Applied biomaterials from sustainable sources

If we look back in time at the history of humanity, we can state that our generation is living an era of outstanding efficiency and progress because of globalization and global competition, even if this is resulting in the rapid depletion of energy sources and raw materials. The environmental impact of non-biodegradable plastic wastes is of increasing global concern: nowadays, imagining a world without synthetic plastics seems impossible, though their large-scale production and their extensive use have only spread since the end of the World War II. In recent years, the demand for sustainable materials has increased significantly and, with a view to circular economy, research has also focused on the enhancement and subsequent reuse of waste materials produced by industrial processing, intensive farming and the agricultural sector. Plastic polymers have been the most practical and economical solution for decades due to their low cost, prompt availability and excellent optical, mechanical and barrier properties. Biodegradable polymers could replace them in many applications, thus reducing the problems of traditional plastics disposability and the dependence on petroleum. Natural biopolymers are in fact characterized by a high biocompatibility and biodegradability and have already prompted research in the field of regenerative medicine. During my PhD, my goal was to use natural polymers from sustainable sources as raw materials to produce biomaterials, which are materials designed to interface with biological systems to evaluate, support or replace any tissue, organ, or function of the body. I focused on the use of the most abundant biopolymers in nature to produce biomaterials in the form of films, scaffolds and cements. After a complete characterization, the materials were proposed for suitable applications in different fields, from tissue engineering to cosmetics and food packaging. Some of the obtained results were published on international scientific and peer-reviewed journals.

Characterization of pyrolysis and oxidation processes of biomaterials, biomasses and biofuels

The urgent need for alternative solutions mitigating the impacts of human activities on the environment has strongly opened new challenges and opportunities in view of the energy transition. Indeed, the automotive industry is going through a revolutionary moment in its quest to reduce its carbon footprint, with biofuels being one of the viable alternatives. The use of different classes of biofuels as fuel additives/standalone components has attracted the attention of many researchers. Despite their beneficial effects, biofuel’s combustion can also result in the production of undesirable pollutants, requiring complete characterization of the phenomena occurring during their production and consumption. Industrial scale-up of biomass conversion is challenging owing to the complexity of its chemistry and transport phenomena involved in the process. In this view, the role of solid-phase and gas-phase chemistry is paramount. Thus, this study is devoted to detailed analysis of physical-chemical phenomena characterizing biomass pyrolysis and biofuel oxidation. The pyrolysis mechanism has been represented by 20 reactions whereas, the gas-phase kinetic models; manually upgraded model (KiBo_MU) and automated model (KiBo_AG), comprises 141 species and 453 reactions, and 631 species and 28329 reactions, respectively. The accuracy of the kinetic models was tested against experimental data and the models captured experimental trends very well. While the development and validation of detailed kinetic mechanisms is the main deliverable of this project, the realized procedure integrating schematic classifications with methodologies for the identification of common decomposition pathways and intermediates represents an additional source of novelty. Besides, the fundamentally oriented nature of the adopted method allows the identification of most relevant reactions and species under the operating conditions different industrial applications, paving the way for reduced kinetic mechanisms. Ultimately, the resulting detailed mechanisms can be used to integrate with more complex fluid dynamics model to accurately reproduce the behavior of real systems and reactors.

Nanocomposites based on poly(caprolactone)-chitosan electrospun nanofibers and metallic oxide nanoparticles. Their potential use to adsorption and photocatalytic degradation of organic contaminants

Pollution of water bodies is one of the most common environmental problems today. Organic pollutants are one of the main drawbacks in this natural resource, among which the following stand out long-lived dyes, pharmaceuticals, and pesticides. This research aims at obtaining nanocomposites based on polycaprolactone-chitosan (PCL-CS) electrospun nanofibers (NFs) containing TiO2 nanoparticles (NPs) for the adsorption and photocatalytic degradation of organic pollutants, using Rhodamine B as a model. The fabricated hybrid materials were characterized by FT-IR, TGA, DSC, SEM, TEM, tensile properties, and the contact angle of water drops. The photoactivity of the NFs was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of rhodamine B (RhB). For this purpose, TiO2NPs were successfully ex-situ incorporated into the polymer matrix promoting good mechanical properties and higher hydrophilicity of the material. The results showed that CS in the NFs increased the absorption and degradation of RhB by the TiO2NPs. CS attracted the pollutant molecules to the active sites vicinity of TiO2NPs, favoring initial adsorption and degradation. In other words, a bait-hook-and-destroy effect was evidenced. It also was demonstrated that the sensitization of TiO2 by organic dyes (e.g., perylene derivative) considerably improves the photocatalytic activity under visible radiation, allowing the use of low amounts of TiO2. (≈0.05 g/1 g of fiber). Hence, the current study is expected to contribute with an environmentally friendly green alternative solution.

Novel biomaterials for regeneration of periapical bone defects in endodontic and implant therapy

Endodontic-related periapical bone defects are a common occurrence in the global populations. Considering the number of root canal treatments performed annually, new strategies and new biomaterials for the management of these bone defects will be important and highlight the need for continued research and development in endodontic field. The present PhD thesis have several objectives and is divided into two main sections: one focused on in vitro and laboratory research and the other on clinical in vivo investigations. The first part, focused on laboratory and in vitro research, investigated 2 main topics: • the microbial communities of apical periodontitis to evaluate the predominant bacterial using 16sr DNA-targeted Nanopore sequencing; • the physical-chemical properties of innovative premixed calcium-silicate based bioceramic sealers for endodontic therapy; The second part, focused on in vivo clinical studies, investigated 2 main topics: • the clinical application of premixed calcium-silicate-based sealers. Ethical committee approval was obtained in 2 separate in vivo studies. The first one is a prospective cohort study with a two-year follow-up where the test group was compared with a control group (considered the gold standard). The second is a pilot prospective cohort study with a 12-month follow-up which set the foundation for a subsequent randomized investigation. Thanks to these investigations, we validated a new technique that innovatively associates a warm obturation technique with calcium-silicate-based sealers. Historically, these sealers were only used with cold techniques. This investigation highlights the possibility for wider utilization and improvements in endodontic techniques. • The outcome of 2 different types of implants characterized by different surface treatments and placed with different techniques. The marginal bone level and periodontal parameters were evaluated with a follow-up of 4 and 10 years. This Ph.D thesis is based on a compilation of published papers I have done during my three-year PhD program.

New biomaterials for packaging: a green approach to biopolymers and biocomposites

The impellent global environmental issues related to plastic materials can be addressed by following two different approaches: i) the development of synthetic strategies towards novel bio-based polymers, deriving from biomasses and thus identifiable as CO2-neutral materials, and ii) the development of new plastic materials, such as biocomposites, which are bio-based and biodegradable and therefore able to counteract the accumulation of plastic waste. In this framework, this dissertation presents extensive research efforts have been devoted to the synthesis and characterization of polyesters based on various bio-based monomers, including ω-pentadecalactone, vanillic acid, 2,5-furan dicarboxylic acid, and 5-hydroxymethylfurfural. With the aim of achieving high molecular weight polyesters, different synthetic strategies have been used as melt polycondensation, enzymatic polymerization, ring-opening polymerization and chain extension reaction. In particular, poly(ethylene vanillate) (PEV), poly(ω-pentadecalactone) (PPDL), poly(ethylene vanillate-co-pentadecalactone) (P(EV-co-PDL)), poly(2-hydroxymethyl 5-furancarboxylate) (PHMF), poly(ethylene 2,5-furandicarboxylate) (PEF) with different amount of diethylene glycol (DEG) unit amount, poly(propylene 2,5-furandicarboxylate) (PPF), poly(hexamethylene 2,5-furandicarboxylate), (PHF) have been prepared and extensively characterized. To improve the lacks of poly(hydroxybutyrate-co-valerate) (PHBV), its minimal formulations with natural additives and its blending with medium chain length PHAs (mcl-PHAs) have been tested. Additionally, this dissertation presents new biocomposites based on polylactic acid (PLA), poly(butylene succinate) (PBS), and PHBV, which are polymers both bio-based and biodegradable. To maintain their biodegradability only bio-fillers have been taken into account as reinforcing agents. Moreover, the commitment to sustainability has further limited the selection and led to the exclusive use of agricultural waste as fillers. Detailly, biocomposites have been obtained and discussed by using the following materials: PLA and agro-wastes like tree pruning, potato peels, and hay leftovers; PBS and exhausted non-compliant coffee green beans; PHBV and industrial starch extraction residues.

Silk Fibroin And Sodium Alginate Blend: Miscibility And Physical Characteristics.

Films of silk fibroin (SF) and sodium alginate (SA) blends were prepared by solution casting technique. The miscibility of SF and SA in those blends was evaluated and scanning electron microscopy (SEM) revealed that SF/SA 25/75 wt.% blends underwent microscopic phase separation, resulting in globular structures composed mainly of SF. X-ray diffraction indicated the amorphous nature of these blends, even after a treatment with ethanol that turned them insoluble in water. Thermal analyses of blends showed the peaks of degradation of pristine SF and SA shifted to intermediate temperatures. Water vapor permeability, swelling capacity and tensile strength of SF films could be enhanced by blending with SA. Cell viability remained between 90 and 100%, as indicated by in vitro cytotoxicity test. The SF/SA blend with self-assembled SF globules can be used to modulate structural and mechanical properties of the final material and may be used in designing high performance wound dressing.

Bipolar Tribocharging Signal During Friction Force Fluctuations At Metal-insulator Interfaces.

Friction and triboelectrification of materials show a strong correlation during sliding contacts. Friction force fluctuations are always accompanied by two tribocharging events at metal-insulator [e.g., polytetrafluoroethylene (PTFE)] interfaces: injection of charged species from the metal into PTFE followed by the flow of charges from PTFE to the metal surface. Adhesion maps that were obtained by atomic force microscopy (AFM) show that the region of contact increases the pull-off force from 10 to 150 nN, reflecting on a resilient electrostatic adhesion between PTFE and the metallic surface. The reported results suggest that friction and triboelectrification have a common origin that must be associated with the occurrence of strong electrostatic interactions at the interface.

Effects Of Sterilization Methods On The Physical, Chemical, And Biological Properties Of Silk Fibroin Membranes.

Silk fibroin has been widely explored for many biomedical applications, due to its biocompatibility and biodegradability. Sterilization is a fundamental step in biomaterials processing and it must not jeopardize the functionality of medical devices. The aim of this study was to analyze the influence of different sterilization methods in the physical, chemical, and biological characteristics of dense and porous silk fibroin membranes. Silk fibroin membranes were treated by several procedures: immersion in 70% ethanol solution, ultraviolet radiation, autoclave, ethylene oxide, and gamma radiation, and were analyzed by scanning electron microscopy, Fourier-transformed infrared spectroscopy (FTIR), X-ray diffraction, tensile strength and in vitro cytotoxicity to Chinese hamster ovary cells. The results indicated that the sterilization methods did not cause perceivable morphological changes in the membranes and the membranes were not toxic to cells. The sterilization methods that used organic solvent or an increased humidity and/or temperature (70% ethanol, autoclave, and ethylene oxide) increased the silk II content in the membranes: the dense membranes became more brittle, while the porous membranes showed increased strength at break. Membranes that underwent sterilization by UV and gamma radiation presented properties similar to the nonsterilized membranes, mainly for tensile strength and FTIR results.

Effect Of Composite Containing An Iodonium Salt On The Bond Strength Of Brackets To Bovine Enamel.

This study investigated the effect of the incorporation of an iodonium salt in experimental composites, on the bond strength of metallic brackets bonded to bovine teeth. Two hundred and seventy bovine teeth were embedded in self-curing acrylic resin and divided into 18 groups (n=15), according to the experimental composite with an iodonium salt at molar concentrations 0 (control), 0.5, or 1%; the light-activation times (8, 20 and 40 s); and the storage times (10 min or 24 h). Metallic brackets were fixed on the tooth surface using experimental composites. Photoactivation was performed with a quartz-tungsten-halogen light-curing unit curing unit for 8, 20 and 40 s. The specimens were stored in distilled water at 37 °C for 10 min or 24 h and submitted to bond strength test at 0.5 mm/min. The data were subjected to three-way ANOVA and Tukey's test (α=0.05). The Adhesive Remnant Index (ARI) was used to classify the failure modes. The shear bond strengths (MPa) at 10 min for light-activation times of 8, 20 and 40 s were: G1 - 4.6, 6.9 and 7.1; G2 - 8.1, 9.2 and 9.9; G3 - 9.1, 10.4 and 10.7; and at 24 h were: G1 - 10.9, 11.1 and 11.7; G2 - 11.8, 12.7 and 14.2; G3 - 12.1, 14.4 and 15.8. There was a predominance of ARI score 3 for groups with 10 min storage time, and ARI score 2 for groups with 24 h storage time. In conclusion, the addition of iodonium salt (C05 and C1) to the experimental composite may increase the bond strength of brackets to bovine enamel using reduced light exposure times.

Control Of The Properties Of Porous Chitosan-alginate Membranes Through The Addition Of Different Proportions Of Pluronic F68.

This work addresses the development and characterization of porous chitosan-alginate based polyelectrolyte complexes, obtained by using two different proportions of the biocompatible surfactant Pluronic F68. These biomaterials are proposed for applications as biodegradable and biocompatible wound dressing and/or scaffolds. The results indicate that thickness, roughness, porosity and liquid uptake of the membranes increase with the amount of surfactant used, while their mechanical properties and stability in aqueous media decrease. Other important properties such as color and surface hydrophilicity (water contact angle) are not significantly altered or did not present a clear tendency of variation with the increase of the amount of surfactant added to the polyelectrolyte complexes, such as real density, average pore diameter, total pore volume and surface area. The prepared biomaterials were not cytotoxic to L929 cells. In conclusion, it is possible to tune the physicochemical properties of chitosan-alginate polyelectrolyte complexes, through the variation of the proportion of surfactant (Pluronic F68) added to the mixture, so as to enable the desired application of these biomaterials.

Avoiding Pitfalls Of Intraoperative Peripheral Endovascular Surgery With The Aid Of Osirix: Expanding The Use Of Virtual Fluoroscopy.

We have shown how the analysis of the angiotomography reconstruction through OsiriX program has assisted in endovascular perioperative programming. We presented its application in situations when an unexpected existence of metallic overlapping artifact (orthopedic osteosynthesis) compromised the adequate visualization of the arterial lesion during the procedure. Through manipulation upon OsiriX software, with assistance of preview under virtual fluoroscopy, it was possible to obtain the angles that would avoid this juxtaposition. These angles were reproduced in the C-arm, allowing visualization of the occluded segment, reducing the need for repeated image acquisitions and contrast overload, allowing the continuation of the procedure.

Comparison Of Different Transfer Impression Techniques Accuracy For Osseointegrated Implants.

Abstract The aim of this study was to evaluate three transfer techniques used to obtain working casts of implant-supported prostheses through the marginal misfit and strain induced to metallic framework. Thirty working casts were obtained from a metallic master cast, each one containing two implant analogues simulating a clinical situation of three-unit implant-supported fixed prostheses, according to the following transfer impression techniques: Group A, squared transfers splinted with dental floss and acrylic resin, sectioned and re-splinted; Group B, squared transfers splinted with dental floss and bis-acrylic resin; and Group N, squared transfers not splinted. A metallic framework was made for marginal misfit and strain measurements from the metallic master cast. The misfit between metallic framework and the working casts was evaluated with an optical microscope following the single-screw test protocol. In the same conditions, the strain was evaluated using strain gauges placed on the metallic framework. The data was submitted to one-way ANOVA followed by the Tukey's test (α=5%). For both marginal misfit and strain, there were statistically significant differences between Groups A and N (p<0.01) and Groups B and N (p<0.01), with greater values for the Group N. According to the Pearson's test, there was a positive correlation between the variables misfit and strain (r=0.5642). The results of this study showed that the impression techniques with splinted transfers promoted better accuracy than non-splinted one, regardless of the splinting material utilized.

Nitric Oxide-releasing Poly(vinyl Alcohol) Film For Increasing Dermal Vasodilation.

Pathological conditions associated with the impairment of nitric oxide (NO) production in the vasculature, such as Raynaud's syndrome and diabetic angiopathy, have stimulated the development of new biomaterials capable of delivering NO topically. With this purpose, we modified poly(vinyl-alcohol) (PVA) by chemically crosslinking it via esterification with mercaptosuccinic acid. This reaction allowed the casting of sulfhydrylated PVA (PVA-SH) films. Differential scanning calorimetry and X-ray diffractometry showed that the crosslinking reaction completely suppressed the crystallization of PVA, leading to a non-porous film with a homogeneous distribution of -SH groups. The remaining free hydroxyl groups in the PVA-SH network conferred partial hydrophylicity to the material, which was responsible for a swelling degree of ca. 110%. The PVA-SH films were subjected to an S-nitrosation reaction of the -SH groups, yielding a PVA containing S-nitrosothiol groups (PVA-SNO). Amperometric and chemiluminescence measurements showed that the PVA-SNO films were capable of releasing NO spontaneously after immersion in physiological medium. Laser Doppler-flowmetry, used to assess the blood flow in the dermal microcirculation, showed that the topical application of hydrated PVA-SNO films on the health skin led to a dose- and time-dependent increase of more than 5-fold in the dermal baseline blood flow in less than 10min, with a prolonged action of more than 4h during continuous application. These results show that PVA-SNO films might emerge as a new material with potential for the topical treatment of microvascular skin disorders.

Strain Gauges's Analysis On Implant-retained Prosthesis' Cast Accuracy.

A proper cast is essential for a successful rehabilitation with implant prostheses, in order to produce better structures and induce less strain on the implants. The aim of this study was to evaluate the precision of four different mold filling techniques and verify an accurate methodology to evaluate these techniques. A total of 40 casts were obtained from a metallic matrix simulating three unit implant-retained prostheses. The molds were filled using four different techniques in four groups (n = 10): Group 1 - Single-portion filling technique; Group 2 - Two-step filling technique; Group 3 - Latex cylinder technique; Group 4 - Joining the implant analogs previously to the mold filling. A titanium framework was obtained and used as a reference to evaluate the marginal misfit and tension forces in each cast. Vertical misfit was measured with an optical microscope with an increase of 120 times following the single-screw test protocol. Strain was quantified using strain gauges. Data were analyzed using one-way ANOVA (Tukey's test) (α =0.05). The correlation between strain and vertical misfit was evaluated by Pearson test. The misfit values did not present statistical difference (P = 0.979), while the strain results showed statistical difference between Groups 3 and 4 (P = 0.027). The splinting technique was considered to be as efficient as the conventional technique. The strain gauge methodology was accurate for strain measurements and cast distortion evaluation. There was no correlation between strain and marginal misfit.

Combining Xanthan And Chitosan Membranes To Multipotent Mesenchymal Stromal Cells As Bioactive Dressings For Dermo-epidermal Wounds.

The association between tridimensional scaffolds to cells of interest has provided excellent perspectives for obtaining viable complex tissues in vitro, such as skin, resulting in impressive advances in the field of tissue engineering applied to regenerative therapies. The use of multipotent mesenchymal stromal cells in the treatment of dermo-epidermal wounds is particularly promising due to several relevant properties of these cells, such as high capacity of proliferation in culture, potential of differentiation in multiple skin cell types, important paracrine and immunomodulatory effects, among others. Membranes of chitosan complexed with xanthan may be potentially useful as scaffolds for multipotent mesenchymal stromal cells, given that they present suitable physico-chemical characteristics and have adequate tridimensional structure for the adhesion, growth, and maintenance of cell function. Therefore, the purpose of this work was to assess the applicability of bioactive dressings associating dense and porous chitosan-xanthan membranes to multipotent mesenchymal stromal cells for the treatment of skin wounds. The membranes showed to be non-mutagenic and allowed efficient adhesion and proliferation of the mesenchymal stromal cells in vitro. In vivo assays performed with mesenchymal stromal cells grown on the surface of the dense membranes showed acceleration of wound healing in Wistar rats, thus indicating that the use of this cell-scaffold association for tissue engineering purposes is feasible and attractive.