O. M. Lemine*a,
M. Bououdinab,
Turki Altouba,
M. Alshammaric,
Kadi Y. Museeryc,
Ali Z. Alanzic and
Latifa Latrousd
aDepartment of Physics, College of Sciences, Imam Mohammad Ibn Saud Islamic University (IMISU), Riyadh 11623, Saudi Arabia. E-mail: mamamin@imamu.edu.sa
bDepartment of Mathematics and Sciences, College of Humanities and Sciences, Prince Sultan University, 11586 Riyadh, Saudi Arabia
cMicroelectronics and Semiconductors Institute, King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia
dLaboratoire de Chimie Minérale Appliquée (LR19ES02), Faculté Des Sciences de Tunis, Université de Tunis El Manar, Campus Universitaire El Manar I, 2092 Tunis, Tunisie
First published on 7th August 2025
This work reports the synthesis, characterization, and magnetic hyperthermia performance of pyrrole-functionalized magnetic biochar (PFMB) nanocomposites prepared via a hydrothermal method. The PFMB system comprises Fe3O4 nanoparticles embedded in a biochar matrix and coated with pyrrole to improve colloidal stability and heating efficiency. Structural and morphological analyses (XRD, FTIR, SEM/EDAX) confirmed the formation of a magnetite phase and successful surface functionalization. Magnetic measurements reveal a transition from ferrimagnetic behavior in bare MB to superparamagnetism in PFMB, with saturation magnetization reduced significantly from 58.8 to 20.8 emu g−1. Magnetic hyperthermia experiments under alternating magnetic fields (AMF) manifest enhanced heating efficiency for PFMB, with sample absorption rate (SAR) values varying considerably from 24.27 to 53.77 W g−1, compared to 12.34–31.80 W g−1 for MB. The results indicate that at higher frequencies (332 kHz and 469 kHz), both MNPs reach the therapeutic hyperthermia threshold of 42 °C in a relatively short time. The heating performance correlates well with both frequency and field amplitude. Intrinsic loss power (ILP) values for PFMB reach 0.70 nH m2 kg−1, aligning with the values reported for established polymer-coated MNPs. These results demonstrate the potential of PFMB nanocomposites as efficient and stable candidates for in vitro magnetic hyperthermia applications.
Pyrrole coating plays a pivotal role in maintaining colloidal stability by mitigating MNP agglomeration, which is a requirement for enhanced heating efficiency of MNPs and for an efficient MH.3 Furthermore, the functionalization of magnetic biochar (MB) with naturally derived caffeic acid introduces surface hydroxyl and carboxyl groups, thus enhancing aqueous dispersibility and biocompatibility while offering potential sites for drug loading or molecular targeting.4,5
The heat generation capability of MNPs under AMF is governed primarily by two relaxation mechanisms: Néel relaxation, involving the reorientation of magnetic moments within the crystal lattice, and Brownian relaxation, in which the entire particle rotates in suspension to follow the magnetic field.6 The efficiency of each mechanism depends on several factors such as particle size, magnetic anisotropy, and matrix confinement. In the PFMB system, both the pyrrole shell and biochar scaffold influence these mechanisms by controlling particle mobility and interparticle interactions. Notably, the pyrrole coating prevents aggregation and maintains interparticle separation, which is crucial to sustaining efficient magnetic relaxation.7 Numerous studies have highlighted the multifunctional advantages of pyrrole-coated MNPs, including improved heating efficiency, enhanced dispersion in aqueous media, and increased thermal stability.2,8,9 For instance, Mol et al.2 demonstrated that Fe3O4 MNPs coated with pyrrole exhibit enhanced biocompatibility and tunable heating capacity. Bao et al.8 reported SAR of 1648 W g−1 for pyrrole-coated magnetite nanorings subjected to simultaneous AMF and near-infrared (NIR) irradiation, along with negligible cytotoxicity. Similarly, Sethulakshimi et al.9 found that plasma polymerization of polyaniline on iron oxide nanoparticles led to increased saturation magnetization and improved biocompatibility.
While substantial advances have been achieved in the development of polymer-coated magnetic nanoparticles (MNPs) for magnetic hyperthermia—particularly with coatings such as poly(acrylic acid) (PAA), polyethylene glycol (PEG), dextran, hyaluronic acid, chitosan, and polyvinylpyrrolidone (PVP)10–13—there remains a notable gap in systematic investigations focused on the magnetothermal performance of pyrrole-coated MNPs. Despite the promising conductive and stabilizing properties of pyrrole, its potential as a surface functionalization agent for enhancing heat dissipation efficiency in magnetic hyperthermia is still underexplored.
Motivated by recent work in which MB and PFMB MNPs were successfully synthesized via a hydrothermal approach for sensing applications,14 we extended our investigation to evaluate their magnetothermal properties. In this study, MB and PFMB were fully characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy with energy-dispersive X-ray analysis (SEM/EDAX), and superconducting quantum interference device (SQUID) magnetometry.
To assess their performance in magnetic hyperthermia, the specific absorption rate (SAR) was measured under varying alternating magnetic field (AMF) frequencies and field strengths. This study provides new insights into the role of pyrrole surface modification in optimizing the heating efficiency of MNPs for theranostic applications.
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Fig. 1 Synthesis of Pyrrole Functionalized Magnetic Biochar (PFMB) nanocomposite (reproduced from our early work14). |
To synthesize PFMB, the carbon precursor was mixed with iron(III) chloride hexahydrate (FeCl3·6H2O), polyethylene glycol (PEG), and pyrrole (Py). The mixture was subjected to ultrasonic dispersion for 1 h to ensure uniform mixing with a Py/Fe molar ratio of 1.5. The resulting suspension was transferred into a 150 mL Teflon-lined autoclave and subjected to hydrothermal treatment at 180 °C for 17 h in a hot-air oven. The final product was collected as a dry powder.
The heating efficiency of the samples was performed using a commercial system “Nanotherics Magnetherm”. The SAR values are calculated by the following equation:
![]() | (1) |
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Fig. 2 (a) XRD diffraction of magnetic biochar powder before and after pyrrole coating, Rietveld refinements of (b) magnetic biochar and (c) biochar coated with pyrrole. |
To further compute both structural and microstructural parameters, Rietveld refinements of the XRD patterns have been performed, see Fig. 2b and c. It is evident that the theoretical pattern based on the standard phase JCPDS card no. 01-088-0315 (blue curve) fits very well the experimental pattern (red curve), since the difference between the two curves (orange curve) gives almost a straight line. The goodness of fit parameter (S) is around 0.17. This indicates that the as prepared powdered samples are pure phases.
Table 1 summarizes the computed structural and microstructural parameters as obtained from the Rietveld refinements. It can be observed that the lattice parameter a is found to be 8.389 Å for magnetic biochar which decrease slight up to 8.379 Å for pyrrole coated magnetic biochar. This slight variation in the lattice parameter is usually associated with the local atomic arrangement (sites occupancy, vacancies), a typical behavior occurring within the inverse spinel cubic structure, where (Fe2+ with an ionic radius of 0.077 nm) occupies octahedral sites and (Fe3+ with an ionic radius of 0.063 nm) occupy tetrahedral sites. This effect has been widely reported in the literature and was found to have a direct effect on the magnetic properties,16 since both ions have different magnetic moments, i.e. 4.89 μB for Fe2+ and 5.92 μB for Fe3+.
Sample | Phase composition (%) | Crystallite size D (nm) | Microstrain ε (%) | Lattice parameters (Å) | Fitting parameters |
---|---|---|---|---|---|
a Rwp: weighted profile R-factor; Re: expected R-factor; Rp: profile R-factor; S: goodness of fit (S = Rwp/Re); χ2 = S2. | |||||
MB | Fe3O4 (magnetite) | 11.1(1) | 0.078(13) | a = b = c = 8.389(1) | Rwp = 2.10%; Re = 12.37%; Rp = 1.64%; S = 0.1695; χ2 = 0.0287 |
α = β = γ = 90° | |||||
PFMB | Fe3O4 (magnetite) | 13.5(1) | 0.711(8) | a = b = c = 8.379(2) | Rwp = 2.26%; Re = 14.17%; Rp = 1.80%; S = 0.1591; χ2 = 0.0253 |
α = β = γ = 90° |
For microstructural parameters, it can be observed that the crystallite D size increases after coating, from 11.1 nm to 13.5 nm, due to the growth of a thin layer of pyrrole. Similarly, the microstrain ε increases significantly from 0.078% up to 0.711%. This is most probably originating from the coating of magnetic biochar with a polymeric layer of pyrrole compound.
The high-magnification SEM image (Fig. 4g) further validates the coating of pyrrole on Fe3O4 within the pyrrole matrix, showing a core–shell-like structure with visible contrast differences. Adding this, the energy-dispersive X-ray spectroscopy (EDAX) elemental profile (Fig. 4h) confirms the presence of key elements including Fe, O, C thereby verifying the elemental composition of the composite. The strong Fe and O peaks indicate the magnetic core, while the presence of Cl and C supports pyrrole shell and possible doping elements. The detection of Na and minor atomic (At) peaks ascribed to residuals from the precursor or synthesis process. These morphological and compositional analyses collectively confirm the successful synthesis of a Fe3O4/biochar@pyrrole composite.
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Fig. 5 (a) Room temperature M–H curves for the MB and PFMB MNPs. (bottom inset) Enlarged view of the M–H curves for the low field region and (b) extrapolated saturation magnetization for MB. |
This significant decrease in Ms upon pyrrole coating is attributed to several factors, including.12,13,15–17 (i) Interfacial disruptions caused by the non-magnetic polymer shell, which weaken dipolar interactions and reduce the collective magnetic response; (ii) the coating process may also influence the cation distribution within the spinel lattice. The magnetic properties of spinel ferrites are strongly governed by the occupancy of Fe ions in tetrahedral and octahedral sites. Interaction of the polymer matrix with the particle surface during the coating procedure can induce local alterations in cation arrangement, affecting the superexchange interactions responsible for ferrimagnetic ordering. This interpretation is corroborated by XRD analysis, which confirmed an inverse spinel structure for the PFMB nanocomposite; and (iii) possible surface oxidation effects promoted by the functional groups of pyrrole, subtly impacting the Fe2+/Fe3+ ratio and the overall magnetization.
These observations from M–H measurements are further supported by the ZFC/FC magnetization curves presented in Fig. 6a and b. The MB MNPs display a broad, gradual increase in the ZFC curve with no distinct blocking temperature (TB), indicating a strong dipolar interaction, characteristic of clustered or multi-domain systems. In contrast, the PFMB exhibits a TB around 290–300 K, reflecting a more uniform size distribution and effective magnetic decoupling provided by the pyrrole coating. This thermal behavior aligns well with the superparamagnetic nature of PFMB observed in the M–H curves at room temperature, confirming the stabilizing effect of the coating on the magnetic core and its role in reducing interparticle interactions.
To further verify the superparamagnetic behavior of the PFMB nanocomposite, the experimental M(H) data were analyzed using the Langevin model of paramagnetism, described by the equation:
![]() | (2) |
The experimental data showed an excellent agreement with the Langevin model, as evidenced by a coefficient of determination R2 = 0.998, as illustrated in Fig. 7. This high correlation further confirms that the PFMB nanocomposite exhibits a superparamagnetic response at room temperature, dominated by the thermal fluctuation of non-interacting magnetic moments, and consistent with M–H loop characteristics.
It can be concluded from the detailed magnetic study that while the pyrrole coating substantially reduces the saturation magnetization, it effectively enhances the superparamagnetic response and thermal stability of the nanocomposite, properties that are crucial for magnetic hyperthermia application.
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Fig. 8 (a–c) Temperature rise at different frequency for MB and PFMB and (d) corresponding SARs values for both MNPs. |
Samples | Frequency (kHz) | Field (mT) | SAR (W g−1) | ILP (nH m2 kg−1) |
---|---|---|---|---|
MB | 169 | 17 | 12.34 | 0.39 |
332 | 17 | 16.11 | 0.26 | |
469 | 16 | 31.8 | 0.41 | |
PFMB | 169 | 17 | 24.27 | 0.78 |
332 | 17 | 28.24 | 0.46 | |
469 | 16 | 53.77 | 0.70 |
For MB MNPs, SAR values ranged from 12.34 W g−1 to 31.80 W g−1, while the PFMB exhibited notably higher SAR values, in the range 24.27 W g−1 to 53.77 W g−1 across the studied frequencies. The enhanced SAR values observed for PFMB can be attributed to several factors. (i) The pyrrole surface functionalization likely improves colloidal stability by mitigating agglomeration, thereby facilitating more efficient heat dissipation. Furthermore, the superparamagnetic behavior of PFMB, as confirmed by magnetic characterization, reduces interparticle magnetic interactions that typically hinder heating performance. It is well known that heat dissipation under an AMF for superparamagnetic MNPs arises from Néel and Brownian relaxations. (ii) The presence of pyrrole reduces magnetic interactions between nanoparticles, which in turn affects the Néel relaxation time—potentially enhancing the heating efficiency. Brownian relaxation may also become faster due to improved dispersion and reduced aggregation. While these factors contribute positively to the heating performance, it is important to note that the overall magnetization tends to decrease due to the pyrrole coating, which can partially offset the heat generation. (iii) The mesoporous and carbonaceous framework of biochar improve heat dissipation by providing a thermally conductive scaffold that improves the overall magnetothermal conversion efficiency. This conductive network also helps dissipate localized heat from individual nanoparticles across a broader volume, minimizing thermal hotspots and supporting a more homogeneous temperature rise during hyperthermia treatment. These effects synergistically contribute to the superior heating capability of PFMB compared to uncoated MB nanoparticles. Earlier studies have demonstrated that chitosan, dextran, PEG, PVP, and PAA coatings enhance heating properties of MNPs by improving dispersion and reducing interparticle magnetic interactions.19–23
To assess the effect of magnetic field strength on the heating ability of PFMB MNPs, experiments were conducted at a fixed frequency of 469 kHz and concentration of 10 mg mL−1, while varying the AMF amplitude (H = 10, 12, 14, and 16 mT). The corresponding temperature rises are illustrated in Fig. 9a. The results clearly demonstrate that the temperature rise is highly dependent on the field amplitude. At lower field strengths (10 mT and 12 mT), the PFMB dispersions fail to reach the therapeutic hyperthermia threshold (42 °C) within the experimental duration, indicating insufficient heat generation under sub-threshold field amplitudes. In contrast, at higher amplitudes (14 mT and 16 mT), the temperature surpasses 42 °C, confirming that high heating ability under these fields. This trend is further supported by the calculated SAR values (Fig. 9b), which exhibit a positive correlation with increasing field amplitude.
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Fig. 9 (a)Temperature rise at different field amplitude and frequency of 469 kHz for PFMB and (b) SAR values. |
The maximum SAR observed for the PFMB nanocomposites in this study, 53.77 W g−1, is within the upper range of SAR values reported for conventional polymer-coated iron oxide nanoparticles and is comparable to previously published values for similarly synthesized MNP systems (see Table 3). However, this value remains substantially lower than the exceptionally high SAR of 1648 W g−1 reported for pyrrole-coated magnetite nanorings subjected to simultaneous AMF and near-infrared (NIR) irradiation, a dual-stimulus strategy known to enhance hyperthermic performance through combined magnetothermal and photothermal effects.8
Synthesis method | Composition | Field (kA m−1) | Frequency (kHz) | SAR (W g−1) | ILP (nH m2 kg−1) | Reference |
---|---|---|---|---|---|---|
Hydrothermal | Pyrole-Fe3O4 | 17 | 469 | 53.77 | 0.46 | This work |
Hydrothermal | Fe3O4-PVP | 17 | 332 | 160 | 0.6 | 19 |
Co-precipitation | Fe3O4-NH4HCO3 | 17.1 | 386.5 | 69.6 | 0.613 | 20 |
Emulsion polymerization | Fe3O4-PDMAEMA | 20.25 | 260 | ∼25 | ∼0.4 | 21 |
Co-precipitation | Fe3O4-Chitosan | 10–20 | 100 | ∼20 | ∼0.3 | 22 |
Hydrothermal | Fe3O4-PAA | 17 | 332 | 36 | 0.59 | 23 |
Hydrothermal | Fe3O4-PEG | 332 | 17 | 70 | ∼0.55 | 19 |
It is essential to emphasize that direct comparisons of SAR values across different studies must be approached with caution, as SAR is not an intrinsic material property but rather a function of numerous experimental and physical variables. Critical parameters influencing SAR include nanoparticle size and morphology, coating nature, magnetic anisotropy, and saturation magnetization, as well as external field parameters such as field amplitude (H), frequency (f). Additionally, calorimetric methods, sample holders, and data processing protocols vary across laboratories, contributing to systematic discrepancies in reported values.
For a more reliable comparison of heating efficiencies reported across different magnetic hyperthermia studies, the concept of Intrinsic Loss Power (ILP) has been introduced. Unlike the specific absorption rate (SAR), which is strongly influenced by experimental parameters such as field amplitude and frequency, ILP offers a normalized metric that facilitates objective evaluation of the intrinsic heating efficiency of magnetic nanoparticles.
It can be determined using the following expression:
ILP = SAR/fH2 | (3) |
The resulting ILP is expressed in nH m2 kg−1 and reflects the intrinsic ability of MNPs to convert electromagnetic energy into heat, independent of the applied field conditions.
As shown in Table 3, the ILP values obtained for PFMB MNPs fall within the range reported for similar polymer-coated MNP systems21–25 and are comparable to those of commercial ferrofluids, which typically exhibit ILP values between 0.2 and 3.1 nH m2 kg−1.26 These values reflect the relatively high intrinsic heating efficiency of PFMB under alternating magnetic field conditions, supporting their promising potential for in vitro magnetic hyperthermia applications.18
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