Molecular imprinting, a common method used in separations and chromatography to isolate specific molecules via surface binding, has been adapted for applications in biomaterials and related sciences. The objective of this study was to determine the effectiveness of different approaches to molecular imprinting by testing for preferential binding of protein on polysiloxane scaffold surfaces. To test preferential rebinding, the scaffolds were exposed to a mixture of the template protein and a competitor protein with similar size but different chemistry. Lysozyme-imprinted polymers rebound 8.13 0.99% of lysozyme without any competition and 5.1 0.3% of the protein during competition. Lysozyme C peptide was imprinted into polysiloxane scaffolds to investigate the epitope approach to molecular imprinting. Without competition, 8.95 11.53% of the lysozyme preferentially bound to the scaffolds, while under competition 1.85 9.47% bound to the scaffolds. Lastly, bone morphogenetic protein 2 (BMP-2) was imprinted into the polymer scaffolds. Results revealed that BMP-2 imprinted scaffolds bound 10.09 6.625% under noncompetitive conditions and a very small 0.65 4.55% during competition. Trends of preferential binding via peptide imprinting and BMP-2 imprinting can be seen, and show promise in future tissue engineering material applications and biomaterial compatibility.

The aim of this work was to investigate the effects of feather availability and imprinting to loose feathers in the litter on the incidence of feather pecking behaviour (FP), condition of the integument and fear reactions in two genotypes of laying hens. Hens that were deprived from loose feathers in the litter (feathers were collected 4 times/week) exhibited a significantly less rate of feather pecking, less number of severe FP and showed a better feather score in the laying period compared to the control groups (no feather treatment) in both Lohmann Tradition (LT) & Lohmann Silver (LS) genotypes. Addition of brown feathers to the floor in LT hens (feathers were added once/week) was associated with a reduction in feather pecking rate, the severe form of this behaviour and improved plumage and skin conditions. Contrary, the addition of white feathers to the floor in LS was associated with the highest rate of feather pecking, the highest severe form of this behaviour as well as the worst feather and skin conditions in the laying period compared to other groups of the same genotype. The LT birds in all feather treatments had a better feather cover than the LS birds. Hens that were imprinted to loose feathers in the litter in the rearing period exhibited a higher rate of FP, higher number of severe FP and showed the worst feather and skin conditions when feathers were collected from the floor during the laying period. Also, these hens reacted more fearful during the tonic immobility test. It is concluded that loose feathers may play a role in the development of feather pecking behaviour in laying hens. Large differences between genotypes were found in respect to the availability of loose feathers, feather pecking and plumage and integument condition. Imprinting of chicks to loose feathers from the floor may affect the incidence of feather pecking later on. Ziel dieser Arbeit war es, die Einflüsse des Federangebotes und der Prägung auf lose Federn in der Einstreu auf die Häufigkeit des Auftretens von Federpicken (FP), den Zustand des Integuments und die Furchtreaktionen an zwei Legehennengenotypen zu untersuchen. Hühnern beider untersuchter Genotypen (Lohmann Tradition (LT) und Lohmann Silber (LS)), denen die losen Federn 4 mal/ Woche aus der Einstreu abgesammelt wurden, zeigten eine geringere Federpickrate, eine geringere Anzahl der schweren Form des FP und eine bessere Gefiederbeschaffenheit in der Legeperiode verglichen mit der Kontrollgruppe (keine Federbehandlung). Das Hinzufügen brauner Federn zur Einstreu bewirkte bei LT Hennen eine Reduktion der FP-Rate, der schweren Form des Federpickens und verbesserte die Gefieder- und Hautbeschaffenheit. Dagegen führte das Hinzufügen weißer Federn in die Einstreu während der Legeperiode bei LS Hennen zur höchsten Federpickrate und Anzahl der schweren Form des Federpickens sowie zur schlechtesten Gefieder- und Hautbeschaffenheit im Vergleich zu anderen Gruppen des gleichen Genotyps. Hühner der LT Linie wiesen in allen Federbehandlungen eine bessere Befiederung als die LS Hühner auf. Hennen, die während der Aufzuchtsperiode auf lose Federn in der Einstreu geprägt wurden, zeigten nach Absammeln der Federn während der Legeperiode eine erhöhte FP-Rate mit einer erhöhten Anzahl der schweren Form des FP und die schlechteste Gefieder- und Hautbeschaffenheit. Außerdem reagierten diese Hühner ängstlicher während des Tests auf tonische Immobilität. Es kann geschlussfolgert werden, dass lose Federn in der Einstreu eine Rolle bei der Entwicklung des Federpickverhaltens von Legehennen spielen und dass Federpicken als Futtersuchverhalten interpretiert werden kann. Grosse Unterschiede zwischen den Genotypen bestanden hinsichtlich der Verfügbarkeit von losen Federn in der Einstreu, des Federpickens sowie der Gefieder- und Integumentbeschaffenheit. Eine Prägung der Junghennen auf lose Federn in der Einstreu könnte das Auftreten von Federpicken zu einem späteren Zeitpunkt beeinflussen.

Thesis (Ph. D.)--University of California, San Diego, 1998. / Vita. Includes bibliographical references (leaves 92-96).

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005. / Weck, Marcus, Committee Member ; Josowicz, Mira, Committee Member ; Janata, Jiri, Committee Member ; Mizaikoff, Boris, Committee Chair ; Huang, Ching-Hua, Committee Member. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1966. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph.D.)--University of Florida, 2005. / Typescript. Title from title page of source document. Document formatted into pages; contains 137 pages. Includes Vita. Includes bibliographical references.

Orientador: Nelson Ramos Stradiotto / Banca: Sonia Maria Alves Jorge / Banca: Leonardo Lataro Paim / Banca: André Luiz dos Santos / Banca: Rodrigo Alejandro Abarza Munoz / Resumo: A vinhaça é um expressivo coproduto da destilação do etanol que apesar de ser considerada poluidora, vem sendo utilizada como fertilizante nas plantações de cana-de-açúcar, colocando em risco a contaminação de aquíferos subterrâneos e salinização do solo. Cerca de 10 a 18 litros de vinhaça são produzidos por litro de etanol destilado e sua constituição é de principalmente sais de potássio, cálcio, magnésio e compostos orgânicos. Dentre estes, os polióis tornam-se importantes compostos por estarem presentes em concentrações altamente significativas e também por apresentar expressiva importância na indústria farmacêutica e alimentícia. Com isso, o conceito de biorrefinarias surge como a possibilidade das usinas terem um pleno aproveitamento deste resíduo, garantindo fins mais lucrativos e ecológicos. Assim, é de grande importância o desenvolvimento de novos métodos para determinação desses compostos, com destaque aos eletroanalíticos, que vem nos últimos anos se destacando por apresentar métodos de análises confiáveis mesmo em baixas concentrações do analito, pequenos volumes de amostra e em matrizes complexas que requerem alta especificidade. Sendo assim, nesse trabalho foi desenvolvido sensores eletroquímicos baseados na técnica de impressão molecular, capaz de produzir polímeros que incorporam as moléculas de interesse em sua estrutura e que são capazes de formar locais específicos de reconhecimento molecular, tornando-se atrativos devido a sua elevada seletividade e estabil... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Vinasse is an expressive co - product of ethanol distillation, which despite being conside red polluting, has been used as fertilizer in sugarcane plantations, which may put at risk the contamination of groundwater and soil salinization. About 10 to 18 liters of vinasse are produced per liter of distilled ethanol and its composition is mainly of salts of potassium, calcium, magnesium and organic compounds. Among these, polyols become important compounds because they are present in highly concentrations and also due to its importance in the pharmaceutical and food industry . With this, the concept of biorefineries becomes a possibility for the sugar cane plants to take full advantage of this residue, guaranteeing more profitable and ecological ends. Thus, the development of new methods for the determination of these compounds is very important, wit h emphasis on electroanalytical methods, which recently has been presenting reliable methods of analysis even at low analyte concentrations, small sample volumes and in complex matrices that require high specificity . So, in this work, we developed electroc hemical sensors based on the molecular imprinted technique, capable of producing polymers that incorporate the molecules of interest in their structure and that are able to form specific sites of molecular recognition . Therefore, this work reports the deve lopment of an electrochemical method for the determination of polyols based on molecularly imprinted polymers (MIP) using go... (Complete abstract click electronic access below) / Doutor

A series of eight novel bidentate ligands, designed for use in the construction of nickel-selective molecularly imprinted polymers (MIP's), have been prepared. The synthetic pathway was established by retrosynthetic analysis of the target molecules to the readily available precursors, pyridine-2-carbaldehyde (or 6-methylpyridine-2-carbaldehyde) and ethyl bromoacetate. The ligands were designed to contain an allyl group for co-polymerisation and amine and pyridyl nitrogen donors, located to permit the formation of 5-membered nickel chelates. The eight novel ligands and their respective precursors were characterized by elemental (high-resolution MS) and spectroscopic (IR and ¹H and ¹³C NMR) analysis. High resolution electron-impact mass spectrometry has also been used, together with B/E linked scan data, to explore the fragmentation patterns of selected ligands. The various nickel(ll) complexes were analyzed using spectroscopic techniques and, in some cases, elemental analysis; computer modelling has also been used to explore conformational effects and complex stability. Numerous MIP's, containing nickel(II) complexes of the bidentate ligands, have been prepared, using ethylene glycol dimethylacrylate (EGDMA) as the cross-linker, azobis(isobutyronitrile) (AlBN) as the polymerization initiator and MeOH as the porogenic solvent. The template nickel(II) ions were leached out with conc. HCI, and the nickel(II) selectivity [in the presence of Fe(Ill)] of the nickel-imprinted polymers was examined by ICP-MS analysis. The ICP-MS data indicate that the MIP's examined exhibit extremely high selectivity for nickel over iron. / KMBT_363 / Adobe Acrobat 9.54 Paper Capture Plug-in

Orientador: Nelson Ramos Stradiotto / Banca: Hideko Yamanaka / Banca: Luiz Henrique Mazo / Resumo: O óleo fúsel é o co - produto da destilação do etanol e é formado pela mistura de álcoois superiores (álcoois com mais de 3 carbonos), ésteres, aldeídos, entre outros . O volume de óleo fúsel produzido em média é 2,5 L de óleo fúsel por 1000 L de etanol, sendo utilizado como combustível nas caldeiras das usinas, bem como precursores de ésteres utilizados em indústrias de cosméticos e em fabricação de plásticos. O presente trabalho teve como objetivo desenvolver um sensor eletroq uimico (GCE/ RGO /AuNP/MIP) baseado em polímeros molecularmente impressos (MIP), utilizando o pirrol (Py) como monômero, contendo nanopartículas de ouro (AuNP) e óxido de grafeno reduzido ( R GO ) para a de terminação do álcool isoamílico, um dos componentes do óleo fusel. Foram realizados estudos eletroquímicos, como estudo de velocidade de varredura, para determinar reversibilidade do sistema e diagnosticar o controle do processo eletródico. Após os estudos eletroquímicos, foram realizadas caract e rizaç ão morfol ógica por Microscopia Eletrônica de Varredura com Canhão de Emissão de Eletrons c om efeito de campo (MEV - FEG) e caracterização eletroquimica por Espectroscopia de Impedancia Eletroquímica (EIS). A pós a caracterização, foi avaliada a performance analítica do sensor GCE/ RGO /AuNP/MIP, utilizando um intervalo de concentração de 1,0 × 10 - 7 até 1,0 × 10 - 4 mol L - 1, encontra ndo um limite de detecção de 8,2 × 10 - 8 mol L - 1 . F oi determinada a concentração de álcool isoamí lico em amostra de óleo fúsel pelo método de adição de padrão e o valor encontrado foi de 1,6 ×10 - 4 mol L - 1 . O método foi validado através de ensaio de recuperação, mostrando que o sensor desenvolvido é promissor para a utilização em determinação de álcool isoamílico em óleo fúsel. / Abstract: The fusel oil is co - product of the distillation of ethanol and is formed by the mixture of higher alcohols (alcohols having more than 3 carbons) esters, aldehydes, etc. The volume of fusel oil produced on average is 2.5 L fusel oil by 1000 L of ethanol, used as fuel in the boilers of the plants, as well as esters of precursors used in the cosmetics and plastics manufacturing. This study aimed to develop an electrochemical sensor (GCE/ RGO /A u NP/MIP) based on molecularly imprinted polymers (MIP), using pyrrole (Py) as the monomer, containing gold nanoparticles (AUNP) and reduced graphene oxide (RGO) for determining the isoamyl alcohol, one of fusel oil compo nents. They were conducted electrochemical studies, such as study of scanning speed, to determine system reversibility and diagnose the control of the electrode process. After the electrochemical studies were conducted morphological caractrização by Scanni ng Electron Microscopy with Electrons Emission Cannon with field effect (SEM - FEG) and electrochemical characterization by spectroscopy Electrochemical Impedance (EIS). After the characterization, the analytical performance of the GCE/ RGO /AuNP/MIP sensor wa s evaluated using a concentration range of 1.0×10 - 7 to 1.0×10 - 4 mol L - 1, encountering a detection limit 8.2×10 - 8 mol L - 1 . Was determined the concentration of isoamyl alcohol in a sample of fusel oil by standard addition method and the value found was 1.6×1 0 - 4 mol L - 1 . The method was validated by recovery test, showing that the sensor is designed promising for use in determining isoamyl alcohol fusel oil. / Mestre

L'objectif de ce mémoire de thèse est de présenter une nouvelle méthode de synthèse des polymères à empreintes moléculaires, permettant le contrôle de la formation de l'empreinte et la formation du réseau polymère au plus proche de la cible, dans le but d'améliorer leurs capacités. Pour atteindre cet objectif, nous avons choisi d'utiliser la polymérisation radicalaire contrôlée pour la formation du réseau, et le procédé de polymérisation par précipitation pour le contrôle de la morphologie des particules contenant les empreintes. / The objectif of this thesis was to find another method for the preparation of imprinting polymers allowing the control of the formation of the recognition sites, as well as the enhancement of their capacities. We think that beginning the polymer network near the template will permit to increase the recognition. In this purpose, we have used atom transfer radical polymerization and precipitation polymerization for the control of particle's morphologies.