Métodos espectrofotométricos em condições estacionária e em fluxo para determinação de Zn(II) foram desenvolvidos com base na formação do complexo de Zn(II) com di-2-piridil cetona saliciloilhidrazona (DPKSH), em meio de etanol-água 50% (V/V) e pH 4,5. Os complexos de Zn(II) com DPKSH foram caracterizados utilizando diferentes técnicas e as respectivas constantes de formação (βl 1,07x105 e β2 1,05x1010) e absortividades molares, em 376 nm, (εl 1,1x104 e ε2 4,5x104) determinadas. Os parâmetros para o método em condição estacionária foram otimizados e, a seguir, construiu-se a respectiva curva analítica. Obteve-se uma faixa de linearidade (lei de Beer) de (0,0293 a 2,01)x10-5mol. L-1, absortividade molar média (em 376 nm, em meio de etanol-água 50% (V/V) e pH 4,5) de 4,83x104 mol-1.L.cm-1 e limite de detecção igual a 1,24x10-7 mol.L-1 (8,11 µg.L-1). Avaliou-se a interferência de 43 íons. Alguns destes que apresentaram interferência positiva são comuns em preparações farmacêuticas e amostras biológicas, porém tal interferência pode ser facilmente eliminada. Aplicou-se o método desenvolvido à preparações farmacêuticas e amostras biológicas. Comparando-se os resultados com a técnica de absorção atômica com chama, obteve-se grande concordância. O método espectrofotométrico em fluxo foi desenvolvido a partir de alguns parâmetros previamente estudados e estabelecidos. Construiu-se a curva analítica e obteve-se uma faixa de linearidade de (0,332 a 7,04)x 10-5 mol.L-1 e limite de detecção 7,46x10-7 mol.L-1 (48,8 µg.L-1). Aplicou-se o método em preparações farmacêuticas e comparando-se os resultados com a técnica de absorção atômica com chama observou-se grande concordância. Com a finalidade de aplicar o método em fluxo a amostras biológicas, foi acoplada ao sistema uma coluna com resina de troca iônica no lugar da alça de amostragem. Após avaliar alguns parâmetros, construiu-se a curva analítica que apresentou uma faixa de linearidade de (0,126 a 3,15)x10-5 mol.L-1 e limite de detecção 2,12x10-7 mol.L-1 (13,9 µg.L-1). / Spectrophotometric methods in stationary and flow conditions were developed for Zn(II) determination based on the complex formation of Zn(II) with di-2-pyridyl ketone salicyloylhydrazona (DPKSH), in ethanol-water 50% (V/V) medium and pH 4.5. The complexes Zn(II)/DPKSH were characterized by several methods and the respective formation constants (β1 1.07x105 and β2 1.05x1010) and molar absorptivities, in 376 nm, (ε1 1.1x104 and ε2 4.5x104) were determinated. Parameters for the stationary method were optimized and, the analytical curve was obtained. A linear behavior (Beer\'s law) was verified in the range (0.0293 and 2.01)x10-5mol.L-1, the medium molar absorptivity (in 376 nm, ethanol-water 50% (V/V) medium and pH 4.5) and the detection limit are 4.83x104 mol-1.L.cm-1 and 1.24x10-7 mol.L-1 (8.11 ppb), respectively. The interference of 43 ions was evaluated. Some of them that showed present a positive interference are commom in pharmaceutical formulations and biological samples, but such interference could be easily eliminated. The developed method was applied to pharmaceutical formulations and biological samples. The results complied well with atomic absorption (flame atomization) technique. A spectrophotometric method in flow was developed upon some previously established parameters. The analytical curve was determined and a linear range was verified between (0.332 to 7.04)x10-5 mol.L-1, and the detection limit 7.46x10-7 mol.L-1 ( 48.8 µg.L-1). This method was applied to pharmaceutical formulations and the results showed a good agreement with atomic absorption (flame atomization) technique. Aiming at employing the flow method to biological samples an ion-exchange resin column was adapted substituting the sampling handle. After evaluating some parameters the analytical curve was determined and it displayed a linear range of (0.126 to 3.15)x10-5 mol.L-1, and detection limit 2.12x10-7 mol.L-1 (13.9 µg.L-1).

Les travaux présentés dans ce manuscrit portent sur l’étude des propriétés photoniques de quatre espèces de diatomées du genre Coscinodiscus : C. wailesii, C. specie, C. radiatus et C. radiatus-cf. Les diatomées sont des micro-algues unicellulaires constituées d’une cellule unique encapsulée dans une matrice inorganique de silice poreuse appelée frustule. Nous avons effectué des cultures de ces espèces, puis extrait les frustules afin de les caractériser, tant du point de vue de leur composition que de leur morphologie, par microscopie électronique et tomographie RX. Le frustule est constitué de trois couches de silice (le foramen, le cribrum et le cribellum) présentant une structure poreuse hiérarchique, s’étendant du micromètre au nanomètre, et formant ainsi une matrice tridimensionnelle complexe pouvant présenter des propriétés photoniques. Le foramen et le cribrum présentent des réseaux de pores de périodicité importante dont les dimensions caractéristiques (taille des pores, pas du réseau…) sont de l’ordre de grandeur des ondes lumineuses. Les propriétés optiques des frustules ont alors été étudiées expérimentalement par imagerie spectrale et théoriquement par simulations numériques par la méthode des éléments finis. Nous avons ensuite mis en évidence un effet de concentration de la lumière visible transmise sur l’axe de la diatomée à quelques dizaines de micromètres derrière le frustule. Cet effet s’avère dépendre de la longueur d’onde incidente ainsi que de l’orientation du frustule. Finalement, nous avons montré, par approche théorique et simulations numériques, que cet effet de concentration de la lumière le long de l’axe est majoritairement dû au foramen et que les autres couches n’ont qu’un effet marginal. Une telle micro et nano-structuration complexe de la matière est actuellement inaccessible à l’échelle industrielle. Cette structure présente cependant des effets de concentration et de filtration des ondes lumineuses d’un grand intérêt dans de nombreux domaines (photovoltaïque, cosmétique, peinture…) et on peut donc envisager raisonnablement une utilisation directe des diatomées. / The work presented in this thesis deals with the study of the photonic properties of four diatom species of the genus Coscinodiscus: C. wailesii, C. specie, C. radiatus et C. radiatus-cf. Diatoms are unicellular microalgae consisting of a single cell encapsulated in an inorganic matrix of porous silica called frustule. We performed cultures of these species, then extracted the frustules to characterize them, both in terms of their composition and their morphology, by electron microscopy and X-ray tomography. The frustule consists of three silica layers (the foramen, cribrum and cribellum) with a hierarchical porous structure, ranging from micrometer to nanometer scale, and thus forming a complex three-dimensional matrix that may have photonic properties. The foramen and cribrum have periodic pores networks whose characteristic dimensions (pore size, lattice constant…) are of the order of light wavelengths. The optical properties of the frustules were then studied experimentally by spectral imaging and theoratically by numerical simulations by finite element method. We demonstrated a concentration effect of visible light transmitted on diatom’s axis a few tens of micrometers behind the frustule. This effect appears to depend on the incident wavelength as well as the orientation of the frustule. Finally, we have shown by theoratical approach and numerical simulations, that light concentration effect along the axis is mainly due to the foramen and the rest of layers have only a marginal effect. Such complex micro and nano-structuring of matter is currently impossible on an industrial scale. This structure, however, has optical effects of light concentration and filtration of great interest in many fields (photovoltaics, cosmetics, paint…) and it is therefore reasonnable to consider a direct use of diatoms.

The aim of this work was to compare authenticity analysis in selected food products with fruit component by using, instrumental and molekular methods. Particularly, the presence of blueberries in fruit–based foodstuffs was verified. The theoretical part is focused on the characterization, chemical composition and botanical classification of blueberries (European blueberry and Canadian blueberry). It also contains an overview of instrumental and molecular diagnostic methods that can be used for the analysis of these fruits. The experimental part focuses on the selection of a suitable method of DNA isolation, and primers for the detection of blueberries in commercial products. DNA analysis was performed by qPCR and HRM analysis. In the experimental part, DNA was isolated in sufficient quality for PCR and the presence of blueberries in foodstuffs was verified by qPCR. Using HRM analysis, we were able to differentiate between bilberry (Vaccinium myrtillus) and blueberry (Vaccinium corymbosum) in control samples and in some commercial products. Certain phenolic acids and some flavonoids specific for blueberries were detected by HPLC. The total content of polyphenols and flavonoids was determined by UV / VIS spectrophotometry.

This work deals with deposition of yttrium oxide layers on silicon substrate (P – type) by using magnetron and reactive magnetron sputtering. Experiments which were made are further described. After that, work is focused on evaluation of deposited layers by using FTIR measurement technique and spectrophotometry. At the end of the work results of experiments are discussed also with the future progress.

This thesis deals with the preparation of the combined alcoholic beverages based on wine and fruit juices. The fruit juices were obtained from the selected fruits as honeysuckle, mulberry, dogwood, rose hips, elderberry, buckthorn and aronia. Some chemical properties e. g. total fenolics, total anthocyanins, vitamin C and sacharides were determined for characterization of the mentioned juices. As well as chemical parameter of juices, the same chemical parameters were determined on wine. There were prepared three sets of combined beverages from wine and juices. The two best evaluated beverages were chosen on the basis of their sensory evaluation. In the end, the same chemical properties were determined in both particular juices and resulting beverages.

This diploma thesis is focused on study of chemical and enzymatical hydrolysis of raw wood material. The aim of this work was to find the suitable method for pretreatment of selected lignocellulose materials. The theoretical part deals with characterization of lignocellulosic material and its components. There are also subscribed various pretreatment methods and their effect on hydrolysis of sawdust. In experimental part of the work the most appropriate approach of pretreatment and hydrolysis of sawdust was studied. Criteria for the selection of suitable method was concentration of saccharides as desired product of hydrolysis and also concentration of the most important microbial inhibitors - polyphenols. Application of 96% ethanol or 5% H2O2 were identified as the most promising pretreatment methods which enhanced yields of fermentable sugars about 30 %. Further, we also performed cultivation of bacteria Burkholderia cepacia and bacteria Burkholderia sacchari using solution obtained by hydrolysis of lignocellulose material.

<p>U ovoj doktorskoj disertaciji proučavano je građenje i termohromno&nbsp;pona&scaron;anje hloro kompleksa kobalt(II) jona u tri različita medijuma:&nbsp;amonijum-nitrat + <em>z</em>formamid (z= 2, 3, 4, 5, 6 i 20), amonijum-nitrat +&nbsp;<em>z</em>N-metilformamid (<em>z&nbsp;</em>= 3, 4, 5, 6 i 20) i amonijum-nitrat +&nbsp; <em>zN,N</em>-dimetilformamid (<em>z</em> = 3) u temperaturnom intervalu od 308,15 do&nbsp;348,15 K. Cilj ovog istraživanja je bio određivanje stabilnosti&nbsp;termohromnih kompleksa kobalta(II) koji se grade sahloridnim i&nbsp;nitratnim jonima i molekulima rastvarača, pronalaženje kvalitativne i&nbsp;kvantitativne zavisnosti konstanti stabilnosti kompleksa kobalta(II) od&nbsp;temperature i molskog odnosa komponenti ispitivanih sistema.&nbsp;Termodinamički parametri, koji karakteri&scaron;u reakcije asocijacije u&nbsp;ispitivanim sistemima izračunati su na osnovu dobijenih konstanti&nbsp;stabilnosti na različitim temperaturama. Drugi deo ovog rada obuhvata&nbsp;fizičko-hemijsku karakterizaciju ispitivanih sistema, i&nbsp; to: merenje&nbsp;gustine, provodljivosti i njihove viskoznosti. Na osnovu dobijenih&nbsp;podataka razmotrene su vrste interakcija koje se javljaju među&nbsp;česticama rastvarača i rastvorene supstance, kao i njihov uticaj na&nbsp;građenje kompleksnih&nbsp; čestica kobalta(II). Ispitivani sistemi su&nbsp;posebno interesantni, jer predstavljaju dobre medijume za ispitivanje&nbsp;termohromizma u praksi.</p> / <p>In this thesis absorption spectra of cobalt(II) chloride in three ammonium nitrate binary mixtures with organic solvents (formamide, N-methylformamide and&nbsp; <em>N,N</em>-dimethylformamide) at different temperatures (from 308.15 to 248.15 K) and compositions have been investigated in the wavelength range 400-800 nm. Influence of the temperature and composition of the mixture on complex formation between cobalt(II) and nitrate ions, chloride ions&nbsp; and/or solvent molecules have been studied. Thermodynamic parameters for cobalt(II)-ligand association in different solventswere also determined. The second part of this work involves physical-chemical characterization of the studied systems, namely: density, electrical conductivity and viscosity measurements. On the basis of the obtained&nbsp;data, the types and nature of the solute-solvent interactions that occur, as well as their impact on the cobalt(II) complex formation were discussed. In all investigated systems, complexes of cobalt(II) change the geometry and colour from pale pink to dark blueupon addition of &nbsp;chloride ions and upon heating/cooling. Hence, additional chemical energy can be stored in such system. Because the effective working temperatures match very well with that readily achievable under sunlight, these thermochromic systems present an &nbsp;example of novel materials suitable for auto-regulated protection and energy storage.</p>

No description available.

<p>U ovoj doktorskoj disertaciji proučavano je građenje&nbsp;kompleksa kobalta(II) sa hloridnim i &nbsp;bromidnim jonima u&nbsp;rastopima koji sadrže jednu neorgansku so i jedno organsko&nbsp;jedinjenje i/ili vodu pri različitom sastavu sistema i na različitim&nbsp;temperaturama. Jedan od sistema je amonijum-nitrat &ndash;&nbsp;acetamid &ndash; voda sastava NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O (z =&nbsp;0,0 1,61 i 2,61), a drugi sistem je amonijum&ndash;nitrat &ndash; dimetilsulfoksid&nbsp;(DMSO) sastava NH₄NO₃∙zDMSO (z = 1 &ndash; 6), &nbsp;na&nbsp;različitim temperaturama (35, 45, 55 i 65 ^oC).&nbsp;Cilj ovog istraživanja je bio određivanje stabilnosti&nbsp;kompleksa kobalta koji se grade sa sa halogenidnim jonima i&nbsp;komponentama rastvarača, pronalaženje kvalitativne i kvantitativne&nbsp;zavisnosti konstanti stabilnosti kompleksa kobalta(II) sa&nbsp;halogenidnim jonima od temperature i molskog odnosa&nbsp;komponenti sistema NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O odnosno &nbsp;NH₄NO₃∙zDMSO, određivanje termodinamičkih parametara koji&nbsp;karakteri&scaron;u reakcije asocijacije u ovim sistemima.</p> / <p>In this dissertation the complex formation between cobalt(II) and halide ions in the melts consisting of one inorganic salt, an organic compound and/or water has been studied at different temperatures. Two molten salt systems have been investigated: 1) &nbsp;ammonium nitrate-acetamide-water system NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O (z = 0.0 1.61 2.61) and 2) ammonium nitratedimethyl sulfoxide NH₄NO₃∙zDMSO (z = 1 &ndash; 6), at four different temperatures: 35, 45, 55 and 65 ^oC. The purpose of this work was to determine stability of cobalt(II) complexes formed with the halide ions and the components of the solvents, to discribe the qualitative and quantitative relationships between the stability of the complexes and the melt composition, as well as the changes in the cobalt(II) coordination due to a complex formation. Thermodynamic parameters for cobalt(II) &ndash; halide association process in these melts were alsodetermined.</p>

<p>U ovoj doktorskoj disertaciji proučavano je građenje kompleksa&nbsp;kobalta(II) sa hloridnim i &nbsp;bromidnim jonima u vodenim&nbsp;rastopima tipa&nbsp;xCa(NO3)2&middot;zH₂O&nbsp;&ndash; (1-x)NH₄NO_3&nbsp;pri različitom sastavu soli (x= 0,3 &ndash; 0,9), različitom sadržaju vode (z= 2,67 &ndash; 6,67) i na različitim temperaturama (45, 55 i 65^oC).</p><p>Istraživanja su imala za cilj proučavanje reakcije građenja&nbsp;kompleksa kobalta(II) sa hloridnim i bromidnim jonima u&nbsp;vodenim rastopima xCa(NO₃)₂&middot;zH₂O &ndash; (1&ndash;x)NH₄NO₃, &nbsp;uticaja&nbsp;temperature, sastava elektrolita i sadržaja vode na proces&nbsp;kompleksiranja, kao i određivanje termodinamičkih parametara&nbsp;koji karakteri&scaron;u reakcije asocijacije u ovim sistemima. Ovakvi&nbsp;rastopi soli su posebno interesantni zbog svoje niske tačke&nbsp;topljenja i visoke latentne toplote topljenja pa se mogu koristiti&nbsp;kao fazno-promenljivi materijali za skladi&scaron;tenje toplotne&nbsp;energije.</p> / <p>In this thesis absorption spectra of cobalt(II) chloride and&nbsp;bromide in calcium nitrate &ndash; ammonium nitrate &ndash; water&nbsp;system of the composition&nbsp; xCa(NO₃)₂&middot;zH₂O &ndash; (1&ndash;x)NH₄NO_3&nbsp;(x= 0.30 - 0.90 and z= 2.67 &ndash; 6.67) have been&nbsp;investigated in the wavelength range 400-800 nm at three&nbsp;different temperatures: 45, 55 and 65^oC.</p><p>Temparature, composition of the melt and water&nbsp;content influence on complex formation reactions between&nbsp;cobalt(II) and halide ions in aqueous xCa(NO₃)₂&middot;zH₂O &ndash;<br />(1&ndash;x)NH₄NO₃ melts have been studied. Thermodynamic&nbsp;parameters for cobalt(II) &ndash; halide association process in&nbsp;different solvents also were determined.</p><p>Investigated systems are interesting because of&nbsp;their high values of latent heat of fusion and low melting&nbsp;points. Due to these reasons, some melts are proposed for&nbsp;<br />heat energy storage materials, usually known as phase&nbsp;change materials (PCM).</p>