Nowadays, novel biomaterials are under intense research because they are part of promising therapies for the treatment of age-related diseases such as osteoporosis and bone defects. In the presented study, composites of poly(ε-caprolactone) (PCL), micro and nano hydroxyapatite (µ-HAp and n-HAp) and carbon nanofibers (CNFs) were prepared. The influence of additives on polymeric matrix was analyzed using scanning electron microscopy (SEM), Raman micro-spectroscopy, Raman mapping, and two-dimensional correlation spectroscopy (2D-COS). The bioactivity in vitro was evaluated by a 21-day incubation of prepared membranes in simulated body fluid (SBF). It was concluded that additives can behave as crystallization nuclei of PCL, but they are also located across the entire surface of PCL spherulites, not only in the center. With an increasing content of HAp additives, polymeric spherulites become smaller. The type of HAp (µ-HAp or n-HAp) influences the PCL matrix differently, as confirmed by 2D-COS. The component whose addition leads to most significant changes in the polymer is CNFs; polymeric spherulites are small to the extent that they are not distinguishable, and the overall amorphousness of the polymer is the highest among all tested materials, as is its hydrophobicity. The bioactivity test indicated that the membrane with the greatest potential for use as a biomaterial in bone tissue engineering is one consisting of n-HAp (15 wt%) and CNFs, as very uniform coverage of the produced apatite was observed on the surface of this membrane after incubation in SBF.
PriyadarshiniB.RamaM.ChetanVijayalakshmiU.. “Bioactive Coating as a Surface Modification Technique for Biocompatible Metallic Implants: A Review”. J. Asian Ceram. Soc. 2019. 7(4): 397–406. https://doi.org/10.1080/21870764.2019.1669861
GuarinoV.GentileG.SorrentinoL.AmbrosioL.. “Polycaprolactone: Synthesis, Properties, and Applications”. In: MarkH.F.KroschwitzJ.I., editors. Encyclopedia of Polymer Science and Technology. New York: John Wiley and Sons, Inc., 2017. Pp. 1–36. https://doi.org/10.1002/0471440264.pst658
8.
AbedalwafaM.WangF.WangL.LiC.. “Biodegradable Poly-Epsilon-Caprolactone (PCL) for Tissue Engineering Applications: A Review”. Rev. Adv. Mater. Sci. 2013. 34(2): 123–140.
9.
MalikmammadovE.TanirT.E.KiziltayA.HasirciV.HasirciN.. “PCL and PCL-Based Materials in Biomedical Applications”. J. Biomater. Sci. Polym. Ed. 2018. 29(7–9): 863–893. https://doi.org/10.1080/09205063.2017.1394711
10.
NayakA.K.. “Hydroxyapatite Synthesis Methodologies: An Overview”. Int. J. ChemTech Res. 2010. 2(2): 903–907.
11.
KattimaniV.S.KondakaS.LingamaneniK.P.. “Hydroxyapatite: Past, Present, and Future in Bone Regeneration”. Bone Tissue Regener. Insights. 2016. 7: 9–19. https://doi.org/10.4137/BTRI.S36138
KareemM.M.TannerK.E.. “Optimising Micro-Hydroxyapatite Reinforced Poly(Lactide Acid) Electrospun Scaffolds for Bone Tissue Engineering”. J. Mater. Sci. Mater. Med. 2020. 31(38): 1–13. https://doi.org/10.1007/S10856-020-06376-8
14.
SaccoL.N.VollebregtS.. “Overview of Engineering Carbon Nanomaterials Such as Carbon Nanotubes (CNTS), Carbon Nanofibers (CNFs), Graphene and Nanodiamonds, and Other Carbon Allotropes Inside Porous Anodic Alumina (PAA) Templates”. Nanomaterials. 2023. 123(260): 1–58. https://doi.org/10.3390/nano13020260
15.
ZhangX.ChenX.SongJ.ZhangJ., et al. “Size-Transformable Nanostructures: From Design to Biomedical Applications”. Adv. Mater. 2020. 32(48): 2003752. https://doi.org/10.1002/adma.202003752
16.
RaoR.N.AlbaseerS.S.. “Nanomaterials in Chromatographic Sample Preparations”. In: HussainC.M., editor. Nanomaterials in Chromatography: Current Trends in Chromatographic Research Technology and Techniques. Amsterdam: Elsevier, 2018. Chap. 7, Pp. 201–231. https://doi.org/10.1016/B978-0-12-812792-6.00007-8
17.
MohamedA.. “Synthesis, Characterization, and Applications Carbon Nanofibers”. In: YaragallaS.MishraR.ThomasS.KalarikkalN.MariaH.J., editors. Carbon-Based Nanofillers and Their Rubber Nanocomposites: Carbon Nano-Objects. London: Elsevier, 2018. Chap 8, Pp. 243–257. https://doi.org/10.1016/B978-0-12-813248-7.00008-0
18.
PajdaM.Wesełucha-BirczyńskaA.KołodziejA.ŚwiętekM., et al. “A Correlation of Raman Data with the Nanomechanical Results of Polymer Nanomaterials with Carbon Nanoparticles”. J. Mol. Struct. 2022. 1264: 133305. https://doi.org/10.1016/j.molstruc.2022.133305
19.
Abd El-AzizA.M.SeragE.KenawyM.Y.El-MaghrabyA.KandilS.H.. “Hydrothermally Reinforcing Hydroxyaptatite and Bioactive Glass on Carbon Nanofiber Scaffold for Bone Tissue Engineering”. Front. Bioeng. Biotechnol. 2023. 11: 1170097. https://doi.org/10.3389/fbioe.2023.1170097
20.
StoutD.A.. “Recent Advancements in Carbon Nanofiber and Carbon Nanotube Applications in Drug Delivery and Tissue Engineering”. Curr. Pharm. Des. 2015. 21(15): 2037–2044. https://doi.org/10.2174/1381612821666150302153406
21.
TranP.A.ZhangL.WebsterT.J.. “Carbon Nanofibers and Carbon Nanotubes in Regenerative Medicine”. Adv. Drug Deliv. Rev. 2009. 61(12): 1097–1114. https://doi.org/10.1016/J.addr.2009.07.010
22.
KołodziejA.Wesełucha-BirczyńskaA.ŚwiętekM.SkalniakŁBłażewiczM.. “Raman Microspectroscopic Investigations of Polymer Nanocomposites: Evaluation of Physical and Biophysical Properties”. Int. J. Polym. Mater. Polym. Biomater. 2019. 68(1–3): 44–52. https://doi.org/10.1080/00914037.2018.1525722
23.
Wesełucha-BirczyńskaA.KołodziejA.ŚwiętekM.MoskalP., et al. “Does 2D Correlation Raman Spectroscopy Distinguish Polymer Nanomaterials Due to the Nanoaddition?”. J. Mol. Struct. 2020. 1217: 128342. https://doi.org/10.1016/j.molstruc.2020.128342
BainoF.YamaguchiS.. “The Use of Simulated Body Fluid (SBF) for Assessing Materials Bioactivity in the Context of Tissue Engineering: Review and Challenges”. Biomimetics. 2020. 5(4): 57. https://doi.org/10.3390/biomimetics5040057
26.
PanahiY.HosseiniM.S.KhaliliN.NaimiE., et al. “Antioxidant and Anti-Inflammatory Effects of Curcuminoid-Piperine Combination in Subjects with Metabolic Syndrome: A Randomized Controlled Trial and an Updated Meta-Analysis”. Clin. Nutr. 2015. 34(6): 1101–1108. https://doi.org/10.1016/j.clnu.2014.12.019
27.
NathanaelA.J.HongS.I.MangalarajD.ChenP.C.. “Large Scale Synthesis of Hydroxyapatite Nanospheres by High Gravity Method”. Chem. Eng. J. 2011. 173(3): 846–854. https://doi.org/10.1016/j.cej.2011.07.053
28.
KhanA.F.AwaisM.KhanA.S.TabassumS., et al. “Raman Spectroscopy of Natural Bone and Synthetic Apatites”. Appl. Spectrosc. Rev. 2013. 48(4): 329–355. https://doi.org/10.1080/05704928.2012.721107
29.
KoutsopoulosS.. “Synthesis and Characterization of Hydroxyapatite Crystals: A Review Study on the Analytical Methods”. J. Biomed. Mater. Res. 2002. 62(4): 600–612. https://doi.org/10.1002/jbm.10280
30.
CiobanuC.S.IconaruS.L.CoustumerP.L.PredoiD.. “Vibrational Investigations of Silver-Doped Hydroxyapatite with Antibacterial Properties”. J. Spectrosc. 2013. 2013(1): 471061. https://doi.org/10.1155/2013/471061
31.
GouadecG.ColombanP.. “Raman Spectroscopy of Nanomaterials: How Spectra Relate to Disorder, Particle Size and Mechanical Properties”. Prog. Cryst. Growth Charact. Mater. 2007. 53(1): 1–56. https://doi.org/10.1016/j.pcrysgrow.2007.01.001
32.
KisterG.CassanasG.BergounhonM.HoarauD.VertM.. “Structural Characterization and Hydrolytic Degradation of Solid Copolymers of D,L-Lactide-co-ε-caprolactone by Raman Spectroscopy”. Polymer. 2000. 41(3): 925–932. https://doi.org/10.1016/S0032-3861(99)00223-2
33.
KołodziejA.Wesełucha-BirczyńskaA.ŚwiętekM.SkalniakŁ.BłażewiczM.. “A 2D-Raman Correlation Spectroscopy Study of the Interaction of the Polymer Nanocomposites with Carbon Nanotubes and Human Osteoblast-Like Cells Interface”. J. Mol. Struct. 2020. 1212: 128135. https://doi.org/10.1016/j.molstruc.2020.128135
34.
KotulaA.P.SnyderC.R.MiglerK.B.. “Determining Conformational Order and Crystallinity in Polycaprolactone via Raman Spectroscopy”. Polymer. 2017. 117: 1–10. https://doi.org/10.1016/j.polymer.2017.04.006
35.
Wesełucha-BirczyńskaA.ŚwiętekM.SołtysiakE.GalińskiP., et al. “Raman Spectroscopy and the Material Study of Nanocomposite Membranes from Poly(ε-caprolactoneε-caprolactone) with Biocompatibility Testing in Osteoblast-Like Cells”. Analyst. 2015. 140(7): 2311–2320. https://doi.org/10.1039/C4AN02284J
36.
GuadagnoL.RaimondoM.VittoriaV.VertuccioL., et al. “The Role of Carbon Nanofiber Defects on the Electrical and Mechanical Properties of CNF-Based Resins”. Nanotechnology. 2013. 24(30): 305704. https://doi.org/10.1088/0957-4484/24/30/305704
37.
VollebregtS.IshiharaR.TichelaarF.D.HouY.BeenakkerC.I.M.. “Influence of the Growth Temperature on the First and Second-Order Raman Band Ratios and Widths of Carbon Nanotubes and Fibers”. Carbon. 2012. 50(10): 3542–3554. https://doi.org/10.1016/j.carbon.2012.03.026
38.
GontijoR.N.ResendeG.C.FantiniC.CarvalhoB.R.. “Double Resonance Raman Scattering Process in 2D Materials”. J. Mater. Res. 2019. 34(12): 1976–1992. https://doi.org/10.1557/jmr.2019.167
39.
Campos-DelgadoJ.KimY.A.HayashiT.Morelos-GómezA., et al. “Thermal Stability Studies of CVD-Grown Graphene Nanoribbons: Defect Annealing and Loop Formation”. Chem. Phys. Lett. 2009. 469(1-3): 177–182. https://doi.org/10.1016/j.cplett.2008.12.082
40.
CooperD.R.D’AnjouB.GhattamaneniN.HarackB., et al. “Experimental Review of Graphene”. Int. Scholarly Res. Not. 2012. 2012(1): 501686. https://doi.org/10.5402/2012/501686
YuZ.W.ChenL.SunS.Q.NodaI.. “Determination of Selective Molecular Interactions Using Two-Dimensional Correlation FT-IR Spectroscopy”. J. Phys. Chem. A. 2002. 106(28): 6683–6687. https://doi.org/10.1021/jp025599z
43.
DridiA.RiahiK.Z.SomraniS.. “Mechanism of Apatite Formation on a Poorly Crystallized Calcium Phosphate in a Simulated Body Fluid (SBF) at 37 44°C”. J. Phys. Chem. Solids. 2021. 156: 110122. https://doi.org/10.1016/j.jpcs.2021.110122
44.
DeyA.BomansP.H.H.MüllerF.A.WillJ., et al. “The Role of Prenucleation Clusters in Surface-Induced Calcium Phosphate Crystallization”. Nat. Mater. 2010. 9(12): 1010–1014. https://doi.org/10.1038/nmat2900
45.
StellaS.M.SridharT.M.RamprasathR.GimbunJ.VijayalakshmiU.. “Physio-Chemical and Biological Characterization of Novel HPC (Hydroxypropylcellulose):HAP (Hydroxyapatite):PLA (Poly Lactic Acid) Electrospun Nanofibers as Implantable Material for Bone Regenerative Application”. Polymers. 2023. 15(1): 155. https://doi.org/10.3390/polym15010155
46.
KawaiT.OhtsukiC.KamitakaharaM.TaniharaM., et al. “A Comparative Study of Apatite Deposition on Polyamide Films Containing Different Functional Groups Under a Biomimetic Condition”. J. Ceram. Soc. Jpn. 2005. 113(9): 588–592. https://doi.org/10.2109/jcersj.113.588
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