The main goal of this work was to synthesize CdSe/CdS (core-shell) nanoparticles stabilized by polymer ligand using entirely aqueous colloidal chemistry at room temperature. First, the CdSe core was prepared using precursors and acid-functionalized poly(vinyl alcohol) as the capping ligand. Next, a CdS shell was grown onto the CdSe core via the layer-by-layer technique. The CdS shell was formed by two consecutive monolayers, as estimated by empirical mathematical functions. The nucleation and growth of CdSe quantum dots followed by CdS shell deposition were characterized by UV-vis spectroscopy, photoluminescent (PL) spectroscopy and transmission electron microscopy (TEM). The results indicated a systematic red-shift of the absorption and emission spectra after the deposition of CdS, indicating the shell growth onto the CdSe core. TEM coupled with electron diffraction analysis revealed the presence of CdSe/CdS with an epitaxial shell growth. Therefore, it may be concluded that CdSe/CdS quantum dots with core-shell nanostructure were effectively synthesized.

Cyclosporine-A-loaded PLGA implants were developed intended for ocular route. Implants were prepared using solvent extraction/evaporation technique followed by casting of the cake into rods in a heated surface. XRD patterns showed that cyclosporine-A was completely incorporated into PLGA. FTIR and DSC results indicated alterations on drug molecular conformation aiming to reach the most stable thermodynamic conformation at polymer/drug interface. Implants provided controlled/sustained in vitro release of the drug. During the first 7 weeks, the drug release was controlled by the diffusion of the cyclosporine-A; and between 7-23 week period, the drug diffusion and degradation of PLGA controlled the drug release.

An HPLC method was developed and validated aiming to quantify the cyclosporine-A incorporated into intraocular implants, released from them; and in direct contact with the degradation products of PLGA. The separation was carried out in isocratic mode using acetonitrile/water (70:30) as mobile phase, a C18 column at 80 ºC and UV detection at 210 nm. The method provided selectivity based on resolution among peaks. It was linear over the range of 2.5-40.0 µg/mL. The quantitation and detection limits were 0.8 and 1.2 µg/mL, respectively. The recovery was 101.8% and intra-day and inter-day precision was close to 2%.

Bioactive glass/polymer hybrids are promising materials for biomedical applications because they combine the bioactivity of these glasses with the flexibility of polymers. In this work it was evaluated the effect of increasing the PVA content of the on structural characteristics and mechanical properties of hybrid. The hybrids were prepared with 70 wt. (%) SiO2-30 wt. (%) CaO and PVA fractions of 20 to 60 wt. (%) by the sol-gel method. The structural and mechanical characterization was done by FTIR, SEM and compression tests. To reduce the acidic character of the hybrids due to the catalysts added, different neutralization solutions were tested. The calcium acetate alcoholic solution was the best neutralizing method, resulting in foams with final pH of about 7.0 and small sample contraction. The foams presented porosity of 60-85 wt. (%) and pore diameters of 100-500 μm with interconnected structure. An increase of PVA fraction in the hybrids improved their mechanical properties. The scaffolds produced provided a good environment for the adhesion and proliferation of osteoblasts.

The sensitivity of 5, 10, 15, 20-tetraphenylporphyrin (H2TPP) to the presence of NO2 gas in diluted solutions and in Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) films was investigated by UV-visible spectroscopy. The shift of Soret and Q bands were analyzed and the energies involved were calculated. The exposure of LB porphyrin films deposited onto glass slides to NO2 has performed as an active chemsensor with 7000 ppm gas concentration. Furthermore, the UV-vis dichroism absorption results associated with the Soret bands have given evidence of the tilt angle of the macrocycle related to the substrate. H2TPP in LB film was tilted by an angle of 51 ± 5° and in the LS film was tilted by an angle of 36° ± 5° indicating the formation of a preferential organization of the molecular films depending on the deposition method.

Adhesion between tiles and mortars are crucial to the stability of ceramic tile systems. From the chemical point of view, weak forces such as van der Waals forces and hydrophilic interactions are expected to be developed preferably at the tiles and polymer modified Portland cement mortar interface. The main goal of this paper was to use organosilanes as primers to modify ceramic tile hydrophilic properties to improve adhesion between ceramic tiles and polymer modified mortars. Glass tile surfaces were treated with several silane derivatives bearing specific functionalities. Contact angle measurements and Fourier Transform Infrared Spectroscopy (FTIR) were used for evaluating the chemical changes on the tile surface. In addition, pull-off tests were conducted to assess the effect on adhesion properties between tile and poly(ethylene-co-vinyl acetate), EVA, modified mortar. The bond strength results have clearly shown the improvement of adherence at the tile-polymer modified mortar interface, reflecting the overall balance of silane, cement and polymer interactions.

The aim of this study was to synthesize and characterize the biodegradable intraocular implants based on poly (D,L-lactide-co-glycolide) (PLGA 75:25) with Cyclosporine-A (CyA) and to evaluate their in vitro drug delivery profile. Thermal analysis was conducted by using Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). Phase analysis and crystallinity of the polymer-CyA samples were assessed through X ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Finally, microstructure and morphology of the systems were investigated by Scanning Electron Microscopy (SEM). The results showed that CyA was successfully incorporated into PLGA network with drug loading of approximately 31.6%. Also, based on FTIR and thermal analyses (TGA/DSC) no significant physical-chemical interaction was detected at the micro-nanoscale level between polymer/drug. SEM micrographs have indicated a uniform drug distribution in PLGA matrix. XRD patterns have showed that the incorporated semi-crystalline structure of CyA has not significantly altered the polymeric mainly amorphous network. In addition, the results have confirmed the chemical and biological drug stability, the drug distribution into the polymeric matrix and the possibility of cyclosporine prolonged delivery system profile.

In this study, novel Chitosan/PVA based films were chemically crosslinked by glutaraldehyde, under pH=(4,00 ±0,05), in order to achieve structures tailored for wound tissue engineering applications. Both precursors and developed films were characterized by FTIR, SEM and XRD in order to determine the presence of chemicals groups and nanostructural order, respectively. The results have shown that the glutaraldehyde crosslinking have altered the crystallinity of pure chitosan and the increase on the C=N bands and simultaneous decrease on NH2 bands suggested that Chitosan/GA crosslinking has preference to occur in carbon-2 of the saccharide ring by the Schiff's base reaction. Also, FTIR spectroscopy clearly showed that crosslinking has also taken place with blends of PVA and chitosan. The mechanical properties presented high degree dependence with on the increase of the content of chitosan and glutaraldehyde. The results have indicated that, by controlling the ratio [PVA]/[chitosan] in the blends and the extent of chemical crosslinking, it was possible to tailor the hybrid network produced aiming to obtain properties of interest for the specific application.

In the present study two novel composites of Calcium phosphates (CaP) and Collagen (COL) were synthesized, hydroxyapatite/Collagen (HA/COL) and hydroxyapatite-btricalcium phosphate/COL (HAbTCP/COL). Collagen was extracted from bovine pericardium submitted to enzymatic digestion and purification by ion-exchange chromatography yielding high purity grade type I collagen. Biocomposites of HAP/COL and HAbTCP/COL were produced with a calcium phosphate/COL ratio of 80/20 (wt. (%)) and were characterized by chemical analysis, light microscopy and scanning electron microscopy, X ray diffraction and FT-infrared spectroscopy. SEM results of the CaP powders showed agglomerates of particles at the nanometric size range with predominantly columnar shape and average chemical composition of [Ca/P] = 1.67. FTIR analysis of collagen has confirmed the major vibrational bands associated with chemical groups like amides and hydroxyls usually found in proteins. SEM micrographs have indicated that both morphological and structural features and chemical composition of the composites were very similar to their precursors, collagen and calcium phosphate components. SDS-PAGE characterization results of protein extracted and purified has showed that bovine type I collagen was successfully obtained. Finally, the biocomposites presented a homogeneous aspect with the calcium phosphate particles aggregated to the collagen fibers. Hence, the novel developed biocomposites have high potential to be used for rebuilding small lesions in bone tissue engineering.

An alternative to etching enamel for retention of an adhesive is to grow crystals on the enamel surface. The potential advantages of crystal growth include easy procedure and less damage to the enamel. These crystals retain the adhesive or are the actual dental restoration. In this work, a paste of synthetic enamel was used to grow crystals of fluoride hydroxyapatite (F-HA) onto the human tooth surface. This technique can be used for several dentistry applications like enamel whitening, strengthening and restoration of early carie lesions. The low cost of reagents and simplicity of the technique along with the biocompatibility of the paste render possible the utilization on the market. The samples were prepared through the application of the paste by the incremental technique. The results obtained by scanning electron microscope (SEM)/EDX have indicated the deposition of a homogeneous layer of calcium phosphate that was grown onto the enamel substrate. The average thickness of the deposited film was in the range of 50-100 µm and with a similar density from the natural enamel observed by radiographic images.

Bone ingrowth requires materials with the existence of open and interconnected pores with diameters larger than 150 µm for proper circulation of nutrients. Such materials must possess enough mechanical strength to avoid failure whilst offering a bioactive surface for bone regeneration. We have developed porous ceramic alumina scaffold with compressive strength that achieves 3.3 MPa by replication method by using the network structure of cellular polymer foam. However, the biocompatibility of ceramics based on Al2O3 requires further improvement so that it could have strong bonding to natural bone tissue. To address this problem of the interface between alumina and bone, we have developed a novel calcium phosphate with Zn2+ (CaP-Zn) coating onto porous alumina ceramic scaffold by impregnating with calcium phosphate/poly(vinyl alcohol) slurry. The tri-dimensional alumina scaffold coated with CaP-Zn was extensively characterized by SEM, EDS and FTIR.

Tissue engineering has evolved from the use of biomaterials for bone substitution that fulfill the clinical demands of biocompatibility, biodegradability, non-immunogeneity, structural strength and porosity. Porous scaffolds have been developed in many forms and materials, but few reached the need of adequate physical, biological and mechanical properties. In the present paper we report the preparation of hybrid porous polyvinyl alcohol (PVA)/bioactive glass through the sol-gel route, using partially and fully hydrolyzed polyvinyl alcohol, and perform structural characterization. Hybrids containing PVA and bioactive glass with composition 58SiO2-33CaO-9P2O5 were synthesized by foaming a mixture of polymer solution and bioactive glass sol-gel precursor solution. Sol-gel solution was prepared from mixing tetraethoxysilane (TEOS), triethylphosphate (TEP), and calcium chloride as chemical precursors. The hybrid composites obtained after aging and drying at low temperature were chemically and morphologically characterized through infrared spectroscopy and scanning electron microscopy. The degree of hydrolysis of PVA, concentration of PVA solution and different PVA-bioglass composition ratios affect the synthesis procedure. Synthesis parameters must be very well combined in order to allow foaming and gelation. The hybrid scaffolds obtained exhibited macroporous structure with pore size varying from 50 to 600 µm.

Híbridos de vidro bioativo/polímero são materiais de grande interesse em aplicações biomédicas devido às suas propriedades, que combinam a bioatividade dos materiais cerâmicos, com a flexibilidade dos polímeros. Para regeneração do tecido ósseo, propriedades mecânicas da matriz são críticas e o módulo e a resistência mecânica do material devem ser similares aos do osso natural. Em trabalhos anteriores desenvolvidos no grupo obtiveram-se espumas híbridas 80% vidro bioativo/20% álcool polivinílico (PVA), para aplicação em engenharia de tecidos. Neste trabalho foi aumentado o teor de PVA dos híbridos para otimizar suas propriedades mecânicas. Os híbridos foram preparados com fase inorgânica 70%SiO2-30%CaO e teores de PVA de 20 a 60%, através da hidrólise ácida de tetraetil ortosilicato, adição de CaCl2, PVA, surfactante e HF. A secagem das espumas mostrou-se crítica, ocorrendo grande contração do gel As amostras foram secas por duas rotas: (1): pré-secagem a 40°C em estufa e secagem a vácuo; (2): pré-secagem a 40°C em estufa com circulação de ar e secagem a alto vácuo. A rota de secagem 2 apresentou maior perda de água e menor contração das amostras. Corpos de prova cúbicos, 10x10x10mm, foram submetidos a ensaios de compressão com velocidade de aplicação de carga de 0,5mm/min. Observou-se que o aumento do teor de polímero na composição das espumas melhorou suas propriedades mecânicas.

Bioactive glass/ polymer hybrids are materials of high interest for biomedicals applications because their assets, they combine the bioactivity of ceramics, with the flexibility of the polymers. In bone regenerations, mechanicals properties of the scaffold are criticisms and they must be similar to the bone properties. In previous works, hybrid foams with 80% bioactive glass and 20% polyvinyl alcohol (PVA) were prepared by sol-gel process to application as scaffold for bone tissue engineering. In this work, the PVA fraction of the hybrids was increase for to improve their mechanicals properties. The hybrids were prepared with composition inorganic of 70%SiO2-30%CaO and PVA fractions of 20 to 60% by sol-gel method. The drying of the foams was a criticism stage, occurring ample contraction from the gel. The samples were drying for two routes: (1) pre-drying at 40ºC for 7 days and drying at vacuum for 48 hours; (2) pre-drying with air circulation at 40ºC for 7 days and drying at high vacuum for 48 hours. The drying route 2 had the most lost of water and the least contraction of samples. Five specimens of hybrids samples with dimensions 10x10x10mm were compressed at 0,5mm/min-1. The increase of PVA fraction in the hybrids improves their mechanicals properties.

Polyvinyl alcohol (PVA), PVA crosslinked with glutaraldehyde hydrogels (PVA/GA), PVA with tetraethylorthosilicate (PVA/TEOS) and PVA/GA/TEOS hybrids with recombinant MPB70 protein (rMPB70) incorporated were chemically characterized by Fourier transform infrared spectroscopy (FTIR). FTIR spectra of PVA hydrogel samples showed the absorption regions of the specific chemical groups associated with poly(vinyl alcohol) (-OH, -CO, -CH2) and PVA/GA confirming the formation of crosslinked hydrogel (duplet -CH). It was observed C-H broad alkyl stretching band (n = 2850-3000 cm-1) and typical strong hydroxyl bands for free alcohol (nonbonded -OH stretching band at n = 3600-3650 cm-1), and hydrogen bonded band (n = 3200-3570 cm-1). The most important vibration bands related to silane alcoxides have been verified on FTIR spectra of PVA/TEOS and PVA/GA/TEOS hybrids (Si-O-Si, n = 1080 and n = 450 cm-1; Si-OH, n = 950 cm-1). FTIR spectra of f PVA hydrogel with rMPB70 incorporated have indicated the specific groups usually found in protein structures, such as amides I, II and III, at 1680-1620 cm-1, 1580-1480 cm-1 and 1246 cm-1, respectively. These results have given strong evidence that recombinant protein rMPB70 was successfully adsorbed in the hydrogels and hybrids networks. These PVA based hydrogels and hybrids were further used in immunological assays (Enzyme-Linked Immunosorbent Assay - ELISA). Tests were performed to detect antibodies against rMPB70 protein in serum samples from bovines that were positive in the tuberculin test. Corresponding tests were carried out without PVA samples in microtiter plates as control. Similar results were found for commercially available microplates and PVA based hydrogels and hybrids developed in the present work regarding to immunoassay sensitivity and specificity response.

Several techniques have been utilized for the preparation of hydroxyapatite (HA) and other calcium phosphates for the development of biomaterials. It is vital to know the reaction kinetics to be able to control the material obtained by the aqueous solution route. In the present work, HA has been produced by different wet precipitation processes and different experimental conditions. Calcium hydroxide, calcium phosphate, ammonium phosphate and phosphoric acid were used as reagents. The precipitate was dried at 100 °C overnight and then some samples were treated at 900 °C for 2 h. The powder samples were characterized by scanning electron microscopy (SEM), X-ray fluorescence (XRF) and X-ray diffraction (XRD) analyses. SEM photomicrographs showed an aggregate powder, granular to dense and suggested typical columnar particles. Qualitative XRF showed that the main components of HA powders were calcium and phosphorus. Pure HA and other phases according to processing parameters were observed by XRD analysis.