Evaluation of the impact of pH of the reaction mixture, type of the stirring, and the reagents' concentration in the wet precipitation method on physicochemical properties of hydroxyapatite so as to enhance its biomedical application potential.

Hydroxyapatite (HAp) constitutes a significant inorganic compound which due to its osteoinductivity, osteoconductivity as well as the ability to promote bone growth and regeneration is widely applied in development of biomaterials designed for bone tissue engineering. In this work, various synthesis methodologies of HAp based on the wet precipitation technique were applied, and the impact of pH of the reaction mixture, the concentration of individual reagents as well as the type of stirring applied (mechanical/magnetic) on the properties of final powders was discussed. Spectroscopic methods (Fourier transform infrared, Raman) and X-ray diffraction allowed to verify the synthesis parameters leading to obtaining calcium phosphate with 96% HAp in phase which indicated higher homogeneity of obtained powder (93.4%) than commercial HAp. Powders' morphology was evaluated using microscopic techniques while specific surface area was determined via Brunauer-Emmett-Teller analysis. Particle size distribution, porosity of powders, and stability of HAp suspensions were also characterized. It was proved that synthesis at pH = 11.0 using mechanical stirring resulted in calcium phosphate with a high phase homogeneity and homogeneous pore size distribution (6-20 nm). Moreover, obtained HAp powder showed 71.8% more specific surface area than commercial material-that is, 110 m3 /g for synthetic HAp and 64 m3 /g in the case of commercial powder-which, in turn, is significant in terms of its potential application as carrier of active substances. Thus it was demonstrated that by applying appropriate conditions of HAp synthesis it is possible to obtain powder with properties enhancing its application potential for medical purposes.

Iron Oxide Magnetic Nanoparticles with a Shell Made from Nanosilver-Synthesis Methodology and Characterization of Physicochemical and Biological Properties.

The interest in magnetic nanoparticles is constantly growing, which is due to their unique properties, of which the most useful is the possibility of directing their movement via an external magnetic field. Thus, applications may be found for them as carriers in targeted drug delivery. These nanomaterials usually form a core in a core-shell structure, and a shell may be formed via various compounds. Here, nanosilver-shelled iron oxide magnetic nanoparticles were developed. Various reaction media and various Arabic gum (stabilizer) solution concentrations were investigated to verify those that were most beneficial one in limiting their agglomeration as much as possible. The essential oil of lavender was proposed as a component of such a medium; it was used alone or in combination with distilled water as a solvent of the stabilizer. The particle size was characterized by dynamic light scattering (DLS), the chemical structure was characterized via FT-IR spectroscopy, the crystallinity was characterized by X-ray diffraction (XRD), and the surface morphology and elemental composition were verified via the SEM-EDS technique. Moreover, UV-Vis spectrophotometry was used to verify the presence of the shell made of nanosilver. Importantly, the particles' pro-inflammatory activity and cytotoxicity towards L929 murine fibroblasts were also characterized. It was demonstrated that a 3% stabilizer solution provided a preparation of Fe3O4@Ag particles, but its stabilizing effect was not sufficient, as a suspension with micrometric particles was obtained; thus it was necessary to apply 4 h of sonication for their crushing. Next, the oil/water reaction medium was verified as beneficial in terms of nanoparticle formation. In such reaction conditions, the formation of particle agglomerates was strongly limited, and after 15 min of sonication a suspension containing only nanoparticles was obtained. The presence of a nanosilver shell was confirmed spectrophotometrically via XRD and SEM-EDS techniques. Importantly, the developed nanomaterials showed no cytotoxicity towards murine fibroblasts and no pro-inflammatory activity.

The Synthesis Methodology and Characterization of Nanogold-Coated Fe3O4 Magnetic Nanoparticles.

Core-shell nanostructures are widely used in many fields, including medicine and the related areas. An example of such structures are nanogold-shelled Fe3O4 magnetic nanoparticles. Systems consisting of a magnetic core and a shell made from nanogold show unique optical and magnetic properties. Thus, it is essential to develop the methodology of their preparation. Here, we report the synthesis methodology of Fe3O4@Au developed so as to limit their agglomeration and increase their stability. For this purpose, the impact of the reaction environment was verified. The properties of the particles were characterized via UV-Vis spectrophotometry, dynamic light scattering (DLS), X-ray diffraction (XRD), and Scanning Electron Microscopy-Energy Dispersive X-ray analysis (SEM-EDS technique). Moreover, biological investigations, including determining the cytotoxicity of the particles towards murine fibroblasts and the pro-inflammatory activity were also performed. It was demonstrated that the application of an oil and water reaction environment leads to the preparation of the particles with lower polydispersity, whose agglomerates' disintegration is 24 times faster than the disintegration of nanoparticle agglomerates formed as a result of the reaction performed in a water environment. Importantly, developed Fe3O4@Au nanoparticles showed no pro-inflammatory activity regardless of their concentration and the reaction environment applied during their synthesis and the viability of cell lines incubated for 24 h with the particle suspensions was at least 92.88%. Thus, the developed synthesis methodology of the particles as well as performed investigations confirmed a great application potential of developed materials for biomedical purposes.

The Impact of the Matricaria chamomilla L. Extract, Starch Solution and the Photoinitiator on Physiochemical Properties of Acrylic Hydrogels.

Matricaria chamomilla L. extract is well-known for its therapeutic properties; thus, it shows potential to be used to modify materials designed for biomedical purposes. In this paper, acrylic hydrogels modified with this extract were prepared. The other modifier was starch introduced into the hydrogel matrix in two forms: room-temperature solution and elevated-temperature solution. Such hydrogels were synthesized via UV radiation, while two types of photoinitiator were used: 2-hydroxy-2-methylpropiophenone or phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide. The main task of performed research was to verify the impact of particular modifiers and photoinitiator on physicochemical properties of hydrogels. Studies involved determining their swelling ability, elasticity, chemical structure via FTIR spectroscopy and surface morphology via the SEM technique. Incubation of hydrogels in simulated physiological liquids, studies on the release of chamomile extract from their matrix and their biological analysis via MTT assay were also performed. It was demonstrated that all investigated variables affected the physicochemical properties of hydrogels. The modification of hydrogels with chamomile extract reduced their absorbency, decreased their thermal stability and increased the cell viability incubated with this material by 15%. Next, hydrogels obtained by using phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide as a photoinitiator showed lower absorbency, more compact structure, better stability in SBF and a more effective release of chamomile extract compared to the materials prepared by using 2-hydroxy-2-methylpropiophenone. It was proved that, by applying adequate reagents, including both photoinitiator and modifiers, it is possible to obtain hydrogels with variable properties that will positively affect their application potential.

Physicochemical Characteristics of Chitosan-Based Hydrogels Modified with Equisetum arvense L. (Horsetail) Extract in View of Their Usefulness as Innovative Dressing Materials.

This work focused on obtaining and characterizing hydrogels with their potential application as dressing materials for chronic wounds. The research included synthesizing chitosan-based hydrogels modified with Equisetum arvense L. (horsetail) extract via photopolymerization, and their characteristics determined with regard to the impact of both the modifier and the amount of crosslinker on their properties. The investigations included determining their sorption properties and tensile strength, evaluating their behavior in simulated physiological liquids, and characterizing their wettability and surface morphology. The release profile of horsetail extract from polymer matrices in acidic and alkaline environments was also verified. It was proved that hydrogels showed swelling ability while the modified hydrogels swelled slightly more. Hydrogels showed hydrophilic nature (all contact angles were <77°). Materials containing horsetail extract exhibited bigger elasticity than unmodified polymers (even by 30%). It was proved that the extract release was twice as effective in an acidic medium. Due to the possibility of preparation of hydrogels with specific mechanical properties (depending on both the modifier and the amount of crosslinker used), wound exudate sorption ability, and possibility of the release of active substance, hydrogels show a great application potential as dressing materials.

Physicochemical Characteristics of Chitosan-Based Hydrogels Containing Albumin Particles and Aloe vera Juice as Transdermal Systems Functionalized in the Viewpoint of Potential Biomedical Applications.

In recent years, many investigations on the development of innovative dressing materials with potential applications, e.g., for cytostatics delivery, have been performed. One of the most promising carriers is albumin, which tends to accumulate near cancer cells. Here, chitosan-based hydrogels containing albumin spheres and Aloe vera juice, designed for the treatment of skin cancers or burn wounds resulting from radiotherapy, were developed. The presence of albumin in hydrogel matrices was confirmed via Fourier transform infrared (FT-IR) and Raman spectroscopy. Albumin spheres were clearly visible in microscopic images. It was proved that the introduction of albumin into hydrogels resulted in their increased resistance to the tensile load, i.e., approximately 30% more force was needed to break such materials. Modified hydrogels showed approximately 10% more swelling ability. All hydrogels were characterized by hydrophilicity (contact angles were <90°) which may support the regeneration of epithelial cells and non-cytotoxicity towards murine fibroblasts L929 and released Aloe vera juice more effectively in an acidic environment than in a neutral one wherein spheres introduced into the hydrogel matrix extended the release time. Thus, the developed materials, due to their chemical composition and physicochemical properties, constitute promising materials with great application potential for biomedical purposes.

Multistep Chemical Processing of Crickets Leading to the Extraction of Chitosan Used for Synthesis of Polymer Drug Carriers.

Chitosan belongs to the group of biopolymers with increasing range of potential applications therefore searching for new raw materials as well as new techniques of obtaining of this polysaccharide are currently a subject of interest of many scientists. Presented manuscript describes preparation of chitosan from crickets. Obtainment of final product required a number of processes aimed at removal of undesirable substances such as waxes, mineral salts, proteins or pigments from above-mentioned insects. Chemical structure of fractions obtained after each step was compared with the structure of commercial chitosan by means of techniques such as X-ray diffraction and FT-IR spectroscopy. Final product was subsequently used for preparation of polymer capsules that were modified with active substance characterized by antibacterial and anticancer activity-nisin. Next, sorption capacity of obtained materials was evaluated as well as a release profile of active substance in different environments. Based on the conducted research it can be concluded that crickets constitute an alternative for shellfish and other conventional sources of chitosan. Furthermore, obtained capsules on the basis of such prepared chitosan can be considered as drug delivery systems which efficiency of release of active substance is bigger in alkaline environments.

The Development of the Innovative Synthesis Methodology of Albumin Nanoparticles Supported by Their Physicochemical, Cytotoxic and Hemolytic Evaluation.

Many studies are being performed to develop effective carriers for controlled cytostatic delivery wherein albumin is a promising material due to its tendency to accumulate near cancer cells. The novelty of this work involves the development of the synthesis methodology of albumin nanoparticles and their biological and physicochemical evaluation. Albumin particles were obtained via the salt-induced precipitation and K3PO4 was used as a salting-out agent. Various concentrations of protein and salting-out agent solutions were mixed using a burette or a syringe system. It was proved that the size of the particles depended on the concentrations of the reagents and the methodology applied. As a result of a process performed using a burette and 2 M K3PO4, albumin spheres having a size 5-25 nm were obtained. The size of nanospheres and their spherical shape was confirmed via TEM analysis. The use of a syringe system led to preparation of particles of large polydispersity. The highest albumin concentration allowing for synthesis of homogeneous particles was 2 g/L. The presence of albumin in spheres was confirmed via the FT-IR technique and UV-Vis spectroscopy. All samples showed no cytotoxicity towards normal human dermal fibroblasts and no hemolytic properties against human erythrocytes (the hemolysis did not exceed 2.5%).

Starch Solutions Prepared under Different Conditions as Modifiers of Chitosan/Poly(aspartic acid)-Based Hydrogels.

Recently, there has been great interest in the application of polysaccharides in the preparation of diverse biomaterials which result from their biocompatibility, biodegradability and biological activity. In this work, the investigations on chitosan/poly(aspartic acid)-based hydrogels modified with starch were described. Firstly, a series of hydrogel matrices was prepared and investigated to characterize their swelling properties, structure via FT-IR spectroscopy, elasticity and tensile strength using the Brookfield texture analyzer as well as their impact on simulated physiological liquids. Hydrogels consisting of chitosan and poly(aspartic acid) in a 2:1 volume ratio were elastic (9% elongation), did not degrade after 30-day incubation in simulated physiological liquids, exhibited a relative biocompatibility towards these liquids and similar swelling in each absorbed medium. This hydrogel matrix was modified with starch wherein two of its form were applied-a solution obtained at an elevated temperature and a suspension obtained at room temperature. Hydrogels modified with hot starch solution showed higher sorption that unmodified materials. This was probably due to the higher starch inclusion (i.e., a larger number of hydrophilic groups able to interact with the adsorbed liquid) when this polysaccharide was given in the form of a hot solution. Hydrogels modified with a cold starch suspension had visible heterogeneous inequalities on their surfaces and this modification led to the obtainment materials with unrepeatable structures which made the analysis of their properties difficult and may have led to misleading conclusions.

Synthesis and Physicochemical Evaluation of Bees' Chitosan-Based Hydrogels Modified with Yellow Tea Extract.

The novelty of the research involves designing the measurement methodology aimed at determining the structure-property relationships in the chitosan-based hydrogels containing yellow tea extract. Performed investigations allowed us to determine the swelling properties of hydrogels in selected time intervals, evaluate the mutual interactions between the hydrogels and simulated physiological liquids via pH measurements and directly assess the impact of such interactions on the chemical structure of hydrogels using Fourier transform infrared (FT-IR) spectroscopy and their wettability by the measurements of the flatness of the drop on the surface of the tested samples via the static drop method. Next, the surface morphology of hydrogels was characterized by the Scanning Electron Miscorcopy (SEM) and their elasticity under the tension applied was also verified. It was proved that incubation in simulated physiological liquids resulted in a decrease in contact angles of hydrogels, even by 60%. This also caused their certain degradation which was reflected in lower intensities of bands on FT-IR spectra. Further, 23% v/v yellow tea extract in hydrogel matrices caused the decrease of their tensile strength. An increase in the amount of the crosslinker resulted in a decrease in the sorption capacity of hydrogels wherein their modification caused greater swelling ability. In general, the investigations performed provided much information on the tested materials which may be meaningful considering their application, e.g., as dressing materials.

Hydroxyapatite Obtained via the Wet Precipitation Method and PVP/PVA Matrix as Components of Polymer-Ceramic Composites for Biomedical Applications.

The aspect of drug delivery is significant in many biomedical subareas including tissue engineering. Many studies are being performed to develop composites with application potential for bone tissue regeneration which at the same provide adequate conditions for osteointegration and deliver the active substance conducive to the healing process. Hydroxyapatite shows a great potential in this field due to its osteoinductive and osteoconductive properties. In the paper, hydroxyapatite synthesis via the wet precipitation method and its further use as a ceramic phase of polymer-ceramic composites based on PVP/PVA have been presented. Firstly, the sedimentation rate of hydroxyapatite in PVP solutions has been determined, which allowed us to select a 15% PVP solution (sedimentation rate was 0.0292 mm/min) as adequate for preparation of homogenous reaction mixture treated subsequently with UV radiation. Both FT-IR spectroscopy and EDS analysis allowed us to confirm the presence of both polymer and ceramic phase in composites. Materials containing hydroxyapatite showed corrugated and well-developed surface. Composites exhibited swelling properties (hydroxyapatite reduced this property by 25%) in simulated physiological fluids, which make them useful in drug delivery (swelling proceeds parallel to the drug release). The short synthesis time, possibility of preparation of composites with desired shapes and sizes and determined physicochemical properties make the composites very promising for biomedical purposes.

Composites Based on Hydroxyapatite and Whey Protein Isolate for Applications in Bone Regeneration.

Hydroxyapatite (HAp) is a bioactive ceramic with great potential for the regeneration of the skeletal system. However, its mechanical properties, especially its brittleness, limit its application. Therefore, in order to increase its ability to transmit stresses, it can be combined with a polymer phase, which increases its strength without eliminating the important aspect of bioactivity. The presented work focuses on obtaining organic-inorganic hydrogel materials based on whey protein isolate (WPI) reinforced with nano-HAp powder. The proportion of the ceramic phase was in the range of 0-15%. Firstly, a physicochemical analysis of the materials was performed using XRD, FT-IR and SEM. The hydrogel composites were subjected to swelling capacity measurements, potentiometric and conductivity analysis, and in vitro tests in four liquids: distilled water, Ringer's fluid, artificial saliva, and simulated body fluid (SBF). The incubation results demonstrated the successful formation of new layers of apatite as a result of the interaction with the fluids. Additionally, the influence of the materials on the metabolic activity according to ISO 10993-5:2009 was evaluated by identifying direct contact cytotoxicity towards L-929 mouse fibroblasts, which served as a reference. Moreover, the stimulation of monocytes by hydrogels via the induction of nuclear factor (NF)-κB was investigated. The WPI/HAp composite hydrogels presented in this study therefore show great potential for use as novel bone substitutes.

The Synthesis Methodology of PEGylated Fe3O4@Ag Nanoparticles Supported by Their Physicochemical Evaluation.

Many investigations are currently being performed to develop the effective synthesis methodology of magnetic nanoparticles with appropriately functionalized surfaces. Here, the novelty of the presented work involves the preparation of nano-sized PEGylated Fe3O4@Ag particles, i.e., the main purpose was the synthesis of magnetic nanoparticles with a functionalized surface. Firstly, Fe3O4 particles were prepared via the Massart process. Next, Ag+ reduction was conducted in the presence of Fe3O4 particles to form a nanosilver coating. The reaction was performed with arabic gum as a stabilizing agent. Sound energy-using sonication was applied to disintegrate the particles' agglomerates. Next, the PEGylation process aimed at the formation of a coating on the particles' surface using PEG (poly(ethylene glycol)) has been performed. It was proved that the arabic gum limited the agglomeration of nanoparticles, which was probably caused by the steric effect caused by the branched compounds from the stabilizer that adsorbed on the surface of nanoparticles. This effect was also enhanced by the electrostatic repulsions. The process of sonication caused the disintegration of aggregates. Formation of iron (II, III) oxide with a cubic structure was proved by diffraction peaks. Formation of a nanosilver coating on the Fe3O4 nanoparticles was confirmed by diffraction peaks with 2θ values 38.15° and 44.35°. PEG coating on the particles' surface was proven via FT-IR (Fourier Transform Infrared Spectroscopy) analysis. Obtained PEG-nanosilver-coated Fe3O4 nanoparticles may find applications as carriers for targeted drug delivery using an external magnetic field.

Review of the Applications of Biomedical Compositions Containing Hydroxyapatite and Collagen Modified by Bioactive Components.

Regenerative medicine is becoming a rapidly evolving technique in today's biomedical progress scenario. Scientists around the world suggest the use of naturally synthesized biomaterials to repair and heal damaged cells. Hydroxyapatite (HAp) has the potential to replace drugs in biomedical engineering and regenerative drugs. HAp is easily biodegradable, biocompatible, and correlated with macromolecules, which facilitates their incorporation into inorganic materials. This review article provides extensive knowledge on HAp and collagen-containing compositions modified with drugs, bioactive components, metals, and selected nanoparticles. Such compositions consisting of HAp and collagen modified with various additives are used in a variety of biomedical applications such as bone tissue engineering, vascular transplantation, cartilage, and other implantable biomedical devices.

Investigations on the Influence of Collagen Type on Physicochemical Properties of PVP/PVA Composites Enriched with Hydroxyapatite Developed for Biomedical Applications.

Nowadays, a great attention is directed into development of innovative multifunctional composites which may support bone tissue regeneration. This may be achieved by combining collagen and hydroxyapatite showing bioactivity, osteoconductivity and osteoinductivity with such biocompatible polymers as polyvinylpyrrolidone (PVP) and poly(vinyl alcohol) (PVA). Here PVA/PVP-based composites modified with hydroxyapatite (HAp, 10 wt.%) and collagen (30 wt.%) were obtained via UV radiation while two types of collagen were used (fish and bovine) and crosslinking agents differing in the average molecular weight. Next, their chemical structure was characterized using Fourier transform infrared (FT-IR) spectroscopy, roughness of their surfaces was determined using a stylus contact profilometer while their wettability was evaluated by a sessile drop method followed by the measurements of their surface free energy. Subsequently, swelling properties of composites were verified in simulated physiological liquids as well as the behavior of composites in these liquids by pH measurements. It was proved that collagen-modified composites showed higher swelling ability (even 25% more) compared to unmodified ones, surface roughness, biocompatibility towards simulated physiological liquids and hydrophilicity (contact angles lower than 90°). Considering physicochemical properties of developed materials and a possibility of the preparation of their various shapes and sizes, it may be concluded that developed materials showed great application potential for biomedical use, e.g., as materials filling bone defects supporting their treatments and promoting bone tissue regeneration due to the presence of hydroxyapatite with osteoinductive and osteoconductive properties.

Physicochemical Investigations of Chitosan-Based Hydrogels Containing Aloe Vera Designed for Biomedical Use.

In this work, synthesis and investigations on chitosan-based hydrogels modified with Aloe vera juice are presented. These materials were synthesized by UV radiation. Investigations involved analysis of chemical structure by FTIR spectroscopy, sorption properties in physiological liquids, strength properties by texture analyzer, surface topography by Atomic Force Microscopy (AFM technique), and in vitro cytotoxicity by MTT test using L929 murine fibroblasts. Particular attention was focused both on determining the impact of the amount and the molecular weight of the crosslinker used for the synthesis as well as on the introduced additive on the properties of hydrogels. It was proven that modified hydrogels exhibited higher swelling ability. Introduced additive affected the tensile strength of hydrogels-modified materials showed 23% higher elongation. The greater amount of the crosslinker used in the synthesis, the more compact the structure, leading to the lower elasticity and lower sorption of hydrogels was reported. Above 95%, murine fibroblasts remained viable after 24 h incubation with hydrogels. It indicates that tested materials did not exhibit cytotoxicity toward these lines. Additionally, materials with Aloe vera juice were characterized by lower surface roughness. Conducted investigations allowed us to state that such modified hydrogels may be considered as useful for biomedical purposes.

Mechanochemical Synthesis of BaTiO3 Powders and Evaluation of Their Acrylic Dispersions.

Barium titanate is a ferroelectric perovskite with unique electric properties; therefore, it is widely applied in the fabrication of inorganic coatings or thin films, capacitors, or in the production of devices for energy storage and conversion. This paper describes the mechanochemical synthesis of BaTiO3 from BaO and TiO2 using a ball mill. XRD analysis allowed concluding that barium titanate was formed after 90 min of mechanochemical grinding. It was also proved by spectroscopic analysis and the band corresponding to Ti-O vibrations on obtained Fourier Transform Infrared (FT-IR) spectra. The specific surface area of obtained powder was 25.275 m2/g. Next, formed perovskite was dispersed in an acrylic poly(ethylene glycol) (superabsorbent polymer suspension, SAP) suspension prepared using microwave radiation. Final suspensions differed in the concentration of SAP applied. It was proven that the increase of SAP concentration does not affect the acidity of the suspension, but it does increase its dynamic viscosity. A sample with 83 wt.% of SAP reached a value of approximately 140 mPa∙s. Dispersions with higher values of SAP mass fraction exhibited lower sedimentation rates. Molecules such as SAP may adsorb to the surface of particles and thus prevent their agglomeration and make them well monodispersed. Based on the performed experiments, it can be concluded that acrylic poly(ethylene glycol) suspension is a suitable fluid that may stabilize barium titanate dispersions.