructured coatings and their applications;
  • Functionalized calcium phosphates;
  • Advanced characterization techniques to investigate the properties of the nanostructured materials (composition, morphology, mechanical properties, solubility, crystallinity, ion release in different media, etc.).

Dr. Elisa Boanini
Dr. Gabriela Graziani
Guest Editors

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Published Papers (5 papers)

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Research

17 pages, 5222 KiB  
Article
Incorporation/Enrichment of 3D Bioprinted Constructs by Biomimetic Nanoparticles: Tuning Printability and Cell Behavior in Bone Models
by Tiziana Fischetti, Giorgia Borciani, Sofia Avnet, Katia Rubini, Nicola Baldini, Gabriela Graziani and Elisa Boanini
Nanomaterials 2023, 13(14), 2040; https://doi.org/10.3390/nano13142040 - 10 Jul 2023
Cited by 1 | Viewed by 1065
Abstract
Reproducing in vitro a model of the bone microenvironment is a current need. Preclinical in vitro screening, drug discovery, as well as pathophysiology studies may benefit from in vitro three-dimensional (3D) bone models, which permit high-throughput screening, low costs, and high reproducibility, overcoming [...] Read more.
Reproducing in vitro a model of the bone microenvironment is a current need. Preclinical in vitro screening, drug discovery, as well as pathophysiology studies may benefit from in vitro three-dimensional (3D) bone models, which permit high-throughput screening, low costs, and high reproducibility, overcoming the limitations of the conventional two-dimensional cell cultures. In order to obtain these models, 3D bioprinting offers new perspectives by allowing a combination of advanced techniques and inks. In this context, we propose the use of hydroxyapatite nanoparticles, assimilated to the mineral component of bone, as a route to tune the printability and the characteristics of the scaffold and to guide cell behavior. To this aim, both stoichiometric and Sr-substituted hydroxyapatite nanocrystals are used, so as to obtain different particle shapes and solubility. Our findings show that the nanoparticles have the desired shape and composition and that they can be embedded in the inks without loss of cell viability. Both Sr-containing and stoichiometric hydroxyapatite crystals permit enhancing the printing fidelity of the scaffolds in a particle-dependent fashion and control the swelling behavior and ion release of the scaffolds. Once Saos-2 cells are encapsulated in the scaffolds, high cell viability is detected until late time points, with a good cellular distribution throughout the material. We also show that even minor modifications in the hydroxyapatite particle characteristics result in a significantly different behavior of the scaffolds. This indicates that the use of calcium phosphate nanocrystals and structural ion-substitution is a promising approach to tune the behavior of 3D bioprinted constructs. Full article
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18 pages, 6420 KiB  
Article
Ionized Jet Deposition of Calcium Phosphates-Based Nanocoatings: Tuning Coating Properties and Cell Behavior by Target Composition and Substrate Heating
by Matteo Montesissa, Giorgia Borciani, Katia Rubini, Francesco Valle, Marco Boi, Nicola Baldini, Elisa Boanini and Gabriela Graziani
Nanomaterials 2023, 13(11), 1758; https://doi.org/10.3390/nano13111758 - 29 May 2023
Cited by 3 | Viewed by 1220
Abstract
Calcium phosphate-based coatings are widely studied in orthopedics and dentistry for their similarity to the mineral component of bone and their capability to promote osseointegration. Different calcium phosphates have tunable properties that result in different behaviors in vitro, but the majority of studies [...] Read more.
Calcium phosphate-based coatings are widely studied in orthopedics and dentistry for their similarity to the mineral component of bone and their capability to promote osseointegration. Different calcium phosphates have tunable properties that result in different behaviors in vitro, but the majority of studies focus only on hydroxyapatite. Here, different calcium phosphate-based nanostructured coatings are obtained by ionized jet deposition, starting with hydroxyapatite, brushite and beta-tricalcium phosphate targets. The properties of the coatings obtained from different precursors are systematically compared by assessing their composition, morphology, physical and mechanical properties, dissolution, and in vitro behavior. In addition, for the first time, depositions at high temperature are investigated for the further tuning of the coatings mechanical properties and stability. Results show that different phosphates can be deposited with good composition fidelity even if not in a crystalline phase. All coatings are nanostructured and non-cytotoxic and display variable surface roughness and wettability. Upon heating, higher adhesion and hydrophilicity are obtained as well as higher stability, resulting in better cell viability. Interestingly, different phosphates show very different in vitro behavior, with brushite being the most suitable for promoting cell viability and beta-tricalcium phosphate having a higher impact on cell morphology at the early timepoints. Full article
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22 pages, 5008 KiB  
Article
Toward Smart Biomimetic Apatite-Based Bone Scaffolds with Spatially Controlled Ion Substitutions
by Edoardo Cianflone, Fabien Brouillet, David Grossin, Jérémy Soulié, Claudie Josse, Sanjana Vig, Maria Helena Fernandes, Christophe Tenailleau, Benjamin Duployer, Carole Thouron and Christophe Drouet
Nanomaterials 2023, 13(3), 519; https://doi.org/10.3390/nano13030519 - 28 Jan 2023
Cited by 7 | Viewed by 1974
Abstract
Biomimetic apatites exhibit a high reactivity allowing ion substitutions to modulate their in vivo response. We developed a novel approach combining several bioactive ions in a spatially controlled way in view of subsequent releases to address the sequence of events occurring after implantation, [...] Read more.
Biomimetic apatites exhibit a high reactivity allowing ion substitutions to modulate their in vivo response. We developed a novel approach combining several bioactive ions in a spatially controlled way in view of subsequent releases to address the sequence of events occurring after implantation, including potential microorganisms’ colonization. Innovative micron-sized core-shell particles were designed with an external shell enriched with an antibacterial ion and an internal core substituted with a pro-angiogenic or osteogenic ion. After developing the proof of concept, two ions were particularly considered, Ag+ in the outer shell and Cu2+ in the inner core. In vitro evaluations confirmed the cytocompatibility through Ag-/Cu-substituting and the antibacterial properties provided by Ag+. Then, these multifunctional “smart” particles were embedded in a polymeric matrix by freeze-casting to prepare 3D porous scaffolds for bone engineering. This approach envisions the development of a new generation of scaffolds with tailored sequential properties for optimal bone regeneration. Full article
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16 pages, 6462 KiB  
Article
Conservation of Archaeological Bones: Assessment of Innovative Phosphate Consolidants in Comparison with Paraloid B72
by Andrea Díaz-Cortés, Gabriela Graziani, Marco Boi, Lucia López-Polín and Enrico Sassoni
Nanomaterials 2022, 12(18), 3163; https://doi.org/10.3390/nano12183163 - 13 Sep 2022
Cited by 2 | Viewed by 1772
Abstract
Aqueous solutions of diammonium hydrogen phosphate (DAP) have been recently proposed for consolidation of archeological bones, as an alternative to traditional products. Here, we investigated several routes to improve the performance of the DAP-based treatment, namely increasing the DAP concentration, adding calcium ions [...] Read more.
Aqueous solutions of diammonium hydrogen phosphate (DAP) have been recently proposed for consolidation of archeological bones, as an alternative to traditional products. Here, we investigated several routes to improve the performance of the DAP-based treatment, namely increasing the DAP concentration, adding calcium ions and adding ethanol to the DAP solution. Archaeological bones dated to about 1–0.8 million years ago were used for the tests. After preliminary screening by FTIR microscopy and FEG-SEM among different formulations, confirming the formation of new hydroxyapatite phases, the most promising formulation was selected, namely a 3 M DAP solution. The strengthening ability of this formulation was systematically compared to that of the most widely used commercial consolidant, namely Paraloid B72. The performance of the two treatments was evaluated in terms of Knoop and Vickers microhardness, resistance to scratch and resistance to material loss by peeling off. The results of the study show that the DAP treatment was able to improve the bone surface properties and also the resistance to material loss by peeling off, which is more dependent on in-depth consolidation. Paraloid B72 led to the formation of a layer of acrylic resin on the bone surface, which influenced the mechanical tests. Nonetheless, Paraloid B72 was able to penetrate in depth and substantially decrease the material loss by peeling off, even more effectively than DAP. The results of this study indicate that the potential of the DAP treatment for bone consolidation is confirmed. Full article
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20 pages, 4364 KiB  
Article
Influence of Synthesis Conditions on Gadolinium-Substituted Tricalcium Phosphate Ceramics and Its Physicochemical, Biological, and Antibacterial Properties
by Inna V. Fadeeva, Dina V. Deyneko, Katia Barbaro, Galina A. Davydova, Margarita A. Sadovnikova, Fadis F. Murzakhanov, Alexander S. Fomin, Viktoriya G. Yankova, Iulian V. Antoniac, Sergey M. Barinov, Bogdan I. Lazoryak and Julietta V. Rau
Nanomaterials 2022, 12(5), 852; https://doi.org/10.3390/nano12050852 - 03 Mar 2022
Cited by 14 | Viewed by 3052
Abstract
Gadolinium-containing calcium phosphates are promising contrast agents for various bioimaging modalities. Gadolinium-substituted tricalcium phosphate (TCP) powders with 0.51 wt% of gadolinium (0.01Gd-TCP) and 5.06 wt% of (0.1Gd-TCP) were synthesized by two methods: precipitation from aqueous solutions of salts (1) (Gd-TCP-pc) and mechano-chemical activation [...] Read more.
Gadolinium-containing calcium phosphates are promising contrast agents for various bioimaging modalities. Gadolinium-substituted tricalcium phosphate (TCP) powders with 0.51 wt% of gadolinium (0.01Gd-TCP) and 5.06 wt% of (0.1Gd-TCP) were synthesized by two methods: precipitation from aqueous solutions of salts (1) (Gd-TCP-pc) and mechano-chemical activation (2) (Gd-TCP-ma). The phase composition of the product depends on the synthesis method. The product of synthesis (1) was composed of β-TCP (main phase, 96%), apatite/chlorapatite (2%), and calcium pyrophosphate (2%), after heat treatment at 900 °C. The product of synthesis (2) was represented by β-TCP (main phase, 73%), apatite/chlorapatite (20%), and calcium pyrophosphate (7%), after heat treatment at 900 °C. The substitution of Ca2+ ions by Gd3+ in both β-TCP (main phase) and apatite (admixture) phases was proved by the electron paramagnetic resonance technique. The thermal stability and specific surface area of the Gd-TCP powders synthesized by two methods were significantly different. The method of synthesis also influenced the size and morphology of the prepared Gd-TCP powders. In the case of synthesis route (1), powders with particle sizes of tens of nanometers were obtained, while in the case of synthesis (2), the particle size was hundreds of nanometers, as revealed by transmission electron microscopy. The Gd-TCP ceramics microstructure investigated by scanning electron microscopy was different depending on the synthesis route. In the case of (1), ceramics with grains of 1–50 μm, pore sizes of 1–10 µm, and a bending strength of about 30 MPa were obtained; in the case of (2), the ceramics grain size was 0.4–1.4 μm, the pore size was 2 µm, and a bending strength of about 39 MPa was prepared. The antimicrobial activity of powders was tested for four bacteria (S. aureus, E. coli, S. typhimurium, and E. faecalis) and one fungus (C. albicans), and there was roughly 30% of inhibition of the micro-organism’s growth. The metabolic activity of the NCTC L929 cell and viability of the human dental pulp stem cell study demonstrated the absence of toxic effects for all the prepared ceramic materials doped with Gd ions, with no difference for the synthesis route. Full article
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