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Keywords = manganese-substituted hydroxyapatite

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19 pages, 4384 KB  
Article
Porous Osteoplastic Composite Materials Based on Alginate–Pectin Complexes and Cation-Substituted Hydroxyapatites
by Galina A. Davydova, Inna V. Fadeeva, Elena S. Trofimchuk, Irina I. Selezneva, Muhriddin T. Mahamadiev, Lenar I. Akhmetov, Daniel S. Yakovsky, Vadim P. Proskurin, Marco Fosca, Viktoriya G. Yankova, Julietta V. Rau and Vicentiu Saceleanu
Polymers 2025, 17(13), 1744; https://doi.org/10.3390/polym17131744 - 23 Jun 2025
Viewed by 981
Abstract
Novel three-dimensional porous composites of alginate–pectin (A/P) with zinc- or manganese-substituted hydroxyapatites (A/P-ZnHA and A/P-MnHA) were synthesized via lyophilization and calcium cross-linking. Powder X-ray diffraction and infrared spectroscopy analyses confirmed single-phase apatite formation (crystallite sizes < 1 µm), with ZnHA exhibiting lattice contraction [...] Read more.
Novel three-dimensional porous composites of alginate–pectin (A/P) with zinc- or manganese-substituted hydroxyapatites (A/P-ZnHA and A/P-MnHA) were synthesized via lyophilization and calcium cross-linking. Powder X-ray diffraction and infrared spectroscopy analyses confirmed single-phase apatite formation (crystallite sizes < 1 µm), with ZnHA exhibiting lattice contraction (*c*-axis: 6.881 Å vs. 6.893 Å for HA). Mechanical testing revealed tunable properties: pristine A/P sponges exhibited an elastic modulus of 4.7 MPa and a tensile strength of 0.10 MPa, reduced by 30–70% by HA incorporation due to increased porosity (pore sizes: 112 ± 18 µm in the case of MnHA vs. 148 ± 23 µm-ZnHA). Swelling capacity increased 2.3–2.8-fold (125–155% vs. 55% for A/P), governed by polysaccharide interactions. Scanning electron microscopy investigation showed microstructural evolution from layered A/P (<100 µm) to tridimensional architectures with embedded mineral particles. The A/P-MnHA composites demonstrated minimal cytotoxicity for the NCTC cells and good viability of dental pulp stem cells, while A/P-ZnHA caused ≈20% metabolic suppression, attributed to hydrolysis-induced acidification. Antibacterial assays highlighted A/P-MnHA′s broad-spectrum efficacy against Gram-positive (Bacillus atrophaeus) and Gram-negative (Pseudomonas protegens) strains, whereas A/P-ZnHA targeted only the Gram-positive strain. The developed composite sponges combine cytocompatibility and antimicrobial activity, potentially advancing osteoplastic materials for bone regeneration and infection control in orthopedic/dental applications. Full article
(This article belongs to the Special Issue Functional Polymer Composites: Synthesis and Application)
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16 pages, 38369 KB  
Article
Biomimetic Scaffolds Based on Mn2+-, Mg2+-, and Sr2+-Substituted Calcium Phosphates Derived from Natural Sources and Polycaprolactone
by Leonard Bauer, Maja Antunović, Hrvoje Ivanković and Marica Ivanković
Biomimetics 2024, 9(1), 30; https://doi.org/10.3390/biomimetics9010030 - 4 Jan 2024
Cited by 2 | Viewed by 2933
Abstract
The occurrence of bone disorders is steadily increasing worldwide. Bone tissue engineering (BTE) has emerged as a promising alternative to conventional treatments of bone defects, developing bone scaffolds capable of promoting bone regeneration. In this research, biomimetic scaffolds based on ion-substituted calcium phosphates, [...] Read more.
The occurrence of bone disorders is steadily increasing worldwide. Bone tissue engineering (BTE) has emerged as a promising alternative to conventional treatments of bone defects, developing bone scaffolds capable of promoting bone regeneration. In this research, biomimetic scaffolds based on ion-substituted calcium phosphates, derived from cuttlefish bone, were prepared using a hydrothermal method. To synthesize Mn2+-substituted scaffolds, three different manganese concentrations (corresponding to 1, 2.5, and 5 mol% Mn substitutions for Ca into hydroxyapatite) were used. Also, syntheses with the simultaneous addition of an equimolar amount (1 mol%) of two (Mg2+ and Sr2+) or three ions (Mn2+, Mg2+, and Sr2+) were performed. A chemical, structural, and morphological characterization was carried out using X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The effects of the ion substitutions on the lattice parameters, crystallite sizes, and fractions of the detected phases were discussed. Multi-substituted (Mn2+, Mg2+, and Sr2+) scaffolds were coated with polycaprolactone (PCL) using simple vacuum impregnation. The differentiation of human mesenchymal stem cells (hMSCs), cultured on the PCL-coated scaffold, was evaluated using histology, immunohistochemistry, and reverse transcription–quantitative polymerase chain reaction analyses. The expression of collagen I, alkaline phosphatase, and dentin matrix protein 1 was detected. The influence of PCL coating on hMSCs behavior is discussed. Full article
(This article belongs to the Section Biomimetic Processing and Molecular Biomimetics)
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16 pages, 8254 KB  
Article
Mangiferin-Enriched Mn–Hydroxyapatite Coupled with β-TCP Scaffolds Simultaneously Exhibit Osteogenicity and Anti-Bacterial Efficacy
by Subhasmita Swain, Janardhan Reddy Koduru and Tapash Ranjan Rautray
Materials 2023, 16(6), 2206; https://doi.org/10.3390/ma16062206 - 9 Mar 2023
Cited by 31 | Viewed by 2525
Abstract
Biphasic calcium phosphate (BCP) containing β-tricalcium phosphate and manganese (Mn)-substituted hydroxyapatite (HAP) was synthesized. Biomedical scaffolds were prepared using this synthesized powder on a sacrificial polyurethane sponge template after the incorporation of mangiferin (MAN). Mn was substituted at a concentration of 5% and [...] Read more.
Biphasic calcium phosphate (BCP) containing β-tricalcium phosphate and manganese (Mn)-substituted hydroxyapatite (HAP) was synthesized. Biomedical scaffolds were prepared using this synthesized powder on a sacrificial polyurethane sponge template after the incorporation of mangiferin (MAN). Mn was substituted at a concentration of 5% and 10% in HAP to examine the efficacy of Mn at various concentrations. The phase analysis of the as-formed BCP scaffold was carried out by X-ray diffraction analysis, while the qualitative observation of morphology and the osteoblast cell differentiation were carried out by scanning electron microscopy and confocal laser scanning microscopy techniques. Gene expressions of osteocalcin, collagen 1, and RUNX2 were carried out using qRT-PCR analyses. Significantly higher (p < 0.05) levels of ALP activity were observed with extended osteoblast induction on the mangiferin-incorporated BCP scaffolds. After characterization of the specimens, it was found that the scaffolds with 10% Mn-incorporated BCP with mangiferin showed better osteogenicity and simultaneously the same scaffolds exhibited higher anti-bacterial properties as observed from the bacterial viability test. This study was carried out to evaluate the efficacy of Mn and MAN in BCP for osteogenicity and antibacterial action. Full article
(This article belongs to the Special Issue Sustainable Nanocomposites and Technologies for Water Treatment)
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16 pages, 9194 KB  
Article
Evaluation of the In Vivo Biocompatibility of Amorphous Calcium Phosphate-Containing Metals
by Pio Moerbeck-Filho, Suelen C. Sartoretto, Marcelo J. Uzeda, Maurício Barreto, Alena Medrado, Adriana Alves and Mônica D. Calasans-Maia
J. Funct. Biomater. 2020, 11(2), 45; https://doi.org/10.3390/jfb11020045 - 23 Jun 2020
Cited by 10 | Viewed by 4872
Abstract
Among the biomaterials based on calcium phosphate, hydroxyapatite has been widely used due to its biocompatibility and osteoconduction. The substitution of the phosphate group by the carbonate group associated with the absence of heat treatment and low synthesis temperature leads to the formation [...] Read more.
Among the biomaterials based on calcium phosphate, hydroxyapatite has been widely used due to its biocompatibility and osteoconduction. The substitution of the phosphate group by the carbonate group associated with the absence of heat treatment and low synthesis temperature leads to the formation of carbonated hydroxyapatite (CHA). The association of CHA with other metals (strontium, zinc, magnesium, iron, and manganese) produces amorphous calcium phosphate-containing metals (ACPMetals), which can optimize their properties and mimic biological apatite. This study aimed to evaluate the biocompatibility and biodegradation of ACPMetals in mice subcutaneous tissue. The materials were physicochemically characterized with Fourier Transform InfraRed (FTIR), X-Ray Diffraction (XRD), and Atomic Absorption Spectrometry (AAS). Balb-C mice (n = 45) were randomly divided into three groups: carbonated hydroxyapatite, CHA (n = 15), ACPMetals (n = 15), and without implantation of material (SHAM, n = 15). The groups were subdivided into three experimental periods (1, 3, and 9 weeks). The samples were processed histologically for descriptive and semiquantitative evaluation of the biological effect of biomaterials according to ISO 10993-6:2016. The ACPMetals group was partially biodegradable; however, it presented a severe irritating reaction after 1 and 3 weeks and moderately irritating after nine weeks. Future studies with other concentrations and other metals should be carried out to mimic biological apatite. Full article
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14 pages, 2424 KB  
Article
Dual Doping of Silicon and Manganese in Hydroxyapatites: Physicochemical Properties and Preliminary Biological Studies
by Katarzyna Szurkowska, Agata Drobniewska and Joanna Kolmas
Materials 2019, 12(16), 2566; https://doi.org/10.3390/ma12162566 - 12 Aug 2019
Cited by 13 | Viewed by 4137
Abstract
Silicated hydroxyapatite powders enriched with small amounts of manganese (Mn2+) cations were synthesized via two different methods: precipitation in aqueous solution and the solid-state method. The source of Mn2+ ions was manganese acetate, while silicon was incorporated using two different [...] Read more.
Silicated hydroxyapatite powders enriched with small amounts of manganese (Mn2+) cations were synthesized via two different methods: precipitation in aqueous solution and the solid-state method. The source of Mn2+ ions was manganese acetate, while silicon was incorporated using two different reagents: silicon acetate and sodium metasilicate. Powder X-ray diffraction (PXRD) analysis showed that the powders obtained via the precipitation method consisted of single-phase nanocrystalline hydroxyapatite. In contrast, samples obtained via the solid-state method were heterogenous and contaminated with other phases, (i.e., calcium oxide, calcium hydroxide, and silicocarnotite) arising during thermal treatment. The transmission electron microscope (TEM) images showed powders obtained via the precipitation method were nanosized and elongated, while solid-state synthesis produced spherical microcrystals. The phase identification was complemented by Fourier transform infrared spectroscopy (FTIR). An in-depth analysis via solid-state nuclear magnetic resonance (ssNMR) was carried out, using phosphorus 31P single-pulse Bloch decay (BD) (31P BD) and cross-polarization (CP) experiments from protons to silicon-29 nuclei (1H → 29Si CP). The elemental measurements carried out using wavelength-dispersive X-ray fluorescence (WD-XRF) showed that the efficiency of introducing manganese and silicon ions was between 45% and 95%, depending on the synthesis method and the reagents. Preliminary biological tests on the bacteria Allivibrio fisheri (Microtox®) and the protozoan Spirostomum ambiguum (Spirotox) showed no toxic effect in any of the samples. The obtained materials may find potential application in regenerative medicine, bone implantology, and orthopedics as bone substitutes or implant coatings. Full article
(This article belongs to the Special Issue Novel Biomaterials for Orthopaedic/Musculoskeletal Tissue Engineering)
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21 pages, 7536 KB  
Article
An Innovative Approach to Manganese-Substituted Hydroxyapatite Coating on Zinc Oxide–Coated 316L SS for Implant Application
by Karuppasamy Prem Ananth, Jinxing Sun and Jiaming Bai
Int. J. Mol. Sci. 2018, 19(8), 2340; https://doi.org/10.3390/ijms19082340 - 9 Aug 2018
Cited by 42 | Viewed by 6246
Abstract
In this paper, the synthesis of porous manganese substituted hydroxyapatite (Mn-HAp) coating on zinc oxide (ZnO) coated stainless steel (316L SS) using the electrodeposition technique is reported. The structural, functional, morphological, and elemental analyses are characterized by various analytical techniques including X-ray diffraction [...] Read more.
In this paper, the synthesis of porous manganese substituted hydroxyapatite (Mn-HAp) coating on zinc oxide (ZnO) coated stainless steel (316L SS) using the electrodeposition technique is reported. The structural, functional, morphological, and elemental analyses are characterized by various analytical techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Results of electrochemical techniques such as cyclic polarization and impedance show that the Mn-HAp coating on ZnO coated 316L SS has the highest corrosion resistance in simulated body fluid (SBF) solution. Moreover, dissolution of metal ions was extremely reduced, as evaluated by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The adhesion and hardness of Mn-HAp/ZnO bilayer coatings have superior mechanical properties over individual coatings. Further, the biocompatibility of in vitro osteoblast attachment, cell viability, and live/dead assessment also confirmed the suitability of Mn-HAp/ZnO bilayer coating on 316L SS for orthopedic applications. Full article
(This article belongs to the Section Materials Science)
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22 pages, 5743 KB  
Article
First-Row Transition Metal Doping in Calcium Phosphate Bioceramics: A Detailed Crystallographic Study
by Guillaume Renaudin, Sandrine Gomes and Jean-Marie Nedelec
Materials 2017, 10(1), 92; https://doi.org/10.3390/ma10010092 - 23 Jan 2017
Cited by 76 | Viewed by 8708
Abstract
Doped calcium phosphate bioceramics are promising materials for bone repair surgery because of their chemical resemblance to the mineral constituent of bone. Among these materials, BCP samples composed of hydroxyapatite (Ca10(PO4)6(OH)2) and β-TCP (Ca3 [...] Read more.
Doped calcium phosphate bioceramics are promising materials for bone repair surgery because of their chemical resemblance to the mineral constituent of bone. Among these materials, BCP samples composed of hydroxyapatite (Ca10(PO4)6(OH)2) and β-TCP (Ca3(PO4)2) present a mineral analogy with the nano-multi-substituted hydroxyapatite bio-mineral part of bones. At the same time, doping can be used to tune the biological properties of these ceramics. This paper presents a general overview of the doping mechanisms of BCP samples using cations from the first-row transition metals (from manganese to zinc), with respect to the applied sintering temperature. The results enable the preparation of doped synthetic BCP that can be used to tailor biological properties, in particular by tuning the release amounts upon interaction with biological fluids. Intermediate sintering temperatures stabilize the doping elements in the more soluble β-TCP phase, which favors quick and easy release upon integration in the biological environment, whereas higher sintering temperatures locate the doping elements in the weakly soluble HAp phase, enabling a slow and continuous supply of the bio-inspired properties. An interstitial doping mechanism in the HAp hexagonal channel is observed for the six investigated cations (Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with specific characteristics involving a shift away from the center of the hexagonal channel (Fe3+, Co2+), cationic oxidation (Mn3+, Co3+), and also cationic reduction (Cu+). The complete crystallochemical study highlights a complex HAp doping mechanism, mainly realized by an interstitial process combined with calcium substitution for the larger cations of the series leading to potentially calcium deficient HAp. Full article
(This article belongs to the Special Issue Calcium Phosphate in Biomedical Applications)
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18 pages, 4950 KB  
Article
A Comparative Study of the Sintering Behavior of Pure and Manganese-Substituted Hydroxyapatite
by Michael Zilm, Seamus D. Thomson and Mei Wei
Materials 2015, 8(9), 6419-6436; https://doi.org/10.3390/ma8095308 - 18 Sep 2015
Cited by 21 | Viewed by 6747
Abstract
Hydroxyapatite (HA) is a widely studied biomaterial for its similar chemical composition to bone and its osteoconductive properties. The crystal structure of HA is flexible, allowing for a wide range of substitutions which can alter bioactivity, biodegradation, and mechanical properties of the substituted [...] Read more.
Hydroxyapatite (HA) is a widely studied biomaterial for its similar chemical composition to bone and its osteoconductive properties. The crystal structure of HA is flexible, allowing for a wide range of substitutions which can alter bioactivity, biodegradation, and mechanical properties of the substituted apatite. The thermal stability of a substituted apatite is an indication of its biodegradation in vivo. In this study, we investigated the thermal stability and mechanical properties of manganese-substituted hydroxyapatite (MnHA) as it is reported that manganese can enhance cell attachment compared to pure HA. Pure HA and MnHA pellets were sintered over the following temperature ranges: 900 to 1300 °C and 700 to 1300 °C respectively. The sintered pellets were characterized via density measurements, mechanical testing, X-ray diffraction, and field emission electron microscopy. It was found that MnHA was less stable than HA decomposing around 800 °C compared to 1200 °C for HA. The flexural strength of MnHA was weaker than HA due to the decomposition of MnHA at a significantly lower temperature of 800 °C compared to 1100 °C for HA. The low thermal stability of MnHA suggests that a faster in vivo dissolution rate compared to pure HA is expected. Full article
(This article belongs to the Section Biomaterials)
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