The Effect of Doping on the Electrical and Dielectric Properties of Hydroxyapatite for Medical Applications: From Powders to Thin Films.

Recently, the favorable electrical properties of biomaterials have been acknowledged as crucial for various medical applications, including both bone healing and growth processes. This review will specifically concentrate on calcium phosphate (CaP)-based bioceramics, with a notable emphasis on hydroxyapatite (HA), among the diverse range of synthetic biomaterials. HA is currently the subject of extensive research in the medical field, particularly in dentistry and orthopedics. The existing literature encompasses numerous studies exploring the physical-chemical, mechanical, and biological properties of HA-based materials produced in various forms (i.e., powders, pellets, and/or thin films) using various physical and chemical vapor deposition techniques. In comparison, there is a relative scarcity of research on the electrical and dielectric properties of HA, which have been demonstrated to be essential for understanding dipole polarization and surface charge. It is noteworthy that these electrical and dielectric properties also offer valuable insights into the structure and functioning of biological tissues and cells. In this respect, electrical impedance studies on living tissues have been performed to assess the condition of cell membranes and estimate cell shape and size. The need to fill the gap and correlate the physical-chemical, mechanical, and biological characteristics with the electrical and dielectric properties could represent a step forward in providing new avenues for the development of the next-generation of high-performance HA-doped biomaterials for future top medical applications. Therefore, this review focuses on the electrical and dielectric properties of HA-based biomaterials, covering a range from powders and pellets to thin films, with a particular emphasis on the impact of the various dopants used. Therefore, it will be revealed that each dopant possesses unique properties capable of enhancing the overall characteristics of the produced structures. Considering that the electrical and dielectric properties of HA-based biomaterials have not been extensively explored thus far, the aim of this review is to compile and thoroughly discuss the latest research findings in the field, with special attention given to biomedical applications.

Advanced Applications of Silk-Based Hydrogels for Tissue Engineering: A Short Review.

Silk has been consistently popular throughout human history due to its enigmatic properties. Today, it continues to be widely utilized as a polymer, having first been introduced to the textile industry. Furthermore, the health sector has also integrated silk. The Bombyx mori silk fibroin (SF) holds the record for being the most sustainable, functional, biocompatible, and easily produced type among all available SF sources. SF is a biopolymer approved by the FDA due to its high biocompatibility. It is versatile and can be used in various fields, as it is non-toxic and has no allergenic effects. Additionally, it enhances cell adhesion, adaptation, and proliferation. The use of SF has increased due to the rapid advancement in tissue engineering. This review comprises an introduction to SF and an assessment of the relevant literature using various methods and techniques to enhance the tissue engineering of SF-based hydrogels. Consequently, the function of SF in skin tissue engineering, wound repair, bone tissue engineering, cartilage tissue engineering, and drug delivery systems is therefore analysed. The potential future applications of this functional biopolymer for biomedical engineering are also explored.

Multifunctional Polymeric Biodegradable and Biocompatible Coatings Based on Silver Nanoparticles: A Comparative In Vitro Study on Their Cytotoxicity towards Cancer and Normal Cell Lines of Cytostatic Drugs versus Essential-Oil-Loaded Nanoparticles and on Their Antimicrobial and Antibiofilm Activities.

We report on a comparative in vitro study of selective cytotoxicity against MCF7 tumor cells and normal VERO cells tested on silver-based nanocoatings synthesized by the matrix-assisted pulsed laser evaporation (MAPLE) technique. Silver nanoparticles (AgNPs) were loaded with five representative cytostatic drugs (i.e., doxorubicin, fludarabine, paclitaxel, gemcitabine, and carboplatin) and with five essential oils (EOs) (i.e., oregano, rosemary, ginger, basil, and thyme). The as-obtained coatings were characterized by X-ray diffraction, thermogravimetry coupled with differential scanning calorimetry, Fourier-transform IR spectroscopy, IR mapping, and scanning electron microscopy. A screening of the impact of the prepared nanocoatings on the MCF7 tumor and normal VERO cell lines was achieved by means of cell viability MTT and cytotoxicity LDH assays. While all nanocoatings loaded with antitumor drugs exhibited powerful cytotoxic activity against both the tumor and the normal cells, those embedded with AgNPs loaded with rosemary and thyme EOs showed remarkable and statistically significant selective cytotoxicity against the tested cancercells. The EO-loaded nanocoatings were tested for antimicrobial and antibiofilm activity against Staphylococcus aureus, Escherichia coli, and Candida albicans. For all studied pathogens, the cell viability, assessed by counting the colony-forming units after 2 and 24 h, was significantly decreased by all EO-based nanocoatings, while the best antibiofilm activity was evidenced by the nanocoatings containing ginger and thyme EOs.

Hydroxyapatite Thin Films of Marine Origin as Sustainable Candidates for Dental Implants.

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical-chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15-18°. The inferred bonding strength adherence values were superior (i.e., ~49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

A Review on Biphasic Calcium Phosphate Materials Derived from Fish Discards.

This review summarizes the results reported on the production of biphasic calcium phosphate (BCP) materials derived from fish wastes (i.e., heads, bones, skins, and viscera), known as fish discards, and offers an in-depth discussion on their promising potential for various applications in many fields, especially the biomedical one. Thus, considerable scientific and technological efforts were recently focused on the capability of these sustainable materials to be transformed into economically attractive and highly valuable by-products. As a consequence of using these wastes, plenty of beneficial social effects, with both economic and environmental impact, will arise. In the biomedical field, there is a strong and continuous interest for the development of innovative solutions for healthcare improvement using alternative materials of biogenic origin. Thus, the orthopedic field has witnessed a significant development due to an increased demand for a large variety of implants, grafts, and/or scaffolds. This is mainly due to the increase of life expectancy and higher frequency of bone-associated injuries and diseases. As a consequence, the domain of bone-tissue engineering has expanded to be able to address a plethora of bone-related traumas and to deliver a viable and efficient substitute to allografts or autografts by combining bioactive materials and cells for bone-tissue ingrowth. Among biomaterials, calcium phosphate (CaP)-based bio-ceramics are widely used in medicine, in particular in orthopedics and dentistry, due to their excellent bioactive, osteoconductive, and osteointegrative characteristics. Recently, BCP materials (synthetic or natural), a class of CaP, which consist of a mixture of two phases, hydroxyapatite (HA) and beta tricalcium phosphate (ß-TCP), in different concentrations, gained increased attention due to their superior overall performances as compared to single-phase formulations. Moreover, the exploitation of BCP materials from by-products of fish industry was reported to be a safe, cheap, and simple procedure. In the dedicated literature, there are many reviews on synthetic HA, ß-TCP, or BCP materials, but to the best of our knowledge, this is the first collection of results on the effects of processing conditions on the morphological, compositional, structural, mechanical, and biological properties of the fish discard-derived BCPs along with the tailoring of their features for various applications.

Fish Bone Derived Bi-Phasic Calcium Phosphate Coatings Fabricated by Pulsed Laser Deposition for Biomedical Applications.

We report on new biomaterials with promising bone and cartilage regeneration potential, from sustainable, cheap resources of fish origin. Thin films were fabricated from fish bone-derived bi-phasic calcium phosphate targets via pulsed laser deposition with a KrF * excimer laser source (λ = 248 nm, τFWHM ≤ 25 ns). Targets and deposited nanostructures were characterized by SEM and XRD, as well as by Energy Dispersive X-ray (EDX) and FTIR spectroscopy. Films were next assessed in vitro by dedicated cytocompatibility and antimicrobial assays. Films were Ca-deficient and contained a significant fraction of ß-tricalcium phosphate apart from hydroxyapatite, which could contribute to an increased solubility and an improved biocompatibility for bone regeneration applications. The deposited structures were biocompatible as confirmed by the lack of cytotoxicity on human gingival fibroblast cells, making them promising for fast osseointegration implants. Pulsed laser deposition (PLD) coatings inhibited the microbial adhesion and/or the subsequent biofilm development. A persistent protection against bacterial colonization (Escherichia coli) was demonstrated for at least 72 h, probably due to the release of the native trace elements (i.e., Na, Mg, Si, and/or S) from fish bones. Progress is therefore expected in the realm of multifunctional thin film biomaterials, combining antimicrobial, anti-inflammatory, and regenerative properties for advanced implant coatings and nosocomial infections prevention applications.

Prototype Orthopedic Bone Plates 3D Printed by Laser Melting Deposition.

Laser melting deposition is a 3D printing method usually studied for the manufacturing of machine parts in the industry. However, for the medical sector, although feasible, applications and actual products taking advantage of this technique are only scarcely reported. Therefore, in this study, Ti6Al4V orthopedic implants in the form of plates were 3D printed by laser melting deposition. Tuning of the laser power, scanning speed and powder feed rate was conducted, in order to obtain a continuous deposition after a single laser pass and to diminish unwanted blown powder, stuck in the vicinity of the printed elements. The fabrication of bone plates is presented in detail, putting emphasis on the scanning direction, which had a decisive role in the 3D printing resolution. The printed material was investigated by optical microscopy and was found to be dense, with no visible pores or cracks. The metallographic investigations and X-ray diffraction data exposed an unusual biphasic α+ß structure. The energy dispersive X-ray spectroscopy revealed a composition very similar to the one of the starting powder material. The mapping of the surface showed a uniform distribution of elements, with no segregations or areas with deficient elemental distribution. The in vitro tests performed on the 3D printed Ti6Al4V samples in osteoblast-like cell cultures up to 7 days showed that the material deposited by laser melting is cytocompatible.

Fabrication of antimicrobial silver-doped carbon structures by combinatorial pulsed laser deposition.

We report on the selection by combinatorial pulsed laser deposition of Silver-doped Carbon structures with reliable physical-chemical characteristics and high efficiency against microbial biofilms. The investigation of the films was performed by scanning electron microscopy, high resolution atomic force microscopy, energy dispersive X-Ray Spectroscopy, X-ray diffraction, Raman spectroscopy, bonding strength "pull-out" tests, and surface energy measurements. In vitro biological assays were carried out using a large spectrum of bacterial and fungal strains, i.e., Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Enterococcus faecalis and Candida albicans. The biocompatibility of the films obtained was evaluated on MG63 mammalian cell cultures. The optimal combination with reasonable physical-chemical properties, efficient protection against microbial colonization and beneficial effects on human cells was found for Silver-doped Carbon films containing 2 to 7 at.% silver. These mixtures can be used to fabricate safe and efficient coatings of metallic implants, with the goal to decrease the risk of implant associated biofilm infections which are difficult to treat and often responsible for implant failure.

Thickness Influence on In Vitro Biocompatibility of Titanium Nitride Thin Films Synthesized by Pulsed Laser Deposition.

We report a study on the biocompatibility vs. thickness in the case of titanium nitride (TiN) films synthesized on 410 medical grade stainless steel substrates by pulsed laser deposition. The films were grown in a nitrogen atmosphere, and their in vitro cytotoxicity was assessed according to ISO 10993-5 [1]. Extensive physical-chemical analyses have been carried out on the deposited structures with various thicknesses in order to explain the differences in biological behavior: profilometry, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and surface energy measurements. XPS revealed the presence of titanium oxynitride beside TiN in amounts that vary with the film thickness. The cytocompatibility of films seems to be influenced by their TiN surface content. The thinner films seem to be more suitable for medical applications, due to the combined high values of bonding strength and superior cytocompatibility.

Nanoprofiles evaluation of ZnO thin films by an evanescent light method.

The extraction efficiency of evanescent light from ZnO nanolayers and their thickness profiles in the range of (1-105) nm was evaluated by a new microscopy technique, differential evanescent light intensity imaging method. It is based on capturing the evanescent light scattered by the layer of the material deposited on glass substrates. The analyzed ZnO films were obtained by pulsed laser deposition at 27°C and 100°C, using a nanosecond UV laser source.

Measuring nanolayer profiles of various materials by evanescent light technique.

The evanescent light photon extraction efficiency of insulator, semiconductor and conductor amorphous nanolayers deposited on glass waveguides was evaluated from Differential Evanescent Light Intensity measurements. The Differential Evanescent Light Intensity technique uses the evanescent field scattered by the deposited nanolayer, enabling nanometer thickness profiling due to the high inherent dark background contrast. The results show that the effective evanescent photon penetration depth increases from metal to semiconductor and then to insulating layers, establishing thus the effective photon-material interaction length for the various materials classes.