Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-22T18:16:20Z No. of bitstreams: 1 JÉSSICA CAMILLA DA COSTA LIMA – DISSERTAÇÃO (UAEMa) 2016.pdf: 6436164 bytes, checksum: 0eb0aed4e907b380df345b619174c509 (MD5) / Made available in DSpace on 2018-06-22T18:16:20Z (GMT). No. of bitstreams: 1 JÉSSICA CAMILLA DA COSTA LIMA – DISSERTAÇÃO (UAEMa) 2016.pdf: 6436164 bytes, checksum: 0eb0aed4e907b380df345b619174c509 (MD5) Previous issue date: 2016-02-24 / Capes / Com o intuito de superar algumas limitações do poli(ácidolático) (PLA), foi feita sua mistura com o copolímero poli(estireno/etileno-butileno/estireno) (SEBS), em diferentes concentrações e avaliadas diversas propriedades. As blendas contendo 5,10, 15 e 20% em massa do SEBS foram preparadas por extrusão seguida de injeção e caracterizadas por ensaios reológicos, difratometria de raios X (DRX), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), calorimetria exploratória diferencial (DSC), análise térmica dinâmico-mecânica (DMTA), temperatura de deflexão térmica (HDT), propriedades mecânicas e a morfologia foi investigada por microscopia eletrônica de varredura (MEV). Estas propriedades foram avaliadas antes e após tratamento térmico de recozimento. Os resultados de reometria de torque indicaram que as blendas apresentam maior estabilidade quando comparadas ao PLA puro. Em baixas frequências (reômetro oscilatório) o PLA e as blendas PLA/SEBS contendo 5 e 10% de SEBS apresentam um comportamento de fluido newtoniano, já as blendas contendo 15 e 20% apresentam um comportamento de fluido pseudoplástico, observa-se também a presença de dois arcos distintos para todas as blendas, indicando que as fases de PLA e SEBS são imiscíveis. Verifica-se para as blendas PLA/SEBS contendo 15 e 20% de SEBS, há uma mudança na inclinação das curvas, esta mudança indica que as mesmas passam a apresentar um comportamento de pseudo-sólido. Nos padrões de DRX das amostras submetidas ao tratamento térmico de recozimento observa-se um pico intenso e bem definido caracterizando cristalinidade considerável das amostras. As análises de DSC e DMTA indicaram que com tratamento térmico ocorreu o desaparecimento da temperatura de cristalização a frio (Tcc) doPLA. As amostras recozidas apresentaram valores de HDT mais elevados. Observou-se um balanço de propriedades mecânicas, no qual o módulo elástico e a resistência à tração tiveram uma pequena redução para as blendas sem tratamento e aumento destas propriedades com tratamento térmico, enquanto que o alongamento, a tenacidade e resistência ao impacto tiveram aumento significativo para as amostras sem e com tratamento térmico. Os resultados de MEV indicaram que com o aumento da concentração do copolímero observa-se aumento do tamanho médio das partículas, provavelmente devido à ocorrência de coalescência. Os resultados de MEV após tratamento térmico em geral, pode-se observar um refinamento no tamanho médio das partículas 7 dispersas de SEBS que influenciou nas propriedades mecânicas. As blendas estudadas no presente trabalho apresentam propriedades muito atrativas, contendo pequenas quantidades do copolímero sintético. Omaterial desenvolvido advém, em sua maior proporção, de fontes renováveis, contribuindo assim, com o meio ambiente. / In order to overcome certain limitations of poly (lactic acid) (PLA) biopolymer, the same was modified with poly (styrene / ethylene-butylene / styrene)(SEBS) copolymer, and the effect of different content of this copolymer on the properties of the blends, before and after heat treatment, was evaluated. The blends containing 5, 10, 15 and 20 wt% of SEBS were prepared by extrusion followed by injection molding and characterized by rheological measurements, X-ray diffraction (XRD) Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and heat deflection temperature (HDT). The results of torque rheometry indicated that the blends exhibited increased stability compared to pure PLA. At low frequencies (oscillation rheometer) PLA and PLA / SEBS blends containing 5 and 10% of SEBS exhibited a Newtonian fluid behavior, and the blends containing 15 and 20% SEBS showed a shear thinning behavior. It was also observed the presence two distinct arcs for all blends, indicating that the SEBS and PLA phases are immiscible. It was also observed that in the PLA / SEBS blends containing 15 and 20% SEBS, there is a change in the slope of the curves. This change indicates that they begin to present a pseudo-solid behavior. In the XRD patterns of the samples subjected to annealing heat treatment a well-defined intense peak was observed for PLA indicating its considerable crystallinity in the samples. The FTIR analysis pointed out, by the presence of characteristic bands, that the PLA presented higher crystallinity after the annealing heat treatment. The annealed samples showed higher HDT values. There was a balance of mechanical properties, wherein the elastic modulus and the tensile strength proved to be inversely proportional to the content of the copolymer, while the elongation and tenacity were directly proportional to this content. The addition of the copolymer caused a significant increase in the impact strength for samples with and withoutheat treatment. The SEM results showed that when the SEBS copolymer content was increased, an increase in the average particle size of SEBS dispersed phase was observed, probably due to the occurrence of coalescence. SEM results for samples after heat treatment showed a decrease in average size of dispersed particles of SEBS, which affected the mechanical properties. The blend studied in this paper presented very attractive properties, and contains small amounts of the synthetic 9 copolymer. The developed material comes, in its most proportion, from renewable sources, thus contributing to the environment.

A incorporação e encapsulamento de fertilizantes em blendas poliméricas são métodos que podem ser usados para reduzir perdas e minimizar a poluição ambiental. Neste trabalho, blendas de Proteína Isolada de Soja (SPI) e Poli(ácido lático) (PLA) foram usadas para incorporar o fertilizante NPK (nitrogênio, fósforo e potássio) granular. A influência de concentração dos biopolímeros na mistura foi examinada por Calorimetria exploratória Diferencial (DSC), Análise Termogravimétrica (TGA) e Microscopia Eletrônica de Varredura (SEM). A incorporação efetiva dos nutrientes no solo é dependente do controle da liberação dos mesmos. Porém as aplicações destes nutrientes estão relacionadas aos métodos e às condições do solo. Um método para reduzir perdas de nutrientes é a liberação controlada dos mesmos. Sendo assim, a preparação de blendas baseadas em biopolímeros constituídos de SPI e PLA, para a liberação controlada, se torna viável. SPI e PLA ou SPI, PLA e NPK foram misturados previamente com plastificante e processados através de mistura mecânica, em um misturador de alto torque do tipo Haake , a temperatura de processo foi mantida a 165 ºC durante 5 minutos à velocidade de 90 rpm. Estes parâmetros foram aplicados para todas as blendas. As blendas foram preparadas seguindo a razão SPI/PLA de 1,5, 2,3 e 4,0, usando diferentes porcentagens de plastificante (5 a 16%). Para a mistura que contém NPK o mesmo método foi utilizado. A adição do fertilizante ocorreu após da fusão do PLA. A taxa de liberação dos nutrientes foi calculada pela condutividade do sistema, decorrente da ionização dos sais dos fertilizantes. A concentração dos íons monitorados aumentou com o tempo, evidenciando a liberação dos fertilizantes. Os testes dinâmicos foram realizados sob agitação contínua com 100 mL de água, 1,6 ±0,2g de amostra e 180 horas. A taxa de liberação é uma função da morfologia das blendas e pode ser controlada pela porosidade das mesmas. O uso de blendas como veículo para o fertilizante diminui a liberação deste de forma apreciável (aproximadamente oito vezes) quando comparado ao componente puro. A redução acontece quando a fase amorfa aumenta, esta fase está relacionada à SPI. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-29T19:38:04Z No. of bitstreams: 1 Dissertacao Luciane Calabria.pdf: 2695342 bytes, checksum: 30e97111b374f9a53e5091c1e5632c46 (MD5) / Made available in DSpace on 2014-05-29T19:38:05Z (GMT). No. of bitstreams: 1 Dissertacao Luciane Calabria.pdf: 2695342 bytes, checksum: 30e97111b374f9a53e5091c1e5632c46 (MD5) / The incorporation and encapsulation of fertilizers in polymers blends are methods that can be used to reduce losses and to minimize environmental pollution. In this work, blends of Soy Protein Isolate (SPI) and Polylactide Acid (PLA) were used to incorporate the granular fertilizer NPK (nitrogen, phosphorus and potassium). The blends were obtained from mechanical mixture in a Haake´s high shear mixer. The influence of concentration of the biopolymers in the blends, was examined by differential scanning calorimetry (DSC), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The morphology of the blends can control the diffusion of the fertilizers, also modulating the release. The effective incorporation of the nutrients to the soil is related to the control release control. However, the applications of these nutrients are linked to the methods and the soil conditions. One method for to reduce losses of nutrients is the slow-release. In this way, the preparation of biopolymers blends based in Soy Protein Isolate (SPI) and Polylactide Acid (PLA) for the controlled-release becomes viable. SPI and PLA or SPI, PLA and NPK were previously mixed whit plasticizers and submited to mechanical mixture, in a Haake high shear mixer. The process was performed at 165 ºC for 5 minutes at speed of 90 rpm. These parameters were applied for all blends containing SPI/PLA rate of 1.5, 2.3 and 4.0. For some blends 5 to 15% of plasticizer was added to study its effects. For the blend containing NPK the same method was utilized with addiction of the fertilizer, after the fusion of the PLA. The release rate of nutrients was estimated by the conductivity promoted by the ionization of thefertilizer salts. The ions concentration increase with time due to the release of the fertilizers. The dynamic tests were conducted in a beaker under continuously agitation with 100 mL of water, 1.6 ±0.2g. of sample and 180 hours. The release rate is a function of the blends morphology, and it can be controlled by the porosity. The use of blends as vehicle decreases the release of the fertilizer when compared to the pure component, for about eight times. The relationship increase with the amorphous phase which is related to the SPI.

A incorporação e encapsulamento de fertilizantes em blendas poliméricas são métodos que podem ser usados para reduzir perdas e minimizar a poluição ambiental. Neste trabalho, blendas de Proteína Isolada de Soja (SPI) e Poli(ácido lático) (PLA) foram usadas para incorporar o fertilizante NPK (nitrogênio, fósforo e potássio) granular. A influência de concentração dos biopolímeros na mistura foi examinada por Calorimetria exploratória Diferencial (DSC), Análise Termogravimétrica (TGA) e Microscopia Eletrônica de Varredura (SEM). A incorporação efetiva dos nutrientes no solo é dependente do controle da liberação dos mesmos. Porém as aplicações destes nutrientes estão relacionadas aos métodos e às condições do solo. Um método para reduzir perdas de nutrientes é a liberação controlada dos mesmos. Sendo assim, a preparação de blendas baseadas em biopolímeros constituídos de SPI e PLA, para a liberação controlada, se torna viável. SPI e PLA ou SPI, PLA e NPK foram misturados previamente com plastificante e processados através de mistura mecânica, em um misturador de alto torque do tipo Haake , a temperatura de processo foi mantida a 165 ºC durante 5 minutos à velocidade de 90 rpm. Estes parâmetros foram aplicados para todas as blendas. As blendas foram preparadas seguindo a razão SPI/PLA de 1,5, 2,3 e 4,0, usando diferentes porcentagens de plastificante (5 a 16%). Para a mistura que contém NPK o mesmo método foi utilizado. A adição do fertilizante ocorreu após da fusão do PLA. A taxa de liberação dos nutrientes foi calculada pela condutividade do sistema, decorrente da ionização dos sais dos fertilizantes. A concentração dos íons monitorados aumentou com o tempo, evidenciando a liberação dos fertilizantes. Os testes dinâmicos foram realizados sob agitação contínua com 100 mL de água, 1,6 ±0,2g de amostra e 180 horas. A taxa de liberação é uma função da morfologia das blendas e pode ser controlada pela porosidade das mesmas. O uso de blendas como veículo para o fertilizante diminui a liberação deste de forma apreciável (aproximadamente oito vezes) quando comparado ao componente puro. A redução acontece quando a fase amorfa aumenta, esta fase está relacionada à SPI. / The incorporation and encapsulation of fertilizers in polymers blends are methods that can be used to reduce losses and to minimize environmental pollution. In this work, blends of Soy Protein Isolate (SPI) and Polylactide Acid (PLA) were used to incorporate the granular fertilizer NPK (nitrogen, phosphorus and potassium). The blends were obtained from mechanical mixture in a Haake´s high shear mixer. The influence of concentration of the biopolymers in the blends, was examined by differential scanning calorimetry (DSC), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The morphology of the blends can control the diffusion of the fertilizers, also modulating the release. The effective incorporation of the nutrients to the soil is related to the control release control. However, the applications of these nutrients are linked to the methods and the soil conditions. One method for to reduce losses of nutrients is the slow-release. In this way, the preparation of biopolymers blends based in Soy Protein Isolate (SPI) and Polylactide Acid (PLA) for the controlled-release becomes viable. SPI and PLA or SPI, PLA and NPK were previously mixed whit plasticizers and submited to mechanical mixture, in a Haake high shear mixer. The process was performed at 165 ºC for 5 minutes at speed of 90 rpm. These parameters were applied for all blends containing SPI/PLA rate of 1.5, 2.3 and 4.0. For some blends 5 to 15% of plasticizer was added to study its effects. For the blend containing NPK the same method was utilized with addiction of the fertilizer, after the fusion of the PLA. The release rate of nutrients was estimated by the conductivity promoted by the ionization of thefertilizer salts. The ions concentration increase with time due to the release of the fertilizers. The dynamic tests were conducted in a beaker under continuously agitation with 100 mL of water, 1.6 ±0.2g. of sample and 180 hours. The release rate is a function of the blends morphology, and it can be controlled by the porosity. The use of blends as vehicle decreases the release of the fertilizer when compared to the pure component, for about eight times. The relationship increase with the amorphous phase which is related to the SPI.

La lésion de nerfs périphériques peut engendrer des déficits moteurs et/ou sensoriels permanents. En dépit des progrès techniques réalisés au cours de ces 25 dernières années, une récupération complète suite à ces lésions n’est pas encore possible aujourd'hui. L’autogreffe nerveuse, toujours considérée comme le standard clinique, est la seule technique capable d’offrir les meilleurs résultats en termes de récupération fonctionnelle. Cependant, la survenue de complications post-opératoires lors d’autogreffes d’un nerf et la quantité limitée de nerfs disponibles conduisent à mettre au point d’autres stratégies alternatives. Dans ce contexte, la mise au point de biomatériaux pour substituts nerveux devient une nécessité clinique. Malgré les efforts de la recherche, ces prothèses ne permettent toujours pas une régénération du nerf à la hauteur de l’autogreffe. Le biomatériau utilisé doit notamment présenter des propriétés physiques et chimiques proches de celui du nerf natif. La soie, aux propriétés mécaniques uniques, représente une bonne alternative pour mettre au point ce type de prothèses. En effet, la protéine de soie déjà utilisée dans le domaine biomédical est biocompatible. Les modifications chimiques de cette protéine améliore et favorise l’adhérence et la croissance cellulaires par l’incorporation de facteurs de croissance ou d’autres molécules d'intérêt. Ce travail de thèse propose de développer un nouveau type de biomatériau à base de soie fonctionnalisée par deux facteurs de croissance : le Nerve Growth Factor (NGF) et le Ciliary NeuroTrophic Factor (CNTF). Étant donné l’architecture complexe qui compose la structure nerveuse, une matrice supportant la repousse des tissus de façon orientée semble primordiale. Nous démontrons, dans un premier temps, le pouvoir de ces nanofibres alignées (produites par electrospinning) à orienter la régénération tissulaire de différents organes par culture d’explants. Les nanofibres de soie alignées, biocompatibles sont bio-activées par ajout de NGF spécifique de la régénération nerveuse. Cette matrice créée présente un gradient de concentration en NGF qui permet d’orienter la repousse axonale en stimulant la croissance axonale dans une seule direction. Afin d’optimiser la croissance de deux populations cellulaires, nous avons incorporé du CNTF pour produire des nanofibres bifonctionnalisées. Ces nanofibres bifonctionnalisées ont conduit à une longueur des neurites 3 fois plus grande à leurs contacts, stimulant la croissance des cellules gliales. Ainsi, nous avons produit des conduits nerveux à base de soie biofonctionnalisée pour implantation chez le rat. Les analyses physico-chimiques et les propriétés mécaniques démontrent le caractère biomimétique de nos tubes de guidage. Les premières études de la locomotion et l’observation de coupes du nerf sciatique de rat, suite à l’implantation de nos conduits donnent des résultats très prometteurs. L’ensemble de ces travaux démontre l’efficacité de nos guides nerveux à base de soie et les présente comme une alternative prometteuse à l’autogreffe nerveuse pratiquée en clinique. / Peripheral nerve injury causes sensory and/or motor functions deficits. Despite technological advances over the past 25 years, a complete recovery from these injuries remains unsatisfactory today. The autograft still considered the "gold standard" in clinical practice. This is the only technique able to offer complete functional recovery. However, the occurrence of postoperative complications in autologous nerve and the limited amount of available nerves lead to develop alternatives strategy.In this context, development of nerve graft substitutes becomes by far a clinical necessity. Despite research efforts, these artificial prostheses design based on biomaterial doesn’t allow nerve regeneration as found in autograft nerve procedures. The biomaterial used must have the physical and chemical properties similar to that of the native nerve. Silk, well known for its unique mechanical properties, proposes a good alternative to develop these prostheses. Indeed, the silk protein is commonly used in the biomedical field and regenerative medicine. This protein biocompatibility may be improved through chemical modifications to promote adhesion and cell growth by the incorporation of growth factors or other molecules of interest. Therefore, this thesis proposes to develop a new type of functionalized silk biomaterial based on two growth factors : Nerve Growth Factor (NGF) and Ciliary NeuroTrophic Factor (CNTF). Given the complex architecture that consists of nerve structure, a matrix which is able to support and manage the outgrowth of tissue becomes essential. We demonstrate the power of these aligned nanofibers (produced by electrospinning) to guide and manage tissue regeneration from different organ explants culture. Aligned silk nanofibers, were biocompatible and bio-activated by adding NGF involved for nerve regeneration. This matrix has been created with a concentration gradient of NGF to guide neuritis outgrowth in only one direction. The presence of this gradient demonstrated a better axonal growth in one direction versus the uniform concentration conditions. Nerve cells consist essentially of two cell populations which are neurons and Schwann cells. To optimize the culture and growth of these two populations, in addition to NGF, we incorporated CNTF to produce bifunctionalized nanofibers. These biofunctionalised nanofibers led to a length 3 times larger on contact with neurites. The glial cells growth, alignment and migration were stimulated by CNTF. Thus, we produced bi-functionalized nerve guidance conduits for rat implantation. The physico-chemical analyzes demonstrate the biomimetic of our guide tubes. Early studies of locomotion and observing histological sections of rat sciatic nerve, following the implementation of our conduits gave very promising results.These studies demonstrate the relevance of our nervous guides’ silk-based developed as an effective alternative to nerve autograft performed in the clinic.

Tato práce se zabývá studiem fluorescenčně značeného hyaluronanu, konkrétně rhodaminylamino hyaluronátu sodného (Hya-Rh, 40 kDa), pomocí dvouohniskové fluorescenční korelační spektroskopie (2f-FCS). Nejdříve byla prostudována literatura týkající se využití FCS techniky v koloidní chemii a při studiu polymerů, přičemž následně byly shrnuty veškeré poznatky o využití 2f-FCS metody. Na základě prvotních měření byl zjištěn vhodný postup přípravy a způsob uchovávání vzorku Hya-Rh používaném pro následující experimenty. Záhy byly prostudovány možné vlivy koncentrace Hya-Rh na jeho difúzní charakteristiky jak ve vodě, tak ve fyziologickém roztoku. Následně bylo studováno chování Hya-Rh a vliv koncentrace solí alkalických kovů ve vodných roztocích těchto solí a fluorescenčně značeného hyaluronanu. Poté bylo sledováno chování Hya-Rh v závislosti na koncentraci velmi nízkomolekulárního hyaluronanu (VLMW HA, 404 kDa) v čisté vodě i ve fyziologickém roztoku, přičemž získané výsledky byly mezi sebou porovnány. Nakonec bylo využití 2f-FCS metody celkově zhodnoceno a popsáno z hlediska studia chování fluorescenčně značeného hyaluronanu v roztocích.

Die vorliegende Arbeit beschäftigt sich mit der theoretischen Beschreibung der komplexen physikalischen Eigenschaften von Netzwerken semiflexibler Polymere. Ausgehend vom mathematischen Modell eines semiflexiblen Polymers, der \"wurmartigen Kette\" (wormlike chain), werden zwei wesentlich neue Konzepte zur Beschreibung dieses ungeordneten Materialzustands eingeführt. Einerseits wird das experimentell beobachtete, glasähnliche Fließen solcher Materialien durch das phänomenologische Modell eines semiflexiblen Polymers mit verallgemeinerter Reibung beschrieben, welche den Gesamteffekt der physikalischen oder auch chemischen Wechselwirkungen der Polymere untereinander widerspiegelt. Andererseits wird das bestehende Konzept der durch seine Nachbarfilamente erzeugten röhrenförmigen Einsperrung eines Filaments erweitert und die experimentell nachgewiesene, räumlich veränderliche Struktur der Röhre erklärt. Die erzielten Ergebnisse werden durch Rechnersimulationen sowie durch experimentelle Daten gestützt.

V poslední době se pozornost polečnosti obrátila k mikroplastům. Jsou produkovány různými odvětvími a šíří se napříč prostředím. Po dlouhou dobu byly považovány za inertní, bez dalšího vlivu na rostliny a jiné živé organismy, avšak jak zjistily nedávné studie, mohly by představovat vážnou hrozbu. Několik vědců, včetně nás, se proto začalo soustředit na jejich transport a transformace v životním prostředí. Většina se však zaměřuje pouze na jejich přítomnost v mořských a sladkých vodách, a proto jejich chování ve vzduchu a půdě zůstává nejasné. Kromě toho byla pozornost soustředěna i na bioplasty. Jsou prezentována jako ekologická alternativa, která má vyřešit všechny dosud zmíněné problémy (a další). Avšak často se zapomíná, že jejich hlavní výhoda může být zároveň nevýhodou. Z tohoto důvodu se tato diplomová práce zaměřuje na negativní účinky spojené s přítomností mikroplastů (konkrétně bioplastu poly-(R)-3-hydroxybutyrátu) v půdě jako jejich běžný receptor. Kombinovali jsme respirometrii, elementární analýzu, termogravimetrii a enzymatické testy, abychom zkoumali fyzikálně-chemické změny v půdě vyvolané přítomností bioplastu. Naše výsledky ukázaly negativní vliv na půdní organickou hmotu a zadržování vody v půdě. V tomto smyslu byl zkoumán i tzv. "priming effect", jelikož docházelo k urychlení a také zpomalení rozkladu půdní organické hmoty. Zaznamenali jsme rozdílný vliv vybraných koncentrací biopolymeru na půdu a také vliv půdních vlastností na průběh degradace. V neposlední řadě zvýšení enzymatické aktivity jasně naznačovalo vliv přítomnosti biopolymeru na mikrobiální komunitu. Na základě takových zjištění jsme došli k závěru, že přidání biopolymeru vede k dlouhodobému dopadu na řadu funkcí půdního ekosystému.

PhD (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Water is a basic resource to mankind. The environment is deteriorating daily due to industrial pollution of water resources. Industrial effluents containing organic pollutants such as dyes are undesirable even at low concentrations in the environment. Natural biomaterials have been applied as adsorbents for dye removal from water systems, however, their application has been limited by their low adsorption capacity. Much attention has been focused on the chemical modification of natural biomass via grafting processes. The modification of natural polymers by graft copolymerization is a promising technique since it functionalizes a biopolymer thus imparting desirable properties. The purpose of the study was to prepare and optimize the working conditions for the pine-magnetite bionanocomposites (PMC) as adsorbents and as photocatalysts modifiers. First, this work focuses on the synthesis and optimization of reaction variables in the preparation of PMC for the removal of methylene blue (MB). The thesis also explores the synthesis of acrylamide and acrylic acid-grafted PMC, resulting in the formation of acrylamide-grafted PMC (GACA) and acrylic acid-grafted pine-magnetite bionanocomposites (GAA), respectively. The grafting of functional groups such as –CO, –NH2 onto cellulose from acrylamides is also explored in detail. The adsorption conditions optimized were used to investigate the adsorption efficiency of GAA and GACA on MB. Finally, the application of PMC and GAA as modifiers for amorphous TiO2 and N-doped TiO2was carried out. The photocatalytic bionanocomposites from PMC (namely PMC–a-C,TiO2 and PMC–a-C,NTiO2) and those from GAA (labeled GAA–a-C,TiO2 and GAA–a-C,NTiO2) are compared by their photocatalytic efficiency on the degradative removal of an alkaline dye mixture formed from Reactive red 120 (RR 120) and Rhodamine B (Rh B). The synthesis procedure for PMC involved treating pinecone biomass with 0.15 M NaOH solution to remove unwanted plant extracts and the subsequent coating of the treated pinecone with iron oxide magnetic particles through a co-precipitation method. The variables used for the experiments were volume of NH4OH (5 to 40 cm3), reaction temperature (40 to 100 °C), effect of time (15 to 60 min) and mass (1.0 to 3.5 g). The PMC and acrylic acid grafted pine-magnetite composite (GAA) were probed for structural morphology and surface properties using various surface characterization instrumental techniques. Strong chemical interactions between pinecone magnetite and acrylic acid were demonstrated by thermogravimetric (TGA), differential thermal analysis (DTA) and X-ray photoelectron spectroscopy (XPS) for these unique bionanocomposites as such suggesting high chemical stability. Grafting acrylic acid was shown by XPS to form polyacrylic acid on the surface of the bionanocomposites and thus capping the surface groups. Significant differences in size were shown by transmission electron spectroscopy (TEM) and scanning electron microscopy (SEM); i.e., smaller particle sizes (Ave = 13.0 nm) for GAA and slightly larger for PMC (Ave = 14.0 nm). Brunauer Emmett Teller (BET) surface analysis demonstrated a larger surface area, pore volume and pore diameter (59.9 m2.g-1, 0.2254 cm3.g-1 and 28.14) for GAA compared to PMC. These characteristics coupled with the point of zero charge for GAA (pHpzc = 6.8) were critical in enhancing the efficiency of GAA adsorption of MB at pH 12 and further enable GAA to have a higher desorption efficiency of up to 99.7% after four cycles of washing with 0.10 M HCl. The adsorption kinetics and isotherm studies indicated that the adsorption process follows the pseudo second order kinetics and Langmuir isotherm respectively. The adsorbent also showed improvement in the adsorption capacity and reusability promising to be used for the removal of dyes in a prototype scale. GAA and MB adsorption mechanism was confirmed to be through intra particle diffusion. The overall performance of the GAA bionanocomposites is hinged on the formation of polyacrylic acid on the surface, its structural morphology, and the enhanced surface properties. Most importantly, the plant-based materials (lignin and cellulose) provide an environment that is rich with surface (–COOH and –OH) groups for the attachment of the magnetite nanoparticles while the polyacrylic acid stabilizes the magnetite onto the pinecone nanoparticles while reducing the point of zero charge for increased adsorption of cationic species. The photocatalytic bionanocomposites were fabricated from the adsorptive bionanocomposites using a simple solgel process in which ~10 wt.% of PMC and GAA, respectively, were used as a starting agent. Titanium butoxide was used as a precursor, acetylacetone as a dispersant and ethylene diamine as a nitrogen source. Using this procedure, amorphous carbon-doped titania (a-C,TiO2) and amorphous carbon and nitrogen co-doped titania (a-C,NTiO2) were fabricated except that the biopolymer was not added. Two sets of amorphous titania bionanocomposites were fabricated. One set was the nitrogen doped forms that had been modified with PMC and GAA (PMC–a-C,TiO2 and GAA–a-C,NTiO2). The other set of photocatalytic bionanocomposites produced in this work were without nitrogen (PMC–a-C,TiO2 and GAA–a-C,TiO2). TEM and SEM micrographs showed that all the photocatalysts consisted of globular, smooth aggregates of nanosized a-CTiO2 and a-C,NTiO2 which decreased in size with N-doping and the incorporation of GAA and PMC to as low as <30 nm. Surface chemical analysis through FTIR, XPS and EDS confirmed the presence of C, O, Ti and N (for the N-doped photocatalysts). In addition, it was demonstrated that N-doping into TiO2 had taken place, albeit with most of the N incorporated as organic nitrogen. It was further demonstrated that because of the absence of high temperature calcination, the process chemicals played a significant role in doping the photocatalysts with carbon resulting in the promotion of photocatalytic activity for a-C,TiO2 to the point of surpassing that of, a-C,NTiO2 and all the PMC-modified photocatalytic bionanocomposites. a-C,TiO2 had an overall 94% removal of the dyes, Rhodamine B (RhB) and Reactive red 120(RR 120), under UV illumination. The benefit of co-doping a-TiO2 with C, N and the biopolymers was realized with the incorporation of GAA as a modifier. The result was 97% removal of the dyes by GAA–a-CTiO2 and 99% for GAA–a-C,NTiO2. It was further observed that the degradation of the binary mixture of the dyes (RhB and RR 120) proceeded through the zero order kinetics for the a-C,TiO2 based photocatalysts and first order kinetics for the N-doped photocatalysts. The work, has, therefore demonstrated the applicability of plant-based biopolymers in the fabrication of nanoadsorbents and nanophotocatalysts. While the photocatalytic degradations were carried out under UV-light, there still remains a number of possible avenues that researchers can build on to improve the visible light-driven photocatalytic bionanocomposites. The research work has proven the effectiveness of novel pinecone magnetic nanoparticle materials and TiO2-based photocatalyst for the degradation of undesirable dyes from wastewater.

For more than a century, plastics have become an increasingly important part of the human society. Thanks to the durability and the many varieties of plastic it has a wide range of applications, but unfortunately the traditional plastic made from fossil oil has its drawbacks. Neither the fact that fossil oil is used, nor that these plastics won’t degrade in nature, are in any way sustainable for the environment in the long run. But out of the shadow of these problems, new technologies for the manufacturing of bioplastics are born. This thesis aims towards mapping out properties of different plastics, fossil based as well as bio-based, and investigating the possibilities to manufacture plastic material from algae, so called blue plastics. Additionally, the thesis shed light on terms related to plastic production and bioplastics.  The result shows that there are multiple approaches to the manufacturing of blue plastics; several divergent polymers (e.g. starch, protein and alginate) can be extracted from algae for the production of plastic material, and there is a large number of algae strains and methods to use. Blue plastics are still not produced in large scale, and therefore suffer from high production costs, which makes it challenging to replace traditional plastics. Another obstacle is bad durability and mechanical properties of some algae-based materials. But the blue side of the spectrum of plastics is still a young field of study and new innovations are yet to be discovered. / I över ett sekel har plast blivit en allt viktigare del i det mänskliga samhället. Tack vare sin tålighet och mångsidighet har plast en mängd olika användningsområden, men tyvärr har den traditionella plasten även sina nackdelar. Varken det faktum att fossil olja används, eller det faktum att dessa plaster inte bryts ned i naturen, kan anses hållbart i längden. Men ur skuggan av dessa problem träder nya tekniker fram, som möjliggör tillverkning av bioplaster. Detta projekt syftar till att kartlägga egenskaperna hos olika plaster, fossilbaserade såväl som biobaserade, samt möjligheterna att tillverka plast med alger som råvara. Dessutom läggs fokus på att förklara vissa termer relaterade till plaster, bioplaster och dess livscykel.  Resultatet visar att det finns ett flertal tillvägagångssätt för tillverkningen av algbaserade plaster. Flera olika polymerer (t.ex. stärkelse, protein och alginat) kan extraheras från alger för vidare produktion av plastmaterial, och dessutom finns ett stort antal olika algarter och tillverkningsmetoder som kan användas. Idag produceras algplaster ännu inte i stor skala, något som innebär att produktionskostnaderna fortfarande är höga och att det således är svårt att konkurrera ekonomiskt med traditionella plaster. Ett annat hinder för algbaserade plaster är i vissa fall låg resistans och sämre mekaniska egenskaper jämfört med traditionella plaster. Men den algbaserade delen av plastspektrumet är fortfarande ung och outforskad, fortfarande finns nya upptäckter och möjligheter som väntar på att bli funna.

Ziel der vorliegenden Arbeit war die Durchführung sowie die Untersuchung ausgewählter Verfahrenswege zur chemischen und thermischen Vernetzung von Polysacchariden und Proteinen aus nachwachsenden Rohstoffen. Darüber hinaus wurden Hypothesen zu den Anwendungsmöglichkeiten der untersuchten vernetzten Polymere erstellt. Hierfür wurden mit analytischen Methoden die physiko-chemischen sowie die technofunktionellen Eigenschaften der Rohstoffe und der vernetzten Biopolymeren untersucht. Verglichen wurden z.B. die IR-Spektren der Ausgangsmaterialien mit denen des vernetzten Biopolymers. Mittels Reaktivextrusion wurden Formkörper hergestellt, deren Eigenschaften durch den Einsatz von geeigneten Weichmachern beeinflusst werden können. Die Temperatur des Extruders sollte möglichst niedrig gehalten werden, d.h. geringer als 90 °C, um unerwünschte Bräunungsreaktionen zu vermeiden. Bei den chemischen Vernetzungen wurden fünf verschiedene Vernetzungsmittel eingesetzt: Glutaraldehyd, Maleinsäureanhydrid, Maleinsäurediethylester, Bernsteinsäureanhydrid und Methylendiphenyldiisocyanat. Die Proben aus der Vernetzung mit Glutaraldehyd weisen einen wasserbindenden Charakter auf und können beispielsweise Einsatz als Hydrogele finden. Die mit Diisocyanaten vernetzten Proben härten im Wasser und können als Füllmaterial Einsatz in der Bauindustrie finden. Aufgrund der starken Vernetzung sind die Proben unlöslich und für die meisten erfolgt der Zersetzungsprozess ab 200 °C. Im Sinne einer Werkstoffbeschreibung wurden alle Proben als Duroplaste eingestuft, da sie keine thermoplastische Eigenschaft aufweisen. Mit dieser Arbeit werden Grundlagen für die Erforschung von Verfahrenswegen für die chemische sowie für die thermische Vernetzung von Polysacchariden und Proteinen gelegt. Die gewonnenen Erkenntnisse können für weitere Arbeiten genutzt werden. / In the present work, the possibilities of conjugation or interactions between polysaccharides, especially hemicelluloses and proteins from different sources of renewable raw materials have been investigated. Sources of polysaccharides are oat spelts xylan and maize spindles. Proteins like acid casein from cow milk and cruciferin, a rapeseed protein isolate, from the canola plant have been used. For the chemical crosslinking, homo-bifunctional reagents (crosslinkers) like glutaraldehyde, maleic anhydride, maleic acid diethyl ester, succinic anhydride, and methylene diphenyl diisocyanate were used. These reagents can react with functional groups of the biopolymers- the hydroxyl groups in the hemicelluloses and amino groups in the proteins. For a thermolinked conjugation of the biopolymers, the reactive extrusion was used as mechanical technique. Both types of biopolymers were successfully blended in a mini-Extruder to form sticks. The plastics characteristics of the sticks could be influenced by the addition of suitable softeners. The extrusion temperature must be kept as low as possible, to avoid the appearance of unwanted brown reactions. To investigate the conjugation of the polysaccharides with casein or cruciferin, the IR spectra of the raw materials with those of the crosslinked biopolymers were compared. Application possibilities of the resulted crosslinked biopolymers have been proposed. Most of the samples are insoluble due to the strong networking after the crosslinking reactions. Their thermal decomposition starts at temperatures around 200 °C. All the samples have been classified as duroplasts since they do not exhibit a thermoplastic characteristic. The work complements basic research about chemical and thermal conjugation between polysaccharides and proteins from renewable raw materials.