Physicochemical Properties of Inorganic and Hybrid Hydroxyapatite-Based Granules Modified with Citric Acid or Polyethylene Glycol.

This study delves into the physicochemical properties of inorganic hydroxyapatite (HAp) and hybrid hydroxyapatite-chitosan (HAp-CTS) granules, also gold-enriched, which can be used as aggregates in biomicroconcrete-type materials. The impact of granules' surface modifications with citric acid (CA) or polyethylene glycol (PEG) was assessed. Citric acid modification induced increased specific surface area and porosity in inorganic granules, contrasting with reduced parameters in hybrid granules. PEG modification resulted in a slight increase in specific surface area for inorganic granules and a substantial rise for hybrid granules with gold nanoparticles. Varied effects on open porosity were observed based on granule type. Microstructural analysis revealed increased roughness for inorganic granules post CA modification, while hybrid granules exhibited smoother surfaces. Novel biomicroconcretes, based on α-tricalcium phosphate (α-TCP) calcium phosphate cement and developed granules as aggregates within, were evaluated for compressive strength. Compressive strength assessments showcased significant enhancement with PEG modification, emphasizing its positive impact. Citric acid modification demonstrated variable effects, depending on granule composition. The incorporation of gold nanoparticles further enriched the multifaceted approach to enhancing calcium phosphate-based biomaterials for potential biomedical applications. This study demonstrates the pivotal role of surface modifications in tailoring the physicochemical properties of granules, paving the way for advanced biomicroconcretes with improved compressive strength for diverse biomedical applications.

Scattering correction for samples with cylindrical domains measured with polarized infrared spectroscopy.

Scattering artifacts are one of the most common effects distorting transmission spectra in Fourier-Transform Infrared spectroscopy. Their increased impact, strongly diminishing the quantitative and qualitative power of IR spectroscopy, is especially observed for structures with a size comparable to the radiation wavelength. To tackle this problem, a wide range of preprocessing techniques based on the Extended Multiplicative Scattering Correction method was developed, using physical properties to remove scattering presence in the spectra. However, until recently those algorithms were mostly focused on spherically shaped samples, for example, cells. Here, an algorithm for samples with cylindrical domains is described, with additional implementation of a linearly polarized light case, which is crucial for the growing field of polarized IR imaging and spectroscopy. An open-source code with GPU based implementation is provided, with a calculation time of several seconds per spectrum. Optimizations done to improve the throughput of this algorithm allow the application of this method into the standard preprocessing pipeline of small datasets.

Aging Process of Biocomposites with the PLA Matrix Modified with Different Types of Cellulose.

In the modern world, many products are disposable or have a very short lifespan, while at the same time, those products are made from materials that will remain in the environment in the form of waste for hundreds or even thousands of years. It is a serious problem; non-biodegradable polymer wastes are part of environmental pollution and generate microplastics, which accumulate in the organisms of living beings. One of the proposed solutions is biodegradable polymers and their composites. In our work, three types of polylactide-based composites with plant-derived fillers: microcellulose powder, short flax fibers, and wood flour at 2 wt.% were prepared. Poly(lactic acid) (PLA)-based biocomposite properties were characterized in terms of mechanical and surface properties together with microscopic analysis and Fourier-transform infrared spectroscopy (FTIR), before and after a UV (ultraviolet)-light-aging process to determine the effects of each cellulose-based additive on the UV-induced degradation process. This research shows that the addition of a cellulose additive can improve the properties of the material in terms of the UV-aging process, but the form of the chosen cellulose form plays a crucial role in this case. The testing of physicochemical properties demonstrated that not only can mechanical properties be improved, but also the time of degradation under UV light exposure can be controlled by the proper selection of the reinforcing phase and the parameters of the extrusion and injection molding process. The obtained results turned out to be very interesting, not only in terms of the cost reduction of the biocomposites themselves, as mainly the waste from the wood industry was used as a low-cost filler, but also that the additive delays the aging process occurring during UV light exposure. Even a small, 2 wt.% addition of some of the tested forms of cellulose delayed surface degradation, which is one of the most important factors affecting the biodegradation process.

Super-Resolved 3D Mapping of Molecular Orientation Using Vibrational Techniques.

When a sample has an anisotropic structure, it is possible to obtain additional information controlling the polarization of incident light. With their straightforward instrumentation approaches, infrared (IR) and Raman spectroscopies are widely popular in this area. Single-band-based determination of molecular in-plane orientation, typically used in materials science, is here extended by the concurrent use of two vibration bands, revealing the orientational ordering in three dimension. The concurrent analysis was applied to IR spectromicroscopic data to obtain orientation angles of a model polycaprolactone spherulite sample. The applicability of this method spans from high-resolution, diffraction-limited Fourier transform infrared (FT-IR) and Raman imaging to super-resolved optical photothermal infrared (O-PTIR) imaging. Due to the nontomographic experimental approach, no image distortion is visible and nanometer scale orientation domains can be observed. Three-dimensional (3D) bond orientation maps enable in-depth characterization and consequently precise control of the sample's physicochemical properties and functions.

Gradient Chitosan Hydrogels Modified with Graphene Derivatives and Hydroxyapatite: Physiochemical Properties and Initial Cytocompatibility Evaluation.

In this study, we investigated preparation of gradient chitosan-matrix hydrogels through a novel freezing-gelling-thawing method. The influence of three types of graphene family materials (GFM), i.e., graphene oxide (GO), reduced graphene oxide (rGO), and poly(ethylene glycol) grafted graphene oxide (GO-PEG), as well as hydroxyapatite (HAp) on the physicochemical and biological properties of the composite hydrogels was examined in view of their potential applicability as tissue engineering scaffolds. The substrates and the hydrogel samples were thoroughly characterized by X-ray photoelectron spectroscopy, X-ray diffractometry, infrared spectroscopy, digital and scanning electron microscopy, rheological and mechanical analysis, in vitro chemical stability and bioactivity assays, as well as initial cytocompatibility evaluation with human umbilical cord Wharton's jelly mesenchymal stem cells (hUC-MSCs). We followed the green-chemistry approach and avoided toxic cross-linking agents, using instead specific interactions of our polymer matrix with tannic acid, non-toxic physical cross-linker, and graphene derivatives. It was shown that the most promising are the gradient hydrogels modified with GO-PEG and HAp.

Influence of ZnO, SiO2 and TiO2 on the aging process of PLA fibers produced by electrospinning method.

The aim of this work was to study the effect of ceramics particles addition (SiO2, ZnO, TiO2) on the ultraviolet (UV) aging of poly(lactic acid) nonwovens fabricated using electrospinning method. The resistance to aging is a key factor for outdoor and medical applications (UV light sterilization). Nonwovens were placed in special chamber with UV light. Changes of physicochemical properties were recorded using differential scanning calorimetry and attenuated total reflection Fourier-transform infrared spectroscopy. The fibers' morphology was studied by using scanning electron microscopy. Obtained results clearly showed that only PLA fibers with ZnO particles gained an increase in UV resistance. The paper presents a description of structural changes taking place under the influence of UV aging processes and describes the mechanisms of this process and the effect of ceramic addition on the lifetime of such materials.

Polylactide/Hydroxyapatite Nonwovens Incorporated into Chitosan/Graphene Materials Hydrogels to Form Novel Hierarchical Scaffolds.

In this study, hierarchical, cylindrical scaffolds based on polylactide (PLA) microfibers incorporated into chitosan (CS) hydrogel were prepared for potential use in bone tissue engineering. PLA nonwovens modified with hydroxyapatite particles (HAp) were obtained using the electrospinning method. Then, three-dimensional scaffolds were created by rolling up the nonwovens and immersing them in CS-based solutions with graphene oxide (GO) or reduced graphene oxide (rGO) dispersed in the polymer matrix. Hydrogels were cross-linked using a novel freezing-thawing-gelling method. A broad spectrum of research methods was applied in order to thoroughly characterize both the nanofillers and the composite systems: scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, attenuated total reflection Fourier transform infrared spectroscopy, rheological and mechanical testing, as well as the assessment of chemical stability, bioactivity and cytocompatibility.

Synthesis and Characterization of Chitosan/Reduced Graphene Oxide Hybrid Composites.

Graphene family materials (GFM) are currently considered to be one of the most interesting nanomaterials with a wide range of application. They can also be used as modifiers of polymer matrices to develop composite materials with favorable properties. In this study, hybrid nanocomposites based on chitosan (CS) and reduced graphene oxide (rGO) were fabricated for potential use in bone tissue engineering. CS/rGO hydrogels were prepared by simultaneous reduction and composite formation in acetic acid or lactic acid and crosslinked with a natural agent-tannic acid (TAc). A broad spectrum of research methods was applied in order to thoroughly characterize both the components and the composite systems, i.e., X-ray Photoelectron Spectroscopy, X-ray Diffractometry, Attenuated Total Reflection Fourier-Transform Infrared Spectroscopy, Scanning Electron Microscopy, ninhydrin assay, mechanical testing, in vitro degradation and bioactivity study, wettability, and, finally, cytocompatibility. The composites formed through the self-assembly of CS chains and exfoliated rGO sheets. Obtained results allowed also to conclude that the type of solvent used impacts the polymer structure and its ability to interact with rGO sheets and the mechanical properties of the composites. Both rGO and TAc acted as crosslinkers of the polymer chains. This study shows that the developed materials demonstrate the potential for use in bone tissue engineering. The next step should be their detailed biological examinations.