In the theoretical part of this thesis are described various types of nanoparticles, such as polymeric particles, liposomes, micelles and solid lipid nanoparticles. There are presented basic informations concerning methods of particles preparation in the laboratory conditions such as solutions of polymers dispersion methods by intensively stirring, coacervation of the solutions of polymers, polymeration methods in dispersions, and the exploitation of methods of dispersion of polymeric solutions in the supercritical solvents. In the folowing part of this thesis are some concise informations about the methods of evaluation of basic parameters of the nanoparticulate systems. There are summarised the trivial informations concerning granulometry of particles, their zeta potential, encapsulation effectivity of drugs, and also about the particles shape factor. The focus of this thesis is in the experiment, the main deal were in minimisation of the particle size prepared by the method of emulsification of biodegradable aliphatic α-hydroxyacids polyesters solutions. The main process arrangement was the selection of the appropriate solvent of polymers in the inner emulsion phase and the founding for the mostly efficient emulsifier during the dispersion process of polymer solutions. In process of the...

Charles Univerzity in Prague Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical Technology Candidate: Dana Svobodová Supervisor: doc. RNDr. Milan Dittrich, CSc. Diploma thesis title: Particles with antimicrobial silver The theoretical part of this diploma thesis outlines a brief overview of recent findings on silver nanoparticles. Further, it concerns the kinetic properties of colloidal systems, methods of evaluating the size and shape of colloidal particles, mechanism of antimicrobial activity of colloidal silver and methods of preparation of nanoparticles. Concise information about the toxicity of silver nanoparticles and their impact on the environment is also included. In the experimental part comprehensive report on the results of measurements of granulometric characteristics of microparticles and nanoparticles by photon correlation spectroscopy (PCS) is included. The influence of various modifications of preparation procedures and processing on stability, size and the polydispersity of the size in terms of the volume and intensity diameter of the particles with elemental silver deposited on the surface was studied. Optimisation of the disperse system, quality control of the content of colloidal particles by subsequent reduction, the possibilities of using centrifuge and...

BSc. Martina Hloušková Supervisor: Ing. Martin Drastík, Ph.D. The aim of this diploma thesis was the optimization and validation of a HPLC method for miconazole determination in samples supplied by the Department of Pharmaceutical Technology. A gradual miconazole release dependent on the composition of the copolymere of glycolic and lactic acid was studied. HPLC analysis was performed using a modern core-shell Column Ascentis Express RP- Amide, 10 cm x 3.0 mm; 2.7 μm. Optimized analytical conditions were: mobile phase methanol:water 70:30, flow rate 0.8 ml/min, temperature 45 řC, injection 5 l and UV detection at 220 nm. Miconazole retention time was 5.65 min. The entire analysis was carried out in 7 minutes. When the optimal conditions of analysis were determined, the method could be validated. The following parameters were monitored during validation: linearity, selectivity, efficiency, LOD, LOQ, repeatability and tailing factor. All of the monitored parameters met the requirements of the Czech Pharmacopoeia.

Doctor of Philosophy / Department of Grain Science and Industry / Xiuzhi Susan Sun / Soy protein is one of the most promising bio-degradable adhesives, with great potential as alternatives synthetic petroleum based adhesives for wood composite industries. However, its intrinsic drawbacks such as low water resistance, high viscosity, and short shelf life still limit its broad application. In this research, soy protein was further modified and characterized to improve adhesion properties, flow-ability, water resistance, and long shelf life, which could facilitate the industrialization of soy protein based adhesives. In this study, we exploited the in situ sodium bisulfite (NaHSO3) modification on soy protein in soy flour-water extracts, and then the modified soy protein was obtained through acid precipitation. First, different concentrations of NaHSO3 were used to modify soy flour slurry, then glycinin-rich and β-conglycinin-rich fractions were precipitated at pH 5.4 (SP 5.4) and pH 4.5 (SP 4.5), respectively. Unmodified sample SP 5.4 and SP 4.5 showed clay-like properties and viscoelastic properties, respectively; whereas with addition of NaHSO3 in range of 2-8 g/L, both SP 5.4 and SP 4.5 had the viscous cohesive phase with good handability and flow-ability. The overall adhesion performance of SP 4.5 was better than SP 5.4; the wet strength of these two fractions was in the range of 2.5-3.2 MPa compared to 1.6 MPa of control soy protein isolate. Then soy protein with various β-conglycinin/glycinin (7S/11S) ratios were extracted from soy flour slurry and characterized for adhesion properties based on the different solubility of 7S and 11S globulins. Seven glycinin-rich soy protein fractions and six β- conglycinin-rich soy protein fractions were obtained. According to the morphology, viscosity, and particle size results, we proposed that proper protein-protein interaction, hydration capacity (glycinin-rich fractions), and certain 7S/11S ratios (β-conglycinin-rich fractions) in modified soy protein are crucial to continuous protein phase formation. The viscous cohesive samples were stable for up to several months without phase separation at room temperature, with the wet adhesion strength of 2.0-2.8 MPa. The soy protein modified with NaHSO3 showed good compatibility with commercial glues applied on plywood and paper labeling fields. The modified soy protein made some functional groups, carboxylic (-COOH), hydroxyl (-OH) and amino groups (-NH2) available, which cross-linked with hydroxymethyl groups (-CH2-OH) from urea formaldehyde (UF) wood glue. The modified soy protein (MSP) with pH 4.8 also acted as an acidic catalyst for the self-polymerization of UF based resin. The wet adhesion strength of MSP/UF blends (40/60) was 6.4 MPa with 100% wood cohesive failure, as compared to 4.66 MPa of UF. As to the paper labeling application, peel strength of MSP on glass substrate increased rapidly, with curing time much shorter than commercial polyvinyl acetate based adhesives (PVAc). And the MSP/ PVAc blends showed shorter curing time, higher water resistance and lower viscosity than pure PVAc. Chemical modification could also enhance the adhesion strength of MSP. 2-octen-1- ylsuccinic anhydride (OSA) was proved to be grafted on soy protein through reaction between amine, hydroxyl groups of protein and anhydride groups. The oily nature and hydrophobic long alkyl chains of OSA mainly contributed to the significant water resistance improvement of MSP.

In the theoretical section of presented diploma thesis are discussed various nanoparticles such as micelles and liposomes, solid lipid nanoparticles and polymeric nanoparticles. Special attention was focused on copolymer PLGA. There are characterized different procedures in the preparation of nanoparticles. From the approches for nanoparticles evaluation are chosen measuring size of nanoparticles and their zeta potential. The experiment was almost unambiguously focused on study of effect of diffrent factors on nanopartlicles size and distribution from linear PLGA and PLGA used for branching of tripentaerythritol and polyacrylic acid. Keywords: nanoparticles, size, size distribution, zeta potential, interactions of nanoparticles

<p>Bioresorbable iron-manganese (Fe-Mn) alloys are considered as a new class of biomaterials for the development of orthopedic fixation devices due to their promising mechanical properties, comparable to the human cortical bone, and the ability to degrade in the physiological environment and release small quantities of metallic ions/particles that are absorbable by the host. The greatest challenge for developing an ideal resorbable Fe-Mn alloy is to increase the degradation rate of the alloy without compromising the alloy biocompatibility, that is, causing zero or minimal local and systemic toxicity to the tissue. Another challenge is to improve osteo-integration through inducing a cascade of events leading to tissue ingrowth.</p> <p> </p> <p>The incorporation of porosity into the Fe-Mn alloys aimed to increase the corrosion rate and to provide the three-dimensional structure for cellular activity and nutrient transport. The Fe-30wt.%Mn alloys with 0-, 5-, 10-, and 60-volume percent porosity were produced through the space holder technique in powder metallurgy. The space-holder material, ammonium bicarbonate (NH₄HCO₃), was sieved to a particle size ranging 355~500 µm. The microstructures and mechanical properties of the alloys, as well as the influence of the degree of porosity on the alloy corrosion rates comparing to the concentrations of the degraded metal ions were investigated. Although the Fe-30Mn alloys containing 60-vol% porosity exhibited the lowest average ultimate compressive strength of 381 MPa among the tested groups, they were still mechanically stronger than a typical human wet compact bone. Furthermore, the alloys had the highest average corrosion rate of 0.98 ± 0.20 mm/year, compared to 0.13 ± 0.07 mm/year for the non-porous Fe-30Mn alloys. Nevertheless, the extract from the 60%-pore group had a cytotoxicity effect to the bone marrow stem cells (BMSCs) at an average normalized cell viability of 58%, which was below the standard viability of 70%, considered as cytotoxic in the indirect cytotoxicity study. The cytotoxicity study also corresponded to the highest level of transition metal ions Mn²⁺ released into the media for the 60%-pore group at an average ion released rate of 7 mg/day, compared to the other groups presenting similar Mn²⁺ released rates about 4 mg/day after 1 day of incubation. The extreme case of the 60%-pore group demonstrated the tradeoff between the corrosion rates and biocompatibility. On the other hand, the 10%-pore group showed an average ultimate compressive strength of 737 MPa comparable to the stainless steel 316L, an average corrosion rate of 0.260 ± 0.09 mm/year, which was 2-fold higher than the non-porous group, and an average cell viability of 86% close to the non-porous group. It is promising based on the above results, however, the osteo-integration of the 10%-pore group in terms of cell-to-cell and alloy-to-cell interactions was not ideal. </p>

Orientador: Márcia Regina de Moura Aouada / Resumo: A crescente preocupação em se consumir produtos que sejam ecologicamente corretos tem motivado pesquisas no desenvolvimento de novos materiais. Nesse sentido, filmes à base de polímeros naturais têm sido desenvolvidos com o objetivo de substituir parcialmente a utilização dos polímeros tradicionais. A utilização desses filmes, além de diminuir a geração de resíduos plásticos descartados no meio ambiente, podem ainda exercer a função de embalagem ativa, estendendo a vida útil dos alimentos. O presente trabalho consiste na elaboração de novos filmes comestíveis à base de gelatina e nanoemulsão de óleos essenciais de manjerona e de pimenta-preta. A gelatina é um polímero natural, biocompatível e biodegradável, possuindo boa capacidade de formar filmes flexíveis. Os óleos essenciais de manjerona e de pimenta-preta possuem boa aceitação por parte dos consumidores, além de excelentes propriedades antioxidantes e antimicrobianas. Quando adicionados às matrizes poliméricas em forma de nanoemulsão, pode contribuir para a diminuição da permeabilidade a vapores de água e aumentar a tenacidade dos filmes. Visando a melhoria da resistência mecânica dos filmes, dispersão de argilas vem sido incorporadas as dispersões filmogênicas. Nesse trabalho, foi utilizada a cloisite Na+. Os filmes produzidos foram caracterizados quanto à análise subjetiva, permeabilidade ao vapor de água, propriedade mecânicas, propriedades térmicas, difração de raios-x, ângulo de contato e microestruturais. As nanoem... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The growing concern to consume products that are ecologically correct has motivated the study in the development of new materials. In this sense, films based in natural polymers have been created with the aim of replacement of the traditional polymers. The use of these films behind to decreasing the generation of plastic waste in the environment, it can still be active packaging, extending the food shelf-life. This present study consists in the elaboration of a film based in gelatin and marjoram and black pepper essential oils nanoemulsions. Gelatin is a natural, biocompatible and biodegradable polymer, it has good flexible and film forming ability. The marjoram and black pepper essential oil has a good acceptance by the consumers, as well as excellent antioxidant and antimicrobial properties. When incorporated to polymer matrices by the nanoemulsions way, they can contributed to the reduction of water vapor permeability and increase film tenacity. By the aim of improve the mechanical proprieties, clay dispersions had been incorporated in the film dispersions. In this study Na+ cloisite was used. The produced films were characterized by the subjective analysis, water vapor permeability, mechanical properties, thermal properties, x-ray diffusion, contact angle and microstructural. The nanoemulsions characterized by the particle size, presented results between 250 and 181nm to black pepper, and 82 and 47nm to marjoram essential oil. Related to the water vapor permeability and t... (Complete abstract click electronic access below) / Mestre

Extensive quantities of apple pomace are generated annually but disposal of this waste is still much disputed. In EU alone, 500 000 tons are produced every year. Without further treatment, the acidic character of apples with their high sugar and low protein content makes the pomace unsuitable for landfilling and animal feedstock. However, further treatment is usually not economically feasible. This study addresses this issue by introducing a new approach for the apple pomace to produce sustainable materials.  The high content of sugars in apple pomace which can be reshaped and reformed at higher temperatures makes the waste material suitable for plastic production. Other components found in apple pomace are 5 % proteins and 1.5 % fats. Fibers are abundant, dietary fibers amounts for more than half (55 %) the original apple pomace weight. Phenols, sorbitol and acids can be found in minor mount, 2 % or less. The apple pomace itself is a mixture of mostly pulp and peel which corresponds to 9/10 of the total mass. Whereas seeds, seed core and stalk are the remaining 1/10. The possibilities of utilizing apple pomace to produce biofilms and 3D shapes have been investigated. The effects of introducing orange pomace, another waste material produced in extensive quantities, to apple pomace samples has also been studied.  Two methods were used to produce bioplastic materials; solution casting and compression molding. Glycerol was used as a plasticizer. Apple pomace, either washed or not washed, was oven-dried and milled into a fine powder. Using compression molding, plates or cups of the two powders with different amounts of glycerol were prepared. Mixtures of apple pomace and orange pomace, with or without glycerol, were prepared in the same way. The apple pomace was also used in a film casting method to produce plastic films. Applying laser cutting to the plates and plastic films, dog-bone specimens were created whose mechanical properties were analysed using a universal testing machine.  Highest values in terms of tensile strength and elongation at max was reached with bioplastics produced from solution casting where the values varied in the range 3.3 – 16 MPa and 11 – 55 % respectively. The compression molding approach resulted in tensile strength values in the range 0.94 – 5.9 MPa whereas the elongation at max was in the range 0.30 – 1.9 %. A possible application for this material could be disposable tableware which does not require high mechanical strength.  It was shown that it is possible to produce 3D structures and plastic films from apple pomace. Washed apple pomace with glycerol has similar properties as not washed apple pomace without the plasticizer. Adding orange pomace to apple pomace samples increases the tensile strength at the expense of the elongation at max. The pressing conditions and powder size greatly effects the mechanical properties, where a larger powder size lower the values for the mechanical properties. This new approach paves the way for a new utilization of apple pomace to replace some petroleum-based materials and at the same time solve the disposal problem of apple pomace.

Visando o desenvolvimento de materiais biodegradáveis para embalagens, blendas de amido/quitosana estruturadas com nanopartículas de montmorilonita (MMT) ou nanofibras de bambu (NFBs) em concentrações de (0,0; 0,5 e 1,0) g de NPs/100 g de polímero foram obtidas pelas técnicas de casting e extrusão. Os bionanocompósitos obtidos das duas técnicas foram caracterizados, bem como foi avaliada a influência da dispersão das nanopartículas sobre as principais propriedades físico-químicas dos bionanocompósitos. Para os filmes produzidos de blendas de amido/quitosana por casting, foram avaliadas as proporções de (5/0; 3,75/0,25; 2,5/2,5; 1,25/0,75 e 0/1) g/100 g base polímero, e a adição dos reforçadores na solução filmogênica. Observou-se uma dispersão assim como uma intercalação satisfatória da MMT nos bionanocompósitos, confirmadas pelas mudanças da cristalinidade devido ao deslocamento do pico característico de 7,2 º para 5,2 º; e os filmes estruturados com NFBs apresentaram variações nas frequências vibracionais dos arranjos moleculares indicando a formação de ligações fortes entre as blendas e os reforçadores. A partir da extrusão da mistura de homo pellets e pellets masterbatch, das blendas de amido/quitosana nas proporções de (100/0; 75/25 e 50/50) g/100 g, foram obtidos compósitos em processo contínuo os quais exibiram propriedades qualitativas satisfatórias assim como mudanças de cristalinidade e interações moleculares. Em relação às propriedades mecânicas, os bionanocompósitos apresentaram um aumento da resposta à tensão assim como da elongação e módulo de elasticidade em relação às concentrações dos reforçadores em cada umas blendas avaliadas. Por outro lado, tanto a formação das blendas como as interações dos reforçadores modificaram significativamente a rede tridimensional dos filmes em relação à taxa de transferência de vapor de água, obtendo-se valores de (155 e 139) g m-2 d-1 para os compósitos obtidos da blenda amido/quitosana 100/0 estruturados com (0,5 e 1,0) g MMT/100 g, respectivamente. Os valores de PVA obtidos são inferiores aos reportados por produtos comerciais como o (PBS) Bionolle&trade; (330 g m-2 d-1) e (PBAT) Ecoflex&reg; (272 g m-2 d-1). Neste trabalho foi possível desenvolver um material promissor com características diferenciadas e alta aplicabilidade no setor de embalagens biodegradáveis para uso industrial. / Aiming at the development of biodegradable packaging materials, starch/chitosan blends structured with montmorillonite nanoparticles (MMT) or bamboo nanofibers (NFBs) at concentrations of (0.0,0.5 and 1.0) g NPs/100 g of polymer were obtained by the casting and extrusion techniques. The obtained bio-nanocomposites were characterized, as well as, how the dispersion of nanoparticles influenced the main physicochemical properties of the films. For the films from starch/chitosan blends produced by the casting method, the proportions of (5/0, 3.75/0.25, 2.5/2.5, 1.25/0.75 and 0/1) g/100 g based on polymer, were tested and the introducing of the reinforcers into filmogenic solution were evaluated. Satisfactory dispersion and exfoliation of MMT in bio-nanocomposites were confirmed by changes of crystallinity due to displacement of the characteristic peak from 7.2 ° to 5.2 °. In the same way, films structured with NFBs showed variations of the vibrational frequencies of the molecular arrangements indicating strong bonds between the polymer blends and the reinforcers. By the extrusion from the mixture of homo pellets and masterbatch pellets, from starch/chitosan blends at proportions of (100/0, 75/25 and 50/50) g/100 g, the obtained films have exhibited changes of the crystallinity and the molecular interactions. In relation to mechanical properties, the films presented increase of the tension response as well as the elongation and modulus of elasticity in relation to the reinforcer concentration in each evaluated blend. On the other hand, the formation of polymer blends and the interactions of reinforcers with the matrix changed significantly the three-dimensional network and consequently the water vapor transmission (WVT). Films produced from starch/chitosan 100/0, nanostructured with (0.5 and 1.0) g MMT/100 g, exhibited lower values of WVT 155 e 139) gm-2 d -1, respectively, when compared to commercial products such as Bionolle &trade; (PBS) 330 g m-2 d-1) and (PBAT) Ecoflex&reg; (272 g m-2 d-1). In this work, it was possible to develop a promising material with desired characteristics in the biodegradable packaging sector with wide application in the industry.

Este trabalho teve como objetivo estudar o potencial do uso de farelo obtido do resíduo da extração do pigmento de cúrcuma (Cúrcuma longa L.) na elaboração de filmes biodegradáveis. Primeiramente, foi conduzido um estudo da extração de corante de cúrcuma por método Soxhlet para simular o processo industrial, dessa forma, utilizaram-se dois tipos de solventes, etanol: isopropanol (1:1) e metanol: acetona (1:1). A partir das tortas foi feito um processo de moagem e peneiragem na tentativa de isolar o amido presente, apesar de não ter obtido sucesso, este processo permitiu obter diferentes frações de farelo de cúrcuma. As frações foram divididas em 80 (F1), 200 (F2), 270 (F3), 400 (F4) mesh e fração centrifugada (F5). A caracterização das tortas de cúrcuma e das frações consistiu em análise da composição centesimal, MEV, difração de raios X e FTIR. A partir destas frações foram elaborados filmes pela metodologia casting. Os filmes foram caracterizados por MEV, difração de raios X, FTIR, análise antioxidante, propriedades mecânicas, solubilidade em água, umidade e permeabilidade ao vapor de água. Os filmes feitos a partir das frações (metanol:acetona) apresentaram melhores propriedades mecânicas e de barreira do que os feitos a partir da frações (etanol:isopropanol), porém industrialmente o solvente utilizado para a extração do pigmento é o etanol:isopropanol. Assim, o filme elaborado a partir da fração FE2 (200 mesh) (etanol:isopropanol) foi o escolhido para realizar o estudo de otimização do processo de elaboração destes filmes por ter as melhores propriedades mecânicas e de barreira do que os filmes feitos a partir das frações FE3 e FE5 . Para o estudo da otimização foi desenvolvido um planejamento experimental 22 com quatro pontos axiais e três pontos centrais para estudar o efeito da temperatura de aquecimento (Ta) e do pH da solução filmogênica sobre as propriedades mecânicas, umidade, solubilidade e permeabilidade ao vapor de água dos filmes plastificados com glicerol (22 g de glicerol/100 g da fração) e sorbitol (30 g de sorbitol/100 g da fração). Os resultados foram avaliados utilizando a metodologia de superfície de resposta e análise de multi-resposta. As condições ótimas obtidas para obter filmes com melhores propriedades mecânicas e funcionais foram: T=84,7ºC e pH 8,3, para filmes com glicerol e T=87,6ºC e pH 8,5 para filmes com sorbitol. Os filmes com glicerol quando comparados com o sorbitol, apresentaram menor índice de cristalinidade, menor teor de curcuminóides pela análise por HPLC e DPPH. Os filmes de farelo de cúrcuma com sorbitol foram mais resistentes, pouco elongáveis e menos permeáveis ao vapor de água do que filmes elaborados com glicerol. / This work aimed to study the potential of the bran residue obtained from the extraction of the pigment from turmeric (Curcuma longa L.) in the preparation of biodegradable films. The extraction of the turmeric dye was conducted by Soxhlet procedure in orer to simulate the industrial process. Two types of solvents were employed ethanol isopropanol (1:1) and methanol acetone (1:1). The pies were crushed and sieved in an attempt to isolate the starch, but no success was achieved. However, this process yielded different fractions, which ensured better characterization of the material. The fractions were divided into 80 (F1), 200 (F2), 270 (F3) and 400 (F4) mesh subfractions and centrifuged (F5). The analysis of pies and turmeric fraction were characterized by chemical composition, SEM, XRD and spectroscopy. Films were prepared from these fractions by film casting methodology, and were characterized by SEM, X-ray diffraction and FTIR analysis; they were also analyzed in terms of their antioxidant, mechanical, water solubility, moisture permeability, and water vapor properties. The films prepared from fractions (methanol: acetone) showed better mechanical and barrier properties than those prepared from the fractions (ethanol: isopropanol), but industrially the solvent used for the extraction of pigment is ethanol: isopropanol. Thus, the film prepared from fractional FE2 (200 mesh) (ethanol: isopropanol) which have the best mechanical and barrier properties than the films prepared from fractions from FE3 and FE5, was chosen for the optimization of the preparation of these films. To this end, we developed an experimental design 22 with four axial points and three focal points, for evaluation of the effect of the heating temperature (Ta) and the filmogenic solution pH on the mechanical properties, moisture, solubility, and permeability to water vapor of the films plasticized with glycerol (22 g fraction glycerol/100 g) and sorbitol (30 g sorbitol/100 g fraction). Results were examined by using response surface methodology and analysis multi-response analysis. The optimum conditions for attainment of films with better mechanical properties and functional characteristics were: T = 84.7 º C and pH 8.3 for films with glycerol, and T = 87.6 ° C and pH 8.5 for films with sorbitol. Compared to films plasticized with sorbitol, the films containing glycerol, had lower crystallinity index, lower content of curcuminoids as verified by HPLC analysis and DPPH. The turmeric bran films plasticized with sorbitol were more resistant, less elongated, and slightly permeable to water vapor compared to films prepared with glycerol.