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Streszczenie:
The development of bone tissue engineering, a field with significant potential, requires a biomaterial with high bioactivity. The aim of this manuscript was to fabricate a nanofibrous poly(L-lactide) (PLLA) scaffold containing nano-hydroxyapatite (nHA) to investigate PLLA/nHA composites, particularly the effect of fiber arrangement and the addition of nHA on the piezoelectric phases and piezoelectricity of PLLA samples. In this study, we evaluated the effect of nHA particles on a PLLA-based electrospun scaffold with random and aligned fiber orientations. The addition of nHA increased the surface free energy of PLLA/nHA (42.9 mN/m) compared to PLLA (33.1 mN/m) in the case of aligned fibers. WAXS results indicated that at room temperature, all the fibers are in an amorphous state indicated by a lack of diffraction peaks and amorphous halo. DSC analysis showed that all samples located in the amorphous/disordered alpha' phase crystallize intensively at temperatures just above the Tg and recrystallize on further heating, achieving significantly higher crystallinity for pure PLLA than for doped nHA, 70 % vs 40 %, respectively. Additionally, PLLA/nHA fibers show a lower heat capacity for PLLA in the amorphous state, indicating that nHA reduces the molecular mobility of PLLA. Moreover, piezoelectric constant d33 was found to increase with the addition of nHA and for the aligned orientation of the fibers. In vitro tests confirmed that the addition of nHA and the aligned orientation of nanofibers increased osteoblast proliferation.

Słowa kluczowe:
Scaffolds, Tissue engineering, Bone tissue engineering, Smart medicine, Biodegradable polymers, Regenerative medicine

Streszczenie:
Nanofibrous materials generated through electrospinning have gained significant attention in tissue regeneration, particularly in the domain of bone reconstruction. There is high interest in designing a material resembling bone tissue, and many scientists are trying to create materials applicable to bone tissue engineering with piezoelectricity similar to bone. One of the prospective candidates is highly piezoelectric poly(vinylidene fluoride) (PVDF), which was used for fibrous scaffold formation by electrospinning. In this study, we focused on the effect of PVDF molecular weight (180,000 g/mol and 530,000 g/mol) and process parameters, such as the rotational speed of the collector, applied voltage, and solution flow rate on the properties of the final scaffold. Fourier Transform Infrared Spectroscopy allows for determining the effect of molecular weight and processing parameters on the content of the electroactive phases. It can be concluded that the higher molecular weight of the PVDF and higher collector rotational speed increase nanofibers’ diameter, electroactive phase content, and piezoelectric coefficient. Various electrospinning parameters showed changes in electroactive phase content with the maximum at the applied voltage of 22 kV and flow rate of 0.8 mL/h. Moreover, the cytocompatibility of the scaffolds was confirmed in the culture of human adipose-derived stromal cells with known potential for osteogenic differentiation. Based on the results obtained, it can be concluded that PVDF scaffolds may be taken into account as a tool in bone tissue engineering and are worth further investigation.

Słowa kluczowe:
scaffolds,polymers,piezoelectricity,bone tissue engineering,nanofibers,regenerative medicine

Streszczenie:
Biodegradability or materials physicochemical stability are the key biomaterials selection parameters for various medical and tissue engineering applications. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a natural copolymer known from its biocompatibility with great support for cells growth and attachment on films and fibers. In our studies, the physicochemical properties of electrospun PHBV fibers and spin-coated films aged for 1, 4 and 8 weeks were analyzed using bulk (FTIR) and surface chemistry (XPS) methods and water contact angle. Further, we characterized the zeta potential changes after aging, by means of electrokinetic measurements, and cell responses to it, using NIH 3T3 murine fibroblasts. Colorimetric MTS cell viability test allowed the assessment of cell proliferation. Additionally, the morphology of fibroblasts and biointerfaces were studied by confocal laser and electron scanning microscopy (CLSM and SEM). These studies indicated that the activity, attachment and proliferation of fibroblasts is independent of aging of PHBV fibers and films. PHBV films show very stable zeta potential over 8 weeks of aging, opposite to PHBV fibers. Importantly, the flat film of PHBV increases cell proliferation, while the fibrous meshes are an excellent support for their stretching. The results of the study revealed clear advantages of PHBV films and fibrous meshes in cell-material interaction.

Słowa kluczowe:
cell morphology, fibroblast, electrospun fibers, PHBV, Zeta potential

Streszczenie:
Piezoelectric polymers are promising energy materials for wearable and implantable applications for replacing bulky batteries in small and flexible electronics. Therefore, many research studies are focused on understanding the behavior of polymers at a molecular level and designing new polymer-based generators using polyvinylidene fluoride (PVDF). In this work, we investigated the influence of voltage polarity and ambient relative humidity in electrospinning of PVDF for energy-harvesting applications. A multitechnique approach combining microscopy and spectroscopy was used to study the content of the β-phase and piezoelectric properties of PVDF fibers. We shed new light on β-phase crystallization in electrospun PVDF and showed the enhanced piezoelectric response of the PVDF fiber-based generator produced with the negative voltage polarity at a relative humidity of 60%. Above all, we proved that not only crystallinity but also surface chemistry is crucial for improving piezoelectric performance in PVDF fibers. Controlling relative humidity and voltage polarity increased the d33 piezoelectric coefficient for PVDF fibers by more than three times and allowed us to generate a power density of 0.6 μW·cm^–2 from PVDF membranes. This study showed that the electrospinning technique can be used as a single-step process for obtaining a vast spectrum of PVDF fibers exhibiting different physicochemical properties with β-phase crystallinity reaching up to 74%. The humidity and voltage polarity are critical factors in respect of chemistry of the material on piezoelectricity of PVDF fibers, which establishes a novel route to engineer materials for energy-harvesting and sensing applications.

Słowa kluczowe:
PVDF, polymer crystallinity, electrospinning, piezoelectricity, voltage polarity

Streszczenie:
Electric field strength and polarity in electrospinning processes and their effect on process dynamics and the physical properties of as-spun fibers is studied. Using a solution of the neutral polymer such as poly(methyl methacrylate) (PMMA) we explored the electrospun jet motion issued from a Taylor cone. We focused on the straight jet section up to the incipient stage of the bending instability and on the radius of the disk of the fibers deposited on the collecting electrode. A new correlation formula using dimensionless parameters was found, characterizing the effect of the electric field on the length of the straight jet, L˜E~E˜0.55. This correlation was found to be valid when the spinneret was either negatively or positively charged and the electrode grounded. The fiber deposition radius was found to be independent of the electric field strength and polarity. When the spinneret was negatively charged, L˜E was longer, the as-spun fibers were wider. The positively charged setup resulted in fibers with enhanced mechanical properties and higher crystallinity. This work demonstrates that often-overlooked electrical polarity and field strength parameters influence the dynamics of fiber electrospinning, which is crucial for designing polymer fiber properties and optimizing their collection.

Słowa kluczowe:
fibers, electrical polarity, charges, electrospinning, PMMA, mechanical properties