Home Technology Fe-containing nominal wollastonite (CaSiO3)–Na2O glass-ceramic: Characterization and biocompatibility
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Fe-containing nominal wollastonite (CaSiO3)–Na2O glass-ceramic: Characterization and biocompatibility

  • Samah S. Eldera EMAIL logo , Sarah Aldawsari , Esmat M. A. Hamzawy and Gehan T. El-Bassyouni
Published/Copyright: April 22, 2025
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Abstract

Wollastonite glass doped with or without 0.5 and 1.0% Fe2O3 was synthesized using a melt-quenching procedure in order to produce new bioactive implants with appropriate magnetic properties. When glasses were sintered at either 1,100 or 1,200°C, combeite (Ca1.543Na2.914Si3O9), pseudowollastonite (Ca3Si3O9), and wollastonite (CaSiO3) with traces of hematite (Fe2O3) in highest Fe-containing sample were obtained. Upon examining the sintered samples at 1,200°C using a field emission scanning electron microscope (FE-SEM), a variety of irregular grains composed of submicron-sized particles were found. Using dynamic light scattering (DLS), the colloidal stability of wollastonite and its composites with Fe2O3 was investigated. The distribution of particle sizes was between approximately 1 μm and 190 nm, and the zeta potential was negative. The Fe2O3 composition of the sintered samples exhibited a variety of magnetic behaviors. FT-IR reflection was used to assess the produced materials’ biocompatibility after a month of immersion in SBF. The soaked samples confirmed that PO 4 3 and Fe(OH)3 were mineralized. Following incubation in SBF, clusters of nanosize calcium phosphate particles were also visible that were spread on the surfaces, as revealed by FE-SEM micrographs and energy dispersive X-ray (EDX) analysis. As the iron content increases, the magnetic characteristics may also be enhanced by the addition of iron. The EDX and FT-IR reflections of the wet sintered samples revealed the mineralization of hydroxyapatite on the surface. Novel magnetic Fe2O3–wollastonite could be very significant since it could open the door to applications as a bone filler and a remedy for hyperthermia.

1 Introduction

Wollastonite, a calcium metasilicate (CaSiO3, CS), was developed to address biocompatibility in glass systems intended to be biomaterials. Additionally, non-cytotoxic and osteoconductive wollastonite has been considered an alloplast bioactive material for bone repair [1,2]. Traces of iron, magnesium, manganese, potassium, sodium, and aluminum may also be present in wollastonite. It may contain 51.7% silicon dioxide and 48.3% calcium oxide. It is made of limestone or calcium carbonates, which are heated to extremely high temperatures in the presence of fluids containing silica [3]. It was discovered that transition metal ions, particularly iron, show uncommon magnetic properties at the solvability frontier of iron oxide and that anti-ferromagnetic transition metal ion groups are present in oxide glasses. The precipitates or nanocrystalline domains showed predicted magnetization due to the potential group in the glass matrix [4]. Iron is supplied at concentrations greater than 5 mol%, which more easily simulates a network former than a modifier [5]. To provide well-considered structural support, metal ions were added to wollastonite as a dopant. In this context, Taha et al. found that osteogenesis and maturation increased when the Fe2O3 nanoparticle concentration increased. Fe2O3 and CS work together to enhance bone formation in a coordinated manner [6]. They claimed that there is insufficient study describing the nanostructure produced by doping calcium silicate with Fe2O3. Because of their extensive use in biological, permanent, and magnetic sensors, materials with magnetic properties have attracted a lot of interest. In the field of nanomedicine, magnetic nanoparticles (M-NPs) are a type of nanomaterial that has been regularly planned for its possible uses. Presentations on drug and gene delivery, hyperthermia rehabilitation, diagnostics, and magnetic imaging have all made use of them [7]. Hematite (α-Fe2O3), maghemite (γ-Fe2O3), and magnetite (Fe3O4) are the three types of iron oxide nanoparticles that are most frequently used for medical applications [8]. These altered designs have several interesting features, such as improved stability in the magnetic field, decreased oxidation sensitivity, and biocompatibility. Hyperthermia is a promising and effective cancer therapy strategy among traditional treatments [1].

Currently, localized perfusion with heated blood, microwave, ultrasound, or any other electromagnetic energy source is used to treat clinical hyperthermia. However, the main challenge in employing these methods is their inability to regulate local tumor heating without causing harm to healthy tissues. Furthermore, intrusive heat is employed in the majority of these therapy techniques. Therefore, magnetic bioactive glass-ceramics have been shown to heat cancer cells without causing harm to healthy tissues, as mentioned by Oskoui and Rezvani [9]. The stability and biomineralization of the graft may be enhanced by the presence of iron oxide (Fe2O3) as a dopant material. In the process of bone regeneration, namely in the development of osteoblastic cells, iron particles are important [10]. It was also taken into account for the bioactive material that was exchanged with Fe2O3, which improved the potential for apatite synthesis [11]. A constant equilibrium between biomineral synthesis and appropriate magnetic properties is necessary for the material to remain nontoxic. Fe2O3, also known as hematite, is an inorganic ferric oxide that is regarded as a paramagnetic mineral with only the Fe3+ oxidation state, whereas Fe3O4, also known as magnetite, is a mixed ferromagnetic material that consumes both Fe2+ and Fe3+ oxidation states of iron. This is the main distinction between the two minerals. Fe2O3 exists in two polymorphs: the gamma and alpha phases. The structure of the alpha phase is symmetrical, but the gamma Fe2O3 is structured in a cubic fashion. Fe3O4 has an inverted spinel structure, which is cubic in shape. In contrast to Fe2O3, which has a relatively low output, Fe3O4 distribution is little more complex and time-consuming [12].

The objective of this study was to examine the incorporation of iron ions into the calcium silicate matrix. In vitro biomineralization as well as size, shape, and physical features were found to be influenced by iron incidence.

2 Materials and methods

How ferric oxide (Fe2O3) affected the wollastonite glass’s bioactivity and characterization was determined. The components of wollastonite (CaSiO3) glass were as follows: SiO2 from silica sand (white silica sand), iron oxide (Fe2O3; Sigma Aldrich 96%), and calcium oxide (CaO) from limestone (CaO: 55.7, Al2O3: 0.22, Fe2O3: 0.02, MgO: 0.1, Na2O: 0.1, K2O: 0.16, and TiO2: 0.02 wt%). The batch compositions with and without Fe2O3 are displayed in Table 1. The addition of 5.0% Na2O (from Na2CO3-BDH) lowered the melting point. To obtain a powder with a grain size of less than 0.038 mm, the batches were thoroughly combined in a ball mill using the melt-quenching process. A global electrical furnace was used to melt the batches in platinum crucibles, with melting points in the range of 1,400–1,450°C.

Table 1

Constituents and chemical composition of glass batches

Samples Batch in oxides Batch
CaO SiO2 Over 100% addition Starting material
Na2O Fe2O3 L.S Silica sand Na2CO3 Fe2O3
G0 48.28 51.72 5.00 00 86.68 51.72 8.5 0.00
G0.5Fe 48.28 51.72 5.00 0.25 86.68 51.72 8.5 0.50
G1.0Fe 48.28 51.72 5.00 0.50 86.68 51.72 8.5 1.00

Differential thermal analysis (DTA-Perkin Elmer DTA-7, USA) was used to determine the thermal history of the glass samples. The glass powder was found at a heating rate of 20°C per minute. The glass was sintered at 1,100 and 1,200°C for 2 h and X-ray diffraction (XRD-BRUKER, D8 ADVANCED, CuO target, = 1.54, Germany) was used to identify the crystalline phases. Field emission scanning electron microscopy combined with energy dispersive X-ray microanalysis (FE-SEM/EDX, model FEJ Quanta 250 Fei, Holland) was used to confirm the microcrystalline structure of sintered glass samples. Fresh crystalline surfaces were etched using a solution of 1% HNO3 + 1% HF before FE-SEM scanning.

With an accuracy of over 1 ± 0.2% and within the range of 0.1 × 10−6 to 103 (emu) of moment measurement, the magnetic characteristics of the powder were assessed using a Lake Shore-7410 vibrating sample magnetometer (VSM) with a magnetic field of 20 kOe.

The Zetasizer (Zeta Potential Analyzer, Nano ZS, Malvern Instrument Ltd, UK) was used to measure the hydrodynamic diameter (particle size), polydispersity index (PDI), and zeta potential of evenly distributed powdered materials at 25°C. For the most promising detection, a 633 nm laser was used. To obtain a concentration of 20 mg·ml−1, the powder was spread out and diluted with distilled water. A particular piece of software (Version 4.0) was utilized for data analysis; each measurement was an average of 12 runs. With the use of an appropriate microscopic procedure, the zeta potential was bestowed upon the voltage of the applied electricity and the mobility of particles under the action of the electricity.

The presence or absence of the calcium phosphate layer on the fresh surface of the synthetic sintered glass-ceramic discs was examined using SBF, which had the same composition as human blood plasma [13]. By incubating sintered discs in SBF for a month at 37°C, the hydroxyapatite formed on the sample surfaces was examined. Kokubo’s method was used to create SBF, which entailed dissolving appropriate concentrations of reagent-grade chemicals in deionized water, including NaCl, NaHCO3, KCl, Na2HPO4, MgCl2·6H2O, Na2SO4, (CH2OH)3CNH2, and CaCl2·H2O [14]. Tris-hydroxymethyl amino methane [(CH2OH)3CNH2] and 1 M HCl were added to the SBF solution to adjust its pH to 7.4 and equal to the content of human blood plasma [15]. Glass discs that were sintered at 1,200°C underwent bioactivity tests. For a month, the samples were kept in closed, sterile polyethylene vials that contained SBF. Samples were taken out of the solution after a month, rinsed with distilled water to stop the reaction, and allowed to dry at room temperature. FE-SEM/EDX and FT-IR reflection (Jasco, FT/IR-4600, USA) are used to characterize disc samples following SBF in order to ensure the establishment of a hydroxyl calcium phosphate layer.

3 Results and discussion

3.1 Sample characterization

3.1.1 DTA and XRD analysis

With the exception of the G1.0Fe sample, the available thermal history of DTA up to 750°C did not reveal any signs of an exothermic or endothermic action. The exothermic crystallization process involves a phase change from an unstable to a stable state. The broad exothermic peak in the DTA curve of the G1.0Fe sample between 508 and 695°C indicates the glass crystallization processes (Figure 1). However, the glass discs were sintered at 1,100 and 1,200°C to provide high-quality sintered samples.

Figure 1 
                     DTA curves of G0, G0.5Fe, and G1.0Fe glasses.
Figure 1

DTA curves of G0, G0.5Fe, and G1.0Fe glasses.

X-ray diffraction patterns of samples sintered at 1,100 and 1,200°C showed that, in addition to pseudowollastonite (CaSiO3, ICDD: 96-900-2180) and wollastonite (CaSiO3, ICDD: 96-900-5779), combeite (Ca1.543Na2.914Si3O9, ICDD: 96-900-7712) is crystallized as a significant phase (Figure 2(a) and (b)). However, traces of hematite were developed in high Fe-containing G1.0Fe sample (Fe2O3, ICDD: 96-901-5965). It forms the primary phase with CaO and SiO2 despite the low ratio of Na2O; however, the crystallization of both pseudowollastonite and wollastonite allowed Na2O to form a phase that contained Ca silicate (combeite, Ca1.543Na2.914Si3O9). The energy of combeite formation may also be thought to be lower than that of pseudowollastonite and wollastonite. The primary constituents of combeite, which is a bioactive silicate, are Na2O, CaO, and SiO2, which are extremely similar to the composition of bioactive compounds. Its crystallization can improve the biocompatibility of glass ceramics that are produced [9,16].

Figure 2 
                     X-ray diffraction patterns of G0, G0.5Fe, and G1.0Fe glasses sintered at (a) 1,100°C and (b) 1,200°C.
Figure 2

X-ray diffraction patterns of G0, G0.5Fe, and G1.0Fe glasses sintered at (a) 1,100°C and (b) 1,200°C.

3.1.2 FE-SEM/EDX analysis

The microstructures of the sintered samples at 1,200°C are depicted in the FE-SEM images (Figure 3). As the Fe2O3 content increases (X = 500 times), the microstructures show irregular grains with decreasing intergrained gaps at high magnification (X = 1,500); however, the grains display dispersed particles embedded in the glassy matrix (Figure 3). However, distinct euhedral crystals in the glassy groundmass were seen at higher magnification (X = 12,000), particularly in the G1.0Fe sample.

Figure 3 
                     SEM images of G0, G0.5Fe, and G1.0Fe glasses sintered at 1,200°C.
Figure 3

SEM images of G0, G0.5Fe, and G1.0Fe glasses sintered at 1,200°C.

3.1.3 Particle size distribution and zeta potential analysis

Using zeta-potential (ξ) and dynamic light scattering (DLS) techniques, the colloidal stability of wollastonite (G0) and its composites with Fe2O3 (G0.5Fe and G1.0Fe) was investigated. From G0 to G1.0Fe, the (PDI) displayed a decreasing order. According to Alangari et al. [17], the limited size distribution of the produced material for the G1.0Fe sample is approved by the low PDI value. As the Fe2O3 content increased, it was observed that the apparent zeta potential of all sintered samples at 1,200°C/2 h displayed a negative trend (Figure 4). When implanted in bone, such an observation might be a useful characteristic for samples that include live cells [17]. The average values of the 12 runs of ζ are shown in Table 2 and Figure 4, which show the zeta potential distribution (G0: −19.8 ± 7.5 mV, G0.5Fe: −24.0 ± 5.38, and G1.0Fe: −6.2 ± 4.71) as well as the size distribution by number (G0: 665.8 nm, GFe0.5: 1167 nm, GFe1.0: approximately 800.5 and 169.2 nm) [18]. Note that the decrease in the particle leads to increase in the surface area and, consequently, increase in the precipitation of the apatite phase. This is clear in G0 (665.8 nm), G0.5Fe (1,167 nm), and G1.0Fe (800.5–1689.2 nm).

Figure 4 
                     Apparent zeta potential and particle size distribution of the sintered samples at 1,200°C/2 h.
Figure 4

Apparent zeta potential and particle size distribution of the sintered samples at 1,200°C/2 h.

Table 2

Particle size, PDI, and apparent zeta potential for powder samples sintered at 1,200°C

Samples Apparent zeta potential (mV) Zeta deviation (mV) Particle size (d·nm) PDI
Peak 1 Peak 2
G0 −19.8 7.50 665.8 0.841
G0.5Fe −24.0 5.38 1,167 0.781
G1.0Fe −6.20 4.71 800.5 169.2 0.619

3.1.4 Magnetic analysis

All of the sintered discs were evaluated using a magnetometer at 1,200°C for 2 h, with or without Fe2O3. The wollastonite structure may exhibit a potential calcium exchange in the samples [19]. According to Akamatsu et al. [20], the influence of anion deficit on the magnetic characteristics was triggered by the presence of various iron valence states. The magnetic characteristics for the samples are shown in Table 3, and the M–H hysteresis curves of base G0 and those containing 0.5 (G0.5Fe) and 1.0% (G1.0Fe) of Fe2O3 at room temperature (RT) are shown in Figure 5. The magnetic types of the two glass-ceramic specimens, G0.5Fe and G1.0Fe, were similar. The materials under study exhibited a range of coercivity (Hci) from 23.248 to 175.39 (G), remnant magnetization (Mr) alternating between 35.502 × 10−6 and 15.814 × 10−3 (emu/g), squareness from 943.59 × 10−6 to 0.27141, and saturation magnetization (Ms) from 37.625 × 10−3 to 58.266 × 10−3 (emu/g) [21]. Therefore, Ms, Hci, Mr, and Mr/Ms values were enhanced when the Fe2O3 content of the materials was increased compared to the base. It is evident from Figure 5 that pure wollastonite behaves in a diamagnetic fashion [3]. As for the integration of 0.5 and 1.0% Fe2O3, there was notable conduct as a ferromagnetic and a paramagnetic material, respectively [10,22]. Consequently, the magnetization of the G0 base doped with Fe2O3 (G0.5Fe and G1.0Fe) improved as the iron replacement increased. The Ms values of G0.5Fe and G1.0Fe were 0.0312 and 0.05826 (emu/g), respectively, due to the addition of iron ions to the wollastonite structure. The G0.5Fe and the G1.0Fe curves exhibit a thin hysteresis cycle and low coercive field found in soft magnetic materials. Thus, a transition metal ion, such as iron, may be chosen to enhance the magnetic characteristics. For a month at 37°C in the current magnetic field, the bioactivity was active in SBF, as shown in the next section on bioactivity, enabling the cells to easily become viable. In the base G0 sample, the traces of iron either from limestone or the additive ingredient may cause the magnetism.

Figure 5 
                     Room temperature M–H loops of G0, G0.5Fe, and G1.0Fe glass samples sintered at 1,200°C.
Figure 5

Room temperature M–H loops of G0, G0.5Fe, and G1.0Fe glass samples sintered at 1,200°C.

Table 3

Magnetic parameters of the sintered samples measured at room temperature for the samples sintered at 1,200°C

Samples Total loop area (erg/g) Coercivity Hci (G) Saturation magnetization Ms (emu/g) × 10−3 Remanence magnetization Mr (emu/g) Squareness SQR (Mr/Ms)
G0 11.583 23.248 37.625 35.502 × 10−6 943.59 × 10−6
G0.5Fe 167.00 173.94 31.262 7.4988 × 10−3 0.23987
G1.0Fe 171.89 175.39 58.266 15.814 × 10−3 0.27141

3.2 Bioactivity

3.2.1 FT-IR analysis following SBF immersion

Using in vitro tests, the synthesized material’s bioactivity was assessed. By immersion in a simulated bodily fluid (SBF), the dynamics of hydroxyapatite (HA) formation, which aids in the creation of strong connections with soft tissues and bones, were assessed using FT-IR and SEM/EDX [23].

In the current study, we investigated the effects of trivalent iron (Fe3+) on the physicochemical and in vitro biological characteristics of wollastonite. By evaluating the formation of hydroxyapatite (HA) cover on the surface using an in vitro bioactivity test, the ability of the produced materials to form bone was investigated [24,25]. The ceramic discs, which were sintered at 1,200°C for 2 h, were immersed in a simulated bodily fluid (SBF) at 37°C for 2 weeks while being kept in a static environment. SBF was set using Kokubo’s standard approach [26], which made it easy for the cells to become viable. Prior to soaking in SBF, Hench proposed a series of five processes to explain the initiation, development, and precipitation of the bone-like apatite phases on top of silicate glass [27].

  1. The exchange of ions from the glass fluid occurs through the exchange of monovalent (Na+) and bivalent (Ca2+) cations from the glass with the SBF protons (H+). This results in the formation of Si–OH bonds (silanol bonds) on the glass surface.

  2. Increasing the pH with respect to alkalinity will damage the Si–O–Si bonds via OH– and produce dissolvable silica Si(OH)4 [28].

  3. Precipitating and decarboxylation Si–OH by the formation of silica gel. The resulting gel can interact with ions from the SBF, making it a key reactor for the formation of apatite.

  4. Ca2+ and PO 4 3 ions disperse through the silica gel, causing an amorphous calcium-phosphate (ACP) layer to form on the gel’s surface [29,30].

For 2 weeks, G0, G0.5Fe, and G1.0 Fe discs were submerged in SBF. FT-IR reflection analysis was used to test the layer on the surfaces of the submerged disks, and the obtained spectra are displayed in Figure 6. The presence of well-designed groups was shown to be associated with carbonated apatite [11]. The IR bands observed at 683 and 650 cm−1 were attributed to the symmetric stretching vibration of Si–O–Si. According to Oskoui and Rezvani, the uniformity of the chemical bond determines the width of the band, and each imperfection weakens the bond by creating strain, which changes the bond’s strength and shows up as minute changes in the bond positions. The band linked to the asymmetric stretching of Si–O–Si shifts to lower wavenumbers as the iron oxide content of the sample increases [9].

Figure 6 
                     FTIR reflection of G0, G0.5Fe, and G1.0Fe glasses sintered at 1,200°C.
Figure 6

FTIR reflection of G0, G0.5Fe, and G1.0Fe glasses sintered at 1,200°C.

At 904 and 941 cm−1, the bands associated with the Si–O–NBO non-bridging silicon–oxygen bond were found. The Si–O–Si bending vibrational mode is associated with the bands at 462 and 563 cm−1. The bending vibration of the PO 4 3 functional group, which is linked to the HA phase’s incidence, is responsible for the bands observed at 407, 426, 438, 453, 472, and 500 cm−1, whereas the octacalcium phosphate (OCP) is responsible for the bands found at 517 and 563 [31]. Because iron is present in the produced material, the wollastonite matrix doped with Fe2O3 exhibits an improvement in the intensity of the detected bands in the infrared reflection. El-Kheshen et al. reported that the band at 570 cm−1 represents the Fe–O bond vibrations in the magnetite crystalline lattice, whereas the band at 550 cm−1 was used to characterize the magnetite [32]. Valverde et al. claimed that these findings indicate the metal oxide bond (M–O–M) basis, which allows the formation of ferrites [33]. As expected, Chukanov concluded that Fe3+ forms precipitates, such as Fe(OH)3 in the progenitor [34]. Consequently, it can be concluded that the fractional substitution of Fe3+ into the wollastonite assembly did not alter the vibrational band variations, indicating structural stability with Fe3+ content that validated the superiority of apatite precipitate following 15 days of immersion in SBF. The FTIR spectrum indicates that iron cations function as glass network modifiers at high concentrations and as glass network formers at lower concentrations.

3.2.2 SEM/EDX analysis post-immersion in SBF

Figure 7 displays the SEM micrographs of the sintered glasses at 1,200°C/2 h and following a month-long soaking in SBF. At low magnification, the base sample displays irregularly collected small crystals, whereas at high magnification, it displays clusters of fine nanoparticles with scattered strings of sub-nano size in between [35,36]. At low magnification, G0.5Fe has a similar texture; however, at high magnification, several collected clusters with strings of sub-nano size in between were visible. Figure 7 shows the high-magnification many-string crystals in the sub-nanoscale and linked irregular shape grains in the microscale for iron ratio G1.0Fe. The phosphate-containing phase was formed, according to the EDX microanalysis, and the Ca/P ratio ranged from 3.06 (G1.0Fe) to 2.06 (G0.5Fe), while that of the base sample was 2.25 (Figure 7). For samples with a Ca/P ratio of 2.0:3.0, Liu et al. found that the CaO phase starts to resemble the major phase, the HA phase [37]. In the end, in vitro testing typically precedes in vivo testing, and both tests give researchers the information they require to approve a testing compound’s success for its future purpose and danger [38].

Figure 7 
                     SEM images and EDX analysis of G0, G0.5Fe, and G1.0Fe glasses sintered at 1200°C and soaked in SBF for a month.
Figure 7

SEM images and EDX analysis of G0, G0.5Fe, and G1.0Fe glasses sintered at 1200°C and soaked in SBF for a month.

4 Conclusion

Nominal wollastonite glass was used as the basis for the preparation of sintered glass ceramics with and without 0.5 and 1.0% Fe2O3. Combeite crystallization was shown as a significant phase in the XRD patterns of samples sintered at 1,100 and 1,200°C, together with pseudo-wollastonite and wollastonite. Samples sintered at 1,200°C had irregular grains with submicron-sized particles in their microstructure. Although the zeta potential recorded negative values, the zeta potential analyzer showed that the particle size distribution varied between approximately 1 μm and 190 nm. Due to the Fe2O3 composition, the sintered samples responded magnetically in a variety of ways, including diamagnetically and paramagnetically. The mineralization of PO 4 3 and Fe(OH)3 was demonstrated by the FT-IR reflection following a month of soaking the sintered samples in SBF. On the surface, clusters of calcium phosphate nanoparticles were visible according to the FE-SEM/EDX study. The biocompatibility of soaked sintered samples confirmed the hydroxyapatite mineralization on the surfaces, a sign of the materials’ bioactivity. The development of a novel magnetic Fe2O3–wollastonite could be crucial since it could open the door to applications as a bone filler and a remedy for hyperthermia.

Acknowledgments

This project was funded by the Deanship of Scientific Research (DSR) at King Abdulaziz University, Jeddah, Saudi Arabia (grant no. G: 546-247-1442). The authors, therefore, acknowledge DSR for technical and financial support.

  1. Funding information: The funding support for the research of this study was granted by the Deanship of Scientific Research (DSR) at King Abdulaziz University, Jeddah, Saudi Arabia (grant no. G: 546-247-1442).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article.

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Received: 2024-12-14
Revised: 2025-02-20
Accepted: 2025-03-14
Published Online: 2025-04-22

© 2025 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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