Ceramic biomaterials: Properties,state of the art and future prospectives

This article gives an overview of ceramics-based biomaterials with particular emphasis on their various properties and health care applications. Furthermore, bio ceramics are grouped as oxide and nitride-based bioinert ceramics, bioresorbable calcium phosphate-based materials and bioactive glasses/glass ceramics. Ceramics and bioglasses are good biomaterials, here mainly focused on bone replacement applications. Mesoporous glasses, nanocrystalline ceramics and composites, having a high surface area, corrosion resistive and better mechanical properties, could be future biomaterials. Controlled porosity with uniform pores distributed biomaterials could be achieved using fine synthesis routes like sol-gel and additive manufacturing. Bioceramics and bioglasses could also be synthesized by agro-food wastes and optimize their properties according to need and applications easily. Moreover, these sustainable resources exhibit inherent porosity due to presence of organic substance attached with inorganic materials. As crystallinity increased, the bioactivity decreases of ceramics. Both properties can be optimised using nano-crystalline and composite biomaterials.     

Effects of the doping concentration of boron on physicochemical,mechanical, and biological properties of hydroxyapatite

Ion doping is an approach to modify properties of materials, like hydroxyapatite (HA), that contributes to designing biomaterials with desired characteristics applicable in bone defect treatments. Recently, boron (B) has been noticed in biomaterial fields due to its beneficial effects on formation, growth, and quality of bone. In this study, B-doped HA nanoparticles with different molar concentrations of B (0.05, 0.1, 0.25, and 0.5) were synthesized through microwave-assisted wet precipitation. The effects of B content on various properties of HA were evaluated. The results demonstrated that the size of HA particles reduced from 106 nm to 89-85 nm in B doped materials. Meanwhile, the crystallinity degree of B doped HA (BHA) samples was between 89.90% and 93.77%, compared to 95.19% of HA. Diametral tensile strength of samples was measured in the ranges of 2.51 and 3.61 with no significant difference among groups. The micro-hardness of HA was 0.88 GPa, whilst doped ones had hardness values of 0.5 GPa–0.68 GPa. Biodegradability of samples increased from less than 1% to approximately 4% after 28 days, while B-doping did not make any change in the degradation rate. Doping dosages were appropriate in terms of bioactivity and cell viability, and B doping caused higher bioactivity and cell proliferation. All changed properties were dose-dependent and more effective in doped groups with a higher amount of B. Despite proliferative effect, 260 μg/l and 770 μg/l of B release in two groups with the highest dopant concentrations did not positively influence the osteogenic activity of cells. Our results demonstrated that doping concentrations that resulted in B release ≤260 μg/l seem more appropriate dosage, especially for bone tissue engineering and substitute applications due to promoted bioactivity and proliferation, as well as no obstructive effects on mechanical properties and osteogenic activities of HA.     

Luminescent Organic–Inorganic Hybrids of Functionalized Mesoporous Silica SBA-15 by Thio-Salicylidene Schiff Base

Novel organic–inorganic mesoporous luminescent hybrid material N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC-SBA-15) has been obtained by co-condensation of tetraethyl orthosilicate and the organosilane in the presence of Pluronic P123 surfactant as a template. N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC) grafted to the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) was used as the precursor for the preparation of mesoporous materials. In addition, for comparison, SBA-15 doped with organic ligand BSTC was also synthesized, denoted as BSTC/SBA-15. This organic–inorganic hybrid material was well-characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy (HRTEM), and photoluminescence spectra, which reveals that they all have high surface area, uniformity in the mesostructure. The resulting materials (BSTC-SBA-15 and BSTC/SBA-15) exhibit regular uniform microstructures, and no phase separation happened for the organic and the inorganic compounds was covalently linked through Si–O bonds via a self-assemble process. Furthermore, the two materials have different luminescence range: BSTC/SBA-15 presents the strong dominant green luminescence, while BSTC-functionalized material BSTC-SBA-15 shows the dominant blue emission.     

Influence of silane structure on curing behavior and surface properties of sol–gel based UV-curable organic–inorganic hybrid coatings

In this study, three usual silane precursors, tetraethoxysilane (TEOS), vinyltrimethoxysilane (VTMS), and 3-methacryloxypropyltrimethoxysilane (MPS), and different binary and triplet blends of them were polymerized via a sol–gel method under acidic conditions. ²⁹Si NMR spectroscopy was used to characterize and quantify the degree of condensation of oligomers. The organic phase was based on a three-acrylate monomer trimethylolpropane triacrylate (TMPTA). The effect of prepared oligomers on the curing behavior of hybrid materials and the interaction between organic and inorganic phases were monitored via photo differential scanning calorimetry (Photo-DSC). Atomic force microscopy (AFM) was used to investigate the surface properties of UV-cured hybrid materials. Photo-DSC results showed that the addition of functionalized oligomers can increase both the photopolymerization rate and the final degree of conversion. They also indicated that oligomers containing MPS are more compatible with the organic phase than other oligomers. Topography and phase trace images of AFM showed that oligomers containing VTMS migrate to the surface of films and affect the water contact angle. In contrast to VTMS, the presence of MPS in oligomers causes the formation of covalent bonds between the organic and inorganic phases in the bulk of the film, and so the surface properties of the film remain unchanged.     

Preparation, characterization and thermal properties of organic–inorganic composites involving epoxy and polyhedral oligomeric silsesquioxane (POSS)

Organic–inorganic hybrids comprising epoxy resin and polyhedral oligomeric silsesquioxanes (POSSs) were prepared via in situ polymerization of the diglycidyl ether of bisphenol A (DGEBA) and 4,4′-diaminodiphenylmethane (DDM). The POSSs have an active functional group that takes part in the ring-opening reaction with the oxirane group. The organic and inorganic moieties are joined by covalent bonds. These covalent bonds enhance the compatibility of the inorganic and organic phases. Scanning electron microscope (SEM) analytical results indicate that there was no obvious phase separation between the inorganic and organic phases. The UV/VIS spectrum of the epoxy hybrid demonstrates the excellent optical transparency of the hybrids—the most important characteristic for their application as protective coatings. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), and nuclear magnetic resonance spectroscopy (NMR) of the char showed that the incorporation of the POSSs into epoxy resin improves the thermal stability of the hybrids.     

In Vitro and In Vivo Characterization of Biodegradable Poly(organophosphazenes) for Biomedical Applications

The need and the growing interest in polymers as biomaterials have led to the synthesis of new polymers with a variety of physico-chemical properties. Biomedical application of such materials not only depends on their physical properties but also on biocompatibility and biodegradability. Polyphosphazenes are a family of ‘hybrid inorganic–organic polymers’ with inorganic elements in the backbone and organic side-groups. The polyphosphazenes constitute a family of greatly diverse performance materials with a broad spectrum of properties. The present review focuses on the biodegradable polyphosphazenes, their biocompatibility, and degradation behavior both in vitro and in vivo. This review also covers the use of biodegradable polyphosphazenes as controlled release devices.     

Organic–inorganic hybrid nanocomposites involving novolac resin and polyhedral oligomeric silsesquioxane

Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was employed as a nanocrosslinker of novolac resin to prepare the organic–inorganic networks. The crosslinking reaction was investigated by means of Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy via model reaction. Thermal analyses indicate that the glass transition temperatures (T_g’s) and thermal stability of the organic–inorganic networks increased with increasing the content of POSS. Contact angle measurements show that the organic–inorganic nanocomposites displayed a significant enhancement in surface hydrophobicity as well as reduction in surface free energy. The improvement in surface properties was ascribed to the presence of POSS moiety in place of polar component of phenolic thermosets.     

Synthesis and properties of Zn and Zn–Mg-doped tricalcium phosphates obtained by Spark Plasma Sintering

β-tricalcium phosphate (Ca₃(PO₄)₂ or TCP) are essential biomaterials because of the chemical composition, high biocompatibility and osseointegration. However, their limited mechanical properties restrict their use to areas where high mechanical performances are not required. Spark Plasma Sintering (SPS) was selected out of the unconventional sintering methods in order to obtain high-density doped-TCP bioceramic materials. The main advantages of SPS are a high heating rate, low sintering temperatures and short residence times, producing bioceramics with full density and fine-grain microstructure. The main purpose was to design, obtain by SPS and characterize undoped β-TCP, 1ZnO-doped β-TCP and 1ZnO-1MgO codoped β-TCP (wt. %) bioceramics. All the obtained samples were visually semitransparent and mainly β-TCP was detected by X-ray analysis. Densification behavior was determined by Archimedes' method and microstructural features of the sintered specimens were analyzed by Field Emission Scanning Electron Microscopy (FE-SEM-EDX). The undoped and doped β-TCP bioceramics were mechanically characterized, specifically the modulus of elasticity and Vickers microhardness. The results are compared with equivalent samples obtained by conventional solid-state sintering (CS) reaction. A first study of biological behavior was carried out, specifically direct cell adhesion of MG-63 human osteoblast-like cells on the polished surfaces of β-TCP, 1ZnO-β-TCP and 1ZnO–1MgO-β-TCP dense samples were determined. The present study concludes that the SPS process together with the doping effect enhanced sinterability, mechanical and biological properties of Zn-TCP and Zn–Mg-TCP based materials.     

Homology of selenium (Se) and tellurium (Te) endow the functional similarity of Se-doped and Te-doped mesoporous bioactive glass nanoparticles in bone tissue engineering

The focus of bone tissue engineering is to realize the regeneration of new functional bone through the synergistic combination of biomaterials, therapeutic agents and cells. Doping of mesoporous bioactive glass (MBG) nanoparticles with therapeutic ions to give them special properties is gaining increasing interest in the design of biomaterials for bone tissue engineering. In this study, we synthesized Se-doped and Te-doped MBG nanoparticles using the sol-gel method, and demonstrated for the first time that the homology of Se and Te endows the functional similarity of bone tissue engineering, and also obtains the desired properties by guiding cell behavior and changing the physicochemical properties of the biomaterial. Results found that MBG nanoparticles doped with Se and Te respectively can be gained similar structure, and thus endowed their similar properties as expected, such as drug sustained release, anticancer and antibacterial properties in a dose-dependent manner. This study provides a feasible strategy for the development of homologous group ions doped nanobiomaterials and their evaluation and basic research in bone tissue engineering.     

高分子复合生物材料的研究进展

本文综述了近年来用于骨修复的各类高分子复合生物材料的研究状况,并从力学性能的改善和降解速率的可调性等角度,总结了高分子复合生物材料与单一组分的材料相比在生物医用领域应用中所表现出的综合使用性能的优越性,提出将与人骨中磷灰石微晶类似的无机纳米粒子与具有降解性能的有机生物材料进行复合,能够得到具有优越骨修复性能的新型骨生物材料。     

Mechanical properties of functionalized SEBS based inorganic hybrid materials

Summary Functional triblock copolymer [polystyrene-b-poly(ethylene-ran-butylene)-b-polystyrene] or SEBS elastomer was used to synthesize flexible organic-inorganic hybrid materials. Modification of elastomer was first achieved via nitration to produce nitrofunctionalized copolymer and its subsequent reduction forming aminofunctionalized copolymer. IR, ¹H NMR and ¹³C NMR spectroscopic analyses provided an evidence of their modified structures. Modified SEBS based hybrid materials were then prepared through solution intercalation technique using layered silicates and in-situ polymerization of metal alkoxides via sol-gel process. In the first attempt, hybrids were prepared by the reinforcement of aminofunctionalized SEBS with organophilic montmorillonite to establish compatibility between organic matrix and inorganic phase. Reinforcement of the modified copolymer was secondly achieved by hydrolytic condensation of tetraethoxysilane using 3-glycidyloxypropyl trimethoxysilane (as a coupling agent) yielding hybrid materials. The chemical interactions between the organic polymer chains and the inorganic networks produced in-situ led to better properties of modified elastomer. Mechanical properties of thin transparent films of these hybrids were measured. Tensile strength of hybrids shows a considerable improvement over pure SEBS as well as aminofunctionalized copolymer in all the systems, which shows an increased interfacial interaction between organic and inorganic phases.     

有机-无机杂化材料制备质子交换膜的研究进展

综述了近年来采用有机-无机杂化材料制备质子交换膜的研究进展，重点介绍了由掺入了质子导电单元或经过磺化的有机-无机杂化材料制得的质子交换膜及由带磺酸基的有机硅通过溶胶-凝胶工艺制备的有机-无机杂化质子材料制得的交换膜，并从制备方法出发分析了每种质子交换膜的性能。     

Marine biological waste as a source of hydroxyapatite for bone tissue engineering applications

The demand for bone graft substitutes for orthopedics and dentistry is constantly growing due to the increase of ageing-related diseases. Synthetic hydroxyapatite (HA) is largely used as a bone graft material thanks to its biocompatibility, osteointegration, osteoconductive and osteoinductive properties and similarity to biological apatite, the main mineral component of bones and teeth. Biogenic apatite has gained attention due to its peculiar intrinsic characteristics: multi-doped ion composition and micro- and nano-scale architecture make natural-derived HA particularly promising for biomedical applications.At the same time, the growing interest in green materials is pushing towards the use of more sustainable biomaterials precursors, including re-use materials: marine waste, such as mollusk-shells, shellfish carapaces, cuttlefish bone, and fishbone have become widely studied sources of biogenic HA. Indeed, they are rich in calcium carbonate (CaCO₃), which can be converted into HA by environmentally sustainable processes. This allows the transformation of waste into valuable materials, while paying attention to the issues of sustainability and circular economy.In this review, we listed and discussed the methods to produce HA starting from shell-derived CaCO₃, describing all the steps and synthesis routes proposed for the conversion procedure, with a special focus on the different species of marine shells used. We discussed the use of HA alone or in combination with other materials (natural and synthetic polymers), used to enhance the mechanical and biological properties.We summarized the types of devices obtained by marine-derived HA, including nanorods, particulates and scaffolds and we described their in vitro and in vivo behavior.The up-to-date literature was summarized in tables with a special focus on the in vitro and in vivo biological evaluation of such materials.In conclusion, composite biomaterials based on marine-derived biogenic HA are reported as potential candidates for synthetic bone substitutes highlighting their potential, limitations and future perspectives.     

Thermoelectric performance of electrodeposited nanostructured polyaniline doped with sulfo‐salicylic acid

Conducting polymers, in present days, are considered to be potential thermoelectric (TE) materials. Among them polyaniline (PANI) is a promising candidate. Nanostructured polyaniline doped with organic dopant is electrodeposited and structurally characterized. Its transport properties are investigated for thermoelectric applications. The analysis of transmission electron microscopy image reveals that the sample is rod like nanostructure. This study shows that the type (inorganic/organic) of dopants plays an important role to influence the dimension of nanostructure and the electrical transport properties of PANI. In this study, organic dopant sulfosalicylic acid is proposed for enhancement of figure of merit through an increase in thermoelectric power and decrease in thermal conductivity. Compared to our earlier work the figure of merit evaluated is two orders higher than that of the inorganic dopant bismuth nitrate doped PANI. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39920.     

Antimicrobial and SEM Studies of Sophorolipids Synthesized Using Lauryl Alcohol

In recent years, researchers have developed biosurfactants for industrial, pharmaceutical and medical applications revealing the promising biological activities of these biomolecules. One of the best studied microbial surfactants are glycolipids, especially sophorolipids (SLs) produced by selected non-pathogenic yeast species of Candida. They are biodegradable, non-toxic and are environmentally friendly. Sophorolipid production was carried out using glucose as the hydrophilic source and lauryl alcohol C_12–14, as the hydrophobic source using Candida bombicola ATCC 22214. Primary characterization of the SL obtained using lauryl alcohol (SLLA) was done by FTIR which depicted the presence of alkyl sophorosides/SLs. Antimicrobial activity testing revealed that SLLA showed complete inhibition against gram negative bacteria, Escherichia coli (ATCC 8739) Pseudomonas aeruginosa (ATCC 9027) at 30 and 1 μg/ml at a contact time of 2 and 4 h respectively. Whereas for gram positive bacteria Staphylococcus aureus (ATCC 6358), Bacillus subtilis (ATCC 6633), complete inhibition was observed at 6 and 1 μg/ml respectively at a contact time of 4 h. The formed SLLA showed noteworthy inhibition against the pathogenic yeast Candida albicans (ATCC 2091) at 50 μg/ml with a contact time of 4 h. These values are remarkably low compared to reported values of oleic acid SLs and linolenic acid SLs which were studied for antimicrobial properties. Scanning electron microscopy analysis of the treated cells revealed the changes in morphology and topography of the microorganisms.     

Bioactivity and osteoinductivity of glasses and glassceramics and their material determinants

Bioactive glasses and glassceramics have been used in both bone repair and tissue engineering applications. An important feature of bioactive glasses and glassceramics, which enables them to be used for desired application, is their biological activity. This activity is manifested by the ability of these materials to form a stable bond with bone tissue (bioactivity) and, in some cases, their ability to promote/initiate osteogenesis (osteoinductivity). A stable material-bone bonding (i.e. bioactivity) results from specific material surface reactions leading to hydroxyapatite (HAp) formation on the material surface. Bioactivity of materials is often evaluated in vitro and the ability of materials to form HAp-like surface layer is usually studied after immersion/incubation of materials in simulated body fluid (SBF). Biological activity of materials can be also defined as their ability to induce specific cell responses leading to faster regeneration of bone tissue. It may be manifested by materials supporting bone cell attachment, proliferation and differentiation (biocompability/osteconductivity), and/or by materials inducing/promoting the expression of multiple bone-related genes that drive osteogenesis (osteoinductivity). Osteoinductivity is often verified in vivo by the materials capability to form bone at etopic (i.e. extraskeletal) sites. However, a lot of in vitro call-based experiments are now offered to determine osteoinductive properties of biomaterials. This review focuses on the silica-based glasses and glass-ceramics, in particular, the sol-gel derived ones, and summarizes their bioactivity and osteoinductivity as major determinants of their biological activity. We highlight the chemistry of bioglasses and glassceramics that affects not only the formation of a stable implant/bone bonding by HAp layer, but also drives the cell response in vitro and in vivo.     

有机/无机酸复合掺杂导电聚苯胺的合成及性能研究

采用化学氧化聚合法以苯胺为单体,过硫酸胺为氧化剂,在有机/无机混合酸的水溶液中合成导电聚苯胺.考察了有机/无机混合酸对聚苯胺性能的影响,并通过四探针、差热分析、红外光谱及拉曼光谱研究聚苯胺掺杂前后结构的变化.结果表明,当聚合温度为20℃、磺基水杨酸和硫酸的摩尔浓度比为0.25:1时,掺杂态聚苯胺电导率和溶解度达到最大值;其中电导率可达13.5 S·cm~(-1),在氮甲基吡咯烷酮(NMP)中溶解度可达85%.差热分析表明,有机/无机酸复合掺杂聚苯胺热稳定性较单一酸掺杂聚苯胺热稳定性有很大的提高;红外光谱和拉曼光谱表明;掺杂后聚苯胺具有导电性是因为其分子链上电荷离域形成了共轭结构.     

Relation between the scratch resistance and the chemical structure of organic–inorganic hybrid coatings

Organic–inorganic hybrid materials can be defined as materials combining organic and inorganic domains in a nanometric scale. The development of these organic–inorganic hybrids has achieved properties from both organic and inorganic materials.     

Design,Characterization, and Antibacterial Performance of MAPLE-Deposited Coatings of Magnesium Phosphate-Containing Silver Nanoparticles in Biocompatible Concentrations

Bone disorders and traumas represent a common type of healthcare emergency affecting men and women worldwide. Since most of these diseases imply surgery, frequently complicated by exogenous or endogenous infections, there is an acute need for improving their therapeutic approaches, particularly in clinical conditions requiring orthopedic implants. Various biomaterials have been investigated in the last decades for their potential to increase bone regeneration and prevent orthopedic infections. The present study aimed to develop a series of MAPLE-deposited coatings composed of magnesium phosphate (Mg₃(PO₄)₂) and silver nanoparticles (AgNPs) designed to ensure osteoblast proliferation and anti-infective properties simultaneously. Mg₃(PO₄)₂ and AgNPs were obtained through the cooling bath reaction and chemical reduction, respectively, and then characterized through X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Selected Area Electron Diffraction (SAED). Subsequently, the obtained coatings were evaluated by Infrared Microscopy (IRM), Fourier-Transform Infrared Spectroscopy (FT-IR), and Scanning Electron Microscopy (SEM). Their biological properties show that the proposed composite coatings exhibit well-balanced biocompatibility and antibacterial activity, promoting osteoblasts viability and proliferation and inhibiting the adherence and growth of Staphylococcus aureus and Pseudomonas aeruginosa, two of the most important agents of orthopedic implant-associated infections.     

Role of ZnO additions on the β/α phase relation in TCP based materials: Phase stability,properties, dissolution and biological response

Guided by the need to manufacture smart biomaterials, capable to replace and regenerate the mineral component of the bone, with optimized mechanical performance and bioresoption rate under physiological conditions, modified synthetic Zinc doped monophasic and/or biphasic β/α-tricalcium phosphate, Znc-Ca_3-x(PO₄)₂ (Zn-TCP), dense bioceramics with different phase proportions and microstructures were synthesized by solid state sintering process.The compositions studied, ranging from 0.125 to 1.000 wt% ZnO were formulated in the Ca₃(PO₄)₂-Zn₃(PO₄)₂ subsystem of the ternary ZnO-CaO-P₂O₅ system. The design and control of compositions and processing conditions, enabled to fulfill the requirement in which Zn²⁺ was incorporated in solid solution in the TCP structure. Consequently, biomaterials with controlled porosity, density, phase proportion and microstructural distribution of α/β-TCP polymorphs were developed.The effect of ZnO content on the final properties was discussed and an improvement in relation to pure TCP samples was obtained. The influence of the surface physico-chemical characteristics on the mechanical performance and “in vitro” solubility in SBF was also studied. In addition “in vitro” biocompatibility was evaluated using MG-63 human osteoblast cells, obtaining synthetic Zn-TCP based biomaterials with improved cell-material interaction.