Over the years, hydrogels have been developed and used for a huge variety of different applications ranging from drug delivery devices to medical products. In this thesis, a poly(2-methyl-2-oxazoline) (POx) / poly(2-n-propyl-2-oxazine) (POzi) bioink was modified and analyzed for the use in biofabrication and targeted drug delivery. In addition, the protein fibrinogen (Fbg) was genetically modified for an increased stability towards plasmin degradation for its use as wound sealant. In Chapter 1, a thermogelling, printable POx/POzi-based hydrogel was modified with furan and maleimide moieties in the hydrophilic polymer backbone facilitating post-printing maturation of the constructs via Diels-Alder chemistry. The modification enabled long-term stability of the hydrogel scaffolds in aqueous solutions which is necessary for applications in biofabrication or tissue engineering. Furthermore, we incorporated RGD-peptides into the hydrogel which led to cell adhesion and elongated morphology of fibroblast cells seeded on top of the scaffolds. Additional printing experiments demonstrate that the presented POx/POzi system is a promising platform for the use as a bioink in biofabrication. Chapter 2 highlights the versatility of the POx/POzi hydrogels by adapting the system to a use in targeted drug delivery. We used a bioinspired approach for a bioorthogonal conjugation of insulin-like growth factor I (IGF-I) to the polymer using an omega-chain-end dibenzocyclooctyne (DBCO) modification and a matrix metalloprotease-sensitive peptide linker. This approach enabled a bioresponsive release of IGF-I from hydrogels as well as spatial control over the protein distribution in 3D printed constructs which makes the system a candidate for the use in personalized medicine. Chapter 3 gives a general overview over the necessity of wound sealants and the current generations of fibrin sealants on the market including advantages and challenges. Furthermore, it highlights trends and potential new strategies to tackle current problems and broadens the toolbox for future generations of fibrin sealants. Chapter 4 applies the concepts of recombinant protein expression and molecular engineering to a novel generation of fibrin sealants. In a proof-of-concept study, we developed a new recombinant fibrinogen (rFbg) expression protocol and a Fbg mutant that is less susceptible to plasmin degradation. Targeted lysine of plasmin cleavage sites in Fbg were exchanged with alanine or histidine in different parts of the molecule. The protein was recombinantly produced and restricted plasmin digest was analyzed using high resolution mass spectrometry. In addition to that, we developed a novel time resolved screening protocol for the detection of new potential plasmin cleavage sites for further amino acid exchanges in the fibrin sealant. / Hydrogele wurden im Laufe der Jahre für eine Vielzahl von Anwendungen, von der Verabreichung von Medikamenten bis hin zu medizinischen Produkten, entwickelt und eingesetzt. In dieser Arbeit wurde eine Poly(2-methyl-2-oxazolin) POx) / Poly(2-n-propyl-2- oxazin) (POzi) Biotinte modifiziert und für den Einsatz in der Biofabrikation und für die gezielte Verabreichung von Medikamenten analysiert. Außerdem wurde das Protein Fibrinogen (Fbg) gentechnisch verändert, um seine Stabilität gegenüber dem Plasminabbau in seiner Funktion als Wundkleber zu erhöhen In Kapitel 1 wurde ein thermogelierendes, druckbares Hydrogel auf POx/POzi-Basis mit Furan- und Maleimid-Funktionen im hydrophilen Polymerrückgrat modifiziert, was die Reifung der Konstrukte nach dem Druck durch Diels-Alder-Chemie bewirkt. Die Modifizierung ermöglichte eine langfristige Stabilität der Hydrogele in wässrigen Lösungen, was für Anwendungen im Bereich der Biofabrikation oder im Tissue Engineering erforderlich ist. Darüber hinaus haben wir RGD-Peptide in das Hydrogel integriert, was zur Zelladhäsion und einer verlängerten Morphologie von Fibroblasten, die auf den Gelen ausgesät wurden, führte. Weitere Druckexperimente zeigen außerdem, dass das POx/POzi-System eine vielversprechende Plattform für den Einsatz als Biotinte in der Biofabrikation ist. Kapitel 2 unterstreicht die Vielseitigkeit der POx/POzi-Hydrogele, indem das System für die gezielte Abgabe von Medikamenten angepasst wird. Wir verwendeten einen von der Natur inspirierten Ansatz für eine biorthogonale Konjugation vom Insuline-like Growth Factor I (IGF- I) an das Polymer unter Verwendung einer Dibenzocyclooctin-Modifikation des Polymers am Ende der Omega-Kette und eines Matrix-Metalloproteasen-empfindlichen Peptid-Linkers. Dieser Ansatz ermöglichte eine bioresponsive Freisetzung von IGF-I aus Hydrogelen sowie eine räumliche Kontrolle über die Proteinverteilung in 3D-gedruckten Konstrukten, was das System zu einem Kandidaten für den Einsatz in der personalisierten Medizin macht. Kapitel 3 gibt einen allgemeinen Überblick über die Notwendigkeit von Wundversiegelungsmitteln und die derzeit auf dem Markt befindlichen Generationen von Fibrinklebern einschließlich der Vorteile und Herausforderungen. Darüber hinaus werden Trends und potenzielle neue Strategien zur Lösung aktueller Probleme und zur Erweiterung der Toolbox für künftige Generationen von Fibrinklebern aufgezeigt. In Kapitel 4 werden die Konzepte der rekombinanten Proteinexpression und des Molecular Engineering auf eine neue Generation von Fibrin Wundklebern angewandt. In einer Proof-of- Concept-Studie haben wir ein neues rekombinantes Fbg Expressionsprotokoll und eine Fbg Mutante entwickelt, die weniger anfällig für einen Abbau durch Plasmin ist. Gezielte Lysine in Plasmin-Schnittstellen in Fbg wurde entweder durch Alanin oder Histidin in unterschiedlichen Teilen des Moleküls ausgetauscht. Das Protein wurde rekombinant hergestellt und eine verminderte Schnittrate wurde mittels hochauflösender Massenspektrometrie gezeigt. Zusätzlich haben wir ein neues zeitaufgelöstes Screening-Protokoll entwickelt, mit dem sich neue potenzielle Plasmin-Spaltstellen für weitere Aminosäurenaustausche in Fibrin-Klebern auflösen lassen.

There is an increased awareness of the textile dyeing and finishing sector’s high impact on the environment due to high water consumption, polluted wastewater, and inefficient use of energy. To reduce environmental impacts, researchers propose the use of dyes from natural sources. The purpose of using these is to impart new attributes to textiles without compromising on environmental sustainability. The attributes given to the textile can be color and/or other characteristics. A drawback however, is that the use of bio-sourced dyes is not free from environmental concerns. Thus, it becomes paramount to assess the environmental impacts from using them and improve the environmental profile, but studies on this topic are generally absent. The research presented in this thesis has included environmental impact assessment, using the life cycle assessment (LCA) tool, in the design process of a multifunctional polyester (PET) fabric using natural anthraquinones. By doing so an eco-design approach has been applied, with the intention to pave the way towards eco-sustainable bio-functionalization of textiles. The anthraquinones were obtained from the root extracts of the madder plant (Rubia tinctorum L.), referred to as madder dye. The research questions were therefore formulated related to the use of madder dye. Three research questions have been answered: (I) Can madder dye serve as a multifunctional species onto a PET woven fabric? (II) How does the environmental profile of the dyeing process of PET with madder dye look like, and how can it be improved? (III) What are the main challenges in using LCA to assess the environmental impacts of textile dyeing with plant-based dyes? It is concluded that there is a potential for the madder dye to serve as a multifunctional species onto PET. Based on the encouraging result, a recommendation for future work would be to focus on the durability of the functionalities presented and their improvement potential, both in exhaustion dyeing and pad-dyeing. LCA driven process optimization of the exhaustion dyeing enabled improvement in every impact category studied. However, several challenges have been identified which need to be overcome for the LCA to contribute to the sustainable use of multifunctional plant-based species in textile dyeing. The main challenges are the lack of available data at the research stage and the interdisciplinary nature of the research arena. It is envisaged that if these challenges are addressed, LCA can contribute towards sustainable bio-functionalization of textiles. / Le secteur de la teinture et de l’ennoblissement textile est de plus en plus conscient de son impact sur l’environnement dû principalement à la consommation élevée de l’eau et à sa pollution, et aux pertes d’énergie. Pour réduire ces impacts, les chercheurs proposent l’utilisation de molécules issues de ressources naturelles, pour traiter les textiles en limitant les impacts sur l’environnement. C’est le cas pour l’obtention de textiles colorés ou pour l’attribution de toute autre fonctionnalité. Cependant, il n’est pas évident que ces molécules bio-sourcées n’aient aucun impact sur l’environnement. On comprend l’importance d’évaluer les impacts de leur utilisation et d’améliorer leur profil environnemental. Or ce type d’étude est peu présent dans la littérature. La recherche présentée dans cette thèse comporte l’évaluation des impacts environnementaux en utilisant l’outil d’analyse du cycle de vie (ACV) pour la conception du traitement d’un tissu de polyester (PET) multifonctionnel avec des anthraquinones naturelles. La méthodologie d’éco conception que nous avons appliquée ouvre la voie à une bio-fonctionnalisation des textiles plus respectueuse de l’environnement. Les anthraquinones ont été obtenues par extraction des racines de plantes de garance et constituent le colorant appelé garance. Les trois questions principales abordées lors de ce travail de recherche sont formulées autour de l’utilisation de la garance : (I) Peut-on traiter les tissus de PET avec de la garance pour obtenir des propriétés multifonctionnelles ? (II) Quel est le profil environnemental du procédé de teinture du PET par la garance et comment l’améliorer ? (III) Quels sont les principaux challenges pour l’utilisation de l’ACV dans l’évaluation environnementale du traitement des textiles par des colorants naturels? Nous avons montré que la garance peut être utilisée pour conférer des propriétés multifonctionnelles au PET. Ensuite, nous avons pu orienter notre étude pour améliorer la durabilité des traitements par les procédés de fonctionnalisation à la fois par épuisement ou par foulardage. En s’appuyant sur l’ACV, l’optimisation de la teinture que nous avons réalisée réduit tous les impacts sur l’environnement. Cette étude nous permet d’identifier les challenges qui doivent être surmontés pour que l’ACV puisse contribuer à l’utilisation de bio-molécules pour la teinture des textiles dans le respect des principes de développement durable. Ils concernent le manque de données pour ces travaux de recherche et leur nature interdisciplinaire. Ainsi, en résolvant ces questions, on peut envisager aboutir à une bio- fonctionnalisation des textiles respectueuse de l’environnement. / Den höga miljöpåverkan från textilfärgning och efterbehandling, på grund av hög vattenförbrukning, dess förorening, och ineffektiv användning av energi, är idag välkänt. För att minska miljöpåverkan föreslår forskningsvärlden användning av färgämnen från naturliga resurser. Syftet med att använda dessa är att ge nya attribut till textilier utan att göra avkall på miljömässig hållbarhet. Attribut som ges kan vara färg och/eller andra egenskaper. En nackdel är dock att användningen av bio-baserade färgämnen är inte fri från att belasta miljön. Det blir därför av största betydelse att bedöma denna miljöpåverkan och förbättra miljöprofilen. Sådana studier är dock i allmänhet sällsynta. Studien som presenteras i denna avhandling har inkluderat miljöpåverkans- bedömning, med hjälp av livscykelanalys (LCA), i designprocessen av en multifunktionell polyester (PET) väv via naturliga antrakinoner. Genom att göra så har ett eko-design tillvägagångssätt använts, med avsikt att bana väg för miljömässigt hållbar bio-funktionalisering av textil. Antrakinonerna erhölls från rot extrakt av växten krapp (Rubia tinctorum L.), och hänvisas till som krapp färgämne. Frågeställningar var därför formulerade relaterat till användningen av krapp färgämne. Tre forskningsfrågor har besvarats: (I) Kan krapp färgämne verka multifunktionellt på en PET väv? (II) Hur ser miljöprofilen ut, från färgningsprocessen av PET med krapp färgämne, och hur kan den förbättras? (III) Vilka är de största utmaningarna med att använda LCA för att bedöma miljökonsekvenserna av textilfärgning med växtbaserade färgämnen? Det kan konkluderas att det finns potential för krapp färgämne att verka multifunktionellt på PET. Baserat på uppmuntrande resultat är en rekommendation för det framtida arbetet att fokusera på kvalitén hos de attribut som presenterats och deras förbättringspotential, både i färgning via färgbad och via foulard. LCA driven processoptimering av textilfärgningen förbättrade i varje miljöpåverkans- kategori som studerats. Emellertid har flera utmaningar identifierats som måste  övervinnas för att LCA skall kunna bidra till en hållbar användning av multifunktionella växtbaserade färgämnen för textil. De största utmaningarna är bristen på tillgängliga data i forskningsstadiet och den tvärvetenskapliga forskningsarenan. Det är tänkt att om dessa utmaningar bemästras kan LCA bidra till en hållbar bio-funktionalisering av textil. / <p>Disputationen kan följas via länk i sal U401b, Textilhögskolan, Högskolan i Borås</p> / Erasmus Mundus Joint Doctorate program: Sustainable Management and Design for Textiles

Detta projekt var ett samarbete mellan Aplex Bio AB och Scilifelab. Projektets mål var att utveckla en molekylär diagnostisk panel med förmågan att detektera och diskriminera mellan 14 olika typer av patogener. Projektet innehåller 4 kapitel med fokus på olika mål. I första kapitlet utvecklades en metod för att karakterisera emissioner av fluorescerande nanopartikel kluster. Den första utvärderade metoden utnyttjade klick-kemi för att binda nanopartiklarna till makrostrukturer uppbyggda av amplifierat DNA. Den andra utvärderade metoden skapade aggregerade komplex av nanopartiklar med amplifierat DNA för att utvärdera partiklarnas emissioner. I kapitel 2 av projektet användes azid-funktionaliserade nanopartiklar levererade av Aplex Bio AB för att tvärbinda DBCO modifierade oligonukleotider. Sedan utvecklades en hybridiserings baserad metod för att kvantifiera relativa mängden oligonukleotider på partiklarna. Denna metod användes för att reproducerbart funktionalisera partiklar och utveckla nanopartikel-sonder som kan binda till DNA genom hybridisering. I kapitel 2 utvärderades även hur effektivt och specifikt de utvecklade nanopartikel-sonderna hybridiserar till DNA. I kapitel 3 utvärderades amplifiering av syntetiska ssDNA sekvenser valda från genetiska markörer av 14 patogener, DNA amplifierades med metoden RCA. Målet var att utvärdera specificiteten av amplifieringen. Specifik amplifiering av varje DNA sekvens i panelen var en förutsättning för att möjliggöra detektion och diskriminering av alla patogener i panelen. I kapitel 4 var målet att utveckla en kostnadseffektiv metod för att funktionalisera nanopartiklar med oligonukleotid sekvenser. För att göra detta användes DBCO-NHS-ester reagens och amin-modifierade oligonukleotider. Förverkligande av detta projekt skulle skapa en diagnostisk panel med potentialen att påverka det diagnostiska fältet på en global skala. När detta projekt är fullt utvecklat kan panelen modifieras för detektion av önskade DNA/RNA sekvenser vilket möjliggör ett mångfalt av applikationer, detta skulle göra panelen konkurrerande med dagens diagnostiska metoder då den kan användas i existerande mikroskopiuppsättningar. / This work was a collaboration between Aplex Bio AB and Scilifelab with the aim of developing a molecular assay capable of detecting and discriminating between 14 different pathogenic targets. There are 4 chapters with focus on different goals. In chapter one a method of evaluating emissions of fluorescent nanoparticle clusters was developed. The first approach of evaluating nanoparticle emissions was to utilize click chemistry to bind nanoparticles to macroscale structures of amplified DNA targets. The second evaluated approach was the formation of aggregated complexes of nanoparticles and amplified DNA targets. The second chapter of the thesis used azide functionalized nanoparticles supplied by Aplex Bio AB to utilize azide groups as crosslinkers and use them to functionalize the nanoparticles with DBCO oligos. A hybridization-based method was then developed to quantify relative oligo densities on the nanoparticles, enabling reproducible oligo functionalization of nanoparticles, producing nanoparticle probes that can bind to DNA. The final task of chapter 2 was evaluating the binding efficiency and specificity of the developed nanoparticle probes. The third chapter of the thesis evaluated amplification of synthetic ssDNA sequences corresponding to genetic markers of 14 pathogenic targets using RCA. The goal was to confirm specificity of chosen padlock probes and corresponding synthetic targets for each pathogen. Specific amplification of each target was a prerequisite to enable detecting and discriminating between the 14 pathogenic targets. In chapter 4 the goal was to develop a cost-effective method of oligo functionalization for nanoparticles. This chapter evaluated two main approaches of using DBCO-NHS-ester reagents to perform DBCO modification of amine-oligos. The realization of this work would develop an assay that has the potential to impact the field of diagnostics on a global scale. When fully developed, the molecular assay can be modified to detect any RNA/DNA targets which enables numerous applications, making the assay a competitive diagnostic tool which can be implemented in existing microscopy systems.

Die Anwendung von körperfremden Materialien zur Behandlung verschiedenster Krankheitsbilder, wie zum Beispiel als Zahnersatz oder Knochenstabilisierung, ist seit Jahrtausenden fester Bestandteil in der Medizin. Während damals hauptsächlich stabile Materialien genutzt wurden, die möglichst wenig mit dem menschlichen Körper interagieren, wird heutzutage ein anderer Ansatz verfolgt. Intelligente Materialien können nicht nur passiv die Heilung unterstützen, sondern aktiv zu ihr beitragen. Ein berühmtes Beispiel hierfür ist das Formgedächtnismaterial Nitinol, das in Stents zur Behandlung verengter Arterien eingesetzt wird. Diese Arbeit beschäftigt sich mit Eisen-Palladium, einem neuen Formgedächtnismaterial, bei dem der Effekt nicht wie bei Nitinol über eine Temperaturänderung sondern durch ein äußeres Magnetfeld induziert wird. Da man somit körpertemperaturbedingte Restriktionen in biomedizinischen Anwendungen umgehen kann, birgt Eisen-Palladium ein hohes Potential für Drug-Delivery Systeme oder mikromechanische Pumpen. Da eine optimale Verträglichkeit des Materials mit seiner biologischen Umgebung absolut unabdingbar ist, untersucht diese Arbeit verschiedene Möglichkeiten, die Oberfläche zu modifizieren und somit die Adhäsion biologischer Zellen zu unterstützen. Zu diesem Zweck wurden das Peptid RGD als spezifische Zelladhäsionssequenz, ein Plasmapolymer auf L-Lysin Basis als unspezifische Beschichtung und die Nanostrukturierung der Eisen-Palladium Oberfläche durch Glanzwinkeldeposition untersucht. Die verwendeten Methoden beinhalten Immunofluoreszenztests zur Quantifizierung der fokalen Kontakte zwischen Zellen und Material, theoretische Dichtefunktionaltheorie Rechnungen, sowie Kontraktilitätsmessungen mittels eines selbst entwickelten Biegebalkenaufbaus. Somit gelingt es in dieser Arbeit, die gegenseitigen Beziehungen des Materials mit der jeweiligen Oberflächenmodifikation mit den lebenden Zellen aus verschiedenen Blickwinkeln zu analysieren. Durch eine Kombination aus experimentellen und theoretischen Methoden werden die Stärken und Schwächen der einzelnen Funktionalisierungsmethoden beleuchtet und die Bildung fokaler Kontakte für eine verbesserte Zelladhäsion wird maßgeblich verbessert.

Die Anwendung von körperfremden Materialien zur Behandlung verschiedenster Krankheitsbilder, wie zum Beispiel als Zahnersatz oder Knochenstabilisierung, ist seit Jahrtausenden fester Bestandteil in der Medizin. Während damals hauptsächlich stabile Materialien genutzt wurden, die möglichst wenig mit dem menschlichen Körper interagieren, wird heutzutage ein anderer Ansatz verfolgt. Intelligente Materialien können nicht nur passiv die Heilung unterstützen, sondern aktiv zu ihr beitragen. Ein berühmtes Beispiel hierfür ist das Formgedächtnismaterial Nitinol, das in Stents zur Behandlung verengter Arterien eingesetzt wird. Diese Arbeit beschäftigt sich mit Eisen-Palladium, einem neuen Formgedächtnismaterial, bei dem der Effekt nicht wie bei Nitinol über eine Temperaturänderung sondern durch ein äußeres Magnetfeld induziert wird. Da man somit körpertemperaturbedingte Restriktionen in biomedizinischen Anwendungen umgehen kann, birgt Eisen-Palladium ein hohes Potential für Drug-Delivery Systeme oder mikromechanische Pumpen. Da eine optimale Verträglichkeit des Materials mit seiner biologischen Umgebung absolut unabdingbar ist, untersucht diese Arbeit verschiedene Möglichkeiten, die Oberfläche zu modifizieren und somit die Adhäsion biologischer Zellen zu unterstützen. Zu diesem Zweck wurden das Peptid RGD als spezifische Zelladhäsionssequenz, ein Plasmapolymer auf L-Lysin Basis als unspezifische Beschichtung und die Nanostrukturierung der Eisen-Palladium Oberfläche durch Glanzwinkeldeposition untersucht. Die verwendeten Methoden beinhalten Immunofluoreszenztests zur Quantifizierung der fokalen Kontakte zwischen Zellen und Material, theoretische Dichtefunktionaltheorie Rechnungen, sowie Kontraktilitätsmessungen mittels eines selbst entwickelten Biegebalkenaufbaus. Somit gelingt es in dieser Arbeit, die gegenseitigen Beziehungen des Materials mit der jeweiligen Oberflächenmodifikation mit den lebenden Zellen aus verschiedenen Blickwinkeln zu analysieren. Durch eine Kombination aus experimentellen und theoretischen Methoden werden die Stärken und Schwächen der einzelnen Funktionalisierungsmethoden beleuchtet und die Bildung fokaler Kontakte für eine verbesserte Zelladhäsion wird maßgeblich verbessert.

Neste trabalho foi realizada a funcionalização de grafite sem prévio tratamento em condições de Fridel-Crafts. Considerando que a grafite não possui hidrogênio em sua estrutura, não se observa uma reação de substituição eletrofílica. Por outro lado, o trabalho mostra o papel da umidade presente no grafite na reação de funcionalização. Dessa forma, foi proposto um mecanismo para a reação com a participação da água adsorvida na grafite estabilizando o carbocátion formado. O grafite funcionalizado obtido na reação foi utilizado como material eletródico. Para a reação de funcionalização, quatro moléculas foram utilizadas: ácido ferrocenomonocarboxílico, cloreto de 4-nitrobenzoíla, cloreto de 3,5-dinitrobenzoíla e ácido 3,4-dinitrobenzóico. Para o estudo das condições ótimas da reação, utilizou-se diferentes potências de radiação no reator de micro-ondas, sendo que a extensão da funcionalização mostrou-se sensível à variação deste parâmetro. Para a caracterização dos materiais, utilizou-se voltametria cíclica e análise térmica (TG e DTA). Resultados de infravermelho e Ramam são apresentados no Apêndice A. Os resultados eletroquímicos mostraram que os materiais funcionalizados em maiores potências apresentaram maior corrente Faradaica, mas ao mesmo tempo, o material obtido foi mais resistivo. A diferença de potencial relacionada ao processo redox do ferroceno aumentou conforme a extensão da funcionalização, uma vez que um sobrepotencial é necessário devido ao fluxo iônico (para a manutenção da eletroneutralidade) relativo ao número de espécies envolvidas. Os resultados eletroquímicos também indicaram que a funcionalização do grafite com os nitro compostos foi baixa. A análise térmica evidenciou que a reação de funcionalização do grafite com o ferroceno resultou em materiais com 15% a 20% (m/m) de material ligado ao grafite. Os materiais funcionalizados a maiores potências apresentaram maior massa ligada ao grafite. A funcionalização com os nitro compostos resultou em materiais com menos de 3% (m/m) de composto ligado ao grafite. Os resultados das duas técnicas mostraram coerência na análise da extensão da funcionalização. O material funcionalizado com o ácido ferrocenomonocarboxilico foi o que apresentou os melhores resultados e propõe-se uma explicação para tal baseado no mecanismo de reação sugerido. Com o objetivo de melhor elucidar o mecanismo da reação, foram realizadas algumas reações na ausência de alguns reagentes. Por exemplo, quando tenta-se funcionalizar o material sem a presença de cloreto de alumínio ou sem a umidade natural do grafite, a reação não ocorre. / In this work natural graphite functionalization in Fridel-Crafts conditions is performed using a one-step microwave assisted reaction. Since there is no hydrogen in graphite structure, it is not possible to observe electrophilic substitution. On the other hand this work shows the role of the moisture present on graphite in the functionalization reaction under this condition. Therefore, a reaction mechanism with the participation of the water naturally adsorbed on graphite stabilizing the formed carbocation has been suggested. After the reaction, the functionalized graphite was used as electrode material. Four molecules were used to functionalize graphite: Ferrocene monocarboxylic acid, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride and 3,4-dinitrobenzoic acid. To study the optimal conditions of the reaction, the microwave radiation power was varied and the extent of the functionalization on graphite was sensitive to this parameter. Two techniques were used to characterize the materials, cyclic voltammetry and thermal analysis (TG and DTA). IR and Raman data are shown in appendix A. Electrochemical results have shown that the materials functionalized at higher microwave radiation power have higher Faradaic current, but are more resistive. The potential difference between the peaks of the redox process of ferrocene increased with the extent of functionalization. This occurs because an overpotencial is needed to compensate the ionic flux (in order to maintain the electroneutrality) related to the number of species involved. The electrochemical results also indicated that the extent of functionalization of graphite with the nitro compounds was low. The thermal analysis have shown that the functionalization of graphite with ferrocene lead to values between 15% to 20% (m/m) of compound in the material. The materials functionalized at higher microwave radiation power presented higher relative mass in the material. The reaction with the nitro compounds lead to less than 3% (m/m) of compound in the final material. The results of both techniques were coherent about the extent of functionalization. The material functionalized with ferrocene monocarboxylic acid showed the best results, and an explanation for that based on the reaction mechanism is suggested. In order to elucidate the reaction mechanism, some experiments were realized in absent of some reagents. When the reaction were carried out without aluminum chloride or with dried graphite, the reaction has not occurred.

Nos últimos anos no Brasil, instituições como o Instituto Nacional de Câncer José Alencar Gomes da Silva e o Ministério da Saúde, reportaram o aumento de casos de câncer de pele. O câncer de pele é uma das doenças mais comuns a nível mundial e pode estar relacionado à exposição à radiação ultravioleta (UV). O objetivo do presente trabalho foi realizar a funcionalização de tecidos sarja 100% algodão com nanopartículas (NPs) de óxido de zinco (ZnO), as quais possuem propriedades para aplicação como protetor solar, melhorando desta forma as características de proteção à radiação UV do algodão. As NPs de ZnO foram sintetizadas pelo processo de precipitação, empregando nitrato de zinco hexahidratado (Zn(NO3)2.6H2O) e hidróxido de sódio (NaOH). A síntese in situ das NPs de ZnO sobre os tecidos foi realizada por meio do processo de esgotamento, usando o equipamento de tingimento têxtil HT (High Temperature). Para este processo foram utilizadas diferentes concentrações de Zn(NO3)2.6H2O (2, 5, 8 e 10% sobre a massa do tecido) e NaOH (0,7; 1,6; 2,5 e 3,0 g/L), respectivamente. A avaliação do fator de proteção UV (FPU) e os testes de resistência à lavagem dos tecidos foram realizados segundo normas as AATCC 183:2004 e AATCC 61:1996, respectivamente. Foram promovidas também aplicações de resinas têxteis comerciais sobre os tecidos funcionalizados e determinação das propriedades físicas. Além disso, foram realizadas caracterizações de vibração molecular, estruturais e morfológicas das NPs de ZnO e para os tecidos funcionalizados foram efetuadas caracterizações estruturais, morfológicas e térmicas. Os resultados mostraram que tanto as NPs de ZnO como as sintetizadas in situ sobre os tecidos apresentaram estrutura cristalina hexagonal wurtzite. As NPs de ZnO mostraram uma morfologia de estrela com pontas muito protuberantes enquanto que as NPs sintetizadas no tecido apresentaram morfologia similar, mas com pontas pequenas. Para todas as concentrações de nitrato de zinco estudadas, antes e após as 20 lavagens, o FPU dos tecidos funcionalizados com NPs de ZnO tiveram categoria de proteção UV entre boa e excelente / In Brazil, institutions such as the José Alencar Gomes da Silva National Cancer Institute (INCA) and the Brazilian Ministry of Health reported increase and appearance of new types of cancer in recent years. Skin cancer is the most common type of disease worldwide and generally might be related to the exposure of the skin to ultraviolet (UV) radiation generated by the sun. The objective of this work was to perform the functionalization of 100% cotton woven fabrics with zinc oxide (ZnO) nanoparticles (NPs), which has interesting properties for applications as solar protector, thus improving the protection characteristics of cotton against UV radiation. ZnO NPs were synthesized by the precipitation process using zinc nitrate hexahydrate (Zn(NO3)2.6H2O) and sodium hydroxide (NaOH). In situ synthesis of ZnO NPs onto the fabric was carried out via exhaust dyeing method, using the textile High Temperature (HT) dyeing machine. For this process, different concentrations of Zn(NO3)2.6H2O (2, 5, 8 and 10% on the weight of fabric) and NaOH (0.7, 1.6, 2.5 and 3.0 g/L) were used. The evaluation of UV protection factor (UPF) and wash durability tests were performed according to AATCC 183:2004 and AATCC 61:1996 standards, respectively. Commercial textile resins applications onto functionalized fabrics and determination of physical properties were also performed. In addition, molecular, structural and morphological characterizations of ZnO NPs were carried out and structural, morphological and thermal analyzes were performed for functionalized fabric. The results showed that both ZnO NPs and those in situ synthesized onto the fabric, exhibited wurtzite hexagonal crystalline structure. The ZnO NPs displayed a star-like morphology with very pronounce tips, while the NPs onto the fabric had a similar morphology but with small tips. For all concentrations of zinc nitrate studied, before and after 20 cycles washing, the UPF of cotton fabrics functionalized with ZnO NPs had an UV-protection category between good to excellent

Este trabalho apresenta os resultados da síntese e caracterização de nanoestruturas de óxido de tungstênio (WO3) obtidos por via ultrassônica em meio não aquoso. Esta técnica tem como vantagens o uso de pouco material e o tempo empregado. A caracterização das nanoestruturas foi realizada por Microscopia Eletrônica de Transmissão (TEM), Microscopia Eletrônica de varredura (MEV), espectroscopia Raman e no infravermelho, termogravimetria e difração de raios-X. A imobilização das nanoestruturas foi realizada em substratos condutores transparentes (ITO) por automontagem camadas por camadas (LbL) e deposição eletroforética (EPD). Foram efetuadas caracterizações eletroquímicas e espectroeletroquímicas com medidas in situ usando UV-Vis. Os resultados eletrocrômicos demostraram a estrutura nanométrica dos filmes obtidos, com parâmetros eletrocrômicos como contraste óptico, tempo de resposta e eficiência eletrocrômica típicos de sistemas nanoestruturados. Alguns aspectos relacionados com o uso de um líquido iônico prótico (PIL) foram mostrados, conferindo melhora na durabilidade dos filmes em relação ao eletrólito H2SO4 1,0 mol L-1. Com o objetivo de modular e incrementar a coloração dos filmes de WO3, foi preparado um viológeno para imobilização superficial através de um grupo ancorador. Os filmes modificados foram investigados por espectroeletroquímica e coordenadas de cor. As coordenadas de cromaticidade foram obtidas por um colorímetro virtual baseado na convenção CIE 1931, dados de cromaticidade para as reações eletrocrômicas dos filmes de WO3 modificado são mostrados em espaços de cor. / The present work describes the synthesis and characterization of WO3 nanoplates in a non-aqueous solvent using ultrasonic irradiation process. This method presents some advantages such as the small amount of reactants and time consumed. WO3 nanoplates have been characterized by TEM and SEM microscopies, Raman and Infrared spectroscopies, thermogravimetric analysis and X-ray diffraction. The nanostructured nanoplates were immobilized by electrostatic layer by layer and Electrophoretic Deposition (EPD) processes onto ITO substrates. Spectroelectrochemical experiments were carried out showing electrochromic performance of the WO3 films such as optical density, response time and chromatic efficiency in a typical way for nanostructured films of WO3. The results using a protic ionic liquid (PIL) as electrolyte, instead of H2SO4, showed improvement in cyclic durability. Cyclic voltammograms were combined with transmittance measurements for all films that undergo typical reversible electrochromic reaction. In order to modulate and improve the colorimetric changes, viologen molecules were prepared with an anchoring group for modifying the surface by the chemisorption of a monolayer. WO3 films with viologen monolayer were investigated using Spectroelectrochemical and color coordinates analysis. A virtual colorimeter was applied for the accurate calculation of CIE 1931 xy color coordinates investigation during the electrochromic reaction of modified films.

Este trabalho apresenta os resultados da síntese e caracterização de nanoestruturas de óxido de tungstênio (WO3) obtidos por via ultrassônica em meio não aquoso. Esta técnica tem como vantagens o uso de pouco material e o tempo empregado. A caracterização das nanoestruturas foi realizada por Microscopia Eletrônica de Transmissão (TEM), Microscopia Eletrônica de varredura (MEV), espectroscopia Raman e no infravermelho, termogravimetria e difração de raios-X. A imobilização das nanoestruturas foi realizada em substratos condutores transparentes (ITO) por automontagem camadas por camadas (LbL) e deposição eletroforética (EPD). Foram efetuadas caracterizações eletroquímicas e espectroeletroquímicas com medidas in situ usando UV-Vis. Os resultados eletrocrômicos demostraram a estrutura nanométrica dos filmes obtidos, com parâmetros eletrocrômicos como contraste óptico, tempo de resposta e eficiência eletrocrômica típicos de sistemas nanoestruturados. Alguns aspectos relacionados com o uso de um líquido iônico prótico (PIL) foram mostrados, conferindo melhora na durabilidade dos filmes em relação ao eletrólito H2SO4 1,0 mol L-1. Com o objetivo de modular e incrementar a coloração dos filmes de WO3, foi preparado um viológeno para imobilização superficial através de um grupo ancorador. Os filmes modificados foram investigados por espectroeletroquímica e coordenadas de cor. As coordenadas de cromaticidade foram obtidas por um colorímetro virtual baseado na convenção CIE 1931, dados de cromaticidade para as reações eletrocrômicas dos filmes de WO3 modificado são mostrados em espaços de cor. / The present work describes the synthesis and characterization of WO3 nanoplates in a non-aqueous solvent using ultrasonic irradiation process. This method presents some advantages such as the small amount of reactants and time consumed. WO3 nanoplates have been characterized by TEM and SEM microscopies, Raman and Infrared spectroscopies, thermogravimetric analysis and X-ray diffraction. The nanostructured nanoplates were immobilized by electrostatic layer by layer and Electrophoretic Deposition (EPD) processes onto ITO substrates. Spectroelectrochemical experiments were carried out showing electrochromic performance of the WO3 films such as optical density, response time and chromatic efficiency in a typical way for nanostructured films of WO3. The results using a protic ionic liquid (PIL) as electrolyte, instead of H2SO4, showed improvement in cyclic durability. Cyclic voltammograms were combined with transmittance measurements for all films that undergo typical reversible electrochromic reaction. In order to modulate and improve the colorimetric changes, viologen molecules were prepared with an anchoring group for modifying the surface by the chemisorption of a monolayer. WO3 films with viologen monolayer were investigated using Spectroelectrochemical and color coordinates analysis. A virtual colorimeter was applied for the accurate calculation of CIE 1931 xy color coordinates investigation during the electrochromic reaction of modified films.

Submitted by Luciana Daniele Trino (lucianadtrino@gmail.com) on 2018-06-08T15:40:25Z No. of bitstreams: 1 Tese_Luciana_Daniele_Trino_POSMAT.pdf: 6699069 bytes, checksum: be06e9652268b5025a7ed7d568576862 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-06-08T17:37:31Z (GMT) No. of bitstreams: 1 trino_ld_dr_bauru.pdf: 6603946 bytes, checksum: dacabdf3e79f4b7c7de3dc9da7bdaa1f (MD5) / Made available in DSpace on 2018-06-08T17:37:31Z (GMT). No. of bitstreams: 1 trino_ld_dr_bauru.pdf: 6603946 bytes, checksum: dacabdf3e79f4b7c7de3dc9da7bdaa1f (MD5) Previous issue date: 2018-04-19 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O titânio e suas ligas são utilizados em diversas aplicações, dentre elas em implantes ortopédicos e dentários devido à sua reconhecida biocompatibilidade. No entanto, falhas e subsequentes efeitos colaterais clínicos ainda são recorrentes em implantes. Neste contexto, melhorias podem ser alcançadas projetando biomateriais nos quais o bulk e a superfície do titânio são independentemente modificadas. Deste modo, filmes finos nanoestruturados de óxidos metálicos, tais como TiO2 e ZnO, podem melhorar as propriedades físico-químicas, a biocompatibilidade e a resistência à corrosão dos implantes de titânio. Além disso, a conjugação de biomoléculas, como peptídeos derivados da proteína da matriz dentinária 1 (DMP1), na superfície dos óxidos metálicos pode melhorar sua bioatividade, acelerando o processo de osteointegração. Dessa forma, o objetivo deste trabalho foi funcionalizar óxidos metálicos com diferentes moléculas bifuncionais e investigar as propriedades físico-químicas de grupos silano, amino, ácido carboxílico, tiol e hidroxila que atuaram como espaçadores entre os óxidos metálicos e os peptídeos da DMP1. Além disso foram realizadas análises de biocompatibilidade, mineralização, resistência à corrosão e à tribocorrosão das superfícies bio-funcionalizadas com os peptídeos da DMP1. Neste trabalho, filmes de TiO2 e ZnO nanométricos foram sintetizados pelo método sol-gel e depositados pela técnica spin coating em substratos de titânio. Posteriormente, os filmes finos de óxidos metálicos foram funcionalizados com (3-aminopropil) trimetoxissilano (APTMS), ácido 3- (4-aminofenil) propiônico (APPA), ácido 3-mercaptopropiônico (MPA) ou polietilenoglicol (PEG), que atuam como espaçadores entre os óxidos metálicos e os peptídeos da DMP1. As análises físico-químicas por XPS, microscopia confocal, AFM, ângulo de contato e energia de superfície revelaram a efetiva modificação das superfícies dos óxidos metálicos com APTMS, APPA, MPA e PEG. Após a bio-funcionalização as análises físico-químicas confirmaram a presença dos peptídeos da DMP1 na superfície dos óxidos metálicos. Além disso, testes biológicos indicaram que os peptídeos puderam modular a afinidade, proliferação e diferenciação de células mesenquimais humanas. Para a amostra contendo o dióxido de titânio, foram observados melhores resultados para o TiO2 funcionalizado com MPA e os peptídeos da DMP1. Já para o óxido de zinco, melhores resultados de biocompatibilidade foram observados para ZnO funcionalizado com APPA e os peptídeos. Além disso, a imobilização dos peptídeos da DMP1 através dos espaçadores APPA e MPA, para ambos os óxidos, levou à formação de biominerais de apatita. Os resultados eletroquímicos indicaram um aumento da resistência à corrosão nos materiais bio-funcionalizados, sendo que melhores resultados foram observados para o TiO2 quando comparado ao ZnO. Além disso a análise de tribocorrosão apresentou menor perda de massa para as amostras de TiO2 bio-funcionalizadas. Considerando os aspectos de biocompatibilidade, diferenciação osteogênica, mineralização, resistência à corrosão e à tribocorrosão a amostra de TiO2 funcionalizada com MPA e os peptídeos da DMP1 foi a que apresentou melhores resultados. Portanto, os resultados obtidos sugerem que a bio-funcionalização de óxidos metálicos é capaz de projetar implantes de melhor qualidade aplicados à medicina regenerativa. / Titanium and its alloys are used in a variety of applications, including orthopedic and dental implants because of their recognized biocompatibility. However, failures and subsequent clinical side effects are still recurrent in implants. In this context, improvements can be achieved by designing biom aterials in which the bulk and surface of the titanium are independently tailored . Thus, nanostructured metal oxides thin films , such as TiO 2 and ZnO, can improve the physicochemical properties, biocompatibility and corrosion resistance of titanium implant s. In addition, the conjugation of biomolecules, such as peptides derived from the dentin matrix 1 protein (DMP1), on the surface of the metal oxides can improve their bioactivity, accelerating the os t eointegration process. Therefore, the objective of thi s work was to functionalize metal oxides with different bifunctional molecules and to investigate the physicochemical properties of silane, amino, carboxylic acid, thiol and hydroxyl groups that act as spacers between metal oxides and DMP1 peptides. In add ition, biocompatibility, mineralization, corrosion and tribocorrosion resistance of the bio - functionalized surfaces were performed. In this work, nanosized TiO 2 and ZnO thin films were synthesized by sol - gel method and deposited by spin coating technique o n titanium substrates. Subsequently, the thin films of metal oxides were functionalized with (3 - aminopropyl) trimethoxysilane (APTMS), 3 - (4 - aminophenyl) propionic acid (APPA), 3 - mercaptopropionic acid (MPA) or polyethylene glycol (PEG), which acted as spac ers between the metal oxides and the DMP1 peptides. The physicochemical analyzes by XPS, confocal microscopy, AFM, contact angle and surface energy revealed the effective modification of the metal oxides surfaces with APTMS, APPA, MPA and PEG. After the bi o - functionalization the physicochemical analyzes confirmed the presence of the DMP1 peptides on the surface of the metal oxides. In addition, biological tests indicated that the peptides could modulate the affinity, proliferation and differentiation of hum an mesenchymal stem cells. For the sample containing the titanium dioxide, better results were observed for the TiO 2 functionalized with MPA and the DMP1 peptides. On the other hand, better biocompatibility results were observed for ZnO functionalized with APPA and peptides. In addition, the immobilization of the DMP1 peptides through the APPA and MPA spacers for both oxides led to the formation of apatite biominerals. The electrochemical results indicated an increase in corrosion resistance in the bio - func tionalized materials, and better results were observed for TiO 2 when compared to ZnO. In addition, the tribocorrosion analysis presented lower mass loss for the bio - functionalized TiO 2 samples. Considering the aspects of biocompatibility, osteogenic differ entiation, mineralization, resistance to corrosion and tribocorrosion, the TiO 2 functionalized with MPA and DMP1 peptides presented the best results. Therefore, the results suggest that the bio - functionalization of metal oxides can design better quality im plants applied to regenerative medicine / 2014/01713-3