Nowadays, despite significant advances in the field of biomaterials for tissue engineering applications, novel bone substituents still need refinement so they can be successfully implemented into the medical treatment of bone fractures. Generally, a scaffold made of synthetic polymer blended with nanofillers was proven to be a very promising biomaterial for tissue engineering, however the choice of components for the said scaffold remains questionable. The objects of the presented study were novel composites consisting of poly(ε-caprolactone) (PCL) and two types of graphene materials: graphene oxide (GO) and partially reduced graphene oxide (rGO). The technique of choice, that was used to characterize the obtained composites, was Raman micro-spectroscopy. It revealed that the composite PCL/GO differs substantially from the PCL/rGO composite. The incorporation of the GO particles into the polymer influenced the structure organisation of the polymeric matrix more significantly than rGO. The crystallinity parameters confirmed that the level of crystallinity is generally higher in the PCL/GO membrane in comparison to PCL/rGO (and even in raw PCL) that leads to the conclusion that the GO acts as a nucleation agent enhancing the crystallization of PCL. Interestingly, the characteristics of the studied nanofillers, for example: the level of the organisation (D/G ratio) and the in-plane size of the nano-crystallites (L_a) almost do not differ. However, they have an ability to influence polymeric matrix differently.

Maghemite (γ-Fe₂O₃) nanoparticles obtained through co-precipitation and oxidation were coated with heparin (Hep) to yield γ-Fe₂O₃@Hep, and subsequently with chitosan that was modified with different phenolic compounds, including gallic acid (CS-G), hydroquinone (CS-H), and phloroglucinol (CS-P), to yield γ-Fe₂O₃@Hep-CS-G, γ-Fe₂O₃@Hep-CS-H, and γ-Fe₂O₃@Hep-CS-P particles, respectively. Surface modification of the particles was analyzed by transmission electron microscopy, dynamic light scattering, attenuated total reflection Fourier transform infrared spectroscopy, and thermogravimetric analysis. Magnetic measurements indicated that the polymer coating does not affect the superparamagnetic character of the iron oxide core. However, magnetic saturation decreased with increasing thickness of the polymer coating. The antioxidant properties of the nanoparticles were analyzed using a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Cellular uptake and intracellular antioxidant activity of the particles were evaluated by an iron assay and flow cytometry, respectively, using L-929 and LN-229 cells. Compared to the control, the phenolic modification significantly reduced intracellular reactive oxygen species (ROS) levels to 35–56%, which was associated with a 6–8-times higher cellular uptake in L-929 cells and a 21–31-times higher cellular uptake in LN-229 cells. In contrast, γ-Fe₂O₃@Hep particles induced a 3.8-times and 14.9-times higher cellular uptake without inducing antioxidant activity. In conclusion, the high cellular uptake and the antioxidant properties associated with the phenolic moieties in the modified particles allow for a potential application in biomedical areas.

Poly(ε-caprolactone) (PCL) is a biocompatible resorbable material, but its use is limited due to the fact that it is characterized by the lack of cell adhesion to its surface. Various chemical and physical methods are described in the literature, as well as modifications with various nanoparticles aimed at giving it such surface properties that would positively affect cell adhesion. Nanomaterials, in the form of membranes, were obtained by the introduction of multi-walled carbon nanotubes (MWCNTs and functionalized nanotubes, MWCNTs-f) as well as electro-spun carbon nanofibers (ESCNFs, and functionalized nanofibers, ESCNFs-f) into a PCL matrix. Their properties were compared with that of reference, unmodified PCL membrane. Human osteoblast-like cell line, U-2 OS (expressing green fluorescent protein, GFP) was seeded on the evaluated nanomaterial membranes at relatively low confluency and cultured in the standard cell culture conditions. The attachment and the growth of the cell populations on the polymer and nanocomposite samples were monitored throughout the first week of culture with fluorescence microscopy. Simultaneously, Raman microspectroscopy was also used to track the dependence of U-2 OS cell development on the type of nanomaterial, and it has proven to be the best method for the early detection of nanomaterial/cell interactions. The differentiation of interactions depending on the type of nanoadditive is indicated by the ν(COC) vibration range, which indicates the interaction with PCL membranes with carbon nanotubes, while it is irrelevant for PCL with carbon nanofibers, for which no changes are observed. The vibration range ω(CH₂) indicates the interaction for PCL with carbon nanofibers with seeded cells. The crystallinity of the area ν(C=O) increases for PCL/MWCNTs and for PCL/MWCNTs-f, while it decreases for PCL/ESCNFs and for PCL/ESCNFs-f with seeded cells. The crystallinity of the membranes, which is determined by Raman microspectroscopy, allows for the assessment of polymer structure changes and their degradability caused by the secretion of cell products into the ECM and the differentiation of interactions depending on the carbon nanostructure. The obtained nanocomposite membranes are promising bioactive materials.

Coating of nanoparticles with gallates renders them antioxidant and enhances cellular internalization. In this study, (amino)silica magnetic particles modified with tannic acid (TA) and optionally with chitosan (CS) were developed, and their physicochemical properties and antioxidant activity were evaluated. The results demonstrated that the TA-modified aminosilica-coated particles, as well as the silica-coated particles with a double TA layer, exhibited high antioxidant activity, whereas the silica-coated particles with no or only a single TA layer were well-internalized by LN-229 cells. In addition, a magnet placed under the culture plates greatly increased the cellular uptake of all TA-coated magnetic nanoparticles. The coating thus had a considerable impact on nanoparticle–cell interactions and particle internalization. The TA-coated magnetic nanoparticles have great potential as intracellular carriers with preserved antioxidant activity.

The aim of this study was to develop multifunctional magnetic poly(ε‐caprolactone) (PCL) mats with antibacterial properties for bone tissue engineering and osteosarcoma prevention. To provide good dispersion of magnetic iron oxide nanoparticles (IONs), they were first grafted with PCL using a novel three‐step approach. Then, a series of PCL‐based mats containing a fixed amount of ION@PCL particles and an increasing content of ascorbic acid (AA) was prepared by electrospinning. AA is known for increasing osteoblast activity and suppressing osteosarcoma cells. Composites were characterized in terms of morphology, mechanical properties, hydrolytic stability, antibacterial performance, and biocompatibility. AA affected both the fiber diameter and the mechanical properties of the nanocomposites. All produced mats were nontoxic to rat bone marrow‐derived mesenchymal cells; however, a composite with 5 wt.% of AA suppressed the initial proliferation of SAOS‐2 osteoblast‐like cells. Moreover, AA improved antibacterial properties against Staphylococcus aureus and Escherichia coli compared to PCL. Overall, these magnetic composites, reported for the very first time, can be used as scaffolds for both tissue regeneration and osteosarcoma prevention.

We describe recent improvements of our method named powder nanobeam diffraction in four-dimensional scanning transmission electron microscopy (4D-STEM/PNBD). The method can change an arbitrary SEM equipped with a 2D-array STEM detector to a user-friendly powder electron diffractometer. It reduces a 4D-STEM dataset to a single 2D powder electron diffraction pattern (using our Python package named STEMDIFF; https://pypi.org/project/stemdiff) and then to 1D radially averaged diffraction profile (using our Python package named EDIFF; https://pypi.org/project/ediff). Moreover, the EDIFF package can compare the final diffractogram with theoretically calculated X-ray diffraction patterns. Both STEMDIFF and EDIFF can be used in the form of simple interactive templates in Jupyter environment, which makes them accessible to common SEM users. The recent improvements in STEMDIFF and EDIFF (better dataset filtering, parallelization, and more flexible user interface) enabled us to analyze not only strongly diffracting nanocrystals but also samples with higher absorption and/or lower diffraction power. The final results obtained from 4D-STEM/PNBD datasets of all six samples analyzed in this contribution (two types of Au nanocrystals, GdF3 and TbF3 aggregates, and Fe3O4 nanoclusters with/without organic shell) were shown to be comparable with the results of the classical TEM/SAED method (selected area electron diffraction in TEM).