Bisserka Samuneva

Sol-gel bioactive glass-ceramics Part I: Calcium phosphate silicate/wollastonite glass-ceramics

In this work we present experimental results about synthesis, structure evolution and in vitro bioactivity of new calcium phosphate silicate/wollastonite (CPS/W) glass-ceramics. The samples obtained were synthesized via polystep sol-gel process with different Ca/P+Si molar ratio (R). The structure of the materials obtained was studied by XRD, FTIR spectroscopy and SEM. XRD showed the presence of Ca15(PO4)2(SiO4)6, β-CaSiO3 and α-CaSiO3 for the sample with R=1.89 after thermal treatment at 1200°C/2h. The XRD results are in good agreement with FTIR analysis. SEM denotes that apatite formation can be observed after soaking in simulated body fluid (SBF).

Organic/Inorganic bioactive materials Part II: in vitro bioactivity of Collagen-Calcium Phosphate Silicate/Wollastonite hybrids

In the present study, novel hybrid materials of Collagen (C) and Calcium Phosphate Silicate/Wollastonite (CPS/W) were synthesized. The CPS/W ceramic was prepared via polystep sol-gel method. The dissolution test of CPS/W ceramic was filled with TRIS-HCl buffer. FTIR depicts that hydroxyl carbonate apatite (OHCO3HA) was observed after 3 days of immersion in TRIS-HCl buffer. Biohybrids of C-CPS/W were produced from diluted hydrochloric acid collagen type I and ceramic powder with different ratios of C and CPS/W equal to 25:75 and 75:25 wt.%. The synthesized hybrids were characterized by FTIR, XRD and SEM. FTIR depicts a “red shift” if amide I could be attributed to the fact that the collagen prefers to chelate Ca2+ from partial dissolution of CPS/W ceramic. The growth of B-type carbonate containing hydroxyapatite (B-CO3HA) on the C-CPS/W hybrids soaked in 1.5SBF was observed. The negatively charged carboxylate groups from the collagen may be responsible for hydroxyapatite (HA) deposition. This fact was confirmed by the “red shift” of carboxylate groups of collagen in FTIR spectra. The formation of HA was observed by FTIR, XRD and SEM.

Sol-gel bioactive glass-ceramics Part II: Glass-ceramics in the CaO-SiO2-P2O5-MgO system

Ceramics, with basic composition based on the CaO-SiO2-P2O5-MgO system with different Ca+ Mg/P+Si molar ratio (R), were prepared via polystep sol-gel technique. The structure of the obtained ceramic materials has been studied by XRD, FTIR spectroscopy, and SEM. X-ray diffraction showed the presence of akermanite and HA for the sample with R = 1.68 and Mg substituted β-TCP and silicocarnotite for the sample with R = 2.16, after thermal treatment at 1200°C/2 h. The obtained results are in good agreement with FTIR. In vitro test for bioactivity in static condition proved that the carbonate containing hydroxyapatite (CO3HA) can be formed on the surface of the synthesized samples. CO3HA consisted of both A- and B-type CO32− ions. SEM micrographs depicted different forms of HA particles, precipitated on the surface after soaking in 1.5 simulated body fluid (SBF).

Organic / inorganic bioactive materials Part I: Synthesis, structure and in vitro assessment of collagen/silicocarnotite biocoatings

The silicocarnotite, as an inorganic part of the coatings, has been synthesized using a polystep sol-gel method. The chemical composition of the prepared silicocarnotite sol is described as 58.12 CaO, 29.42 P2O5, 12.45 SiO2 (wt%), where Ca/P+Si = 1,67. The acid soluble type I collagen, as an organic part of the obtained coatings, was mixed with silicocarnotite powder in a weight ratio of 25:75 and 75:25 weight ratio without cross-linkage. The acidity of the obtained mixture was readjust with 25% NH4OH to pH = 9.0. The mixture was then dried at 37°C for 12 h.The growth of B-type carbonate containing hydroxyapatite (B-type CO3HA) in which CO32+→PO43− on the surface of collagen/silicocarnotite coatings soaked in 1.5 simulated body fluid (1.5 SBF) was observed. The nucleation of B-type CO3HA was estimated on the obtained coatings after 3 days immersion in 1.5 SBF. The negatively charged carboxylate groups from the collagen surface may be responsible for the HA deposition. This was confirmed by the “red shift” of carboxylate groups of collagen molecules in the FTIR spectra. After soaking in 1.5 SBF, the morphology of prepared coatings and HA formation was observed by SEM.

Characterization of superparamagnetic MgxZn1−x Fe2O4 powders

Structural and magnetic properties of MgxZn1−xFe2O4 powders have been studied with respect to the application for thermal cancer therapy (magnetic hyperthermia). MgxZn1−xFe2O4 (x=0.1–0.5) powders with particle sizes between 5 and 8 nm were produced by citrate method. The X-ray diffraction patterns of the samples correspond to a spinel phase. The lattice constant and the volume of the elementary cell increase when x changes from 0.1 to 0.5. The FTIR-spectra ascertain the spinel phase formation. The Mossbauer studies reveal the presence of extremely small particles, which undergo superparamagnetic relaxation at room temperature. The core-shell model has been applied to explain quadruple doublets. The quadruple splitting at “shells” is bigger than those at “cores” whereas the isomer shifts remain close. Magnetic studies confirm the presence of extremely small particles that behave as superparamagnetic ones.

Composite Glass-Ceramics in the Systems MgO-SiO2, MgO-Al2O3-SiO2 and Fluorapatite Obtained by Sol-Gel Technology

The crystallization processes in the synthesis of composite glass-ceramics in the systems fluorapatite (FA)-MgO·SiO2 gel-glass (GG) and FA-MgO·Al2O3·SiO2 (GG) have been studied. The composites were prepared by mixing of MgO·SiO2 and MgO·Al2O3·2SiO2 gel-glasses with FA (from 20 mol% to 80 mol%). The obtained samples were thermally treated at 950°C, 1050°C, 1150°C and 1250°C for 2 hours and the structural changes were investigated, applying XRD-analysis, IR-spectroscopy, Raman spectroscopy and SEM. It has been proved that depending on the chemical composition of the gel-glass and the temperature of treatment, composite glass-ceramics may be prepared consisting only FA, FA and a silicate phase or FA, other phosphate phases and a silicate phase. Because of the absence of calcium or aluminum ions in the composition of the GG, FA is easily decomposed and phases as 7CaO·2MgO·3P2O5 and MgO·2P2O5 are formed.

Silica hybrid nanocomposites

In this work we present experimental results about the formation, properties and structure of sol — gel silica based biocomposite containing Calcium alginate as an organic compound. Two different types of silicon precursors have been used in the synthesis: tetramethylortosilicate (TMOS) and ethyltrimethoxysilane (ETMS). The samples have been prepared at room temperature. The hybrids have been synthesized by replacing different quantitis of the inorganic precursor with alginate. The structure of the obtained hybrid materials has been studied by XRD, IR Spectroscopy, EDS, BET and AFM. The results proved that all samples are amorphous possessing a surface area from 70 to 290 m2/g. It has also been established by FT IR spectra that the hybrids containing TMOS display Van der Walls and Hydrogen bonding or electrostatic interactions between the organic and inorganic components. Strong chemical bonds between the inorganic and organic components in the samples with ETMS are present. A self-organized nanostructure has been observed by AFM. In the obtained hybrids the nanobuilding blocks average in size at about 8–14 nm for the particles.

SOL-GEL NANOMATERIALS WITH ALGAL HETEROPOLYSACCHARIDE FOR IMMOBILIZATION OF MICROBIAL CELLS, PRODUCING α-GALACTOSIDASE AND NITRILASE

ABSTRACT The main purpose of the present work is the sol-gel synthesis and structure of the hybrid nanomaterials as matrices for two types of cells, producing hydrolytic enzymes. The effect of different percent of algal polysaccharide included in them on the hydrolytic activity of fungal and bacterial cells was investigated. The hybrid sol-gel nanomaterials were synthesized from tetraethylortosilicate (TEOS) as a silicon precursor and heteropolysaccharide (AHPS) from the red microalga Dixonella grisea as an organic part. The structure of these matrices was investigated using different methods: FT-IR, XRD, BET-Analysis, EDS, SEM and AFM. The sol-gel hybrids were used for the immobilization of fungal (Humicola lutea) and bacterial (Bacillus sp.) cells, producing α-galactosidase and nitrilase, respectively. It was established the effect of the quantity of the heteropolysaccharide in the matrices on the activity of these hydrolytic enzymes. Using 20% AHPS in the hybrid nanomaterials the α-galactosidase yield exceeded over two-fold the enzyme titre of the free cells in the third cycle of repeated batch shake flask cultivation. These results correlated with a dense growth of immobilized mycelium observed with scanning electron microscopy (SEM). The increase of the percentage of organic part in the sol-gel matrix up to 20% led to an increase in the nitrilase activity. The addition of 40% AHPS did not significantly affect the decrease of the nitrile biodegradation.

Synthesis and Selected Properties of Silicate Hybrids Containing Sepharose

The main purpose of the present work is the sol-gel synthesis, structure and application of hybrid inorganic–organic hybrids based on different silica precursors and addition of the organic compound sepharose (SP). The structural evolution of the hybrid materials containing different amounts of SP is examined. Formation of silica nanocomposites by self-assembling processes was studied by AFM and roughness analysis. The average size of nanoparticles on the sample surface is about 7 to 14 nm and the formation of their self-organized structures is observed. The hybrids are used for immobilization of bacterial cells, producers of thermostable nitrilase. The biocatalysts show good operational stability for a long period-18 days, as well as high thermostability. The degradation capability is greater for the encapsulated cells in the hybrid matrix with 5% SP.

Sol Gel Synthesis and Structure of Hybrid Nanomaterials with Strong Chemical Bonds

Sol-gel synthesis at molecular level and low temperature gives us a possibility to obtain new materials with non-traditional physical and chemical properties of special interest, highly homogeneous and pure. Recently a great attention has been paid to this method because of synthesizing new hybrid (organic-inorganic) materials having nanoscaled structure. The newly synthesized hybrid coatings and bulk materials can be successfully applied in optics, electronics, technics, medicine, and biotechnology. The chemical composition of hybrids and the nature of chemical bonds between the organic and inorganic components in their structure are the most important parameters determining physico-chemical behavior of these materials. The different organic-inorganic hybrids can be classified into two broad families, according to the nature of chemical bond between their organic and inorganic components: Class I — hybrid systems in which one of components (organic, biologic or inorganic) is entrapped within a network of the other component and Van der Walls Hydrogen bonding or electrostatic interactions are found; Class II — hybrid materials in which the inorganic and organic parts are chemically bonded by a covalent or ionic-covalent bond. The hybrids belonging to Class II are more appropriate for obtaining of nanomaterials with high mechanical and corrosion resistance.